1 15 3 https://www.nal.usda.gov/exhibits/speccoll/files/original/62f7399c340eba5e215718304bfbac19.pdf e3f2b4b55454ed73c4ece6477b153742 PDF Text Text Ram D Number °5385 Author Erickson, Mitchell D, D ^ot Scanned Midwest Research Institute Report/Article TitlB Analytical Methods for By-Product RGBs - Preliminary Validation and Interim Methods Journal/Book TitlB Year 1982 Month/Day October 11 Color D Number of Images 246 UBSCriDtOn NOtBS Task 51, Interim Report No. 4, EPA Contract No. 68-01-5915, MRI Project No. 4901 -A(51) Friday, March 08, 2002 Page 5385 of 5427 �Office of Toxic Substances Washington DC 20460 United States Environmental Protection Agency EPA-560/5-82-006 October, 1982 Toxic Substances v>EPA Analytical Methods for By-Produet PCBsPreliminary Validation and Interim Methods 100.0 T —T"—T 100.0 100.0 l3c 12 H 6 Ci 4 T 280 285 290 T-—r 295 300 305 Da I tons 3tO 315 320 325 �DISCLAIMER This document has been reviewed and approved for publication by the Office of Toxic Substances, Office of Pesticides and Toxic Substances, U.S. Environmental Protection Agency. Approval does not signify that the contents necessarily reflect the views and policies of the Environmental Protection Agency, nor does the mention of trade names or commercial products constitute endorsement or recommendation for use. �ANALYTICAL METHODS FOR BY-PRODUCTS PCBs—PRELIMINARY VALIDATION AND INTERIM METHODS By Mitchell D. Erickson, John S. Stanley, Kay Turman, Gil Radolovich, Karin Bauer, Jon Onstot, Donna Rose, and Margaret Wickham Midwest Research Institute 425 Volker Boulevard Kansas City, MO 64110 TASK 51 INTERIM REPORT NO. 4 EPA Contract No. 68-01-5915 MRI Project No. 4901-A(51) October 11, 1982 For U.S. Environmental Protection Agency Office of Toxic Substances Field Studies Branch TS-798 Washington, D.C. 20460 Attn: Dr. Frederick W. Kutz, Project Officer Mr. David P. Redford, Task Manager �PREFACE This report presents the results of a preliminary method validation accomplished on MRI Project No. 4901-A, Task 51, "PCB Analytical Methodology Task," for the Environmental Protection Agency (EPA Prime Contract No. 6801-5915) during the period April 24 to August 31, 1982. The document was prepared by Drs. Mitchell D. Erickson (Task Leader) and John S. Stanley and Ms. Kay Turman, with assistance from Kathy Funk, Cindy Melenson, and Gloria Sultanik. The laboratory work was conducted by Kay Turman, and Donna Rose, with assistance from Steven Turner. The gas chromatography/mass spectrometry analysis was performed by Gil Radolovich, Margaret Wickham, Jon Onstot, and Arbor Drinkwine. Statistical analysis of the data was provided by Karin Bauer. Editorial comments were provided by Rudena Mallory and Jeanne Robson. The EPA Task Manager, David Redford, has been especially helpful and encouraging. The helpful comments of Ann Carey, Frederick W. Kutz, and John Smith, all of EPA, are also appreciated. SEARCH INSTITUTE C J/mn E. Going, Head Environmental Analysis Section Approved: James L. Spigarelli, Director Analytical Chemistry Department ill �CONTENTS Preface Figures Tables 1. 2. 3. 4. 5. iii vii ix Introduction Summary Experimental Preparation of PCB stock solutions and working standards. Gas chromatography/electron impact mass spectrometry. . . Determination of PCB response factors (GC/EIMS) Validation of method steps Validation with product and product waste samples . . . . Method Validation Preparation of analytical methods Gas chromatography/mass spectrometry of PCBs Validation of selected method steps Validation of product and product waste method with samples Discussion References ' i 1 2 3 3 8 8 19 20 24 24 26 38 45 56 70 Appendix A - Supplementary GC/EIMS Data on PCB Congeners A-l Appendix B - Analytical Method: The Analysis of Incidentally Generated Chlorinated Biphenyls in Commercial Products and Product Wastes B-l Appendix C - Analytical Method: The Analysis of Incidentally Generated Chlorinated Biphenyls in Air C-l Appendix D - Analytical Method: The Analysis of Incidentally Generated Chlorinated Biphenyls in Industrial Wastewater D-l �FIGURES Number 1 2 3 4 5 6 1 8 9 Plot of average response factor versus homolog for 77 PCB congeners 27 Plot of response factor per isomer versus homolog for 77 PCB congeners 28 Plot of response factor per isomer versus homolog for 77 PCB congeners, determined on a single day 32 Retention times of 77 PCB congeners relative to 3,3*4,4'tetrachlorobiphenyl-de (RRT of 1.00) 36 Capillary gas chromatography/electron impact ionization mass spectrometry (CGC/EIMS) chromatogram or the calibration standard solution required for quantitation of PCBs by homolog 39 Reconstructed ion chromatogram for SIM analysis of the CMA-A sample no. 2110 59 SIM ion plots for monochlorobiphenyls (188 and 190 Daltons) and the 13C6-monochlorobiphenyl surrogate (194 Daltons) in CMA-A sample no. 2110 60 SIM ion plots for dichlorobiphenyls (222 and 224 Daltons) in CMA-A sample no. 2110 61 SIM ion plots for trichlorobiphenyls (256 and 258 Daltons) in CMA-A sample no. 2110 62 10 SIM ion plots for tetrachlorobiphenyls (290 and 292 Daltons), 3,3',4,4'-tetrachlorobiphenyl-d6 (298 Daltons), and the 13C12-tetrachlorobiphenyl surrogate (304 Daltons) in CMA-A sample no. 2110 63 11 SIM ion plots for pentachlorobiphenyls (326 and 328 Daltons) in CMA-A sample no. 2110 64 SIM ion plots of hexachlorobiphenyls (360 and 362 Daltons) in CMA-A sample no. 2110 65 12 13 SIM ion plots of heptachlorobiphenyls (394 and 396 Daltons) in CMA-A sample no. 2110 66 vii �FIGURES (continued) 14 15 16 SIM ion plots of octachlorobiphenyls (428 and 430 Daltons) and the ^Cj^-octachlorobiphenyl surrogate (442 Daltons) in CMA-A sample no. 2110 67 SIM ion plots of nonachlorobiphenyl (464 and 466 Daltons) in CMA-A sample no. 2110 68 SIM ion plots of decachlorobiphenyl (498 and 500 Daltons) and the 13C12-decachlorbiphenyl (510 Daltons) in CMA-A sample no. 2110 69 Vlll �TABLES (continued) Number 34 35 Pagj PCB Concentration (pg/g) of CMA-A Samples Treated With Various Cleanup Procedures (Surrogate Compound Correceted) 55 Recovery ( ) of Carbon-13 Labeled Surrogate Compounds % From Diarylide Yellow and Phthalocyanine Blue and Green Pigments 57 XI �TABLES Number Page 1 Numbering of PCB Congeners 5 2 Working Solutions for PCB Response Factors 6 3 Approximate Concentration of Individual PCB Congeners in Dilute Working Standards 7 Concentrations of Congeners in PCB Calibration Standards (ng/ml) 9 4 5 6 7 8 9 Composition of Surrogate Spiking Solution (SS100) Containing 13C-Labeled PCBs 10 Operating Parameters for Capillary Column Gas Chromatographic System 11 DFTPP Key Ions and Ion Abundance Criteria for Quadrupole Calibration 12 Operating Parameters for Quadrupole Mass Spectrometer System 13 Operating Parameters for Magnetic Sector Mass Spectrometer System 14 10 Characteristic Single lion Monitoring (SIM) Ions for PCBs . 15 11 Limited Mass Scanning (LMS) Ranges for PCBs 16 12 Characteristic Ions for 13C-Labeled PCB Surrogates 17 13 Pairings of Analyte, Calibration, and Surrogate Compounds . 18 14 Commercial Product and Product Waste Stream Samples Received for Preliminary Method Validation Studies. . . . 21 15 Preliminary Method Validation Samples 22 16 Comparison of Average Relative Response Factors (RRF) for 77 Commercially Available PCB Congeners Measured Over Several Days as Four Replicates Each Versus Single Measurements of All Congeners in a Single Day 30 IX �TABLES (continued) Number 17 18 Page Average Relative Response Factors (RRF) for PCB Congeners in Solution 1 Measured as Replicates on a Single Day and as Single Measurements for Day-to-Day Basis Measured Average Response Factor (RRF) and Corresponding Upper and Lower 95% Confidence Limits 19 20 31 Relative Response Factors Measured Versus 3,3',4,4'-Tetrachlorobiphenyl-de by Electron Impact Mass Spectrometry Quadrupole (Finnigan 4023) and Magnetic Sector (Varian (MAT 311A) Instruments 34 35 Relative Retention Time (RRT) Ranges of PCB Homologs Versus d6-3,3' ,4,4'-Tetrachlorobiphenyl 37 21 Recovery Data for Acid Cleanup 40 22 Recovery Data for Florisil Column Protocol Cleanup 41 23 Recovery Data for Florisil Slurry Protocol Cleanup 42 24 Recovery Data for KOH Protocol Cleanup 43 25 Recovery Data for Alumina Protocol Cleanup 44 26 Uncorrected PCB Concentrations (pg/g) in CMA-A Samples. . . 46 27 Corrected PCB Concentrations (pg/g) in CMA-A Samples. . . . 47 28 Uncorrected and Corrected PCB Concentrations (|Jg/g) in CMA-E Sample (Dilution Preparation) 49 Uncorrected PCB Concentration (|Jg/g) in the CMA-A Sample Matrix (Internal Standard Calculation) 50 Corrected PCB Concentration ((Jg/g) in the CMA-A Sample Matrix 51 Uncorrected PCB Concentration (|Jg/g) of Spiked CMA-A Samples Determined by the Internal Standard Quantitation Method 52 Corrected PCB Concentration (|Jg/g) of Spiked CMA-A Samples Determined by Surrogate Recovery Correction 53 29 30 31 32 33 PCB Concentration (|Jg/g) of CMA-A Samples Heated With Different Cleanup Procedures (Internal Standard Quantitation) 54 �SECTION 1 INTRODUCTION The Environmental Protection Agency (EPA) is in the process of preparing rules for regulation of certain polychlorinated biphenyls (PCB) which are generated as by-products in the manufacture of commercial products (U.S. EPA, 1982). This regulation is under the Toxic Substances Control Act (PL 94-469), and EPA's Office of Toxic Substances has been assigned the task of preparing the rule. As part of the rule, EPA is suggesting analytical methods for PCBs in air (stack gas and fugitive emissions), wastewater, product waste streams, and final products to assist organizations seeking an exclusion under this rule. To assist EPA in this mission, Midwest Research Institute (MRI) was asked to prepare appropriate analytical methodologies. A literature review and recommendation of general analytical approaches (Erickson and Stanley, 1982; Stanley and Erickson, 1982) constituted the first phase. The second phase, reported here, covers initial method validation and preparation of interim methods. As part of the method validation, four 13C-PCB surrogates were synthesized and are reported separately (Roth et al., 1982). The third phase will involve interlaboratory validation and method refinement. This report presents the initial results of method validation for analysis of by-product PCBs in product and product waste samples. Specifically, gas chromatography/electron impact mass spectrometry retention time and response factor data for 77 PCB congeners for two different gas chromatography/ mass spectrometry systems, recoveries from several proposed cleanup steps, and recoveries from industrial samples using a variety of the method options are presented. �SECTION 2 SUMMARY The objective of this study was to present EPA with appropriate methodologies for the analysis of by-product PCBs in commercial products, product waste streams, wastewaters, and air. In addition, EPA requested preliminary analytical studies to provide data in support of the proposed methods. This document presents proposed analytical methods for the analysis of by-product polychlorinated biphenyls in commercial products and product waste streams (Appendix B), wastewater (Appendix C), and air (Appendix D). The proposed methods are based on determination of PCBs using gas chromatography/ electron impact mass spectrometry (GC/EIMS). Capillary column gas chromatography (CGC) and packed column gas chromatography (PGC) are presented as alternate approaches. The 13C-labeled PCB surrogates are added to samples prior to any sample preparation to allow method flexibility for a wide spectrum of matrices. Recovery of the surrogates will allow determination of the quality of analytical data. This method is valid only if the surrogates are thoroughly incorporated into the matrix. The analytical method for commercial products and product waste streams relies heavily on a strong quality assurance program consisting of use of four 13C-labeled surrogate PCBs, blanks, duplicates, spiked samples, and quality control samples. The analytical methods for water and wastewater are based on EPA Methods 608 and 625, revised to include the use of the 13Clabeled surrogates. Likewise, the air method is a revision of a proposed method for PCBs in air and flue gas emissions. This document presents relative response factors (RRF) of 77 PCB congeners which were used to determine the average RRF for PCBs by homolog. Statistical analysis of the data was performed to check the validity of the response factor data and to extrapolate RRFs for the unavailable congeners. Relative retention time (RRT) data for the 77 PCB congeners are also presented. The RRF and RRT data were determined on both magnetic sector and quadrupole mass spectrometer systems. Preliminary studies were undertaken to check the validity of the proposed methods for the analysis of PCBs in commercial products and product waste streams. Data are presented for analysis of individual cleanup procedures as well as for analysis of product and product waste samples. The data indicate that the proposed method is applicable and useful for analysis of the matrices studied. However, these studies are preliminary and additional validation is necessary and ongoing. �SECTION 3 EXPERIMENTAL The method validation was conducted in three stages: (a) determination of GC/EIMS parameters for 77 PCB congeners; (b) validation of individual method steps with clean matrices; and (c) validation of selected method options with real samples. PREPARATION OF PCB STOCK SOLUTIONS AND WORKING STANDARDS Source of Standards Seventy-seven PCB congeners were acquired from Ultra Scientific, Inc., Hope, Rhode Island, and Analabs, North Haven, Connecticut. Quality control gas chromatography/flame ionization detection (GC/FID) data for the specific isomers were requested to verify the 99% purity assigned to these compounds. The GC/FID data supported the reported purity. In addition, all available nuclear magnetic resonance spectra used for specific isomer identification were requested but not supplied. Weighing Procedures Accurate mass measurement required calibration of a Cahn microbalance with National Bureau of Standards (NBS) certified masses of 5 and 10 mg. The balance was calibrated with the NBS standards followed by calibration of an in-house working standard mass. The calibration of the microbalance with the NBS certified masses was witnessed by a representative of the MRI quality assurance office. The mass of the working standard was measured between all measurements of individual PCB isomers to ensure that the balance was operating accurately. A record of the measured working standard mass was kept in a laboratory notebook. The mean value for the working standard was 10.037 ± 0.002 mg (0.02% relative standard deviation). When all measurements were completed, the mass of the NBS certified standards was determined as a final measure of the accuracy of the Cahn microbalance. Preparation of Solutions Preparation of PCB standard stocks began after accurate performance of the Cahn balance was demonstrated with the certified NBS and daily working standard. An aluminum weighing pan was preshaped such that complete transfer of the weighing pan plus sample could be made directly into the appropriate dilution vessel. The Cahn balance was tared to compensate for the weight of the aluminum boat, and the PCB standards were added via a micro spatula. The mass of the particular PCB was determined with the Cahn balance. �The aluminum pan containing the PCB standard was transferred to the dilution vessel using clean forceps, taking care not to spill any of the sample. The dilution vessel was capped tightly until solvent was added. All PCB congeners were dissolved in toluene (Burdick and Jackson, distilled in glass). Masses of 0.1 to 5 mg were dissolved in a total of 1.0 ml toluene while masses of approximately 10 mg and greater were dissolved in 5.0 ml toluene. The solvent was delivered volumetrically by pipette. Room temperature and solvent temperature were recorded at the time of standard dissolution. Volumetric pipettes used for solvent delivery were calibrated so that the most accurate determination of analyte concentration could be calculated. Toluene was pipetted into a tared vessel, and the total mass was measured. Density of the solvent at the specific room temperature was used to calculate the actual volume dispensed. This calibration was performed for all pipettes used for volumetric delivery of solvent. The stock solutions were sonicated in an ultrasonic bath for at least 15 sec after the volumetric addition of toluene to ensure complete dissolution of the PCBs. The solution level was etched on the side of the dilution vessel as a means of detecting losses by evaporation. The individual PCB congeners were referred to by the congener number indicated in Table 1. The stable labeled PCBs, 3,3',4,4'-tetrachlorobiphenyl-d6, 4-chlorobiphenyl-13Cg, 3,3',4,4'-tetrachlorobiphenyl-13C12, 2,2',3,3',5,5',6,6,'• octachlorobiphenyl-13Ci2> and decachlorobiphenyl-13Ci2 were assigned congener numbers of 210 to 214, respectively, for the purpose of this work. Sample labels were generated in duplicate to identify the specific PCB isomer stock solution and to document entries in the laboratory notebook. Table 2 presents the dilute working solutions that were prepared for determination of the response factors for the PCB congeners. The working solutions were prepared as 10 ml total volume. Table 3 presents the approximate concentration of each congener that was in the dilute working standard used for response factor determination. Tetrachlorobiphenyl-dg was added to 1.0 ml of each solution as the internal standard. All stocks were added to the working solutions in volumes of 20, 200, 250, 400, 500, or 1,000 | l The syringes were calibrated at j. these volumes. Calibration of the 10-ml volumetric flasks used for working standards was accomplished by measuring the difference between the mass of the empty flask and the mass of the flask plus toluene added to the appropriate dilution mark. The density of toluene at the correct solvent temperature was used to calculate the final volume of each solution. The dilute working solutions were divided into multiple aliquots. One hundred micrograms of tetrachlorobiphenyl-de was added to each of the 1.0-ml aliquots of the solutions that were used to establish CGC/EIMS response factors. The remaining dilute working solutions were stored in at least four crimp seal vials and refrigerated. The solvent meniscus was marked in permanent form to note losses of solvents from evaporation or spills. All solutions, stock standards and working solutions, were stored in a refrigerator. All vials removed from storage were first brought to room temperature and then sonicated for at least 15 to 30 sec before removing any of the solution. �Mb. Structure No. Honoetilorobiohenyli 1 2 3 2 3 4 D<eh1arob1ph«ny!s 4 5 6 7 8 9 10 11 12 13 1415 2.2' 2.3 2,3' 2,4 2,4' 2,5 2,6 3,3' 3,4 3,4' 3,5 4,4' TrlehlaroMehtnyls 16 17 13 19 20 21 22 23 24 25 26 27 23 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 15 46 47 48 49 50 51 2,2', 3 2,2', 4 2,2', S 2,2', 6 2,3,3' 2,3,4 2,3,4' 2,3,5 2,3,6 2,3', 4 2, 3', 5 2, 3', 6 2,4,4' 2,4,5 2,4,6 2, 4 ' , 5 2, 4'. 5 2 ' , 3, 4 2', 3,5 3,3', 4 3,3',S 3,4,4' 3,4,5 3.4', S NTJMBERING OF PCB CONGENERS a Structure Ha, Tttnehl orofal phtnyl s 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 2,2'.5.5' 2,2'.5,6' 2,2', 5,6' 2.3.3',4 2,3,3'. 4' 2,3,3', S 2,3,3'. 5' 2.3.3'. 6 2.3,4,4' 2,3,4,5 2,3,4.6 2, 3, 4', 5 2, 3,4', 6 2,3,5,6 2, 3', 4, 4' 2. 3'. 4,5 2,3'. 4,5' 2,3'. 4, 6 2,3', 4 ' , 5 2,3' ,4'. 6 2,3' ,5, 5' 2,3',5'.6 2,4,4', 5 2,4,4' .6 2'. 3 4,5 3,3' 4,4' 3,3' 4,5 3,3' 4,5' 3,3' 5,5' 3. 4, 4 ' , 5 Pentachl orobl cheny 1 s 82 83 84 85 86 37 88 39 90 91 92 93 94 TttracMoromehwyli 95 96 97 2, 2', 3,3' 98 2 2' 3 4 2;2','3,4' 99 100 2. 2'. 3.5 101 2,2', 3, 5' 2,2',3,6 102 2.2' .3.6' 103 2,2',4,4' 104 2,2' ,4, 5 2,2', 4,5' 2,2', 4, 6 2,2', 4, 6' TABLE 1. Structure 2,2',3.3',4 2.2'. 3. 3', S 2,2', 3, 3' .6 2,2', 3, 4, 4' 2,2'.3.4.5 2, 2'. 3, 4, 5' 2,2', 3, 4, 6 2,2', 3, 4, 5' 2,2', 3, 4 ' , 5 2, 2', 3, 4'. 5 2.2* .3,5,5' 2,2', 3,5, 6 2,2'.3,5,5' 2, 2', 3.5', 5 2,2',3,6,6' 2,2'. 3'. 4.5 2,2',3'.4,5 2,2' ,4. 4'. 5 2 2' .4,4'. 6 2,2'. 4, 5, 5' 2,2' ,4, 5, 6' 2,2', 4,5'. 5 2,2' .4. 6,5' NO. Structure 161 162 163 164 165 166 167 168 169 2,3.3 I ,4,5',6 2, 3, 3'. 4 ' , 5, 5' 2, 3,3'. 4 ' , 5, 6 2, 3, 3', 4 ' , S ' , 6 2, 3,3', 5. 5 ' , 5 2. 3. 4, 4 ' , 5, 6 2,3', 4, 4 ' . 5. 5' 2,3',4,4',5'.S 3,3',4,4',5.S' Pentaehl orobi oheny 1 s 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 2,3, 3', 4,4' 2,3,3',4,5 2, 3, 3'. 4'. 5 2,3, 3'. 4, 5' 2.3, 3', 4, 6 2.3, 3'. 4' ,6 2.3.3' ,5,5' 2,3,3',5,6 2,3.3', 5', 6 2,3,4. 4'.5 2,3,4,4'. 6 2,3,4,5,6 2,3, 4 ' , 5, 6 2,3',4,4',5 2, 3', 4, 4 ' , 6 2,3' ,4, 5,5' 2,3', 4, 5 ' , 5 2' ,3, 3', 4,5 2' .3. 4, 4 ' . 5 2' .3. 4, 5, 5' 2'. 3, 4.5, 6' 3, 3' ,4, 4 ' , 5 3,3',4,5,5' Hexaehlorobiofienyls 128 129 130 131 132 133 134 135 '136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 2,2', 3,3', 4, 4 ' 2,2', 3, 3', 4, 5 2,2', 3,3', 4, 5' 2,2'. 3, 3'. 4,6 2,2', 3,3', 4, 6' 2,2'.3,3',5,5' 2,2'. 3, 3', 5, 6 2,2', 3, 3' ,5, 5' 2, 2'. 3,3'. 6, 6' 2,2* ,3,4,4', 5 2,2'.3,4,4 I .S 1 2, 2 ' , 3, 4, 4', 6 2, 2 ' , 3, 4, 4 ' . 6' 2,2', 3, 4, 5, 5' 2,2', 3, 4, 5, 6 2,2' ,3, 4. 5,6' 2,2', 3, 4, 5 ' , 6 2,2', 3. 4, 5, 5' 2,2'. 3. 4 ' , 5, 5' 2,2', 3. 4 ' , 5,5 2,2', 3, 4 ' . 5, 5' 2, 2' ,3, 4', 5 ' , 5 2,2',3,4',6,6' 2,2' .3,5, 5'. 5 2,2', 3, 5,6, 6' 2, 2 ' , 4, 4 ' , 5, 5' 2.2', 4, 4 ' , 5, 5' 2,2', 4 , 4 ' , 6, 5' 2,3,3', 4, 4 ' , 5 2,3, 3', 4, 4 ' , 5' 2,3, 3', 4, 4 ' . 5 2,3, 3'. 4, 5, 5' 2,3,3'. 4, 5.5 HexachlorobiBnefiyls Heotactilorobiohenyl s 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 2, 2', 3, 3' , 4 , 4 ' ,5 2, 2 ' , 3, 3', 4 , 1 ' , 5 2, 2', 3, 3', 1,5,5' 2, 2'. 3, 3 ' , 1,5, 5 2, 2 ' , 3, 3 ' , 1,5, 5' 2. 2'. 3, 3', 4 , 5 ' , 5 2, 2', 3, 3 ' , 4, 5, 5' 2.2',3,3',4',5,a 2, 2 ' , 3, 3', 5, 5 ' , 5 2, 2 ' , 3, 3 ' , 5, 5, 5' 2. 2'. 3, 4. 4 ' , 5, 5' 2, 2', 3, 4, 4 ' , 5,6 2, 2 ' , 3. 4, 4 ' , 5, 5' 2, 2'. 3, 4, 4 ' , = ' , 6 2, 2', 3, 4, 4 ' , i, 5' 2, 2 ' , 3, 4, 5, 5' ,6 2, 2 ' , 3, 4, 5. 6, 6' 2, 2 ' , 3, 4 ' , 5,5' ,5 2. 2 ' , 3, 4 ' , 5, 5, 6' 2, 3, 3', 4, 4 ' . 5,5' 2, 3, 3', 4, 4 ' , 5, 5 2, 3, 3' ,4, 4 ' , 5 ' , 5 2,3, 3', 4, S, 5 ' , a 2,3,3'.4',S,5',5 Octacnl orjb • cne«y 1 s 194 195 196 197 198 199 200 201 202 203 204 205 2 , 2 ' , 3, 3', 4 , 4' , 5 , 5 ' 2, 2', 3, 3' , 4 , 4 ' ,5,5 2 , 2 ' , 3 , 3 ' ,4,1', = , 5 ' 2, 2', 3, 3 ' , 4,1', 5, 5' 2, 2 ' , 3 , 3 ' , 1,5,5' ,5 2, 2 ' , 3, 3 ' , 4, 5, 5, 5' 2, 2 ' , 3,3', 4, 5' , 5 , 5 ' 2, 2 ' , 3, 3'. 4, 5. 5 ' . 5' 2, 2'. 3, 3', 5, 5' ,5,5' 2, 2 ' , 3, 4, 4 ' , 5, 5 ' . 6 2, 2 ' , 3, 4, 4' , 5 , 6 , 5 ' 2,3. 3', 4, 4 ' . 5, 5 ' , 5 Monsehtcrobi;ns''yl s 206 207 208 2. 2 ' , 3, 3 ' , 1,1', 5, s ' , 5 2. 2', 3,3', 4 , 1 ' , 5, 5, 5' 2, 2 ' , 3, 3'. 4, 5, 5 ' , 5,5' DecachloHjOionenyi 209 2,2',3,3'4,4',5,5'.5,5' Adapted from Ballschmiter K, Zell M. 1980. Analysis of polychlorinated biphenyls (PCB) by glass capillary gas chromatography. Composition of technical Aroclorand Clophen-PCB mixtures, Fresenius Z. Anal Chera 302:20-31. �TABLE 2. PCB Soln. homolog no. 1 Soln. no. 2 Soln. no. 3 Soln. no. 4 WORKING SOLUTIONS FOR PCB RESPONSE FACTORS Soln. no. 5 PCB congener no. Soln. Soln. Soln. Soln. no. 6 no. 7 no. 8 no. 9 Soln. Soln. Soln. Soln. no. 10 no. 11 no. 12 no. 13 1 2 3 Dichloro- 11 5 7 8 9 10 4 12 14 Trichloro- 29 21 31 26 24 28 18 33 30 Tetrachloro- 47 44 40 49 50 52 53 54 66 61 65 69 72 Pentachloro- 121 97 88 93 101 103 100 104 a 115 87 116 119 Hexachloro- 136 129 128 137 138 141 143 151 139 153 154 155 156 Heptachloro- 181 171 183 185 Octachloro- 195 194 198 200 202 204 Nonachloro- 207 208 206 Decachloro- 209 9 9 Soln. no. 14 Monochloro- 15 70,75,77 Total congeners a 10 7 6 6 5 5 4 4 3 3 3 3 Congener no. 112 was added to this solution but, on analysis, was determined to have a mass of 286 and appeared to be a diaminotrichlorobiphenyl. This congener was omitted from any further consideration. �TABLE 3. APPROXIMATE CONCENTRATION OF INDIVIDUAL PCB CONGENERS IN DILUTE WORKING STANDARDS5 PCB horaolog Concentration (pg/ml) Monochlorobiphenyl 50 Dichlorobiphenyl 50 Trichlorobiphenyl 50 Tetrachlorobiphenyl Pentachlorobiphenyl 100 Hexachlorobiphenyl 100 Heptachlorobiphenyl 100 Octachlorobiphenyl 200 Nonachlorobiphenyl 200 Decachlorobiphenyl a 100 200 Tetrachlorobiphenyl-de was added to all solutions as an internal standard at *> 100 |Jg/ml. �Preparation of Calibration Standard and Spiking Mixtures A mixture of 11 congeners was used for calibration. This solution was spiked into solvent for protocol step validation experiments and into product and product waste samples for standard addition experiments. These congeners were determined to be the best standards for quantitation calibration based on the average relative response factor for each PCB homolog, as will be discussed in Section 5. Table 4 presents the composition of the 11-component solutions that are specified as the calibration standards, CSxxx, where the xxx is used to encode the nominal concentration in nanograms per milliliter. A more concentrated solution was diluted as necessary to prepare spiked samples and the appropriate standards for GC/EIMS analysis. The internal standard, tetrachlorobiphenyl-dg, was added to all standards and final extracts before GC/ EIMS analysis. The standards contained the four 13C-labeled PCBs that were added from the spiking solution shown in Table 5. GAS CHROMATOGRAPHY/ELECTRON IMPACT MASS SPECTROMETRY The capillary gas chromatography parameters used are shown in Table 6. The quadrupole and magnetic sector mass spectrometer parameters used are shown in Tables 7 through 9. The characteristic ions for single ion monitoring and limited mass scanning are presented in Tables 10 through 12. All data generated for relative response factors and concentration levels of PCBs in sample extracts were calculated based on the area of the primary quantitation ion specified in Table 10. The quantitation ions for the 13Clabeled monochloro-, tetrachloro-, octachloro-, and decachlorobiphenyl were 194, 304, 442, and 510 Daltons, respectively. The pairings of analyte, calibration, and surrogate compounds are presented in Table 13. DETERMINATION OF PCB RESPONSE FACTORS (GC/EIMS) The response factors for 77 PCB isomers were determined by GC/EIMS using the working standards prepared as described in Tables 2 and 3. A high resolution capillary column (J&W Scientific Durabond DB-5, 15 m, 0.25 |Jm film thickness) was used for the separation of the PCB mixtures. Scanning mass spectrometry was used to calculate response factors for the PCB isomers present in each solution versus a known quantity of tetrachlorobiphenyl-dgThe quadrupole GC/EIMS system was tuned daily prior to any acquisition of data for PCB response factor calculations. The system was brought to operating temperature for at least 15 min. The fluorocarbon FC-43 was introduced to the ion source, and 176 and 502 Daltons were manually adjusted 'to a two-to-one ratio. This was accomplished by adjusting the multiplier voltage to 300 mV while monitoring 176 Daltons. A selected ion monitor acquisition was set up for 176 and 502 Daltons with a variance of 1 Dalton. The ratio of the two values was tuned to the two-to-one ratio as described above. The mass spectrometer was operated in the normal full scan acquisition mode after tuning with the FC-43. Approximately 100 ng of decafluorotriphenylphosphine was injected and the ratio of the values of 198/442 was monitored. �TABLE 4. CONCENTRATIONS OF CONGENERS IN PCS CALIBRATION STANDARDS (ng/ml)a Homolog Congener no. CS1000 CS100 CS050 CS010 1 1 1,040 104 52 10 1 3 1,000 100 50 10 2 7 1,040 104 52 10 3 30 1,040 104 52 10 4 50 1,520 152 76 15 5 97 1,740 174 87 17 6 143 1,920 192 96 19 7 183 2,600 260 130 26 8 202 4,640 464 232 46 9 207 5,060 506 253 51 10 209 4,240 424 212 42 4 255 255 255 255 1 211 (RS) 104 104 104 104 4 212 (RS) 257 257 257 257 8 213 (RS) 407 407 407 407 10 a 210 (IS) 214 (RS) 502 502 502 502 Concentrations given as examples only. �TABLE 5. COMPOSITION OF SURROGATE SPIKING SOLUTION (SS100) CONTAINING 13C-LABELED PCBs3 Congener no. Compound Concentration (|jg/ml) 211 104 212 ,3' (13C12)3 ,4,4'-tetrachlorobiphenyl 257 213 (13C12)2 ,2', 3, 3', 5, 5' ,6,6'-octachlorobiphenyl 214 a 1 13 (I1, 2', 3 ,4',5',6'- C6)4-chlorobiphenyl (13C12)decachlorobiphenyl Concentrations given as examples only. 10 395 502 �TABLE 6. OPERATING PARAMETERS FOR CAPILLARY COLUMN GAS CHROMATOGRAPHIC SYSTEM Parameter Value Gas chromatograph Finnigan 9610 Column 15 m x 0.255 mm ID Fused silica Liquid phase DB-5 Liquid phase thickness 0.25 urn Carrier gas Helium Carrier gas velocity 45 cm/sec Injector On-column (J&W) Injector temperature Optimum performance Injection volume 1.0 Mlb Initial column temperature 110°C (2 min)c Column temperature program . 110° to 325°C at 10°C/min d Separator None Transfer line temperature 280°C (J&W) a Measured by injection of air or methane at 270°C oven temperature. b For on-column injection, follow J&W instructions regarding injection technique. c With on-column injection, the initial temperature equals the boiling point of the solvent; in this instance toluene. d C12Clio elutes at 270°C. Programming above this temperature ensures a clean column and lower background on subsequent runs. e Fused silica columns may be routed directly into the ion source to prevent separator discrimination and losses. 11 �TABLE 7. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA FOR QUADRUPOLE CALIBRATION Mass Ion abundance criteria 197 198 199 Less than 1% of mass 198 100% relative abundance 5-9% of mass 198 275 10-30% of mass 198 365 Greater than 1% of mass 198 441 442 443 Present but less than mass 443 Greater than 40% of mass 198 17-23% of mass 442 12 �TABLE 8. OPERATING PARAMETERS FOR QUADRUPOLE MASS SPECTROMETER SYSTEM Parameter Value Mass spectrometer Finnigan 4023 Data system Incos 2400 Scan range 95-550 Scan time 1 sec Resolution Unit Ion source temperature 280°C Electron energy3 70 eV Trap current 0.2 mA Multiplier voltage -1,600 V Preamplier sensitivity 106 A/V a Filaments should be shut off during solvent elution to improve instrument stability and prolong filament life, especially if no separator is used. 13 �TABLE 9. OPERATING PARAMETERS FOR MAGNETIC SECTOR MASS SPECTROMETER Parameter SYSTEM Value Mass spectrometer Finnigan MAT 311A Data system Incos 2400 Scan range 98-550 Scan mode Exponential Cycle time 1.2 sec Resolution 1,000 Ion source temperature 280°C pt Electron energy 70 eV Emission current 1-2 mA Filament current Optimum Multiplier -1,600 V a Filaments should be shut off during solvent elution to improve instrument stability and prolong filament life, especially if no separator is used. 14 �TABLE 10. CHARACTERISTIC SINGLE ION MONITORING (SIM) IONS FOR PCBs Ion (relative intensity) Homo log Primary Secondary Ca2H9Cl 188 (100) 190 (33) CigHgCla 222 (100) 224 (66) 226 (11) C12H7C13 256 (100) 258 ( 9 9) 260 (33) Ci2H6Cl4 292 (100) 290 (76) 294 (49) Ci2HsCl5 326 (100) 328 ( 6 6) 324 (61) C12H4C16 360 (100) 362 (82) 364 (36) Ci2H3Cl7 394 (100) 396 ( 8 9) 398 ( 4 5) £12^2^-8 430 (100) 432 ( 6 6) 428 (87) Ci2HClg 464 (100) 466 (76) 462 (76) C 498 (100) 500 ( 7 8) 496 ( 8 6) 12CllO Source: a Tertiary _a Rote JW, Morris WJ. 1973. Use of isotopic abundance ratios in identification of polychlorinated biphenyls by mass spectrometry. J Assoc Offie Anal Chem 56(1):188-199. / None available. 15 �TABLE 11. LIMITED MASS SCANNING (LMS) RANGES FOR PCBs ft Mass range (Daltons) Compound C^Cl, 186-190 C12H8C12 220-226 C12H7C13 254-260 C12H6C14 288-294 C12H5C15 322-328 C12H4C16 356-364 Lj *i oXloL^J-V 386-400 \_, -i OJlOvjJ^Q 426-434 \j i O-H-W-L o 460-468 1210 494-504 C12D6C14 294-300 13 192-196 13 300-306 13 438-446 C612C6H9C1 C12H6C14 C12H2C18 13 506-516 C12C110 a Adapted from Tindall GW, Wininger PE. 1980. Gas chromatography-mass spectrometry method for identifying and determining polychlorinated biphenyls. J Chromatogr 196:109-119. 16 �TABLE 12. CHARACTERISTIC IONS FOR 13C-LABELED PCB SURROGATES Primary Ion (relative intensity) Secondary Tertiary 13 194 (100) 196 (33) a 13 304 (100) 306 (49) 302 (78) 13 442 (100) 444 (65) 440 (89) 13 510 (100) 512 (87) 514 (50) Compound C612C6H9C1 C12H6C14 C12H2C18 Ci2Cl10 a None available. 17 �TABLE 13. PAIRINGS OF ANALYTE, CALIBRATION, AND SURROGATE Analyte Congener no. I 2,3 4-15 16-39 40-81 82-127 128-169 170-193 194-205 206-208 209 Calibration standard Compound 2-C12H9Cl 3- and 4-C12H9Cl C12HgCl2 C12H7C13 C^HsCls Cl^EUClg C12H3C17 C12H2Clg Ci2HCla C12C110 Congener no. 1 3 7 30 50 97 143 183 202 207 209 Compound 2 4 2,4 2,4, 6 2,2' ,4,6 2,2' ,3', 4, 5 2,2' ,3,4,5 ,6' 2,2' ,3', 4, 4',5',6 2,2' Q Q t 5,5' ,6,6' 2,2' 3 3' 4, 4', 5, 6, 6' r L Lior COMPOUNDS Surrogate Congener no. 211 211 211 212 212 212 212 213 213 213 214 Compound 13 C6-4 C6-4 13 C6-4 13 C12-3 ,3' ,4,4' 13 C12-3 ,3' ,4,4' 13 C12-3 ,3' ,4,4' 13 C12-3 ,3' ,4,4' 13 Ci2-2 ,2' ,3,3' ,5,5' ,6,6' 13 3 3* Ci2-2 ,2' ,0,0 ,5,5' ,6,6' 13 C12-2 ?' ,3,3' 5 5 r ,6,6' 1ft 13 �The response of 198 Daltons was 100% full scale and 442 Daltons was adjusted from 40 to 45% of the base peak. These criteria were met daily before data acquisition for response factor calculations was initiated. All working standards were brought to room temperature and sonicated before injection into the GC/MS system. Solution No. 1 was analyzed daily as a means of normalizing response factors calculated from day to day. This allowed some compensation for differences in sensitivity due to subtle changes in the mass spectrometer operation from day to day. Also, a solution of tetrachlorobiphenyl-de (internal standard) was analyzed separately. Four replicates of each working standard were analyzed to calculate variances of the response factors. The solutions were sonicated at least 15 sec prior to removal of sample for injection. The syringe and needle were rinsed with 200- to 300-|Jl of toluene between injections. The gas chromatograph was operated at 110°C for 2 min, and programmed at 10°C/min to 325°C. One microliter injections were made with a J&W on-column injection system. Helium carrier flow was adjusted to 45 cm/sec. The peak shape of the eluting PCBs was monitored. If excessive tailing was noted, the injection end of the fused silica capillary column was removed and shortened by at least 10 cm. Tables 6, 7, and 8 present the instrument and operating parameters that were used to measure the response factors for the individual PCB isomers in the working solutions. Response factors (RF) were calculated using the area of the peaks for these ions according to the equation: A M _ ~r PCB rj IS OT — Kr A IS WPCB A where MPCB = .IS = ..IS = PCB = Area of the quantitation peak of the specific PCB, Mass (in nanograms) of the internal standard injected, Area of the quantitation peak of the internal standard, and Mass (nanograms) of the specific PCB injected. All relative response factor data were subjected to Student's t-test at the 95% confidence level to test for significant differences for day-to-day and solution-to-solution variances. VALIDATION OF METHOD STEPS A limited number of experiments were completed as preliminary validation steps for the proposed method presented in Appendices B through D. The experiment included evaluation of several of the cleanup procedures using solvent spiked with the 13C-labeled surrogates and a mixture of PCB congeners representing each of the possible homologs. The laboratory cleanup procedures followed the protocol steps except where noted. One hexane solvent blank was analyzed by each procedure with the samples to monitor interferences and contamination. 19 �All samples were analyzed by CGC/EIMS in the full scan mode using the Finnigan 4023 system. Tables 6, 7, and 8 present the instrumental parameters. VALIDATION WITH PRODUCT AND PRODUCT WASTE SAMPLES Sources of Samples Product waste samples were received from Dow Chemical Company (Kent Hodges) and Vulcan Materials Company (Thomas Robinson) through the cooperation of the Chemical Manufacturers Association (Robert Fensterheim). These samples are aliquots of the materials used for the Chemical Manufacturers Association (CMA) round robin study (CMA, 1982). The CMA and associates supplied samples of chlorinated benzene waste streams, mixtures of chlorinated benzenes, composite waste streams from a chlorinated aliphatic process and a benzene column bottom sample. Table 14 presents an inventory of all the samples received. Product samples were received from the Dry Color Manufacturers Association (J. Lawrence Robinson and Maria DaRoche). These samples included diarylide yellow, phthalocyanine green, and phthalocyanine blue pigments that were used in the Dry Color Manufacturers Association (DCMA) round robin study of an analytical method, reported by the DCMA (1981). These samples are also included in the inventory in Table 14. The samples supplied by industry are examples of the samples which will be analyzed using the method in Appendix B. However, since no attempt was made to span the range of products and product wastes, the samples analyzed do not include all matrices which an analyst could encounter. Experimental Design Table 15 presents an overview of the preliminary method validation samples. The samples from Table 14 that were used for these studies included the chlorinated benzene waste stream, CMA-A; the benzene column bottom sample, CMA-E; and the yellow, blue, and green pigment samples, DCMA-1, DCMA-4, and DCMA-8, respectively. Blind quantitation standards and quality control samples were prepared by the MRI quality control staff either through spiked addition or by dilution of particular sample matrices. Other quality control procedures included the analysis of duplicate samples and blanks and the validation of cleanup steps. Two sets of samples were prepared and run at separate times. This first sample set us designated by numbers 10 through 110 and the second sample set is designated by numbers 2001 through 2210Q in Table 15. The sample preparations ranged from addition of the 13C-labeled surrogates followed by dilution and injection, to preparation of pigment samples via sulfuric acid dissolution and hexane extraction or methylene chloride extraction with Florisil cleanup. 20 �TABLE 14. COMMERCIAL PRODUCT AND PRODUCT WASTE STREAM SAMPLES RECEIVED FOR PRELIMINARY METHOD VALIDATION STUDIES3 Sample no. Quantity Sample description Sample source CMA-A 100 ml Chlorinated benzene waste stream CMA-B 100 ml Mixture of chlorinated benzenes Dow Chemical Co. with Aroclor 1254 spike CMA-C 100 ml Blind spike of CMA-B with the addition of 64 ppm of PCB isomers Dow Chemical Co. CMA-A 5 ml Vulcan Materials Co. CMA-B 5 ml CMA-C 5 ml CMA-D 5 ml CMA-E 5 ml Chlorinated benzene waste stream Mixture of chlorinated benzenes with Aroclor 1254 spike Blind spike of CMA-B with the addition of 64 ppm of PCB isomers Composite waste stream sample from a chlorinated aliphatic process Benzene column bottoms sample Diarylide yellow pigment Phthalocyanine green pigment Phthalocyanine blue pigment Phthalocyanine blue pigment Phthalocyanine green pigment DCMA DCMA DCMA DCMA DCMA DCMA-1 DCMA-4 DCMA-6 DCMA-8 DCMA-9 100 100 100 100 100 g g g g g Dow Chemical Co. Vulcan Materials Co. Vulcan Materials Co. Vulcan Materials Co. Vulcan Materials Co. a Aliquots of CMA-A, CMA-B, and CMA-C were received from two sources, who indicated that they were identical. MRI has assumed that both aliquots are the same. 21 �TABLE 15. PRELIMINARY METHOD VALIDATION SAMPLES Sample no. Description Preparation 10 20A 20B 60 110 2001 2005 2010 CMA-A CMA-A CMA-A Hexane blank CMA-E Hexane blank CMA-A3 CMA-A 0.1 g/10 ml hexane 0.1 g/10 ml hexane 0.1 g/10 ml hexane None None None • 0.1 g/1 ml hexane 0.1 g/1 ml hexane 0.1 g/1 ml hexane 0.5-0.2 g/1 ml hexane 0.1 g/1 ml hexane 0.1 g/1 ml hexane 0.1 g/1 ml hexane 0.1 g/1 ml hexane None DCMA-A DCMA-A (0.1 g) DCMA-B DCMA-B (0.1 g) Base Base (0.1 g) DCMA-B (1.0 g) DCMA-B (1.0 g) DCMA-B (1.0 g) DCMA-B (1.0 g) DCMA-B (1.0 g) DCMA-B DCMA-B DCMA-B DCMA-A DCMA-A DCMA-A None 2020 CMA-A 2025Q 2030 2040 2050 2060Q 2070Q 2080 2090 2100 2110 2120 2130 2135 2140 2150 2160 2170Q 2175 2180 2185 2190 2195 2200Q 2210Q CMA-A CMA-A + CS002 CMA-A + CS005 CMA-A + CS010, CMA-A + CSXXX CSxxx Blank, CMA-AD Blank, CMA-AD Blank CMA-A DCMA-13 DCMA-1 DCMA-1 DCMA-1 + no. 11 (50 ppm) DCMA-1 + no. 11 (20-80 ppm) DCMA-4 DCMA-4 DCMA-4' DCMA-8 DCMA-8* DCMA-8 CSxxx Dilution factor 1/100 1/100 1/100 None None None 1/10 1/10 1/10 1/10 1/10 1/10 1/10 1/10 None 1/10 1/10 1/10 1/10 1/10 1/10 1/100 1/100 1/100 1/200 1/200 1/100 1/100 1/100 1/50 1/50 1/50 None a No surrogates added to assess any background interferences for these compounds. b Prepared from aliquot received from Dow Chemical Company; all other CMA-A samples prepared from aliquot received from Vulcan Materials Company. 22 �The CMA-A and CMA-E samples were each analyzed after 1/10 or 1/100 dilution, depending on the operating sensitivity of the mass spectrometer. The CMA-A chlorinated benzene waste was the most extensively studied matrix of the available samples. Sample preparation included the simple dilution described above with and without the addition of the four surrogates. The samples prepared without surrogates allowed measurement of the background that might interfere with the four surrogate compounds. Duplicate samples of the CMA-A were analyzed at the same dilution in two separate experiments. The CMA-A matrix was also analyzed by standard addition methods with total spiked PCS levels of the 11-compound spiking solution (CS050) at approximately 70, 140, and 270 ng/sample. The CMA-A matrix was also prepared using the sulfuric acid and ethanolic KOH procedures discussed in Section 9.3.2 of Appendix D, Cleanup of the Analytical Method: The Analysis of By-Product Chlorinated Biphenyls in Commercial Product and Product Wastes (Appendix B). Variations of the analytical procedures used by the Dry Color Manufacturers Association (1981) for the analysis of PCBs in various pigments were also applied to the CMA-A matrix. The DCMA procedures included acid dissolution followed by hexane extraction from the acid (DCMA Preparation A) and Florisil treatment of the concentrated sample matrix (DCMA Preparation B). The homogenization and centrifugation steps required by the DCMA-B procedure were not included for the CMA-A matrix. All samples except those representing blanks were spiked with the surrogates at levels of 100 to 500 ng and were mixed thoroughly before beginning the sample preparation. The typical CMA-A sample size was 0.1 g. The diarylide yellow (DCMA-1), phthalocyanine green (DCMA-4), and pthalocyanine blue (DCMA-8) pigments were also studied in these preliminary validations. The yellow pigment was prepared according to the recommended DCMA-B procedure, while the green and blue pigments were analyzed following the DCMA-A procedure. The preparation of the pigments followed the DCMA procedures except that the preparation was scaled to 1 g of the yellow pigment instead of the recommended 5 g. Blanks, duplicates, and spiked samples were also analyzed with the set of DCMA samples. Sample Analysis All extracts were analyzed by capillary column gas chromatography/electron impact mass spectrometry (CGC/EIMS). Limited mass scanning (LMS) or selected ion monitoring (SIM) mass spectrometry methods were used for extract analysis, depending on the level of PCBs in the sample extracts and the complexity of the matrix. The parameters for analysis via CGC/LMS and CGC/ MS-SIM are presented in Tables 6 through 13. 23 �SECTION 4 METHOD VALIDATION PREPARATION OF ANALYTICAL METHODS Analytical methods were prepared for the analysis of by-product PCBs in: * Commercial products and product wastes (Appendix B). * Air (Appendix C). * Industrial wastewater (Appendix D). The analysis of commercial products and product wastes was covered in one method since the diversity of matrices in both categories dictates the same generalized approach. Air was defined to include stack gases, fugitive emissions, and static (room, other container, or outside) air. Commercial Products and Product Wastes Method The objective was to devise an analytical method suitable for enforcement of the regulation concerning by-product PCBs in commercial products and product wastes. A detailed rationale for selection of the techniques used in the method may be found in a separate report (Erickson and Stanley, 1982). Sample Workup-The general approach taken with sample preparation (collection, preservation, extraction, and cleanup) was to provide a framework within which any reasonable technique could be used. This is the only acceptable approach to a method designed to cover "any" matrix. , The use of 13C-labeled recovery surrogates in conjunction with GC/EIMS was judged to be the most suitable approach (Erickson and Stanley, 1982; Stanley and Erickson, 1982; Roth et al., 1982). Using the recovery surrogates, any losses of PCBs would be detected and could be corrected for in the calculation of the PCB concentration. 24 �When surrogates are not fully incorporated into the matrix, their recovery will not be representative of the analyte PCB recoveries and recovery assessment will not be possible. It is incumbent upon the analyst to recognize this problem and use good scientific judgment with samples that present a potential problem. Nonextractable solid polymers may be an example of a matrix presenting incorporation problems. PCB Determination-As discussed elsewhere (Erickson and Stanley, 1982; Stanley and Erickson, 1982) , GC/EIMS appears to be the only acceptable general technique for determining PCBs in commercial products and product wastes. The use of either capillary or packed column GC is permitted. While strong arguments are presented for both techniques (Stanley and Erickson, 1982), the analytical results should be comparable for both techniques provided proper instrument calibration and operation, analytical, and quality control procedures are followed as described in the analytical methods. Quantitation-The analytical objective of these methods is to determine if the sample contains quantifiable PCBs and, if so, at what concentration. On the assumption that a general knowledge of the congener distribution is important, reporting of the concentration by homolog is proposed in the reporting form. Since a "total PCB" value is also important for summary and comparative purposes, space for this value is also provided on the reporting form. Other reporting formats, including "largest isomer or resolvable peak" or "all peaks greater than a regulatory value," may be easily accommodated using different tabulations and reporting procedures. The PCB concentrations found may be lower than the actual value due to nonquantitative recovery during extraction or cleanup. The measured recoveries of the surrogates may be used to derive a corrected concentration. The analyst must take care that the surrogates are thoroughly incorporated into the matrix prior to extraction, as discussed above. The analyst must also guard against improper corrections because of errors in surrogate quantitation. These errors may arise from background interferences. A more thorough discussion of quantitation options is presented in a previous report (Erickson and Stanley, 1982). Air Method The sample collection, preservation, extraction, and cleanup aspects were taken from the work of Haile and Baladi (1977). The determination, using GC/ EIMS, is identical to that in the commercial products and product wastes method except that recovery surrogates are not used. Wastewater Method The water method is a direct modification of the commercial products and product wastes method. As noted in this method, the cleanup and extraction procedures for EPA Methods 608 (U.S. EPA, 1979b) and 625 (U.S. EPA, 1979a) may be used. It is anticipated that, unless conditions dictate otherwise, most analysts will choose this option. 25 �Quality Control Each method includes a strong quality control (QC) section. Given the complexity of the matrices and complexity of the analyte (209 compounds), the need for QC is evident. The various aspects of the QC section were designed assuming a reasonably large (10 to 100) batch of samples. For small batches of samples, the percentage of effort spent on QC can become sizeable. Alternate Methods The methods presented here are intended to be primary methods capable of generating the best quality data technologically feasible. The development and acceptability of secondary (alternate, equivalent, or screening) methods is not addressed in this report. GAS CHROMATOGRAPHY/MASS SPECTROMETRY OF PCBs Analysis for PCBs requires the use of selected representative standard compounds since all 209 congeners are not available. One of the major disadvantages of many instrumental methods for PCB analysis is the large variance of the instrumental response factors for PCB congeners, both within a homolog and between homologs. These large differences in response factors create problems in selecting representative compounds for quantitation purposes. The response factors of 77 of the possible 209 PCB congeners measured by GC/EIMS are presented in Tables 16 and 17. The data suggests that the EIMS response factor variance among PCB congeners is small relative to other detectors such as the electron capture detector or negative chemical ionization mass spectrometry. Relative Response Factors Quadrupole Mass Spectrometer-The relative response factors (RRF) of the 77 PCB congeners were determined with the Finnigan 4023 quadrupole mass spectrometer as discussed in the experimental section. The RRFs were determined two ways to assess the effects of instrumental variability. The replicate RRF determinations are the average of four replicate analyses for each of the PCB congeners, all determined on a single day to assess the variability of the measurement. The single RRF determinations are single values from an experiment in which all 14 solutions containing all 77 congeners were run on one day to minimize instrumental variability with time. The data are presented in Appendix A. The RRFs vary from approximately 0.2 for decachlorobiphenyl to 4.1 for 2-chlorobiphenyl. Figures 1 and 2 present a visual comparison of average replicate and single RRFs of PCB congeners determined as replicate measurements and as single measurements . 26 �4.5 4.0 Quadrupole Mass Spectrometer 3.5 3.0 ! — 2 o 2.5 cd M-l <1> CO 0 2.0 . CO 0) to CO eu | c I. O »PH 1.0 1 2 7 3 0.5 J_ 3 I 4 5 6 7 Homolog (degree of chlorination) 10 Figure 1. Plot of average response factor versus homolog for 77 PCB congeners. Each average is the mean response per congener, i.e., mean of four replicates with the Finnigan 4023 quadrupole mass spectrometer. This plot indicates the number of data points that overlap for specific isomers. �3.Or— 1 Quadrupole Mass Spectrometer 2.5 2.0 o 0} 1.5 N5 00 1.0 4 2 1 2 1 2 2 1 7 0.5 - _L _1_ _L JL X 3 4 5 6 7 10 Homolog (degree of chlorination) Figure 2. Plot of response factor per isomer versus homolog for 77 PCB congeners, determined on a single day. Each value is representative of single measurements of each congener with the Finnigan 4023 quadrupole mass spectrometer. This plot indicates the number of data points that overlap for specific isomers. �Table 16 is a summary of the RRF data, where the replicate and single measurements are averaged over all measured isomers for a homolog. The relative standard deviation (Table 16) for the replicate measurements reflects the variance of the average RRF for each isomer within a homolog. The absolute area of the internal standard, Congener No. 210, varied by only 4.4% for all solutions during the single day experiment, as compared to 9.9% for the 7 days required to complete the replicate analyses. The relative standard deviations based on the four replicate analyses for each of the PCB congeners, ranged from 0.4 to 9.1%, indicating the reproducibility of the injection for each solution. The average response factors from replicate determinations and single measurements were subjected to a Student's t-test to determine if there were any significant differences in measured response factors. No significant difference was found for the average response factor values for any of the PCB homologs except the heptachlorobiphenyl isomers. A more detailed presentation of the Student's t-test for these values is presented in Table A-2 of Appendix A. A solution of 3,3',4,4'-tetrachlorobiphenyl-de (Congener No. 210) and Solution No. 1 (Table 2) were both analyzed daily. The solution of Isomer No. 210 was used to tune the quadrupole mass spectrometer to the desired working conditions. Solution No. 1 was used to determine fluctuations of response factors from day to day due to differences in instrumental operating parameters. Table 17 presents the data for single day replicate measurements and day-to-day determination of the response factors for the PCB congeners in Solution No. 1. The relative standard deviations calculated for the single day measurements are considerably lower than the relative standard deviations from day-to-day analyses. This is a reflection of the reproducibility on the part of the operator as well as of the stability of the quadrapole mass spectrometer system on a given day. The relative standard deviation calculated for day-to-day analyses is indicative of the variation that might be expected for routine analysis of PCBs. A Student's t-test of the Solution No. 1 data (Table 17) indicated that there are significant differences in response factors from day to day compared to single day measurements for PCB Congener Nos. 1, 11, 29, and 207. A more detailed presentation of this t-test is presented in Table A-3 of Appendix A. Magnetic Sector Mass Spectrometer— The RRFs for the 77 PCB congeners were also determined with a Varian MAT 311A double focusing magnetic sector mass spectrometer. The RRF values were determined by single measurements of all congeners on a single day. The data are presented in Appendix A and summarized in Figure 3. Extrapolation of Response Factor Data to All Congeners-Since all 209 PCB congeners were not available for determination of RRFs, it was necessary to extrapolate the average RRF data to project the range of response factors that might be encountered. This extrapolation was based on the assumption that the number of measured isomers (n) are a representative sample of the entire set of the possible isomers (N). Thus it was assumed that the mean for the measured isomers (n) is an unbiased estimate of the mean for the possible isomers (N). 29 �TABLE 16. AVERAGE RELATIVE RESPONSE FACTORS (RRF) FOR 77 COMMERCIALLY AVAILABLE PCB CONGENERS MEASURED OVER SEVERAL DAYS AS FOUR REPLICATES EACH AND RRF FOR SINGLE MEASUREMENTS OF ALL CONGENERS IN A SINGLE DAY PCB homolog No. of isomers RRF from replicate measurements Relative standard deviation ( ) % RRF from single b measurement Relative standard deviation ( ) % 3 3.331 19.3 2.739 9.3 Dichloro- 10 2.027 22.0 2.048 15.7 Trichloro- 9 1.573 21.7 1.592 18.1 Tetrachloro- 16 0.950 18.4 0.946 20.0 Pentachloro- 12 0.720 16.7 0.725 17.6 Hexachloro- 13 0.513 15.1 0.500 19.1 Heptachloro- 4 0.361 6.6 0.308 8.0 Octachloro- 6 0.253 11,9 0.224 17.3 Nonachloro- 3 0.229 14.7 0.188 16.2 Decachloro- 1 0.213 2.8 0.179 Monochloro- - a Four replicate measurements of the RRF were made for each isomer. For example, the three monochlorobiphenyl isomers were measured four times each. Hence, the RRF and relative standard deviation ( ) were calculated from 12 distinct % values. b A single measurement for each of the 77 PCB congeners was completed in a single day. Hence, the RRF reported is the average of one measured RRF for each isomer within a homolog. For example, the RRF and relative standard deviation ( ) reported for the monochlorobiphenyls were calculated from three distinct % values. 30 �TABLE 17. AVERAGE RELATIVE RESPONSE FACTORS (ERF) FOR PCB CONGENERS IN SOLUTION 1 MEASURED AS REPLICATES ON A SINGLE DAY AND AS SINGLE MEASUREMENTS FOR DAY-TO-DAY BASIS3 Congener no. Single day measurements Relative std. Std. deviation ( ) % RRF deviation £ Day-to-day measurements Std. Relative std. RRF deviation deviation ( ) % 1 0.118 2.905 3.544 0.452 12.767 11 3.073 0.073 2.363 2.733 0.300 10.977 29 2.195 0.048 2.188 2.005 0.171 8.535 47 1.062 0.059 5.591 1.032 0.061 5.876 121 0.948 0.020 2.127 0.955 0.036 3.747 136 0.689 0.016 2.336 0.685 0.046 6.688 181 0.383 0.009 2.379 0.377 0.028 7.347 195 0.263 0.003 1.184 0.270 0.022 8.304 207 0.237 0.008 3.547 0.257 0.030 11.757 209 a 4.073 0.213 0.006 2.837 0.223 0.023 10.352 See Tables 6 and 8 for CGC/EIMS operating conditions. b These values calculated from four replicates. c These values calculated from 11 separate analyses. 31 �2.50 Magnetic Sector Mass Spectrometer 2.00 1.50 to C N3 O p. CO 0) 1.00 - 0.50 - 10 Homolog (degree of chlorination) Figure 3. Plot of response factor per isomer versus homolog for 77 PCB congeners, determined on a single day. Each value is representative of single measurements of each congener with the Varian Fat 311A magnetic sector mass spectrometer. This plot indicates the number of data noints that overlap for specific isomers. �Table 18 presents the upper and lower 95% confidence limits for the measured average RRFs. The extrapolation was necessary for the dichloro- through octachlorobiphenyl homologs. The projected upper and lower limits of the average RRF ranged from 13% for each PCB homolog for trichlorobiphenyls to approximately 6.5% for the dichlorobiphenyls. The projected ranges for the tetrachloro- to octachlorobiphenyls were between these values. Comparison of Magnetic Sector and Quadrupole RRF Data-The two instruments used operate on entirely different principles, so the results may represent the range of RRFs to be expected from these compounds on different instruments. Table 19 presents a summary of the data. As expected, the RRF trends are much different. Since quadrupole spectrometers discriminate at the high masses, the RRFs for high homologs (higer masses) are much lower than corresponding values for the magnetic detector spectrometer. A statistical analysis of the data (Student's t-test presented in Table 4 of Appendix A) confirmed that the average RRFs are significantly different for many of the homologs. However, the relative standard deviations for the average RRF of each homolog are not significantly different. Thus, the extrapolation from a single calibration isomer to all isomers of a homolog should have similar precision for the two instrument types. Relative Retention Times Relative retention times (KRT) were also calculated from the data generated for relative response factor measurements with both the quadrupole and magnetic sector mass spectrometer instruments. All RRTs for each PCB congener were calculated versus 3,3',4,4'-tetrachlorobiphenyl-de- Figure 4 is a plot of the RRT data versus PCB homolog. All data points for the 77 PCB congeners measured with the quadrupole mass spectrometer are presented. This plot also indicates that the relative retention window for the dichloro- to octachlorobiphenyl homologs may be larger than that actually measured if more of the possible congeners were present. Table 20 presents the observed range of RRTs for the 77 PCB congeners and additional congeners, identified only by homolog, in an Aroclor mixture (1016, 1254, 1260). These RRTs were established using a 15-m fused silica DB-5 capillary column. It must be recognized that the RRT windows on other columns may be substantially different. Table 20 also presents a projected RRT window for PCB anaysis. The overlap of the retention windows of each homolog must be considered in establishing an instrumental analysis approach to quantitation of the specific PCB homologs. This consideration has been accounted for in the GC/MS requirements for PCB analysis in Appendices B to D. The relative retention times of the 77 PCB congeners as determined with both the quadrupole and magnetic sector mass spectrometers are presented in tabular form in Appendix A. 33 �TABLE 18. MEASURED AVERAGE RELATIVE RESPONSE FACTOR (RRF) AND CORRESPONDING UPPER AND LOWER 95% CONFIDENCE LIMITS PCB homolog Monochloro- No. of possible isomers (N) Average measured response RRF No. of available isomers (n) Sample std. deviation (S) T Lower a limit T, Upperb limit - 3 3 3.331 0.643 Dichloro- 12 10 2.027 0,447 1.896 2.158 Trichloro- 24 9 1.573 0.341 1.366 1.780 Tetrachloro- 42 16 0.950 0.175 0.877 1.023 Pentachloro- 46 12 0.720 0.120 0.654 0.786 Hexachloro- 42 13 0.513 0.078 0.474 0.552 Heptachloro- 24 4 0.361 0.024 0.326 0.396 Octachloro- 12 6 0.253 0.030 0.231 0.275 Nonachloro- 3 3 0.229 0.034 Decachloro- 1 1 0.213 a Lower 95% limit = RRF -S("'j1* +-c 1 n \ \. N 34 - - �TABLE 19. RELATIVE RESPONSE FACTORS MEASURED VERSUS 3,3',4,4'-TETRACHLORO BIPHENYL-d6 BY ELECTRON IMPACT MASS SPECTROMETRY QUADRUPOLE (FINNIGAN 4023) AND MAGNETIC SECTOR (VARIAN MAT 311A) INSTRUMENTS No. of isomers measured RRF Quadrupole_ Mean RSD" ( ) % Magnetic sector RSDa ( ) % Mean 3 2.739 9.3 2.329 8.5 Dichloro- 10 2.048 15.7 1.663 13.8 Trichloro- 9 1.592 18.1 1.167 21.3 Tetrachloro- 16 0.946 20.0 0.902 14.0 Pentachloro- 12 0.725 17.6 0.780 17.4 Hexachloro- 13 0.500 19.1 0.640 19.4 Heptachloro- 4 0.308 8.0 0.497 12.1 Octachloro- 6 0.224 17.3 0.463 15.3 Nonachloro- 3 0.188 16.2' 0.467 22.5 Decachloro- 1 0.179 - 0.586 PCB homolog Monochloro- a Relative standard deviation. 35 - �H2<-'10 Relative Retention Times of PCB Congeners by Homolog Versus 3. 3'. 4. 4' Tetrachlorobiphenyl-d, C]2H,C19 2M2 7 ° 204 202 2OO C12H2CI8 195 194 185 171 183 181 C12H3CI7 PCB homologs 198 ** 155 C12H4CI6 154 139 153 138 129 136 15t 143 141 137 128 156 97 . „ 121 II6 104 103I009388 101119 115 C12H5CI5 15 545053 Cl2H6CI4 30 C12H7CI3 10 4 C12H8CI2 1 C,2H9CI, 9 7 8 5 14 5247 44 72 -«061 66 6577 2631 33 29 28 21 18 24 lt'^15 2 3 1 1 0.40 0.50 1 0.60 1 1 1 1 0.70 0.80 0.90 1.00 1 1.10 1 1.20 1 1.30 1 1.40 Relative retention time Figure 4. Retention times of 77 PCB congeners relative to 3,3',4,4'-tetrachlorobiphenyl-d6 (RRT of 1.00) The dashed line indicates that not all of the possible isomers of a particular homolog were measured. Relative retention times were determined on a J&W DB-5, 15-m fused silica column in a Finnigan 4023 GC/EIMS system. Temperature program: 110°C for 2 min,. then 10°C/min to 325°C. �TABLE 20. RELATIVE RETENTION TIME (RRT) RANGES OF PCB HOMOLOGS VERSUS d6-3,3',4,4'-TETRACHLOROBIPHENYL PCB homo log No. of isomers measured Observed range of RRTsa Calibration solution Congener Observed no. RRT3 Projected range of RRTsD 3 0.40-0.50 1 3 0.43 0.50 0.35-0.55 Dichlorobiphenyl 10 0.52-0.69 7 0.58 0.35-0.80 Trichlorobiphenyl 9 0.62-0.79 30 0.65 0.35-1.10 Tetrachlorobiphenyl 16 0.72-1.01 50 0.75 0.55-1.05 Pentachlorobiphenyl 12 0.82-1.08 97 0.98 0.80-1.10 Hexachlorobiphenyl 13 0.93-1.20 143 1.05 0.90-1.25 Heptachlorobiphenyl 4 1.09-1.31 183 1.15 1.05-1.35 Octachlorobiphenyl 6 1.19-1.36 202 1.19 1.10-1.50 Nonachlorobiphenyl 3 1.31-1.42 207 1.33 1.25-1.50 Decachlorobiphenyl 1 1.44-1.45 209 1.44 1.35-1.50 Monochlorobiphenyl a The RRTs of the 77 congeners and a mixture of Aroclor 1016/1254/1260 were measured versus de-3,3',4,4'-tetrachlorobiphenyl (internal standard) using a 15-m J&W DB-5 fused silica column with a temperature program of 110°C for 2 min, then 10°C/min to 325°C, helium carrier at 45 cm/sec, and an on-column injector. A Finnigan 4023 Incos quadrupole mass spectrometer operating with a scan range of 95-550 Daltons was used to detect each PCB congener. b The projected relative retention windows account for overlap of eluting homologs and take into consideration differences in operating systems and lack of all possible 209 PCB congeners. 37 �Selection of Congeners for a Calibration Standard The data generated from the RRF and RRT measurements were used to select the PCB congeners for an analytical quantitation/calibration standard for GC/EIMS analysis of PCBs. Selection of the standard compounds was based primarily on the ratio of the measured response factor to the average response factor for a particular homolog. The PCBs with KRFs closest to the average values were selected as standard compounds. In addition, the RRT was considered to assure that the selected PCB congeners did not coelute. Two monochlorobiphenyls were selected for the calibration standard because the average RRF and RRT did not clearly coincide with any of the three possible isomers. One isomer (2-chlorobiphenyl) had a substantially different RRF. This isomer was quantitated separately. 4-Chlorobiphenyl was selected as the calibration isomer for the two remaining isomers. Figure 5 is a CGC/EIMS chromatogram of the 11-component PCB calibration standard. The composition of this solution is identified in Tables 4 and 20 along with the observed RRT of each of the 11 congeners. VALIDATION OF SELECTED CLEANUP STEPS As part of the overall method validation, several of the cleanup techniques were validated. A mixture of the 11 calibration standard congeners and three recovery surrogates (the 13C-octachlorobiphenyl was unavailable for these experiments) was diluted in an appropriate solvent and then subjected to the cleanup procedures as described in Appendix B. After the cleanup, the internal standard was added and the volume adjusted. The samples were analyzed by CGC/EIMS using a quadrupole spectrometer operated under the condition listed in Tables 6 through 8. Data were collected in the full scan mode and quantitated using the primary ions listed in Table 10 and the congener pairs listed in Table 13. A blank was run through the procedure alongside the recovery spikes. As expected, no PCBs except the internal standard were observed in the blanks. The results for the 11 calibration congeners were calculated as percentage recovery. Tables 21 through 25 present the uncorrected recoveries, calculated using Equation 12-1 of Appendix B, using the internal standard (Congener No. 210); the actual percentage recoveries of the 13C-labeled recovery surrogates, calculated using Equation 12-2 of Appendix B; and the corrected recoveries of the calibration congeners, calculated using Equation 12-3 of Appendix B. Inspection of Tables 21 to 25 reveals that the accuracy of the corrected recoveries is higher than for the uncorrected recoveries (104% versus 77% average). On the other hand, the precision of the uncorrected recoveries is slightly higher than for the corrected recoveries (11% versus 9% relative standard deviation average). This is the expected trend since the uncorrected recovery relies on two GC/MS measurements (area of the PCB congener peak and area of the internal standard peak) and the corrected recovery relies on those two values and the area of the surrogate peak. Thus, these results indicate that accuracy is improved by recovery correction, at a sacrifice of precision. 38 �T3 4-1 ^-v rH Cfl cn oi cd C 00 0 Ol rJ •U G s v 100.0 U co -' ^£3 O rH rH C C 01 X! D. •H XI 01 XI tX 'H XI 1 i—1 C C Ol Ol XI XI a ex •rH XI Xi ^-s O O 0) M rJ 0 0 CO rH rH X! 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Capillary gas chromatography/electron impact ionization mass spectrometry (CGC/EIMS) chromatogram or the calibration standard solution required for quantitation of PCBs by homolog, This chromatogram includes PCBs representative of each homolog, three ^C-iabeled surrogates, and the deuterated internal standard. The concentration of all components and the CGC/EIl^S parameters are presented in Tables 4, 5, 6 and 9. �TABLE 21. RECOVERY DATA FOR ACID CLEANUP' Congener no. -P- o PCB homolog 1 3 7 30 50 97 143 183 202 207 209 X Standard deviation Relative standard deviation ( ) % Monochlorobiphenyl Monochlorobiphenyl Dichlorobiphenyl Trichlorobiphenyl Tetrachlorobiphenyl Pentachlorobiphenyl Hexa chlo rob ipheny 1 Heptachlorobiphenyl Octachlorobiphenyl Nona chlo rob ipheny 1 De ca chlo rob ipheny 1 211 212 214 X Standard deviation Relative standard deviation ( ) % 13 Ce-nionochlorobiphenyl Ci2~tetrachlorobiphenyl 13 Ci2~o!ecachlorobiphenyl 13 a 0.52 0.50 0.52 0.52 0.76 0.87 0.96 1.30 2.30 2.50 2.10 2.60 5.30 10.20 Spike No. 1 not analyzed. b Total spike level (pg) Corrected via surrogate response. c Not detected. d Large background signal prevented quantitation of the compound. e Not applicable. Spike 2 ( recovery) % Corrected Uncorrected 100.0 83.4 82. £ NQ3 78.0 99.5 81.2 85.9 80.7 83.2 87.3 86.2 7.5 9 70.2 87.1 91.3 82.9 11.2 13 142.4 118.8 117.5 NQ 89.6 114.2 93.2 98.5 88.4 91.1 95.7 104.9 17.7 17 _ — - Blank NDC ND ND ND ND ND ND ND ND ND ND ND ND ND - �TABLE 22. Congener no. RECOVERY DATA FOR FLORISIL COLUMN CLEANUP PCB homo log 1 3 7 30 50 97 143 183 202 207 209 X Standard deviation Relative standard deviation ( ) % Monochlorobiphenyl Monochlorobiphenyl Dichlorobiphenyl Trichlorobiphenyl Tetrachlorobiphenyl Pentachlorobiphenyl Hexa chlo r ob ipheny 1 Heptachlorobiphenyl Octachlorobiphenyl Nonachlorobiphenyl Decachlorobiphenyl 211 212 214 X Standard deviation Relative standard deviation ( ) % 13 Total spike level (pg) 0.52 0.50 0.52 0.52 0.76 0.87 0.96 1.30 2.30 2.50 2.10 Spike 1 ( recovery) % Corrected" Uncorrected 57.9 63.0 66.0 69.4 70.7 73.4 72.6 76.6 77.8 78.1 77.7 71.2 6.7 9 90.6 98.6 103.2 160.5 163.6 169.7 168.1 177.2 102.5 102.9 102.4 130.9 35.8 27 Spike 2 ( recovery) % Corrected Uncorrected 54.9 58.3 60.0 62.3 62.4 66.1 67.0 72.3 72.3 70.5 72.8 65.4 6.2 10 _ C6-monochlorobiphenyl 13 C12-tetrachlorob ipheny 1 13 C12~decachlorobiphenyl a Corrected via surrogate response, b Not detected, c Not applicable. 2.60 5.30 10.20 63.9 43.2 75.9 61.0 16.5 27 - 57.6 47.9 69.6 58.4 10.9 19 95.4 101.2 104.4 130.0 130.3 138.1 140.1 151.0 103.8 101.3 104.5 118.2 19.8 17 - Blank NDb ND ND ND ND ND ND ND ND ND ND c ND ND ND - �TABLE 23. RECOVERY DATA FOR FLORISIL SLURRY CLEANUP Congener no. PCB homolog 1 3 7 30 50 97 143 183 202 207 209 X Standard deviation Relative standard deviation ( ) % Mpnochlorobiphenyl Monochlorobiphenyl Dichlorobiphenyl Trichlorobiphenyl Tetrachlorobiphenyl Pentachlorobiphenyl Hexachlorobiphenyl Hep ta chlorob iphenyl Octachlorobiphenyl Nona chlo r ob iphenyl Decachlorobiphenyl 211 212 214 X Standard deviation Relative standard deviation ( ) % 13 Total spike level (pg) 0.52 0.50 0.52 0.52 0.76 0.87 0.96 1.30 2.30 2.50 2.10 Spike 1 ( recovery) % Corrected" Uncorrected 80.5 81.2 87.5 NQC 90.0 96.0 95.5 95.1 97.2 95.1 96.2 91.4 6.3 7 96.0 96.8 104.4 NQ 91.6 97.6 97.2 96.8 91.2 89.4 90.4 95.1 4.5 5 Spike 2 ( recovery) % Corrected Uncorrected 71.1 72.7 75.0 76.4 80.1 83.5 82.0 79.8 88.8 87.6 83.7 80.1 5.8 7 _ C6-monochlorob iphenyl 13 C12-tetrachlorobiphenyl 13 C12~decachlorobiphenyl 2.60 5.30 10.20 83.9 98.3 106.5 92.5 7.5 8 a Corrected via surrogate response. b Not detected. c Large background signal prevented quantitation of this compound. d Not applicable. - 92.9 94.8 98.1 85.5 89.6 93.5 91.6 89.3 101.0 99.5 95.2 93.7 4.7 5 Blank NDb ND ND ND ND ND ND ND ND ND NDd - _ 76.7 89.4 87.9 84.7 6.9 8 - ND ND ND - �TABLE 24. RECOVERY DATA FOR KOH CLEANUP Congener no. 1 3 7 30 50 97 143 183 202 207 209 X PCB homolog Monochlorobiphenyl Mono chlo rob iphenyl Dichlorobiphenyl Trichlorobiphenyl Tetrachlorob iphenyl Pentachlorob iphenyl Hexachlorob iphenyl Heptachlorob iphenyl Octachlorob iphenyl Nona chl o rob iphenyl Decachlorob iphenyl Total spike level ( j ) |g 0.52 0.50 0.52 0.52 0.76 0.87 0.96 1.30 2.30 2.50 2.10 Standard deviation Relative standard Spike 1 ( recovery) % Uncorrected 60.2 69.0 73.5 75.0 79.7 85.8 84.0 81.2 89.2 88.2 69.9 77.8 9.1 12 Corrected" 82.6 94.6 100.8 83.5 88.7 95.4 93.4 90.3 113.0 111.8 88.6 94.8 10.2 11 Spike 2 ( recovery) % Uncorrected Corrected 67.7 73.6 77.5 77.6 80.7 85.0 85.0 81.3 89.3 87.6 71.9 79.7 6.8 9 90.1 98.0 103.3 89.2 92.9 97.7 97.7 93.5 117.5 115.3 94.6 99.1 9.5 10 Blank NDb ND ND ND ND ND ND ND ND ND NDC - deviation ( ) % _ 211 212 214 X Standard deviation 13 C6-monochlorobiphenyl 13 C12-tetrachlorob iphenyl 13 C12-decachlorob iphenyl Relative standard deviation ( ) % a Corrected via surrogate response, b Not detected, c Not applicable. 2.60 5.30 10.20 72.9 89.9 78.9 80.6 8.6 11 - _ 75.1 87.0 76.0 79.4 6.6 8 - ND ND ND - �TABLE 25. RECOVERY DATA FOR ALUMINA CLEANUP Congener no. PCB homolog 1 3 7 30 50 97 143 183 202 207 209 X Standard deviation Relative standard deviation ( ) % Mono chlo rob iphenyl 211 212 214 X Standard deviation 13 Monochlorobiphenyl Dichlorob iphenyl Trichlorob iphenyl Tetrachlorob iphenyl Pentachlorobiphenyl Hexachlorob iphenyl Heptachlorobiphenyl Octachlorob iphenyl Nona chlorob iphenyl Decachlorob iphenyl Total spike level (|Jg) 0.52 0.50 0.52 0.52 0.76 0.87 0.96 1.30 2.30 2.50 2.10 Spike 1 ( recovery) % Corrected Uncorrected 63.1 60.0 67.9 NQC 67.2 70.4 69.4 75.8 76.8 77.3 74.0 70.2 5.9 8 97.1 92.2 104.8 NQ 97.2 101.9 100.4 109.7 92.2 92.9 88.9 97.8 6.5 7 Spike 2 ( recovery) % Uncorrected 61.1 58.4 66.4 NQ 66.3 68.3 67.5 75.1 75.3 76.8 78.3 70.1 6.9 10 13 Cj2~tetrachlorob iphenyl 13 C12~decachlorobiphenyl Relative standard 2.60 5.30 10.20 64.8 69.1 83.2 72.4 9.6 13 deviation ( ) % a Corrected via surrogate response. b Not detected. c Large background signal prevented quantitation of this compound. d Not applicable. - Blank 101.0 96.2 109.4 NDb ND ND ND ND ND ND ND ND ND NDd NQ 102.2 105.4 104.2 115.8 89.5 91.2 93.0 100.8 8.4 8 - _ _ C6-monochlorob iphenyl Corrected 60.7 64.9 84.2 69.9 12.5 18 - ND ND ND - �The preliminary data presented here contain an apparent anomaly: the low recovery of the 13C-tetrachlorobiphenyl surrogate (Congener No. 212) from the Florisil column cleanup. These two data points contribute substantially to the imprecision of the surrogate recoveries and induce some very high (130 to 177%) corrected recoveries for the tri- through hepta- compounds. The experiment should be repeated. VALIDATION OF THE PRODUCT AND PRODUCT WASTE METHOD WITH INDUSTRIAL SAMPLES Strategy Selected samples, obtained from industrial sources, were subjected to a variety of sample preparations as listed in Table 15 and then analyzed by CGC/EIMS. This section presents the results of this preliminary validation and, where possible, compares our values with those of previous analyses of the same sample. The results for quality control samples are also reported. The most extensively studied matrix was the CMA-A chlorinated benzene waste stream sample. This particular sample was chosen because of the wide distribution of PCB homologs (mono- through decachlorobiphenyls). Sample preparation with this matrix included simple dilution, treatment with sulfuric acid, Florisil, and saponification with ethanolic potassium hydroxide. The CMA-A samples were analyzed in duplicate in two sets of experiments. The 11 PCB congeners used for calibration purposes were spiked into the CMA-A matrix for standard addition experiments. Blind spiked samples and quantitation standards, prepared by the MRI quality control personnel as analytical performance checks, were analyzed along with the other samples. First Sample Set Tables 26 and 27 present the uncorrected and corrected concentrations found for CMA-A samples in preliminary studies of the application of the proposed methods for commercial products and product wastes. Sample 10 was analyzed without surrogates to approximate the analytical procedure used by most other laboratories. As anticipated, the uncorrected values compare well with 20A and 20B, while the corrected values are slightly lower than the values for 10. Both corrected and uncorrected values for the duplicate samples 20A and 20B are in agreement. The values for samples 10, 20A, and 20B average about 400 pg/g. These values are higher than the mean of 280 JJg/g reported in the CMA round robin but are in good agreement with the values (402 |Jg/g) reported by the sample supplier (Appendix E of Pittaway and Horner, 1982). The homolog distribution of our data agrees in general with the CMA data and the data that accompanied the samples. Sample 110 (CMA-E) was determined to contain about 18 (Jg/g PCB (Table 28) mostly as the dichloro homolog. These results are slightly higher than the CMA round robin data, which had a mean reported value of 9 pg/g. The isomer distribution agrees with most of the CMA round robin data (Pittaway and Horner, 1982). 45 �TABLE 26. Congener no. 1 3 7 30 50 97 143 183 202 207 209 UNCORRECTED PCB CONCENTRATIONS (Mg/g) IN CMA-A SAMPLES PCB homolog 10 Dilution, no surrog. 20A Dilution 20B Dilution 1 1 2 3 4 5 6 7 8 9 10 9 19 64 55 60 50 56 60 0 0.9 9.3 11 21 70 52 63 40 48 84 0 0 20 10 19 64 49 55 36 38 68 0 0 20 408 358 96b 108 154 94 97 152 414 Total 211 212 214 1 4 10 a No surrogates added. b NSa NS NS Surrogate recovery (percent). 46 �TABLE 27. CORRECTED PCS CONCENTRATIONS (iig/g) IN CMA-A SAMPLES Congener no. 1 3 7 30 50 97 143 183 202 207 209 PCB homo log 10 Dilution, no surrog. 20A Dilution 20B Dilution 1 1 2 3 4 5 6 7 8 9 10 NSa NS NS NS NS NS NS NS NS NS NS 11 22 73 49 58 37 44 78 0 0 13 11 21 68 50 57 37 39 70 0 0 13 385 366 Total a No surrogates added. 47 �Second Sample Set CMA Product Waste Samples— The corrected and uncorrected concentrations of the PCB homologs for duplicate CMA-A samples from a more extensive study are presented in Tables 29 and 30. Sample 2005 was spiked only with the internal standard so that any interferences corresponding to the 13C-labeled PCBs could be measured. Samples 2010 and 2020 are duplicate samples of CMA-A. The four surrogate compounds were added to approximately 0.1 g of each sample. The mixture was diluted to 1.0 ml and the internal standard added. Sample 2025Q is a sample that was submitted for PCB analysis by the MRI quality control department. This sample was weighed by QC personnel and the final preparation completed as described for the previous samples. The MRI QC coordinator calculated the final concentration for 2025Q from the extract concentration of each PCB homolog and weight of the CMA-A sample recorded in the QC laboratory record book. The surrogate-corrected values reported for samples 2010 through 2025Q are in good agreement with the total PCB concentration and homolog distribution reported in the CMA round robin (Pittaway and Horner, 1982). Tables 31 and 32 present the data from a standard addition experiment with the CMA-A sample matrix. The 11 PCB congener calibration standard was added to three separate aliquots of the CMA-A matrix to give spike levels ranging from approximately 20 to 100 | g of the monochlorobiphenyl and 50 to j 200 (Jg of decachlorobiphenyl. Samples 2030, 2040, and 2050 were prepared in the analytical laboratory. Sample 2060Q was prepared as a blind spike of the CMA-A matrix by MRI quality control personnel. The uncorrected amount found did not increase linearly with the spike level. In fact, at the highest spike level (Sample 2050) the amounts found for each homolog were less than the spike. No explanation is immediately available for this data trend, although the low recoveries of the 13C-octa- and tetrachlorobiphenyl surrogates indicated that the data are at best marginally valid. Tables 33 and 34 present data for CMA-A samples that were subjected to three different cleanup methods (concentrated H2S04, Florisil column chromatography, and saponification with alcoholic KOH). The data from the sulfuric acid cleanup was difficult to interpret because of interferences. As noted previously (Erickson and Stanley, 1982), the acid cleanup results in large losses of lower chlorinated PCB homologs. The poor recoveries of the surrogates shown in Table 33 are clearly outside of the QC criteria in Section 14.2.2 of Appendix B and indicate that the analyses are invalid. These results would not be reported as analyses for compliance with the proposed regulation. All of the blank samples (2001, 1080, 2100, and 2120) were analyzed along with the sample discussed above and found to contain no detectable PCBs. 48 �TABLE 28. UNCORRECTED AND CORRECTED PCS CONCENTRATIONS (pg/g) IN CMA-E SAMPLE (DILUTION PREPARATION) Congener no. 1 3 7 30 50 97 143 183 202 207 209 PCB homolog 110 Uncorrected 110 Corrected 1 1 2 3 4 5 6 7 8 9 10 1.2 1.8 10.5 0 0 0 0.02 0 0.05 0 0.06 1.5 2.4 13.8 0 0 0 0.02 0 0.03 0 0.04 13.4 17.7 b Total 211 212 214 a 76a 103/91C 151 1 4 10 Surrogate recovery (percent). b Not applicable. c Samples run twice on magnetic sector instrument for low and high masses. Congener no. 212 monitored in both runs. 49 �TABLE 29. UNCORRECTED PCB CONCENTRATION ((Jg/g) IN THE CMA-A SAMPLE MATRIX (INTERNAL STANDARD CALCULATION) CMA-A 2005 8/4/82 CMA-A 2010 8/4/82 CMA-A 2020 8/5/82 CMA-A 2025 8/5/82 Monochlorobiphenyl 26 23 37 40 Dichlorobiphenyl 35 28 41 48 Trichlorobiphenyl 17 14 46 50 Tetrachlorobiphenyl 20 31 33 36 Pentachlorobiphenyl 32 29 29 31 Hexachlorobiphenyl 29 23 21 22 Heptachlorobiphenyl 18 12 12 14 PCB homo log CGC/EIMS analysis date Octachlorobiphenyl 5.4 4.1 3.4 4.2 Nonachlorobiphenyl 2.6 2.2 2.0 3.5 Decachlorobiphenyl 12 10 Total PCB 197 176 9.7 11 234 260 Recovery ( ) of Surrogate Compounds % 13 NSa 64 84 89 13 NS 96 96 101 Ci 2 -octachlorobiphenyl NS 73 67 72 C12-decachlorobiphenyl NS 68 69 73 Ce-monochlorobiphenyl C12~tetrachlorobiphenyl 13 13 a NS = no surrogate added. b Final concentration determined from sample weight recorded by QC coordinator. c 302 Daltons used for quantitation. 50 �TABLE 30. CORRECTED PCB CONCENTRATION (|Jg/g) IN THE CMA-A SAMPLE MATRIX CMA-A 2010 8/4/82 CMA-A 2020 8/5/82 CMA-A, 2025Q 8/5/82 Monochlorobiphenyl 37 44 44 Dichlorobiphenyl 44 48 53 Trichlorobiphenyl 15 47 49 Tetrachlorobiphenyl 33 34 34 Pentachlorobiphenyl 30 30 31 Hexa chlo robipheny 1 24 21 22 Heptachlorobiphenyl 16 18 19 PCB homo log CGC/EIMS analysis date Octachlorobiphenyl 5.4 4.9 5.7 Nona chlo rob ipheny 1 3.1 3.0 4.8 Decachlorobiphenyl 15 14 16 Total PCB 223 264 280 a NS = no surrogates added. b Final concentration determined from sample weight recorded by QC coordinator. 51 �TABLE 31. PCB homolog CGC/EIMS analysis date UNCORRECTED PCB CONCENTRATION (|Jg/g) Of SPIKED CHA-A SAMPLES DETERMINED RY THE INTERNAL STANDARD QUANTITATION METHOD CMA-A 2030 Total sample Spike concentration level 8/5/82 CMA-A 2040 Total sample Spike level concentration 8/5/82 CMA-A 2050 Total sample Spike concentration level 8/6/82 CMA-A 2060Q Total sample Spike concentration level 8/6/82 Blind quantilat ion standard Total sample Spike concentration level 8/6/82 Monochlorobiphenyl 60 20 80 49 92 100 100 82 140 184 Dichlorobiphenyl 56 10 58 25 58 51 69 42 53 94 Trichlorobiphenyl 65 10 75 25 39 51 44 42 87 94 Tetrachlorobiphenyl 47 15 55 36 43 75 50 61 110 137 Pentachlorobiphenyl 48 17 58 42 64 86 73 70 140 157 Hexachlorobiphenyl 40 19 48 46 61 95 67 77 160 173 Heptachlorobiphenyl 40 25 58 62 87 130 87 100 340 234 Octachlorobiphenyl 46 45 82 110 100 230 110 180 560 414 Nonachlorobiphenyl 51 49 93 120 130 250 140 200 530 450 Decachlorobiphenyl 60 42 110 100 140 210 140 170 430 369 513 252 717 615 814 1,280 920 2,550 2,306 N5 Total PCB 1,020 Recovery ( ) of surrogate compounds % I3 C6-monochlorobiphenyl 89 79 76 93 88 I3 Ci2-tetrachlorobiphenylb 94 93 84 93 88 Cj2-octachlorobiphenyl 62 56 41 53 78 65 57 48 64 79 13 13 C12-decachlorobiphenyl a Concentration in ng/ml rather than |jg/g since this sample was prepared by dilution of stock solutions of standards by QC personnel, b 302 Daltons used for quantitation. �TABLE 32. CORRECTED PCB CONCENTRATION (pg/g) OF SPIKED CHA-A SAMPLES DETERMINED BY SURROGATE RECOVERY CORRECTION PCB homolog CGC/EIMS analysis date CMA-A 2030 Spike Total sample concentration cone. 8/5/82 CMA-A 2040 Total sample Spike concentration cone. 8/5/82 CHA-A 2050 Spike Total sample concentration cone. 8/6/82 CMA-A 2060 Spike Total sample cone. concentration 8/6/82 Blind quantitation standard 2070Q Spike Total sample concentration cone. 8/6/82 Monochlorobiphenyl 67 20 100 49 120 100 110 82 160 184 Dichlorobiphenyl 63 10 74 25 76 51 74 42 60 94 TrichJorobiphenyl 70 10 80 25 46 51 47 42 99 94 Tetrachlorobiphenyl 50 15 58 36 52 75 53 61 130 137 Pentachlorobipheriyl 51 17 63 42 77 86 78 70 160 157 Hexachlorobiphenyl 43 19 52 46 72 95 72 77 190 173 Heptachlorobiphenyl 64 25 100 62 210 130 160 100 430 234 Octachlorobiphenyl 74 45 150 110 250 230 210 180 720 414 Nonachlorobiphenyl 81 49 170 120 330 250 270 200 680 450 Decachlorobiphenyl 91 42 180 100 280 210 220 170 540 369 Total PCB 650 250 1,030 60 2 1,280 1,290 1,020 3,190 2,310 a 1,510 Concentration in ng/ml rather than pg/g since this sample was a blind quantitation sample. �TABLE 33. PCB CONCENTRATION ((Jg/g) OF CMA-A SAMPLES TREATED WITH DIFFERENT CLEANUP PROCEDURES (INTERNAL STANDARD QUANTITATION) PCB homolog CGC/EIMS analysis date CMA-A 2090 acid cleanup 8/9/82 Monochlorobiphenyl ND3 CMA-A 2110 Florisil cleanup 8/9/82 CMA-A 2130 alcoholic KOH cleanup 8/9/82 4.4 31 Dichlorobiphenyl 4.4 14 44 Trichlorobiphenyl 0.4 31 44 Tetrachlorobiphenyl 25 18 25 Pentachlorobiphenyl 19 17 20 Hexachlorobiphenyl 7.9 5.6 6.3 Heptachlorobiphenyl 5.9 2.2 3.8 Octachlorobiphenyl 2.4 6.0 2.6 Nonachlorobiphenyl 38 2.4 2.6 Decachlorobiphenyl 16 9.5 6.4 Total PCB 119 110 186 % Recovery ( ) of surrogate compounds 13 74 8 145 13 0 0 367 13 115 97 110 13 173 129 64 C6-monochlorobiphenyl Ci2~tetrachlorobiphenyl Ci2'°ctachlorobiphenyl C12~decachlorobiphenyl a ND = not detected. b 302 Daltons used for quantitation. 54 �TABLE 34. PCB CONCENTRATION (|Jg/g) OF CMA-A SAMPLES TREATED WITH VARIOUS CLEANUP PROCEDURES (SURROGATE COMPOUND CORRECTED) CMA-A 2090 acid cleanup 8/9/82 CMA-A 2110 Florisil cleanup 8/9/82 CMA-A 2130 alcoholic KOH cleanup 8/9/82 Monochlorobiphenyl NDa 28 11 Dichlorobiphenyl 30 86 15 PCB homolog CGC/EIMS analysis date Trichlorobiphenyl 0.3 (0.2)b 200 (16) 15 (20) 110 (9.3) 8.4 (11) (8.3) 110 (8.9) 6.8 (9.0) (3.5) 3.5 (2.2) 2.9 (2.9) Tetrachlorobiphenyl 17 (11) Pentachlorobiphenyl 13 Hexachlorobiphenyl 5.3 Heptachlorobiphenyl 2.6 1.2 1.8 Octachlorobiphenyl 1.1 3.1 1.2 1.2 1.2 3.1 4.2 Nona chl o r ob ipheny 1 Decachlorobiphenyl Total PCB 17 3.9 546 (159) 90 (78) 68 (77) a ND = not detected. b 13 C12-tetrachlorobiphenyl was not quantifiable due to interferences. The values reported were calculated using 1*Ce-inonochlorobiphenyl. Values in parenthesis were calculated using 13Ci2~°ctachlorobiphenyl. 55 �DCMA Pigment Samples-Eight DCMA pigment samples were analyzed following the preparation described in the experimental section (Table 15). The results are presented in Table 35. The diarylide yellow pigment (DCMA-1) was analyzed in duplicate and as a blind spike supplied by the MRI quality control department. This sample is reported to contain 3,3'-dichlorobiphenyl at levels of approximately 70 M8/g (Dry Colors Manufacturing Association, 1981). No analyte or surrogate PCBs were detected in the duplicate 1-g samples of the pigment and a known spike of the sample. The lack of detected PCBs indicates a loss of analytes in the sample preparation. The CGC/EIMS analysis of a sample of the yellow pigment spiked by MRI quality control personnel yielded an uncorrected concentration of 76 |Jg/g of 3,3'-dichlorobiphenyl based on the internal standard quantitation and a corrected concentration of 63 Mg/g, based on 120% recovery of the 13C6-4-monochlorobiphenyl surrogate. The level of the 3,3'-dichlorobiphenyl added by the QC personnel was reported to be 60 M8/8- Hence, the total dichlorobiphenyl concentration should have been approximatey 130 |Jg/g (70 |Jg/g endogenous plus 60 (Jg/g added). The phthalocyanine green pigment (DCMA-4) was also analyzed in duplicate following dissolution and fractionation with a Florisil column. This pigment reportedly contains only decachlorobiphenyl at approximately 40 |Jg/g based on the results of the DCMA round robin study (Dry Color Manufacturing Association, 1981). Our analysis of duplicate samples yielded uncorrected concentration levels of 24 and 27 [Jg/g of decachlorobiphenyl by the internal quantitation method. The corrected concentration for both samples was 13 (Jg/g with recovery of the 13Ce-decachlorobiphenyl surrogate at 190 and 210%. Phthalocyanine blue (DCMA-8) was also analyzed as a single sample. Pentachloro- and hexachlorobiphenyls were detected but the concentrations were below the quantitation limits for that particular day. The total PCB concentration of this pigment, as discussed in the results of the DCMA round robin (1981), is reported to be 90 |Jg/g. The DCMA pigment sample analyses did not produce valid results. These data suggest that further development or validation of extraction/cleanup procedure would be necessary to provide acceptable PCB analyses of these samples. All of the blank samples (2001, 2080, and 2100) analyzed along with the DCMA samples were found to contain no detectable PCBs. DISCUSSION The determination of PCBs is a complex problem. The inaccessability of standards for all 209 congeners has traditionally been circumvented by the use of commercial mixtures (e.g., Aroclors) as standards. Quantitation has often been addressed in terms of relating the analyte to an Aroclor standard to give a "total PCB" concentration. Determination of PCBs synthesized as by-products in commercial products or product waste presents three special problems: (a) the analyte does not generally resemble a commercial PCB mixture, so quantitation against Aroclor standards would be incorrect; (b) the matrix often contains high concentrations of other chlorinated organics which are not easily separated during a cleanup procedure and which interfere with the qualitative and quantitative analysis; and (c) the matrix is undefined and can include gases, liquids, or solids of any purity and complexity. 56 �TABLE 35. RECOVERY ( ) OF CARBON-13 LABELED SURROGATE COMPOUNDS FROM DIARYLIDE YELLOW % AND PHTHALOCYANINE BLUE AND GREEN PIGMENTS PCB surrogate DCMA-1 21403 DCMA-1 21503 DCMArl 2160b DCMA-1 2170QC 2175d 2180d DCMA-8 21906 DCMA-8 2200Q 13 ND8 ND ND 120 ND ND ND 12 l3 ND ND ND ND ND ND 94 52 13 ND ND ND 200 120 107 92 71 13 ND ND ND 250 190 210 150 77 C6-Monochlorobiphenyl C12-Tetrachlorobiphenyl C12-Octachlorobiphenyl C12-Decachlorobiphenyl a Samples 2140 and 2150 are duplicates prepared by the DCMA-B method. b Sample 2160 was spiked with 50 |jg/g of 3,3'-dichlorobiphenyl and prepared by the DCMA-B method. c Sample 2170Q was spiked by MRI quality control personnel with 3,3'-dichlorobiphenyl and was prepared by the DCMA-B method. d Samples 2175 and 2180 are duplicates prepared by the DCMA-B method, e Sample 2180 was prepared by the DCMA-A method. f Sample 2200Q was weighed by MRI quality control personnel. preparation by the DCMA-A method. g The four surrogate compounds were added but not detected. An unknown mass of sample was supplied for �In this situation, analytical methods require a different philosophy than the classic approach for a single analyte in a defined matrix where all steps, reagents, and apparatus are specified. The method proposed here leaves many of the analytical steps to the discretion of the analyst while ensuring the reliability of the results with a strong quality control program. Thus, an analyst familiar with general analytical techniques for a product, may readily adapt in-house extraction/cleanup procedures to incidental PCB analysis. Even when the recoveries are not optimized, the 13C-labeled surrogate recoveries will mimic those of the analyte PCBs. As long as the 13C recovery surrogates are thoroughly incorporated, their recoveries can be used to derive corrected analyte PCB concentrations. Several of the method validation analyses presented above, especially Tables 33 and 35, illustrate the importance of the recovery surrogates in QC. The techniques employed are common methods validated for PCB analysis by other laboratories without the 13C-surrogate data. Analyses of this type may have been used by a testing laboratory and erroneous results reported. The complexity of the matrix and the high probability of chlorinated organic interferents precluded the use of GC/ECD. The best available technique is GC/EIMS. During the validation work presented above, the anticipated difficulty of qualitatitve and quantitative data interpretation was confirmed. In addition to the inherent problems resulting from extrapolation from a standard to several analytes, interpretation of the complex peak clusters is a tedious, subjective, and error-prone process. The volume of data for one sample is staggering; for sample 2110, 286 peaks were identified and integrated in the PCB mass chromatograms as shown in Figures 6 through 16. Of these, 58 peaks met the qualitative criteria and were identified as PCBs. Clearly different analysts will obtain different results for those peaks which marginally fit the qualitative criteria. This very high data density relative to other common GC/MS analyses has a much higher potential for error and mistakes. In addition it should be noted that, for many of the samples analyzed in this study, the data interpretation is more time-consuming than the rest of the analytical process. The integration methods are also prone to error. Integration is always conducted interactively with the mass spectrometric data system, either manually or automatically. The selection of baseline criteria, background sensitivity, integration method (valley-to-valley, baseline-to-baseline, etc.), and retention window all affect automatic quantitation. The position of the cursor and integration method affect the manual quantitation results. The day-to-day instrumental variability with quadrupole systems also appears to adversely affect data quality, despite tight calibration specifications. The magnitude of this error soruce should be further documented. The above discussion presents some of our understanding of some of the major problems with analysis for by-product PCBs. Further work will be devoted to characterizing and reducing these problem areas. Even with forseeable improvements in the method, the data for by-product PCBs in many commercial product and product waste samples will exhibit low precision and accuracy. 58 �lie 08/09/82 16:20:60 SAMPLE: SAMPLE 12110 dlA-A FLOMSIL 1/IODIL ItAHCE; G 1.1759 LABEL: H 0. 4.9 OMAN: A 1ULIMJ A. 1.9 DATA: 49011109^5 91 CALI: IHDCAIJWWl 1)1 BASE: U 2fl. SCAIJS 1 TO 1750 3 128450^1. 169.0 Ln vo 1009 15:59 Figure 6. Reconstructed ion chromatogram for 1299 19:00 1409 22:10 1660 25:29 SCAil mm SIM analysis of the CMA-A sample No. 2110. �MASS CHBOIIATOCRAIIS 88/09/82 16:20:00 SAIIPLE: SAIIPLE I2MO CIIA-A FLOftlStL RAflCE: C I.I750 LAHEI.: H 0. 4.0 DATA: 198III09U5 HI CAM: MIDTAUWW H1 l/IODIL 1ULHU OVAII: A 0. 1.0 BASE: 020. 83 SCAIJS 703 TO 900 3 I80.0-, 700 11:95 850 M:27 Figure 7. SIM ion plots for monochlorobiphenyls (188 and 190 Daltons) and the1 monochlorobiphenyl surrogate (194 Daltons) in CMA-A sample No. 2110. 900 SCAJf 14:15 TlliH �MASS aiCOHATOGRAIIS 08/09/82 16:28:60 SANFLE: SAIIPLE 12118 QIA-A FLOBISIL RANGE: C 1.1758 LABEL: H «. 4.9 DATA: 1991II99V5 81 CAII: IIIDCAUWWI HI 1/IODIL 1UI.IHJ QUAII: A 9. 1.9 BASE: U 28. SCAIIS 768 TO 1199 3 222. 1198 SC'J! 17:25 Tim- Figure 8. SIM ion plots for dichlorobiphenyls No. 2110. (222 and 224 Daltons) in Cl'A-A san.nle �HASS CHROMA TOGRAIIS DATA: 4991II09V5 fll 08/69/82 16:28:98 CALI: IIIDCALIttOVI (14 SAMPLE: SAIIPLE 12lie QIA-A FLORISIL I/IODIL IULHU RANGE; G 1.1759 LABEL: H 9. 4.9 QUAII: A 9. 1.9 BASE: U 29. 3 199.8 SCAMS 859 TO 1150 torn 256 1156129. 256.977 ^ 9.5W _8Z5_ Ni 1093 89. 258 1384579. 258.877 ± 8.599 859 13:27 Figure 9. 990 14:15 SIM ion plots for 950 15:92 15:59 1959 1199 16:37 17:25 1150 SCAM 18:12 TKIE trichlorobiphenyls (256 and 258 Daltons) in CVA-A sample No. 2110. �71.3-1 NASS OffiOmTOGRAIIS DATA: 499IIM9V5 II •8/09/82 (6:20:99 HALI: IIIDCAIJWWI SI SAHTLE: SAIIPLE 12110 QIA-A FLOWS! L I/I00IL IULUU BAMCE: G 1.1759 LABEL: II 9. 4.9 OUAII: A 0. 1.9 BASE: U 29. 3 1222 SCAHS 1959 TO 13TO 217296. 299 . 109.9-, 292 . CTi OJ 39.7-1 137728. 298. 298.089 0.590 62.7-1 217344. 304. 304.091 0.509 1350 SCAN 21:22 TIME Figure 10. SIM ion plots for tetrachlorobiphenyls (290 and 292 Daltons), 3 , 3 ' , 4 , 4 ' - t e t r a c h l o r o biphenyl-dg (298 Daltons), and the 13 C 1 2-tetrachlorobiphenyl surrogate (304 Daltons) in O'A-A sample No. 2110. �MASS CUBOIIATOGRAMS DATA: 4901IW9V5 II1669 08/09/82 16:28:89 CALI: IIIDCAI.II09VI 11 SAMPLE: SAMPLE I2II0 CMA-A FLORISIL I/IOD1L 1ULIIU RANGE: G 1.1750 LABEL: II 9, 4.0 WAII: A 9. I.0 BASE: U 29. 3 SCAIB J2W TO f? 15897B. 12.57 326 326.097 * 0.500 i 81.3- 129280. 328 J 328.098 * 0.500 1200 19:06 1250 19:47 1390 20:35 Figure 11. SIM ion plots for pentachlorobiphenyls No. 2110. 1400 22:10 1450 22:57 SCAN 23:15 TIIIE (326 and 328 Daltons) in CMA-A sample �MASS dffiOHATOCRAItS 08/09/82 16:20:08 SAMPLE: SAMPLE 12110 QIA-A FLORISIL I/IOniL RANGE: G IHIAH: A 0. 1.1759 LADEL: II 0. 4.0 1ULIHJ 1.0. SCAMS 1250 TO I500 DATA: 198IIWOV5 81 CALI: IHDCALHOT"! M ;SE: 0 28. 3 15C784. 97.-In 308.108 * 9.599 CT> Ln 106. 154880. 362 302.108 0.S00 1450 22:57 Figure 12. SCAN 23:15 TIHE SIM ion plots of hexachlorobiphenyls ( 6 and 362 Daltons) in CFA-A sample No. 2110. 30 �MASS UIROIIATOGRAIIS DATA: 4991H99V5 II 08/09/82 16:29:89 CAM: HI DCAll »W I 111 SAMPLE: SAIIPLE 12119 C1IA A FLORISIL 1/I0DIL 1ULIHJ RANGE: G 1.1756 LABEL: II 9. 4.9 OWAH: A 9. 1.9 HASP: U 29. 3 99.9 SCAMS 1359 TO 45568. ^91.118 ± 9.599 56384. 396.118 ± 9.599 1359 21:22 Figure 13. 1459 22:57 1559 SCAN 21:32 TIME SIM ion plots of heptachlorobiphenyls (39* and 306 Daltons) in CMA-A sample No. 2110. �MASS dlBffllATOGRAIIS 08/W82 16:20:80 SAMPLE: SAMPLE 12110 QIA-A FLORISIL RAMGE: G 1.1750 LABEL: II 0. 4.0 79.3-1 DATA: 4901H09V5 »l CALIt HIDCAUI0WI HI I/16DIL 1ULIHJ CUAII: A 0. 1.0 BASE: 0 20. ISC SCAMS IfM TO 165!) 3 29728. 428 . 128 •11856. 430.129 0.500 42304. I00.9-! 442 * 1450 22:57 Figure 14. 1509 23:45 1550 24:32 1608 25:20 SIM ion plots of octachlorobiphenyls ( 4 2 8 and 430 Daltons) and the chlorobiphenyl surrogate ( 4 4 2 Daltons) in CMA-A sample No. 2llo. 112.132 0.5W IC50 SCAN :!fi:07 TIME ^ �MASS aiBOHATOGRAIIS DATA: 4961II99V5 II 68/09/82 16:28:60 CALI: IIIDCALIWWI lit SAMPLE: SAMPLE I2H6 CIIA-A FLOIIISIL I/10D1L 1ULIMJ RAMCE: G 1.17561 LABEL: II 6. 4.9 OUAII: A 6. 1.6 BASE: U 29. 3 STAIIS 1559 TO 89.5-1 24256. 1565 1631 164.139 ± 0.599 461 . 109.6- < 27164. oo 466 466.139 * 6.590 1569 24:42 Figure 15. 1580 25:01 1620 25: 39 1616 25:58 SCAN TIME SIM ion plots of nonachlorobiphenyl (464 and 466 Daltons) in CMA-A sample No. 2110, �MASS aiBWIATOGRAIIS 98/89/82 16:28:88 SAHTLEi SAIITLE 12118 QIA-A FLOW SI L BAHGE: G 1.1758 LABEL: N 9. 4.8 99.9-1 1669 DATA: 49eil»9V5 11669 CALI: IHDCALI»WI 01 I/1001L 1ULIHJ QUAH: A 9. 1.8 BASE: U 29. SCAIB 1658 TO 17B!) 3 79232. 4W. 149 * 8.599 498 . 88I92. 499.500 * e.598 43849. 5S9.588 8.588 1709 Figure 16. SIM ion plots of decachlorobiphenyl (498 and 500 Daltons) and the decachlorobiphenyl (510 Daltons) in QIA-A sample No. 2110. 13C i2~ SCAN TIME �SECTION 5 REFERENCES Dry Color Manufacturers Association. 1981. An analytical procedure for the determination of polychlorinated biphenyls in dry phthalocyanine blue, phthalocyanine green, and diarylide yellow pigments. 1117 North 19th Street, Arlington, VA 22209. Erickson MD, Stanley JS. 1982. Midwest Research Institute. Methods of analysis for incidentally generated PCBs literature review and preliminary recommendations. Draft interim report no. 1. Washington, DC: Office of Toxic Substances, U.S. Environmental Protection Agency. Contract 68-01-5915. Haile CL, Baladi E. 1977. Midwest Research Institute. Methods for determining the total polychlorinated biphenyl emissions from incineration and capacitor and transformer filling plants. Washington, DC: U.S. Environmental Protection Agency. Contract 68-02-1780. EPA 600/4-77-048. Pittaway AR, Horner TW. 1982. Heiden, Pittaway Associates. Statistical analysis of data from a round robin experiment on PCB samples. Washington, DC: Chemical Manufacturers Association report. Roth RW, Keys JR, Chien DHT, et al. 1982. Midwest Research Institute. Methods of analysis for incidentally generated PCBs--synthesis of 13C-PCB surrogates. Draft interim report no. 3. Office of Toxic Substances, U.S. Environmental Protection Agency. Contract 68-01-5915. Stanley JS, Erickson MD. 1982. Midwest Research Institute. Peer review and authors' replies to 'methods of analysis for incidentally generated PCBs-literature review and preliminary recommendations.1 Draft interim report no. 2. Washington, DC: Office of Toxic Substances, U.S. Environmental Protection Agency. Contract 68-01-5915. USEPA. 1979a (December 3). U.S. Environmental Protection Agency. neutrals, acids, and pesticides—method 605. 44 FR 69540. Base/ USEPA. 1979b (December 3). U.S. Environmental Protection Agency. Organochlorine pesticides and PCBs—method 608. 44 FR 69501. USEPA. 1982 (June 8). U.S. Environmental Protection Agency. Polychlorinated biphenyls (PCBs); manufacture, processing, distribution, and use in closed and controlled waste manufacturing processes. FR 74 24976. 70 �APPENDIX A SUPPLEMENTARY GC/EIMS DATA ON PCB CONGENERS A-l �The following data support the method validation section for gas chromatography/electron impact mass spectrometry (GC/EIMS) of polychlorinated biphenyls (PCB). Table A-l lists the average relative response factors (RRF) for the 77 commercially available PCB congeners determined as four replicates. Table A-2 presents results of the Student's t-test used to determine the significance of differences for average RRFs for PCB homologs measured on a single day versus multiple days. The data in Table A-2 indicate that only the average RRFs for the heptachlorobiphenyl homolog are significantly different. Table A-3 presents the results of the Student's t-test used to determine the significance of differences for the average RRFs for the PCB homologs determined with the quadrupole and magnetic sector mass spectrometers. All 77 PCB congeners were determined in a single day for each of the instrument studies. This comparison indicates that the average RRF values are significantly different, which was expected. However, the relative standard deviations are not significantly different, indicating that the selection of the calibration standards is appropriate. These conclusions are discussed more fully in the text. Table A-4 presents results of the Student's t-test used to determine significance of differences for the RRFs for the 11 congeners in Solution No. 1, which was analyzed daily. An example of the data generated for multiple analysis of Solution No. 1 is presented in Figures 1 to 23. This information includes a capillary GC/EIMS chromatogram of Solution No. 1, the mass spectra of each component in this solution, and a graphic illustration of the distribution of several measurements of each congener about the average response factor. It should be noted that the standard deviation and relative standard deviation presented in these plots are different from that reported in the text due to calculation of the standard deviation using N weighting rather than the correct N-l weighting. All other standard deviations reported in this document are based on the N-l weighting. The relative retention times of the 77 PCB congeners with respect to 3,3",4,4'-tetrachlorobiphenyl-de determined with the Finnigan 4023 quadrupole and the Varian MAT 311A mass spectrometers are presented in Table A-5. A relative retention time unit of 0.01 (10 sec) is required for resolution of two specific congeners based on the gas chromatography parameters used to generate these numbers. A-2 �TABLE A-l. RELATIVE RESPONSE FACTORS FOR COMMERCIALLY AVAILABLE PCB CONGENERS (QUADRUPOLE) Congener no. Degree of chlorination Average relative response factor Standard deviation Coefficient of variation (%) 1 2 3 1 1 1 4.073 2.951 2.969 0.118 0.056 0.028 2.905 1.894 0.956 4 5 7 8 9 10 11 12 14 15 2 2 2 2 2 2 2 2 2 2 1.232 1.959 2.008 2.049 2.148 1.880 3.073 1.929 2.083 1.909 0.008 0.035 0.027 0.023 0.061 0.031 0.073 0.036 0.098 0.089 0.646 1.803 1.366 1.134 2.846 1.658 2.363 1.877 4.702 4.686 18 21 24 26 28 29 30 31 33 3 3 3 3 3 3 3 3 3 1.104 1.586 1.051 1.714 1.587 2.195 1.526 1.706 1.688 0.012 0.018 0.033 0.013 0.028 0.048 0.067 0.024 0.031 1.089 1.110 3.105 0.731 1.733 2.188 4.418 1.409 1.863 40 44 47 49 50 52 53 54 61 65 66 69 70 72 75 77 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 0.597 0.712 1.062 0.831 0.957 0.732 0.750 0.958 0.975 1.086 1.139 1.058 1.091 0.980 1.185 1.095 0.013 0.007 0.059 0.019 0.025 0.011 0.008 0.013 0.069 0.022 0.068 0.012 0.050 0.048 0.061 0.050 2.152 0.946 5.591 2.245 2.574 1.504 1.006 1.344 7.094 1.994 5.966 1.110 4.548 4.870 5.113 4.595 1 (continued) A-3 �TABLE A-l (continued) Degree of chlorination Average relative response factor Standard deviation Coefficient of variation ( ) % 87 88 93 97 100 101 103 104 115 116 119 121 5 5 5 5 5 5 5 5 5 5 5 5 0.617 0.611 0.574 0.719 0.727 0.653 0.566 0.824 0.853 0.785 0.762 0.948 0.011 0.005 0.010 0.008 0.003 0.004 0.009 0.025 0.061 0.013 0.022 0.020 1.710 0.744 1.677 1.139 0.428 0.538 1.627 3.048 7.146 1.654 2.911 2.127 128 129 136 137 138 139 141 143 151 153 154 154 155 156 6 6 6 6 6 6 6 6 6 6 6 6 6 6 0.499 0.431 0.689 0.533 0.433 0.462 0.419 0.490 0.473 0.549 0.221 0.511 0.587 0.599 0.005 0.004 0.016 0.008 0.008 0.026 0.010 0.005 0.013 0.050 0.001 0.010 0.011 0.044 1.093 0.813 2.336 1.582 1.946 5.686 2.353 0.986 2.826 9.101 0.570 2.039 1.828 7.431 171 181 183 185 7 7 7 7 0.346 0.383 0.380 0.336 0.002 0.009 0.010 0.006 0.640 2.379 2.501 1.729 195 198 200 202 204 8 8 8 8 8 0.263 0.262 0.301 0.250 0.221 0.003 0.008 0.007 0.007 0.007 1.184 2.887 2.392 2.663 3.200 206 207 208 9 9 9 0.193 0.237 0.259 0.003 0.008 0.003 1.723 3.547 1.315 209 10 0.213 0.006 2.837 Congener no. Relative to 3,3',4,4'-tetrachlorobiphenyl-dg. All relative response factors were calculated as the average of four replicate measurements made on the same day. A-4 �TABLE A-2. STUDENT'S TWO-SIDED t-TEST TO DETERMINE SIGNIFICANT DIFFERENCES BETWEEN QUADRUPOLE RESPONSE FACTORS CALCULATED ON THE SAME DAY VERSUS MULTIPLE DAYS PCB homolog MonochloroDichloroTrichloroTetrachloroPentachloroHexachloroHeptachloroOctachloroNonachloroDecachloro- Number of isomers 3 10 9 16 12 13 4 6 3 1 Average RRF from replicate measurements 3.331 2.027 1.573 0.950 0.720 0.513 0.361 0.253 0.229 0.213 Standard deviation 0.643 0.447 0.341 0.175 0.120 0.078 0.024 0.030 0.034 0.006 Average RRF from single , measurement Standard deviation 2.739 2.048 1.592 0.946 0.725 0.500 0.308 0.224 0.188 0.179 0.254 0.322 0.289 0.189 0.127 0.096 0.025 0.039 0.030 c t-Statistic 1.478 -0.119 -0.131 0.0618 -0.1085 0.377 3.119 1.398 1.5,91 Significant at 95% level? No No No No No No Yes No 5 > a Four replicate measurements of the RRF were made for each isomer. For example, the three monochlorobiphenyl isomers were measured four times each. Hence, the average RRF and standard deviation were calculated from 12 distinct values. b A single measurement for each of the 77 PCB congeners was completed in a single day. Hence, the average RRF reported is the average of one measured RRF for each isomer within a homolog. For example, the average RRF and standard deviation reported for the monochlorobiphenyl was calculated from three distinct values. c Single measurement. d Cannot test significance of difference between single measurements. �TABLE A-3. COMPARISON OF THE AVERAGE RELATIVE RESPONSE FACTORS (RRF) DETERMINED WITH QUADRUPOLE (FINNIGAN 4023) AND MAGNETIC SECTOR (VARIAN MAT 311A) MASS SPECTROMETERS'" PCB homolog Number of isomers MonochloroDichloroTrichloroTetrachloroPentachloroHexachloroHeptachloroOctachloroNonachloroDecachloro- 3 10 9 16 12 13 4 6 3 1 Finnigan 4023 quadrupole MS Standard deviation RRF 2.739 2.038 1.592 0.946 0.725 0.500 0.308 0.224 0.188 0.179 0.250 0.32 0.29 0.19 0.13 0.10 0.025 0.04 0.93 Varian MAT 311A magnetic sector MS Standard RRF deviation 2.329 1.663 1.167 0.902 0.780 0.640 0.497 0.463 0.467 0.586 RRFs significantly different at the , 95% confidence level Variances significantly different at the 95% confidence level No Yes Yes No No Yes Yes Yes Yes e No No No No No No No No No 0.199 0.229 0.248 0.130 0.136 0.124 0.060 0.071 °;a05 a The RRF and standard deviation reported in this table for the quadrupole and magnetic sector mass spectrometers were determined as single measurements of all congeners in a single day with each instrument. b Student's two-sided t-test was used to determine significant differences of the RRFs. c An F-test was used to determine significant differences of the standard deviations, where F = (std dev!)2/(std dev2)2 with (n-1, n-1) degrees of freedom. d Single measurement. e Cannot test significance of difference between single measurements. �TABLE A-4. PCB STUDENT'S TWO-SIDED t-TEST TO DETERMINE SIGNIFICANT DIFFERENCES OF THE AVERAGE RELATIVE RESPONSE FACTOR (RRF) FOR SOLUTION NO. 1 FOR REPLICATE ANALYSIS ON A SINGLE DAY VERSUS SINGLE ANALYSES ON MULTIPLE DAYS Replicate analyses on single day no. RRF Standard deviation 1 11 29 47 121 136 181 195 207 209 4.073 3.073 2.195 1.062 0.948 0.689 0.383 0.263 0.237 0.213 0.118 0.073 0.048 0.059 0.020 0.016 0.009 0.003 0.008 0.006 congener Single analyses, on multiple days Standard RRF deviation 3.241 2.538 1.899 1.015 0.959 0 . 683 0.374 0.275 0.269 0.230 0.201 0.161 0.100 0.059 0.043 0.058 0.035 0.028 0.032 0.027 t-Statistic Significant differences of RRF at 95% confidence limit? 7.468 6.204 5.483 1.268 -0.479 0.186 0.662 -1.137 -2.479 -1.599 Yes Yes Yes No No No No No Yes No a The RRF and standard deviations were calculated from four replicate measurements completed in the same day. b The RRF and standard deviatons were calculated from seven single measurements from seven different days. �TABLE A-5. RELATIVE RETENTION TIMES (RRT) OF 77 COMMERCIALLY AVAILABLE PCB CONGENERS MEASURED VERSUS 3,3'4,4'-TETRACHLOROBIPHENYL-d6 DETERMINED WITH MAGNETIC SECTOR (VARIAN MAT 311A) AND QUADRUPOLE (FINNIGAN 4023) MASS SPECTROMETERS RRT RRT PCB congener no. 311A 4023 Monochloro1 2 3 0.403 0.481 0.474 0.425 0.490 0.499 Dichloro4 5 1 8 9 10 11 12 14 15 0.518 0.598 0.559 0.590 0.563 0.521 0.649 0.660 0.616 0.677 0.536 0.606 0.579 0.606 0.577 0.534 0.660 0.671 0.628 0.681 Trichloro18 21 24 26 28 29 30 31 33 0.665 0.762 0.685 0.729 0.745 0.719 0.641 0.741 0.760 0.678 0.767 0.694 0.738 0.753 0.728 0.653 0.752 0.769 Tetrachloro40 44 47 49 50 52 53 54 61 65 66 69 70 72 75 77 0.870 0.838 0.814 0.811 0.746 0.804 0.763 0.720 0.898 0.822 0.905 0.800 0.880 0.853 0.816 1.002 0.875 0.843 0.819 0.817 0.751 0.810 0.773 0.731 0.898 0.826 0.908 0.807 0.904 0.856 0.821 1.003 PCB congener no. 311A 4023 Pentachloro87 88 93 97 100 101 103 104 105 116 119 121 0.979 0.913 0.907 0.976 0.878 0.945 0.870 0.829 0.988 0.985 0.964 0.911 0.978 0.915 0.908 0.979 0.884 0.945 0.874 0.836 0.987 0.986 0.965 0.914 Hexachloro128 129 136 137 138 139 141 143 151 153 154 155 156 1.163 1.128 0.994 1.118 1.108 1.037 1.096 1.050 1.020 1.074 1.002 0.929 1.194 1.156 1.127 0.996 1.115 1.103 1.038 1.093 1.051 1.021 1.073 1.004 0.931 1.188 Heptachloro171 181 183 185 1.189 1.178 1.154 1.166 1.187 1.174 1.148 1.161 Octachloro194 195 198 200 202 204 1.355 1.326 1.275 1.203 1.194 1.209 1.351 1.317 1.265 1.199 1.188 1.203 (continued) A-8 �TABLE A-5 (continued) RRT RRT PCB congener no. 311A 4023 Nonachloro206 207 208 1.414 1.336 1.319 1.399 1.330 1.318 PCB congener no. 311A 4023 Decachloro209 1.453 1.440 A-9 �-Iflfl.O E1C DATA: r-<:91VQ2 1765 SCAIIS CS/01/82 8:33:00 CALI: C.ilOIUI 03 OUT OF SAMPLE: FCB MIXTURE—SOLUTION 01 1UL UIJ COUUS.t -16CO HIV (0-6 79EV .2IIA PCS--I1H 40-2II-335-C/ "OII-COl" R.MKE: C I.I2PO LABEL: t! 0, 4.0 OUAH-. A tt. I 0 J 0 BA<;| BASE: H 20. I TO I209 I TO I2CO 3 1. 328 599016. i-H C (U r^ c J3 •H 43 0) a. fX, vj O 1 : rH o t-i 0 --I rC <~M ^» U •H 43 O C 01 in 1 CN ^ 01 W.«20 -H 43 o 43 O -*" o 0. R59 CM u § PH 1 1 J^l 4J 0) to 1 X a 1 If If) U ^. <fr „ •^ 1 II en CM « •* m •* •• i CM i—i 43 CJ cd CO ^ u n CM * CM CNI | I CM I * || to CM CM 1 en - <r •\ •V ^ ro - ro en -; •s si- 1 ** - to H ^ **ll * ^ ^" O OJ M ** § :• in " to to •* <u cd 4J 43 cd C •£* 43 ft 0> PC 1 43 y cfl O CO - 43 0 M 0 rH 43 CJ 6-Octachloro : ,H -g 43 0 0.912 c ^ [-; a. (U 4= Ul ^ P« H-J tachlorobiph O i—* _r? t.1 C iphenyl-dg a) 2 t-i 0 C i orobiphenyl ^*. lorobiphenyl *rt 1 w ft (i 96 .orobiphenyl i-H t CM C °- CM ' 0.315 i 200 3:20 • i ISO 6-.10 . 1 COO je : eo , '" L "*"I~*~ *• -^ • i 1.102 "—* COO 13:20 _'•£' ItJ.0 1C: IB SCAII TIME Figure A-l. Fused silica capillary gas chromatogram of PCB Solution No. 1 analyzed with electron impact mass spectrometry. Experimental conditions for separation and analysis of the PCBs are presented in the experimental section of report. �UV.'. SVECi'tlUil GV20/32 16:42:00 * PATA: 498IE20W7 (Witt CAM: CALF.20UI 07 1:50 E: rest iimiiue — SOLUTIOII BI IUL iiu -J%8 L-lfV 10 6 70I:V .2IIA Bi!5 -1MI 1 10 -211- 525- 10/ "IJJI-COL J33IAKCED <S 15B 2H OT) ICO 9523:-. 50.0- 126 ^ T ti/n no Figure A-2. 1161 i*U ico 173 101! Electron impact ionization mass spectrum of 2-monochlorobiphenyl. �tt'I-CII'JRI U>:12:W * HATA: :: FOB IIIXTIII::;—soi.Minni ni »« mi IKO iaiv io-6 /ot-:v .M\ imr> j-.u (S I5K 2II OTI U17J DASJ; II/'E: CAM: CAM-JttH /:'j» >/ "n;i toi." C329C. 189.0-1 I I-1 NJ 59.0- 99 U~ IP -^-r-^M-. , T-p-^^-, ll/E (00 Figure A-3. 120 220 Electron impact ionization mass spectrum of 3,5-dichlorobiphenyl, �W5/20/I52 1C:'12:00 ^ I!:'H f.AI.1; r;ALK2ft»l IU SAIIPLH: PCB IIIXTIIRE—f.OLUYIOII 11 IIH. IIU COJ1DS.: -1550 HIV 10-6 /OCV .2IIA DBS-1511 110-211-325-10/ "iKlBillAilCIiD (S 15D 211 01) HAM: H/J-: KW niC: 271072. f 255 100.0 1928( II 16 59.0- U) • 10 93 *>-n ft Z W ,1 1?3 if 1 T .Vii^ l._ .iii Li 169 i IIIwll ll/n Figure A-4. \yt 110 ICO ll iiill 100 1 1. I?G »LiJ.. 280 KG I-L.^ i-l 22t} \l •l ?]S 240 2»iC» Electron impact ionization mass spectrum of 2,4,5-trichlorobiphenyl. �MASS M'ECIRHII 05/2t)/82 IS:4?:W + ?):r.1 (Ml: SA!ir»>;: rcc tiixTiim-—SIU.UTIMI n iw. MM BA'JK II/C: 2 '9 P.IIJ: 3&10J2. 0» C«!l»S.: -1550 HIV Mi> 7»JiV .2IIA 1)115-1511 IIR-2II-325--IO/ "iKJ-ljm.1 211 OT> 2 0 iee.0-i 39369 2- i2 1 e 1 • in r\ 8 I8 255 i: 3 '9 1 ii/n J Jilu^jll k 1eo 1 T ' lk-,,1 1 1. l vlll ^ lll^ l 1 50 l ?1 J,l. » ?96 H"--j |—"* 2Wt .,| I,2?i_T213_rJ r-*" 250 I ' 1 ' 1 ' XY3«3 Figure A-5. Electron impact ionization mass spectrum of 2,2',4,A'-tetrachloroblphenyl. �HAW srcciwiii DMA: 'icuil:2r;'f»/ 07:>0 (J7 85/29/82 I6:12:0fl ^ I V : 00 CAM: CAI.I-WI SAUPLE: riJtt HlXTUnC-—SOLUTIOJI ill IUL J I U UGHIS.: -I550 HIV IO-6 70I-V .2IIA 08'j-Ctll IIO-2II-325-IO/ "«;] OH." BASE Il/Et 2:i:} HIC: 12C3M. EKIIAHCED (s isn 211 OT» 59.9 --r^ 350 Figure A-6. Electron impact ionization mass spectrum of 3,3'4 ,4' -tetrachlorobiphenyl-d^. �IIAS-; «)AiA: I'micyv-)"/ nwi UAI.I: tMf.»»l 05/M/«? 10:12:00 + 11:01 SAiim-t res MiXTunti— r,oi.ufi(iii n sw. IIM ar,»S.: -15W) BIV 10-0 /tfl-Y .2IW IWi Till IIO-2II-323-IO/ (s isn 211 on r.n: 05 "»KJ COI." 3078 180.0 2-36 "7 59.9- 191 99 2 «J 163 I "*"* 19-1 2*> .MUl'^rJ it/'-: Figure A-7. |llL,_,,U J50 li5.lV2.ix 'J«0 Electron impact ionization mass spectrum of 2,3',4,5',6-pentachlorobiphenyl. �IIACS SH3MWUI 85/20/J52 16:12:00 ' 12:06 SAtimi: rcc MIXTURE—SOLUTION ni HJI. im I>ATA: CAM: CAI.K20WI II3 323501. COIffiS.; -I5!i0 EIIY 10-5 70EV .2!l-\ DB5 I'jll 110-211 325- It)/ "OSI-COI." DBIAUCl-n <S ISO 2\\ 811 100.0- 25661. 29fl 50.0- It'li 350 u Figure A-8. Electron impact ionization mass spectrum of 2,2',3,3',6,6'-hexachlorobiphenyl. �IIVJS SrtCTtnfll ItAfA: 1?iUE2T,V»7 IKKJI aV.W/R:> H>:'I2:Ofl ^ M:2I iMl : CAI.E2WI 01 SAllI'LE: r«.B IIIXUli::;— -SDUiriO'l 01 HH. 111! COi!D:i.: -IWU DIY 10 0 TDtV .2JIA llffi I'-ll 1 10-211-325- IO/ "flH-Cor BA';C ll/li: :>V3 niC: 3755J?. nr.i,\i:ci;u is 150 211 OT» IOH.O IGOC1. i? 120 50.0 1 i 1 |i 7 liy 6 i: 0 4 .1 ir 129 IGO 3 1 149 ll I [1 lijW^M K9 IK? I 1" Ti 2W 22» 249 1680 3 1 i i—' oo 50.0- 3'.9 1 289 ,11 JJ-r^L•^*-i-» I111,.. ??*!|,. . 274 >*Wvi 1 ' i il • » • . | i • ILL - i i 3CO | • 300 • •i 1 i ' [ • • * •r ISO Figure A-9. Electron impact ionization mass spectrum of 2,2',3,4,4',5,6-heptachlorobiphenyl. �HAY; si'tornini JIATA: 1!HMI-2Wli/ ()r)7l CA.I.I: CAI.E?C!M 0.1 95/20/82 lti:42:W + Ifi: II SAiirLE: njB uixiimi: — souinoii ai mi. iiu cniros.: -I559 ia iv so r, voi-v .?IIA m^-r.ii n')-2ll-32r.-l'-)/ EII)IAt:r;GD (S 1511 211 OD BASE II/E: I/O KM): 'JJOB11. "OII-COI." i; ') 100.0 I6C7. 50.0- 2 r, i '3 p«125 T 95 I5C lee 120 149 100 183.0-1 1 |R7 159 51 "T8 II I «S ' 209 229 ^ 269 21« IGT. 3! 0 29 1 50.8393 271 I I . ll/fi 209 Figure A-10. I I1 1 \\.,m 388 3ji 1,1.1,,, 320 I 1 •I, i | 310 368 I 1, • • i • | •i i . |i i • • | . i . . ! i i . . | • . ' 308 1«8 120 «0 Electron impact ionization mass spectrum of 2,2',3,3',4,4',5,6-octachlorobiphenyl. �I»ATA: 'IOOIE5AW7 0970 CMI: CAI.K2MM OJ 05/20/82 l«:12:0fl ^ lfi:l'.» SAiffLE: rcis mxiuiw- — soumnii n iw. RASE »/f: Ifti HIO: 123016. lt!J OKWS.t -IfBW DIV 10 li 70EV .2IIA IWK-IriH IIO-2II-325-IO/ "UH--COI." BOIMXED (S I5B 2H OT> 1 G 17661. 1 2 2 50.0- 111 1BO 10 fl 125 1 t 1* l ' f • 101 1 it i I-J-1-.-H J 10 o II •PI 2 1 1 T \L\ 11LjllLjll^llL I 20 N/E 183.9- 1 » IwJ*. iw» III ^?V IllllM^^-JJ llti*^,^ alii . 2^1 220 |i|iii _ 240 I 260 230 41-1 ji 3 2 50.0- 357 290 i l.it, ni . 3dO Figure A-ll. 1 .,332 320 31? 3W jjll. 3CO -,-r-i-i-r- 3(KI 4W> 120 13 1 - 4G8 I, Electron impact ionization mass spectrum of 2,2',3,3',4,4',5,6,6f-nonachlorobiphenyl. �liAG'J SI'ECTBUll r II-MA: '190i 9 >/.WC2 10:12:00 + 17:13 CAI.l: CAM SAiii'LK: ten iiixitirr- soi.urinn ui an. nu ClISiDS.: -1559 HIV 10-6 70EV .2IIA D»r»-I5ll 110-711-325-!0/ Eii!)Ata:nD (s i5n 211 OT> w'JW UIWJ3 '"I f)3 BAJiC H/C: 21 i '• Rir, : 439208. "DJl-COL" 2 1 100.0- 228I6. I7« 2 9 50.0- 107 160 96 II/E 'i 108 262 231 Jl|ljYjl|h. 159 1 2?7 . 3f« 259 - •J 356 50.0- 228I 3 14« 321 ii/n Figure A-12. J-lOJULff^-.J 350 L^^MJEL 1 1, 150 ... 5C3 Electron impact ionization mass spectrum of 2 , 2 ' , 3 , 3 ' , 4 , 4 ' , 5 , 5 ' , 6 , 6 ' - d e c a c h l o r o b i p h e n y l . �ra Ltn.-oi.ii mss: 200 <Rei-.amr:Oi.ii MASS.uiPtD-G TiiTi!Aanc!:iH!miHiYL. isosrei: 15210 J:tT:D-0 nnR.'.Oil.U!:i)-CIFi!BIY[.. ISOIII-i: 0210 r.t*)/«iiT./T.H;.,\:iT.i <AV : i.ocoi i. not ST.IJS-V.- (.1.000 * ST.DEV.0.009 i.e i ts3 N> 0.899 HATE 5/I1/82 Figure A-13. 5/21/02 6/ 3/02 Response factor plotted on a day-to-day basis for the internal standard, 3,3',4,4'-tetrachlorobiphenyl-d6, in Solution No. 1. �RESl'OllSIi L I B : 0 1 . 2 i IIASS: 1«8 (IW.COIIl'iOI. I. MASS: 2!l<!) OlP:2-liai!)ll1IU)l!0-Bin«3IYl..JSCHER fll EEF : I)-G TEHACIILORO-BiriltliYI.. ISOIIEI! 0210 tAKEA/atF.ALEAl/tAIIT./Rb'F.AIIT.) (AV: 'J.51-11 5.600 ... 0.431 ST.TiEV.- n.ni Sl.'il 4. oca 1 NJ u> 3.C80 BATH ^'1-1/02 5/2-1/32 Figure A-14. Relative response factor for 2-monochlorobiphenyl in Solution No. 1 calculated versus 3,3',4,4'-tetrachlorobiphenyl-d6 on a day-to-day basis. �B:Ol.^i MASS: 222 (KKI-.ailinOI. l> IIAC,S: 2!«5> aiP:3.3--nioii.onn-Binn3ivL. ISWIHR tin B1-F:D-C TKTKACmjmO-ltiniHIYL. 1SOIJER B2IO T./l:m:.AIIT. > (AV: 2.7.}2» .t.AW ST.niv.- t 0.206 X ST.DEY.II-..1G6 3 r n.naa S'tt =• l i . • 2.J18H :; 2.C8!l 2.VC3 i to *• X 2.683 X X X 2.5*3 :< 2.480 •H 2.393 •> oon 5/24/02 6/ 3/32 Figure A-15. Relative response factor for 3,3'-dichlorobiphenyl in Solution No. 1 calculated versus 3,3',4,4'-tetrachlorobiphenyl-dg on a day-to-day basis. �1.111:01.1i IttSS: 256 (RiiF-COllPiOI. li IHSS.- 2!)OI aip:2.i.5-TRiciiinr.o-niriiiiiiYj.. isotiER r.29 REFrH-O TL:inAaiI.Ol;0~BirilFJIVI.. ISOMER II2IO i:nA)/(AiiT./Ki;r.AiiT.) <AV : 2.0051 2.^(10 ST.DLV.0. IR3 £ ST.IEY.n. I38 SMI = i.e 2. x I NJ 1.999 1.899 1.709 DATE 5/11/82 5/2-1/82 6/ 3/B2 Figure A-16. Relative response factor for 2,4,5-trichlorobiphenyl in Solution No. 1 calculated versus 3,3',4,4'-tetrachlorobiphenyl-d6 on a day-to-day basis. �RESrOKSF 1.111:01.5. IUSS: 202 (MF. COUP: 01. I , IKSS: 29CI niP:2.2M.'r-TFiRAciii.ojH)-iiirii0iYL. isoum: iw REf:D-0 lEll:AaiLi?r.O-Diri!BM.. ISOIinn U2IO (AnP,\/nCI:.A!:i'A)/(AIIT./!iLl;.AIIT.) (AV: 1.032) 1.280 ST.PMV.0.058 Z Sf.DEY.5.596 1.9 >( 1.190 •• i ro * O" X X X X ): O.C33 DATK l'l/82 5/21/02 G/ 3/02 Figure A-17. Relative response factor for 2,2',4,4'-tetrachlorobiphenyl in Solution No. 1 calculated versus 3,3',4,4'-tetrachlorobiphenyl-c^ on a day-to-day basis. �r-rsroiiSK UB.-OI.GI iwss: 326 (i!r.r.coiir oi.ii MASS: a\T-.2.y .1.5'.r.-rciiTAan.oi;o-mriiBiYi.. isomin : 11121 RCF:n-s iF.ii:Aaii.oi:o-iiii'iiaiYi.. isounK ir»io (Ar.t A/Cnp./.l:M>/(AIJT./r;nF./MIT.) (AV: O.'tIO) i. can ; -SU'liV.(1.952 Z ST.C-EV.T 477 Sl'il » 6. £39 i S3 -J DATE 5/11/82 5/21/82 6/ 3/82 Figure A-18. Relative response factor for 2,3',4,5',6-pentachlorobiphenyl in Solution No. 1 calculated versus 3,3',4,4'-tetrachlorobiphenyl-d6 on a day-to-day basis. �1.18:91.7. IIASS: 3C9 (l:EF.CO!H':fll. I. IIASS: diP^^'.s.s'.e.e'-iiiLVAaiLenn-BmiBiYJ.. isoiirc a i3t> BEF-.D-6 TElfiAaiI.OKO-|im!BIYI.. ISOIIKIt B2IO iiiiA^iAnT./iraF.AiiT.) <AV : o.ocs* O.J'O'.I ST.PEY.- O.OH £ ST.9EY.0.370 i.e X o.ynn * Is) 00 6.609 0.509 DATE 5/1V82 C/ 3/82 Figure A-19. Relative response factor for 2,2',3,',6,6'-hexachlorobiphenyl in Solution No. 1 calculated versus 3,3',4,4'-tetrachlorobiphenyl-d6 on a day-to-day basis. �RESPONSE i.in : oi.n, iwss: 391 (nnr.raiirrfli.ii MASS: air:2.2\3.i.i'.5.c-iiEi'T'.a!i.or.o-niniFiiYi.. isoiinn i lot EEF:«-c rETR/.ciu.ono-iiiMiBn'i.. iswim: 11210 : (AREA/niH .Ar,FA»/(AIIT./UtF.AIIT.) (AV: O.UO 0.377) ST.I'EV.0.827 x si.LEY.- tt.1?0 V.035 0. MO SMI - 1.0 x U.303 0.380 _• i isj VO I— 0.370 0.360 6.350 0.310 0.330 0.320 DATE 5/11/82 5/21/82 C/ 3/82 Figure A-20. Relative response factor for 2,2',3,4,4',5,6-heptachlorobiphenyl in Solution No. 1 calculated versus 3,3',4,4'-tetrachlorobiphenyl-d6 on a day-to-day basis. �r.Fsro;isr i.iitroi.o, IIASS 430 (nHP.cniir oi.i, IIASS REP:no Ti;u;.\aiLono-i;iriinj\'i.. isotinn U2io : : aiP:2,2'.3.3 t .1.4'.!;.6-Oi:TAOILORO-BIl l IK.ilV1.. ISWIFR 0 105 tlT. > (AV: 0.2/B> 1'. J/U sr.nr.v.s 0.021 ? Z Sf.DCV.7.972 '<; 0. ^-fi) sK 0. 203 - 1.0 •\c u_«. . .- , . _ _ i 1 0 O v *VM% 0 .270 , | 0.269 * X X 0.259 )C X n -MO — 5/2-1/82 Figure A-21. •• — • ' • II- »- — 1 C/ 3/02 Relative response factor for 2,2',3,3' ,4,4',5,6-octachlorobiphenyl in Solution No. 1 calculated versus 3,3' ,4,4'-tetrachlorobiphenyl-d^ on a day-to-day basis. �nnsronst LIB : OI.IOI HAGS: 101 (RnF.cniir oM air:2.2\3.3vi.i\5,G.<v-i;niiAciiLORiHiiriiniivi..: REF:iM> TErc/xiiioRo-DiFiintm.. isotmn 11210 (Am:4/RE»--.ARirA>/<AMT./r.FF.AHr.J <AV: 0.320 2301 0.257) ST.WiV.O.P29 5; sT.rtv.I I 239 SDil - 1.0 0.209 -v0.2J10 0.2/0 I u> 0.250 0.210 0.239 0.220 DATE Figure A-22. 5/14/82 5/21/82 6/ Relative response factor for 2,2',3,3',4,4',5,6,6'-nonachlorobiphenyl in Solution No.!1 calculated versus 3,3*,4,4'-tetrachlorobiphenyl-d6 on a day-to-day basis. �BESrOMSE L I B : O I . H i MASS: 498 (C£F.COIir : 0l. li MASS: 2991 air:2.2\3.r.4.1\5.5\G.6'-DECAaH.ORa-BIM!iaiYL. ISOIIHIi Q 209 BEF:D 6 TETIUdlLOBO-BlPliraril, ISOilEII (1210 i!EA>/(AIIT./i;EF.MIT.) <AV: 0.223) 0.270 ST.IlS-V.C.«22 Z Sf.OEV.9.8/7 n ?;T MM •= 1.8 r. • •• 0.210 I U> NJ 0.2JO 0.220 ) 0.210 I x 0.200 0. I'M DATIi 5/M/82 5/2-1/U2 C/ 3/32 Figure A-23. Relative response factor for 2,2' ,3,3',4,4',5,5',6,6'-decachlorobiphenyl in Solution No. 1 calculated versus 3,3',4,4'-tetrachlorobiphenyl-d6 on a day-to-day basis. �APPENDIX B ANALYTICAL METHOD: THE ANALYSIS OF BY-PRODUCT CHLORINATED BIPHENYLS IN COMMERCIAL PRODUCTS AND PRODUCT WASTES B-l �THE ANALYSIS OF BY-PRODUCT CHLORINATED BIPHENYLS IN COMMERCIAL PRODUCTS AND PRODUCT WASTES 1.0 Scope and Application 1.1 This is a gas chromatographic/electron impact mass spectrometric (GC/EIMS) method applicable to the determination of chlorinated biphenyls (PCBs) in commercial products and product wastes. The PCBs present may originate either as synthetic by-products or as contaminants derived from commercial PCB products (e.g., Aroclors). The PCBs may be present as single isomers or complex mixtures and may include all 209 congeners from monochlorobiphenyl through decachlorobiphenyl listed in Table 1. 1.2 The detection and quantitation limits are dependent upon the complexity of the sample matrix and the ability of the analyst to remove interferents and properly maintain the analytical system. The method accuracy and precision will be determined in future studies. 1.3 This method is restricted to use by or under the supervision of analysts experienced in the use of gas chromatography/mass spectrometry (GC/MS) and in the interpretation of gas chromatograms and mass spectra. Prior to sample analysis, each analyst must demonstrate the ability to generate acceptable results with this method by following the procedures described in Section 14.2. 1.4 The validity of the results depends on equivalent recovery of the analyte and 13C PCBs. If the *3C PCBs are not thoroughly incorporated in the matrix, the method is not applicable. 1.5 During the development and testing of this method, certain analytical parameters and equipment designs were found to affect the validity of the analytical results. Proper use of the method requires that such parameters or designs must be used as specified. These items are identified in the text by the word "must." Anyone wishing to deviate from the method in areas so identified must demonstrate that the deviation does not affect the validity of the data. Alternative test procedure approval must be obtained from the Agency. An experienced analyst may make modifications to parameters or equipment identified by the term "recommended." Each time such modifications are made to the method, the analyst must repeat the procedure in Section 14.2. In this case, formal approval is not required, but the documented data from Section 14.2 must be on file as part of the overall quality assurance program. B-2 �TABLE 1. NUMBERING OF PCB CONGENERS3 NO. Structure NO. Henoe(ilaroa<oh«ny1» 1 2 3 2 3 4 D<eh1orob1p(itny1t 4 5 6 7 3 9 10 11 12 13 14 15 }:]; 2)4 !:$' 2,6 3,3' 3,4 1:1' 4,4' Trlehlorablphtnyli 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 13 34 35 36 37 33 39 40 41 42 43 44 45 46 47 48 49 50 51 2.2'.3 2.2', 4 2.2', 5 2.2'. 6 2.3.3' 2.3,4 2.3.4' 2,3.5 2.3.6 2. 3', 4 2, 3'. 5 2, 3'. 6 2.4.4' NO. 52 53 54 5$ 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 105 106 107 108 109 110 2,2*. 5.5' 2,2',5.6* 2.2'.6.6' 2.3,3- .4 2.3,3'. 4' 2,3,3'. 5 2.3,3'.5' 2,3.3'. 6 2.3.4,42.3.4.5 2,3,4.6 2.3,4'. S 2, 3,4', 6 2,3.5,6 2,3' 2,3' 2.3' 2.3* 2.3' 2.3' 2.3' 2.3' in 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 4.4' 4,5 4,5' 4,6 4'. 5 4'. 6 5.5' S',8 2,4,4'. 5 2.4.4', 6 2'. 3, 4. 5 3,3'. 4. 4' 3,3',4,5 3,3'.4.5' 3,3'.5.5' 3,4.4'. 5 Structure 2,3.3' .4' 2.3.3' ,5 2.3.3' '.5 2.3.3' .5' 2.3.3' .6 2.3.3' ',6 2.3.3' ,5' 2.3,3' ,6 2.3.3' ',6 2.3,4.4 .5 2.3.4,4 ,6 2.3.4,5 6 2,3.4', .6 2.3'.*, 2.3'. 4. '.'6 2.3',4, ,5' 2.3". 4, 2'.3.3' 4J5 2'.3.4,4 '.5 2',3.4,. ,5' 2'.3.4.i .6' 3.3' .4.4 '.5 3.3'. 4.. .5' HemchU robtptienyls 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 15$ 156 157 158 159 160 PenUcM orcb< phtny 1 i 2.2'.3.3',4 2.2', 3. 3'. 5 2.2',3.3',6 2,2',3,4. 4' 2.2'. 3. 4. 5 2.2', 3, 4.5' 2,2'. 3,4.6 2,2'.3,4, 6' 2.2'.3.4',5 2,2'. 3,4'. 6 2.2',3,5,5' 2,2'. 3,5,6 2,2'.3.5,6' 2.2', 3, 5'. 6 2.2'. 3. 6.6' 2.2', 3'. 4.5 2,2'. 3' .4. 6 2.2', 4, 4' .5 2,2-.4.4'.6 2.2'. 4, 5,5' 2, 2' .4,5.6' 2.2',4.5',6 2, 2'. 4,6.6' 2.2', 4. 5 2.2' .4, 5' 2.2". 4, 6 2,2',4.6' NO. rtntacli oroMphenylj Tetneft 1 oreo 1 pinny 1 $ 82 83 84 2,4',S 85 2.4'.6 86 2'. 3. 4 87 2'. 3,5 88 3,3', 4 89 3.3',! 90 3,4,4' 91 3.4,5 92 3.4'.S 93 94 TttneM orob< ohnyl » 95 96 97 2.2'. 3.3' 2.2'. 3,4 98 2.2'.3,4' 99 2.2'. 3,5 100 2.2'.3.S' 101 2.2',3.6 102 2.2' .3,6' 103 2.2-.4.4 1 104 2,4.5 2.4.6 structure 2.2',3.. '.4,4' 2.2'. 3.. '.4.5 2.2'. 3. : '.4,5' 2.2'. 3.: '.4.6 2.2'. 3.: ',4.6' 2. 2'. 3,. '.5,5' 2.2' .3.. '.5,6 2.2* .3.: ',5, ' 2.2'. 3.: ',6, ' 2.2' .3,4 ,*'. 2.2'. 3. 4 .4'. ' 2,2' .3. 4 ,*', Z,2'.3,4 ,4' . ' 2.2'. 3.4 .5,5' 2,2'. 3, 4 .5.6 2.2'.3.4 .5,6' 2.2'. 3, 4 .5'. 6 2.2'. 3. 4 .6,6' 2.2', 3.4 '.5.5' 2,2',3.4 '.5,6 2,2'. 3, 4'.5.6' 2,2'. 3, 4 '.5- ,6 2.2'. 3.4 '.6.6' 2.2'.3.S .5' .6 2.2'. 3.S .6,6' 2,2' .4.4 '.5.5' 2,2'. 4.4 '.5.6' 2.2'. 4. 4 ',6,6' 2,3,3'. 4 .4'. 5 2.3, 3'. 4 ,4'.S' 2.3,3'. 4 .4'. 6 2.3,3'. 4 .5.5' 2.3.3'. 4 .5.6 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 2, 2'. 3, 3', 4. 4 ' , 5 2.2' .3. 3 ' . 4. 4 ' , 6 2, 2', 3. 3 ' , 4. 5. 5' 2, 2 ' , 3, 3 ' , 4. 5. 6 2,2'. 3. 3 ' , 4. 5 ' , 6 2, 2'. 3. 3 ' , 4.6. 6' 2, 2', 3. 3 ' , 5, 5 ' . 6 2. 2 ' . 3. 3 ' , 5, 6, 6' 2.2'. 3, 4, 4 ' , 5.5' 2. 2' .3, 4, 4'. 5, 6 2. 2' .3. 4. 4 ' , £ . 6 ' 2,2'.3,4,4',5',6 2, 2 ' , 3, 4, 4 ' . 6, 6' 2.2>.3,4,5.5'.6 2. 2'. 3, 4,5. 6, 6' 2,2', 3. 4 ' . 5. 5 ' . 6 2, 2', 3, 4 ' , 5,6, 6' 2.3, 3'. 4. 4', 5,5' 2, 3, 3', 4,4', 5, 6 2, 3, 3', 4, 4 ' , 5' ,6 2. 3, 3', 4, 5. 5 ' . 6 2.3,3' .4' .5.3'. 6 Ocucnlorotiionenyls 194 195 196 197 198 199 200 201 202 203 204 205 2,2', 3. 3'. .4', 5. 5' 2, 2'. 3, 3 ' , , 4 ' , 5, 6 2, 2 ' , 3, 3 ' . ,4', = , 5 ' 2, 2', 3, 3', ,4' ,5, 6' 2, 2', 3. 3 ' , S . S ' . S 2, 2', 3. 3 ' , ,5.6,6' 2.2', 3. 3 ' . .5'. 6. 6' 2, 2', 3, 3 ' , . S . 5 ' , 5 ' 2.2', 3, 3' .5. 5 ' , 6, 6' 2, 2'. 3, 4 . 4 ' , 5, 5 ' , 6 2.2* .3, 4, 4' ,5. 6.6' 2.3.3',4,4'f5,5',6 206 207 208 2.2'.3,3'.4.4',5,5',6 2, 2'. 3. 3 ' , 4, 4 ' . 5, 5, 6' 2. 2'. 3, 3'. 4, 5. 5 ' , 6, 6' NofueHloro61on«nyls Bteichlorebfomnyl Anil. Clw*., 302. 20-31 (I960). B-3 2.3,3'. 4, 5 ' , 6 2, 3, 3'. 4 ' . 5. 5' 2. 3.3'. 4'. 5, 6 2, 3. 3'. 4'. 5 ' , 6 2,3, 3'. 5, 5 ' . 6 2, 3, 4. 4 ' . 5.6 1 2.3',4,4'.5.5 2.3',4.4',5'.5 3. 3' .4. 4'. 5, 5' HtptieM orab< phtny 1 1 209 **dopt*d froa ttllicftrfttr, K. >nd Ztll, *., FrtstMus 2. Structure Htmehlorooiphtnylt Z.2',3.3'4,4',5,5',6.6' �2.0 Summary 2.1 The process or product must be sampled such that the specimen collected for analysis is representative of the whole. Statistically designed selection of the sampling position, time, or discrete product units should be employed. The sample must be preserved to prevent PCB loss prior to analysis. Customary inventory storage may be adequate for products. For intermediates, process samples, and other non-product specimens, storage at 4°C with optional preservation at low pH is recommended. 2.2 The sample is mechanically homogenized and subsampled if necessary. The sample is then spiked with four 13C PCB surrogates and the surrogates incorporated by further mechanical agitation. 2.3 The surrogate-spiked sample is extracted and cleaned up at the discretion of the analyst. Simple dilution or direct injection is permissible. Possible extraction techniques include liquidliquid partition, thermal desorption, and sorption onto resin columns followed by solvent desorption. Cleanup techniques may include liquid-liquid partition, sulfuric acid cleanup, saponification, adsorption chromatography, gel permeation chromatography, or a combination of cleanup techniques. The sample is diluted or concentrated to a final known volume for instrumental determination. 2.4 The PCB content of the sample extract is determined by capillary (preferred) or packed column gas chromatography/electron impact mass spectrometry (CGC/EIMS or PGC/EIMS) operated in the selected ion monitoring (SIM), full scan, or limited mass scan (IMS) mode. 2.5 PCBs are identified by comparison of their retention time and mass spectral intensity ratios to those in calibration standards. 2.6 PCBs are quantitated against the response factors for a mixture of 11 PCB congeners, using the response of the 13C surrogate to compensate for losses in workup and determination and instrument variability. 2.7 The PCBs identified by the SIM technique may be confirmed by full scan CGC/EIMS, retention on alternate GC columns, other mass spectrometric techniques, infrared spectrometry, or other techniques, provided that the sensitivity and selectivity of the technique are demonstrated to be comparable or superior to GC/EIMS. 2.8 The analysis time is dependent on the extent of workup employed. The time required for instrumental analysis of a single sample, excluding data reduction and reporting, is about 30 to 45 min. 2.9 Appropriate quality control (QC) procedures are included to assess the performance of the analyst and estimate the quality of the results . These QC procedures include the demonstration of laboratory capability: periodic analyst certification, the use of control B-4 �charts, and the analysis of blanks, replicates, and standard addition samples. A quality assurance (QA) plan must be developed for each laboratory. 2.10 While several options are available throughout this method, the recommended procedure to be followed is: 2.10.1 The sample is collected according to a scheme which permits extrapolation of the sample data to the whole product or product waste. 2.10.2 The sample is preserved to prevent any loss of PCBs or changes in matrix which may adversely affect recovery. 2.10.3 The sample is mechanically homogenized and subsampled if necessary. 2.10.4 The sample is spiked with four 13C PCB surrogates (4-chlorobiphenyl; 3,3',4,4'-tetrachlorobiphenyl; 2,2',3,3',5,5*,6,6"-octachlorobiphenyl; and decachlorobiphenyl). 2.10.5 Normally, the sample is extracted, although dilution may also be used. 2.10.6 The extract is cleaned up and concentrated to an appropriate volume. 2.10.7 An aliquot of the extract is analyzed by CGC/EIMS operated in the SIM mode. On-column injections onto a 15-m DB-5 capillary column, programmed (for toluene solutions) from 110° to 325°C at 10°/min after a 2-min hold is used. Helium at 45-cm/sec linear velocity is used as the carrier gas. 2.10.8 PCBs are identified by retention time and mass spectral intensities. 2.10.9 PCBs are quantitated against the response factors for a mixture of 11 PCB congeners. 2.10.10 The total PCBs are obtained by summing the amounts for each homolog found, and the concentration is reported as micrograms per gram. 3.0 Interferences 3.1 Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware, leading to discrete artifacts and/or elevated baselines in the total ion current profiles. All of these materials must be routinely demonstrated to be free from interferences by the analysis of laboratory reagent blanks as described in Section 14.4. B-5 �3.1.1 3.1.2 3.2 4.0 Glassware must be scrupulously cleaned. All glassware is cleaned as soon as possible after use by rinsing with the last solvent used. This should be followed by detergent washing with hot water and rinses with tap water and reagent water. The glassware should then be drained dry and heated in a muffle furnace at 400°C for 15 to 30 min. Some thermally stable materials, such as PCBs, may not be eliminated by this treatment. Solvent rinses with acetone and pesticide quality hexane may be substituted for the muffle furnace heating. Volumetric ware should not be heated in a muffle furnace. After it is dry and cool, glassware should be sealed and stored in a clean environment to prevent any accumulation of dust or other contaminants. It is stored inverted or capped with aluminum foil. The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required. All solvent lots must be checked for purity prior to use. Matrix interferences may be caused by contaminants that are coextracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the sources of samples. Safety 4.1 The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. 4.2 Polychlorinated biphenyls have been tentatively classified as known or suspected human or mammalian carcinogens. Primary standards of these toxic compounds should be prepared in a hood. Personnel must wear protective equipment, including gloves and safety glasses. Congeners highly substituted at the meta and para positions and unsubstituted at the ortho positions are reported to be the most toxic. Extreme caution should be taken when handling these compounds neat or in concentrated solutions. This class includes 3,3',4,4'-tetrachlorobiphenyl (both natural abundance and isotopically labeled). B-6 �4.3 4.4 5.0 Diethyl ether should be monitored regularly to determine the peroxide content. Under no circumstances should diethyl ether be used with a peroxide content in excess of 50 ppm, as an explosion could result. Peroxide test strips manufactured by EM Laboratories (available from Scientific Products Company, Cat. No. P1126-8 and other suppliers) are recommended for this test. Procedures for removal of peroxides from diethyl ether are included in the instructions supplied with the peroxide test kit. Waste disposal must be in accordance with RCRA and applicable state rules. Apparatus and Materials 5.1 Sampling containers - Amber glass bottles, 1-liter or other appropriate volume, fitted with screw caps lined with Teflon. Cleaned foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, samples should be protected from light using foil or a light-tight outer container. The bottle must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination. 5.2 Glassware - All specifications are suggestions only. Catalog numbers are included for illustration only. 5.2.1 Volumetric flasks - Assorted sizes. 5.2.2 Pipets - Assorted sizes, Mohr delivery. 5.2.3 Micro syringes - 10.0 Ml for packed column GC analysis, 1.0 pi for on-column GC analysis. 5.2.4 Chromatographic column - Chromaflex, 400 mm long x 19 mm ID (Kontes K-420540-9011 or equivalent). 5.2.5 Gel permeation chromatograph - GPC Autoprep 1002 (Analytical Bio Chemistry Laboratories, Inc.) or equivalent. 5.2.6 Kuderna-Danish Evaporative Concentrator Apparatus 5.2.6.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked. Ground glass stopper size (519/22 joint) is used to prevent evaporation of solvent. 5.2.6.2 Evaporative flask - 500 ml (Kontes K-57001-0500 or equivalent). Attached to concentrator tube with springs (Kontes K-662750-0012 or equivalent) . 5.2.6.3 Snyder column - Three ball macro (Kontes K-503000-0121 or equivalent). B-7 �5.3 Balance - Analytical, capable of accurately weighing 0.0001 g. 5.4 Gas chromatography/mass spectrometer system. 5.4.1 Gas chroraatograph - An analytical system complete with a temperature programmable gas chromatograph and all required accessories including syringes, analytical columns, and gases. The injection port must be designed for oncolumn injection when using capillary columns or packed columns. Other capillary injection techniques (split, splitless, "Grob," etc.) may be used provided the performance specifications stated in Section 7.1 are met. 5.4.2 Capillary GC column - A 12-20 m long x 0.25 mm ID fused silica column with a 0.25 (Jm thick DB-5 bonded silicone liquid phase (J&W Scientific) is recommended. Alternate liquid phases may include OV-101, SP-2100, Apiezon L, Dexsil 300, or other liquid phases which meet the performance specifications stated in Section 7.1. 5.4.3 Packed GC column - A 180 cm x 0.2 cm ID glass column packed with 3% SP-2250 on 100/120 mesh Supelcoport or equivalent is recommended. Other liquid phases which meet the performance specifications stated in Section 7.1 may be substituted. 5.4.4 Mass spectrometer - Must be capable of scanning from 150 to 550 daltons every 1.5 sec or less, collecting at least five spectra per chromatographic peak, utilizing a 70-eV (nominal) electron energy in the electron impact ionization mode and producing a mass spectrum which meets all the criteria in Table 2 when 50 ng of decafluorotriphenyl phosphine [DFTPP, bis(perfluorophenyl)phenyl phosphine] is injected through the GC inlet. Any GC-to-MS interface that gives acceptable calibration points at 10 ng per injection for each PCB isomer in the calibration standard and achieves all acceptable performance criteria (Section 10) may be used. Direct coupling of the fused silica column to the MS is recommended. Alternatively, GC-to-MS interfaces constructed of all glass or glasslined materials are recommended. Glass can be deactivated by silanizing with dichlorodimethylsilane. 5.4.5 A computer system that allows the continuous acquisition and storage on machine-readable media of all mass spectra obtained throughout the duration of the chromatographic program must be interfaced to the mass spectrometer. The data system must have the capability of integrating the abundances of the selected ions between specified limits and relating integrated abundances to concentrations using the calibration procedures described in this method. The computer must have software that allows B-8 �TABLE 2. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA Mass Ion abundance criteria 197 198 199 Less than 1% of mass 198 100% relative abundance 5-9% of mass 198 275 10-30% of mass 198 365 Greater than 1% of mass 198 441 Present, but less than mass 443 442 Greater than 40% of mass 198 443 17-23% of mass 442 B-9 �searching any GC/MS data file for ions of a specific mass and plotting such ion abundances versus time or scan number to yield an extracted ion current profile (EICP). Software must also be available that allows integrating the abundance in any EICP between specified time or scan number limits. 6.0 Reagents 6.1 Solvents - All solvents must be pesticide residue analysis grade. New lots should be checked for purity by concentrating an aliquot by at least as much as is used in the procedure. 6.2 Calibration standard congeners - Standards of the PCB congeners listed in Table 3 are available from Ultra Scientific, Hope, Rhode Island; or Analabs, North Haven, Connecticut. 6.3 Calibration standard stock solutions - Primary dilutions of each of the individual PCBs listed in Table 3 are prepared by weighing approximately 1-10 mg of material within 1% precision. The PCB is then dissolved and diluted to 1.0 ml with hexane. The concentration is calculated in mg/ml. The primary dilutions are stored at 4°C in screw-cap vials with Teflon cap liners. The meniscus is marked on the vial wall to monitor solvent evaporation. Primary dilutions are stable indefinitely if the seals are maintained. The validity of primary and secondary dilutions must be monitored on a quarterly basis by analyzing four quality control check samples (see Section 14.2). 6.4 Working calibration standards - Working calibration standards are prepared that are similar in PCB composition and concentration to the samples by mixing and diluting the individual standard stock solutions. Example calibration solutions are shown in Table 3. The mixture is diluted to volume with pesticide residue analysis quality hexane. The concentration is calculated in ng/ml as the individual PCBs. Dilutions are stored at 4°C in narrow-mouth, screw-cap vials with Teflon cap liners. The meniscus is marked on the vial wall to monitor solvent evaporation. These secondary dilutions can be stored indefinitely if the seals are maintained. These solutions are designated "CSxxx," where the xxx is used to encode the nominal concentration in ng/ml. 6.5 Alternatively, certified stock solutions similar to those listed in Table 3 may be available from a supplier, in lieu of the procedure described in Section 6.4. 6.6 DFTPP standard - A 50-ng/|Jl solution of DFTPP is prepared in acetone or another appropriate solvent. 6.7 Surrogate standard stock solution - The four 13C-labeled PCBs listed in Table 4 may be available from a supplier as a certified solution. This solution may be used as received or diluted further. These solutions are designated "SSxxx," where the xxx is used to encode the nominal concentration in (Jg/ml. B-10 �TABLE 3. Homolog CONCENTRATIONS OF CONGENERS IN PCS CALIBRATION STANDARDS (ng/ml)a Congener no. CS100 CS1000 CS050 CS010 1 1 1,040 104 52 10 1 3 1,000 100 50 10 2 7 1,040 104 52 10 3 30 1,040 104 52 10 4 50 1,520 152 76 15 5 97 1,740 174 87 17 6 143 1,920 192 96 19 7 183 2,600 260 130 26 8 202 4,640 464 232 46 9 207 5,060 506 253 51 10 209 4,240 424 212 42 4 255 255 255 255 1 211 (RS) 104 104 104 104 4 212 (RS) 257 257 257 257 8 213 (RS) 407 407 407 407 10 a 210 (IS) 214 (RS) 502 502 502 502 Concentrations given as examples only. B-ll �TABLE 4. COMPOSITION OF SURROGATE SPIKING SOLUTION (SS100) CONTAINING 13 C-LABELED PCBsa Congener no. Compound Concentration ((jg/ml) 211 104 212 (13C12)3,3',4,4'-tetrachlorobiphenyl 257 213 (13C12)2,2(,3,3',5,5',6,6'-octachlorobiphenyl 395 214 a (l',2',3',4l,5',6l-13C6)4-chlorobiphenyl (13C12)decachlorobiphenyl 502 Concentrations given as examples only. B-12 �6.8 Internal standard solution - A solution of d6-3,3',4,4'-tetrachlorobiphenyl is prepared at a nominal concentration of 1-10 mg/ml in hexane. The solution is further diluted to give a working standard. 6.9 Solution stability - The calibration standard, surrogate, and DFTPP solutions should be checked frequently for stability. These solutions should be replaced after 6 months, or sooner if comparison with quality control check samples indicates compound degradation or concentration change. 6.10 Quality control check samples will be supplied by the Agency. 7.0 Calibration 7.1 The gas chromatograph must meet the minimum operating parameters shown in Tables 5 and 6, daily. If all criteria are not met, the analyst must adjust conditions and repeat the test until all criteria are met, 7.2 The mass spectrometer must meet the minimum operating parameters shown in Tables 2, 7, and 8, daily. If all criteria are not met, the analyst must retune the spectrometer and repeat the test until all conditions are met. 7.3 The PCB response factors (RF ) must be determined using Equation 7-1 for the analyte homologs? A x M. RF = -£ ~ Eq. 7-1 P A is x Mp where RF = response factor of a given PCB congener A = area of the characteristic ion for the PCB congener ™ peak M = mass of PCB congener injected (nanograms) A. = area of the characteristic ion for the internal standard peak M. = mass of internal standard injected (nanograms) IS Using the same conditions as for RF , the surrogate response factors (RF ) must be determined using Equation 7-2. s A x M. w *= t f ^ where A = area of the characteristic ion for the surrogate peak M s = mass of surrogate injected (nanograms) Other terms are the same as defined in Equation 7-1. B-13 �TABLE 5. OPERATING PARAMETERS FOR CAPILLARY COLUMN GAS CHROMATOGRAPHIC SYSTEM Recommended Parameter Tolerance Liquid phase Finnigan 9610 15 m x 0.255 mm ID Fused silica DB-5 (J&W) Liquid phase thickness 0.25 |Jm Carrier gas Helium Carrier gas velocity 45 cm/sec Injector Injector temperature On-column (J&W) c Optimum performance Other Optimum performance Injection volume 1.0 plc 70°C (2 min)d 70°-325°C at 10°C/min£ Other Other Other Transfer line temperature None 280°C Glass jet or othe p Optimum6 Tailing factor 0.7-1.5 0.4-3 Peak width 7-10 sec < 15 sec Gas chromatograph Column Other Other Other nonpolar or semipolar < 1 pro Hydrogen Optimum performance p Initial column temperature Column temperature program Separator a Substitutions permitted with any common apparatus or technique provided performance criteria are met. b Measured by injection of air or methane at 270°C oven temperature. c For on-column injection, manufacturer's instructions should be followed regarding injection technique. d With on-column injection, initial temperature equals boiling point of the solvent; in this instance, hexane. e C 12 Cl 1 o elutes at 270°C. Programming above this temperature ensures a clean column and lower background on subsequent runs. f Fused silica columns may be routed directly into the ion source to prevent separator discrimination and losses. g High enough to elute all PCBs, but not high enough to degrade the column if routed through the transfer line. h Tailing factor is width of front half of peak at 10% height divided by width of back half of peak at 10% height for single PCB congeners in solution CSxxx. i Peak width at 10% height for a single PCB congener is CSxxx. B-14 �TABLE 6. OPERATING PARAMETERS FOR PACKED COLUMN GAS CHRQMATOGRAPHY SYSTEM Tolerance Recommended Parameter Gas chromatograph Finnigan 9610 Other3 Column 180 cm x 0.2 cm ID glass Other Column packing 3% SP-2250 on 100/ 120 mesh Supelcoport Other nonpolar or semipolar Carrier gas Helium Hydrogen Carrier gas flow rate 30 ml/min Optimum performance Injector On-column Other Injector temperature 250°C Optimum Injection volume 1.0 pi S 5 |Jl Initial column temperature 150°C, 4 min Other Column temperature program 150°-260°C 3t 8°/min Other Separator Glass jet Other Transfer line temperature 280°C Optimum Tailing factor 0.7-1.5 0.4-3 Peak width 10-20 sec < 30 sec o a Substitutions permitted if performance criteria are met. b High enough to elute all PCBs. c Tailing factor is width of front half of peak at 10% height divided by width of back half of peak at 10% height for single PCB congeners in solution CSxxx. d Peak width at 10% height for a single PCB congener in CSxxx. B-15 �TABLE 7. OPERATING PARAMETERS FOR QUADRUPOLE MASS SPECTROMETER SYSTEM Parameter Recommended Tolerance Mass spectrometer Finnigan 4023 Other3 Data system Incos 2400 Other Scan range 95-550 Other Scan time 1 sec Otherb Resolution Unit Optimum performance Ion source temperature 280°C 200°-300°C Electron energy 70 eV Optimum performance Trap current 0.2 mA Optimum performance Multiplier voltage -1,600 V Optimum performance Preamplifier sensitivity 10"6 A/V Set for desired working range a Substitutions permitted if performance criteria are met. b Greater than five data points over a GC peak is a minimum. c Filaments should be shut off during solvent elution to improve instrument stability and prolong filament life, especially if no separator is used. B-16 �TABLE 8. OPERATING PARAMETERS FOR MAGNETIC SECTOR MASS SPECTROMETER SYSTEM Parameter Tolerance Recommended Mass spectrometer Finnigan MAT 31 1A Other3 Data system Incos 2400 Other Scan range 98-550 Other Scan mode Exponential Other Cycle time 1.2 sec Otherb Resolution 1,000 > 500 Ion source temperature 280°C 250°-300°C Electron energy 70 eV 70 eV Emission current 1-2 mA Optimum Filament current Optimum Optimum Multiplier -1,600 V Optimum a Substitutions permitted if performance criteria are met. b Greater than five data points over a GC peak is a minimum. c Filaments should be shut off during solvent elution to improve instrument stability and prolong filament life, especially if no separator is used. B-17 �If specific congeners are known to be present and if standards are available, selected RF values may be employed. For general samples, solutions CSxxx and SSxxx or a mixture (Tables 3 and 4), with a similar level of internal standard (de-3,31,4,4'-tetrachlorobiphenyl) added, may be used as the response factor solution. The PCB-surrogate pairs to be used in the RF calculation are listed in Table 9. Generally, only the primary ions of both the analyte and surrogate are used to determine the RF values. If alternate ions are to be used in the quantitation, the RF must be determined using that characteristic ion. The RF value must be determined in a manner to assure ±20% accuracy and precision. For instruments with good day-to-day precision, a running mean (RF) based on seven values determined once each day may be appropriate. Other options include, but are not limited to, triplicate determinations of a single concentration spaced throughout a day or determination of the RF at three different levels to establish a working curve. If replicate RF values differ by greater than ±10% RSD, the system performance should be monitored closely. If the RSD is greater than ±20%, the data set must be considered invalid and the RF redetermined before further analyses are done. 7.4 7.5 8.0 If the GC/EIMS system has not been demonstrated to yield a linear response or if the analyte concentrations are more than two orders of magnitude different from those in the RF solution, a calibration curve must be prepared. If the analyte and RF solution concentrations differ by more than one order of magnitude, a calibration curve should be prepared. A calibration curve should be established with triplicate determinations at three or more concentrations bracketing the analyte levels. The relative retention time (RRT) windows for the 10 homologs and surrogates must be determined. If all congeners are not available, a mixture of available congeners or an Aroclor mixture (e.g., 1016/1254/1260) may be used to estimate the windows. The windows must be set wider than observed if all isomers are not determined. Typical RRT windows for one column are listed in Table 10. The windows may differ substantially if other GC parameters are used. Sample Collection, Handling, and Preservation 8.1 Amber glass sample containers should have Teflon-lined screw caps. With noncorrosive samples, methylene chloride-washed aluminum foil liners may be substituted. The volume and configuration are determined by the amount of sample to be collected and its physical properties. For dry powders, other containers such as heavy-walled polyethylene bags may be appropriate. B-18 �TABLE 9. PAIRINGS OF ANALYTE, CALIBRATION, AND SURROGATE COMPOUNDS Analyte Congener no . 1 2,3 Calibration standard Compound 2-C12H9Cl 3- and 4-C12H9Cl 1 C "ID 1 £ OQ f* TT f> "I ^ 1 2 8 2 P IT PI /•A — Cl **U ~ o 1 P IIP! L ^ 2 6 ^ •*- 4 ^ oZ" 1Z / OO 1O T L.^2"5^'-'-5 128-169 170-193 194-205 206-208 209 C12H4C16 C12H3C17 C12H2C18 C12HC19 Ci2CliQ 4 ID" oy *-*l2**7'-'^-3 P TT O T Congener no. I 3 7 30 50 97 143 183 202 207 209 Compound 2 4 2,4 2,4 ,6 2,2 ',4,6 2,2 ',3', 4, 5 2,2 ',3,4,5 ,6' 2,2 ',3', 4, ,5', 6 4' 2»2 ',3,3',5, 5', 6, 6' 2,2 ',3,3',4, 4', 5, 6, 6' C12Clio w a Ballschmiter numbering system, see Table 1. Surrogate Congener no. Compound 211 211 211 212 212 212 212 213 213 213 214 13 C6-4 C6-4 13 C6-4 13 Cl2-3,3' ,4 ,4' 13 C12-3,3' ,4 ,4' 13 Cl2-3,3' ,4 ,4' 13 C12-3,3' ,4 ,4' 13 Cl2-2,2' ,3 ,3' , 5,5', 6, 6' 13 C12-2,2' ,3 ,3' ,5,5' ,6, 6' 13 C12-2,2' ,3 ,3' ,5, 5', 6, 6' 13 C12C110 13 �TABLE 10. PCB homo log RELATIVE RETENTION TIME (RRT) RANGES OF PCB HOMOLOGS VERSUS de-3,31.4,4'-TETRACHLOROBIPHENYL No. of isomers measured Observed range of RRTs3 Calibration solution Congener Observed no. RRT3 Projected range of RRTs 3 0.40-0.50 1 3 0.43 0.50 0.35-0.55 10 0.52-0.69 7 0.58 0.35-0.80 9 0.62-0.79 30 0.65 0.35-1.10 Tetrachloro 16 0.72-1.01 50 0.75 0.55-1.05 Pentachloro 12 0.82-1.08 97 0.98 0.80-1.10 Hexachloro 13 0.93-1.20 143 1.05 0.90-1.25 Heptachloro 4 1.09-1.30 183 1.15 1.05-1.35 Octachloro 6 1.19-1.36 202 1.19 1.10-1.50 Nonachloro 3 1.31-1.42 207 1.33 1.25-1.50 Decachloro 1 1.44-1.45 209 1.44 1.35-1.50 Monochloro Dichloro Trichloro a The RRTs of the 77 congeners and a mixture of Aroclor 1016/1254/1260 were measured versus 3,3',4,4'-tetrachlorobiphenyl-de (internal standard) using a 15-m J&W DB-5 fused silica column with a temperature program of 110°C for 2 min, then 10°C/min to 325°C, helium carrier at 45 cm/sec, and an oncolumn injector. A Finnigan 4023 Incos quadrupole mass spectrometer operating with a scan range of 95-550 daltons was used to detect each PCB congener. b The projected relative retention windows account for overlap of eluting homologs and take into consideration differences in operating systems and lack of all possible 209 PCB congeners. B-20 �8.2 Sample bottle preparation 8.2.1 8.2.2 Sample bottles are heated to 400°C for 15 to 20 min or rinsed with pesticide grade acetone or hexane and allowed to air dry. 8.2.3 8.3 All sample containers and caps should be washed in detergent solution, rinsed with tap water, and then with distilled water. The bottles and caps are allowed to drain dry in a contaminant-free area. Then the caps are rinsed with pesticide grade hexane and allowed to air dry. The clean bottles are stored inverted or sealed until use. Sample collection 8.3.1 8.3.2 Discrete product units - If the product is small enough that one or more discrete units would be used as the analytical sample, a statistically random sampling approach is recommended. 8.3.3 Liquids or free-flowing solids - If possible, the source is mixed thoroughly before collecting the sample. If mixing is impractical, the sample should be collected from a representative area of the source. If the liquid is flowing through an enclosed system, sampling through a valve should be randomly timed. 8.3.4 8.4 The primary consideration in sample collection is that the sample collected be representative of the whole. Therefore, sampling plans or protocols for each individual producer's situation will have to be developed. The recommendations presented here describe general situations. The number of replicates and sampling frequency also must be planned prior to sampling. Solids - Larger bulk solids which must be subsampled to get a reasonably sized analytical sample must be treated on a case-by-case basis. A representative sample should be obtained by designing a sampling location selection scheme such that all parts of the whole have a finite, known probability of inclusion. Based on such a scheme, the PCS content of the sample can be used to extrapolate to the content of the whole. Sample preservation - Product samples should be stored as the bulk or packaged product inventory would be stored, or in a cool, dry, dark area. Intermediates, process samples, or other non-product specimens should be stored at 4°C. If there is a possibility of microbial degradation, addition of HgSC^ during collection to a pH < 2 is recommended. A test strip is used to monitor pH. Storage times in excess of 4 weeks are not recommended. B-21 �If residual chlorine is present in the sample, it should be quenched with sodium thiosulfate. EPA Methods 330.4 and 330.5 may be used to measure the residual chlorine.1 Field test kits are available for this purpose. 9.0 Sample Preparation Since a wide variety of matrices may be subjected to analysis by this method, the extraction/cleanup procedure cannot be specified. This section describes general guidelines for subsampling, addition of 13C surrogates, dilution, extraction, cleanup, extract concentration, and other sample preparation procedures. 9.1 Sample homogenization and subsampling - The sample is homogenized by shaking, blending, shredding, crushing, or other appropriate mechanical technique. A representative subsample of 100 g or other known mass is then taken. The sample size is dependent upon the anticipated PCB levels and difficulty of the subsequent extraction/ cleanup steps. Note: The precision of the mass determination at this step will be reflected in the overall method precision. Therefore, an analytical balance must be used to assure that the weight is accurate to ±1% or better. 9.2 Surrogate addition - An appropriate volume of surrogate solution SSxxx is pipetted into the sample. The final concentration of the surrogates must be in the working range of the calibration and well above the matrix background. The surrogates are thoroughly incorporated by further mechanical agitation. For nonviscous liquids, shaking for 30 sec should be sufficient. For viscous liquids or free-flowing solids, 10-min tumbling is recommended. In cases where inadequate incorporation may be expected, such as solids, overnight equilibration with agitation is recommended. Note: The volume measurement of the spiking solution is critical to the overall method precision. The analyst must exercise caution that the volume is known to ±J% or better. Where necessary, calibration of the pipet is recommended. 9.3 Sample preparation (extraction/cleanup) - After addition of the surrogates, the sample is further treated at the discretion of the analyst, provided that the GC/EIMS response of the four surrogates meets the criteria listed in Section 7.0. The literature pertaining to these techniques has been reviewed.2 Several possible techniques are presented below for guidance only. The applicability of any of these techniques to a specific sample matrix must be determined by the precision and accuracy of the 13C PCB surrogate recoveries, as discussed in Section 14.2. B-22 �9.3.1 Extraction1 9.3.1.1 Dilution - In some cases, where the PCB concentration is high, a simple volumetric dilution with an appropriate solvent may be sufficient sample preparation. 9.3.1.2 Direct injection - If sample viscosity permits, direct injection with no dilution is permissible. 9.3.1.3 Liquid-liquid extraction - If the matrix is aqueous (or another solvent in which PCBs are only slightly soluble), a liquid-liquid partition may be effective. The solvent, number of extractions, solvent-to-sample ratio, and other parameters are chosen at the analyst's discretion. 9.3.1.4 Sorbent column extraction - PCBs may be isolated from free-flowing liquids onto sorbent columns. The selection of sorbent (XAD, Porapak, carbonpolyurethane foam, etc.) will depend on the nature of the matrix. The available methods have been reviewed.2 9.3.1.5 Thermal desorption - If the matrix is nonvolatile, thermal desorption of the PCBs onto a sorbent column, filter, or cold trap may be an effective extraction/cleanup method. 9.3.2 Cleanup - Several tested cleanup techniques are described below. All but the base cleanup (9.3.2.8) were previously validated for PCBs in transformer fluids.3 Depending upon the complexity of the sample, one or more of the techniques may be required to fractionate the PCBs from interferences. For most cleanups a concentrated (1-5 ml) extract should be used. 9.3.2.1 Acid cleanup 9.3.2.1.1 Place 5 ml of concentrated sulfuric acid into a 40-ml narrow-mouth screwcap bottle. Add the sample extract. Seal the bottle with a Teflon-lined screw cap and shake for 1 min. 9.3.2.1.2 Allow the phases to separate, transfer the sample (upper phase) with three rinses of 1-2 ml solvent to a clean container and concentrate to an appropriate volume. B-23 �9.3.2.1.3 9.3.2.1.4 9.3.2.2 Analyze as described in Section 10.0. If the sample is highly contaminated, a second or third acid cleanup may be employed. Florisil column cleanup 9.3.2.2.1 9.3.2.2.2 Place a 20-g charge of Florisil, activated overnight at 130°C, into a Chromaflex column. Settle the Florisil by tapping the column. Add about 1 cm of anhydrous sodium sulfate to the top of the Florisil. Pre-elute the column with 70-80 ml of hexane. Just before the exposure of the sodium sulfate layer to air, stop the flow. Discard the eluate. 9.3.2.2.3 Add the sample extract to the column. 9.3.2.2.4 Carefully wash down the inner wall of the column with 5 ml of hexane. 9.3.2.2.5 Add 200 ml of 6% ethyl ether/hexane and set the flow to about 5 ml/min. 9.3.2.2.6 Collect 200 ml of eluate in a KudernaDanish flask. All the PCBs should be in this fraction. Concentrate to an appropriate volume. 9.3.2.2.7 9.3.2.3 Variations among batches of Florisil (PR grade or equivalent) may affect the elution volume of the various PCBs. For this reason, the volume of solvent required to completely elute all PCBs must be verified by the analyst. The weight of Florisil can then be adjusted accordingly. Analyze the sample as described in Section 10.0. Alumina column cleanup 9.3.2.3.1 B-24 Adjust the activity of the alumina (Fisher A450 or equivalent) by heating to 200°C for 2 to 4 hr. When cool, add 3% water (wt:wt) and mix until uniform. Store in a tightly sealed bottle. Allow the deactivated alumina to equilibrate at least 1/2 hr before use. Reactivate weekly. �9.3.2.3.2 Variations between batches of alumina may affect the elution volume of the various PCBs. For this reason, the volume of solvent required to completely elute all of the PCBs must be verified by the analyst. The weight of alumina can then be adjusted accordingly. 9.3.2.3.3 Place a 50-g charge of alumina into a Chromaflex column. Settle the alumina by tapping. Add about 1 cm of anhydrous sodium sulfate. Preelute the column with 70-80 ml of hexane. Just before exposure of the sodium sulfate layer to air, stop the flow. Discard the eluate. 9.3.2.3.4 Add the sample extract to the column. 9.3.2.3.5 Carefully wash down the inner wall of the column with 5 ml of hexane. 9.3.2.3.6 Add 295 ml of hexane to the column. 9.3.2.3.7 Discard the first 50 ml. 9.3.2.3.8 Collect 250 ml Kuderna-Danish PCBs should be Concentrate to of the hexane in a flask. All of the in this fraction. an appropriate volume. 9.3.2.3.9 Analyze the sample as described in Section 10.0. 9.3.2.4 Silica gel column cleanup 9.3.2.4.1 Activate silica gel (Davison Grade 950 or equivalent) at 135°C overnight. 9.3.2.4.2 Variations between batches of silica gel may affect the elution volume of the various PCBs. For this reason, the volume of solvent required to completely elute all of the PCBs must be verified by the analyst. The weight of silica gel can then be adjusted accordingly. B-25 �9.3.2.4.3 Place a 25-g charge of activated silica gel into a Chromaflex column. Settle the silica gel by tapping the column. Add about 1 cm of anhydrous sodium sulfate to the top of the silica gel. 9.3.2.4.4 Pre-elute the column with 70-80 ml of hexane. Discard the eluate. Just before exposing the sodium sulfate layer to air, stop the flow. 9.3.2.4.5 Add the sample extract to the column. 9.3.2.4.6 Wash down the inner wall of the column with 5 ml of hexane. 9.3.2.4.7 Elute the PCBs with 195 ml of 10% diethyl ether in hexane (v:v). 9.3.2.4.8 Collect 200 ml Kuderna-Danish PCBs should be Concentrate to of the eluate in a flask. All of the in this fraction. an appropriate volume. 9.3.2.4.9 Analyze the sample as described in Section 10.0. 9.3.2.5 Gel permeation cleanup 9.3.2.5.1 Set up and calibrate the gel permeation chromatograph with an SX-3 column according to the Autoprep instruction manual. Use 15% methylene chloride in cyclohexane (v:v) as the mobile phase. 9.3.2.5.2 Inject 5.0 ml of the sample extract into the instrument. Collect the fraction containing the PCBs (see Autoprep operator's manual) in a Kuderna-Danish flask equipped with a 10-ml ampul. 9.3.2.5.3 Concentrate the PCB fraction to an appropriate volume. 9.3.2.5.4 Analyze the sample as described in Section 10.0. B-26 �9.3.2.6 Acetonitrile partition 9.3.2.6.1 Place the sample extract into a 125-ml separately funnel with enough hexane to bring the final volume to 15 ml. Extract the sample four times by shaking vigorously for 1 min with 30-ml portions of hexane-saturated acetonitrile. 9.3.2.6.2 Combine and transfer the acetonitrile phases to a 1-liter separatory funnel and add 650 ml of distilled water and 40 ml of saturated sodium chloride solution. Mix thoroughly for about 30 sec. Extract with two 100-ml portions of hexane by vigorously shaking about 15 sec. 9.3.2.6.3 Combine the hexane extracts in a 1-liter separatory funnel and wash with two 100-ml portions of distilled water. Discard the water layer and pour the hexane layer through an 8-10 cm anhydrous sodium sulfate column into a 500-ml Kuderna-Danish flask equipped with a 10-ml ampul. Rinse the separatory funnel and column with three 10-ml portions of hexane. 9.3.2.6.4 Concentrate the extracts to an appropriate volume. 9.3.2.6.5 Analyze as described in Section 10.0. 9.3.2.7 Florisil slurry cleanup 9.3.2.7.1 Place the sample extract into a 20-ml narrow-mouth screw-cap container. Add 0.25 g of Florisil (PR grade or equivalent). Seal with a Teflon-lined screw cap and shake for 1 min. 9.3.2.7.2 Allow the Florisil to settle; then decant the treated solution into a second container with rinsing. Concentrate the sample to an appropriate volume. Analyze as described in Section 10.0. B-27 �9.3.2.8 Base cleanup4 9.3.2.8.1 Quantitatively transfer the concentrated extract to a 125-ral extraction flask with the aid of several small portions of solvent. 9.3.2.8.2 Evaporate the extract just to dryness with a gentle stream of dry filtered nitrogen, and add 25 ml of 2.5% alcoholic KOH. 9.3.2.8.3 Add a boiling chip, put a water condenser in place, and allow the solution to reflux on a hot plate for 45 min. 9.8.2.8.4 After cooling, transfer the solution to a 250-ml separatory funnel with 25 ml of distilled water. 9.3.2.8.5 Rinse the extraction flask with 25 ml of hexane and add it to the separatory funnel. 9.3.2.8.6 Stopper the separatory funnel and shake vigorously for at least 1 min. Allow the layers to separate, and transfer the lower aqueous phase to a second separatory funnel. 9.3.2.8.7 Extract the saponification solution with a second 25-ml portion of hexane. After the layers have separated, add the first hexane extract to the second separatory funnel and transfer the aqueous alcohol layer to the original separatory funnel. 9.3.2.8.8 Repeat the extraction with a third 25-ml portion of hexane. Discard the saponification solution, and combine the hexane extracts. 9.3.2.8.9 Concentrate the hexane layer to an appropriate volume, and analyze as described in Section 10.0. B-28 �10.0 Gas Chromatographic/Electron Impact Mass Spectrometric Determination 10.1 Internal standard addition - An appropriate volume of the internal standard solution is pipetted into the sample. The final concentration of the internal standard must be in the working range of the calibration and well above the matrix background. The internal standard is thoroughly incorporated by mechanical agitation. Note: The volumetric measurement of the internal standard solution is critical to the overall method precision. The analyst must exercise caution that the volume is known to be ±1% or better. Where necessary, calibration of the pipet is recommended. 10.2 Tables 2, and 5 through 8 summarize the recommended operating conditions for analysis. Figure 1 presents an example of a chromatogram. 10.3 While the highest available chromatographic resolution is not a necessary objective of this protocol, good chromatographic performance is recommended. With the high resolution of CGC, the probability that the chromatographic peaks consist of single compounds is higher than with PGC. Thus, qualitative and quantitative data reduction should be more reliable. 10.4 After performance of the system has been certified for the day and all instrument conditions set according to Tables 2, and 5 through 8, inject an aliquot of the sample onto the GC column. If the response for any ion, including surrogates and internal standards, exceeds the working range of the system, dilute the sample and reanalyze. If the responses of surrogates, internal standards, or analytes are below the working range, recheck the system performance. If necessary, concentrate the sample and reanalyze . 10.5 Record all data on a digital storage device (magnetic disk, tape, etc.) for qualitative and quantitative data reduction as discussed below. 11.0 Qualitative Identification 11.1 Selected ion monitoring (SIM) or limited mass scan (LMS) data The identification of a compound as a given PCB homolog requires that two criteria be met: 11.1.1 (1) The peak must elute within the retention time window set for that homolog (Section 7.5); and (2) the ratio of two ions obtained by SIM (Table 11) or by LMS (Table 12) must match the natural ratio within ±20%. The analyst must search the higher mass windows, in particular M+70, to prevent misidentification of a PCB fragment ion cluster as the parent. B-29 �-a 4-1 x~* "nj C too 0 cn M QJ l-i QJ K C C/5 1101 100.0 0 TJ rH CO 1 rH 01 rH rH 1 rH rH K*~l rH r*. £*"! ^ C 0) O CO C C c !>•» QJ QJ OJ x; r^ C 0) C QJ XI P. XI P, XI -H rH P. •H Xl o XI O M >> C Ol rH rH xi . x;, pi p -H _fl -H _ /*-* •H -H O O X> XI /—^ O 0) O r-l V-l 4-1 rH CO 60 XI O O O rH H rC XI CJ O O O r-l 1-1 C C CO D 0 r-l 4-1 rH X o o cn S 2 — <r -<r 01 c oj p. H i rH ^r •H f>~> Xi r-iiG -> rH ^ rH > . Xi ro x; p. -H x: xi P* p. O •rt o o CO VJ S-i O rH 4-1 OJ (-I O 1 O rH ^O 4-1 CJ -H l-l H 1 ^D •* O> PL, | m <J P O rH X! O •H O | XI u o c o a x: CO - c CN CN co 117-1 OJ GI3 CN T T 1 I A V. ' 1 " I 1 rH ' £*-» C 0) XI o x ; p. ^-, XI C O rH >. >-l XI -H •H 0) 0 Xl XI 4-1 rC 0) CO rH O rH p>^ CO 0 - 0 rJ O o o O ZZ rH u i v£> v£> VD rH x: 1 -H XI 0 P 0 0 cfl )-i Ml 0 CO P, <-" C OJ 0) H XI 1 P. -H C P . 4-» XI 0 CO rH 4-1 m x; •• CO U CO X Ol SC 1 ^ r-1 cfl O CO D CO OJ Q QJ Q 0 a o ^ *> in v o. m Q) X: ^3•* ^r A pr] 1 ^O co •^ CO •s Ol •> ^ in »> --^ «> ^ ro m v£) *. n •- ^i" n ~^j" * r. CO »\ •CN r> Ol CO CO 01 *^ - l?.0f) oj ii™ A Ol i oi * Ol M78 l;ilc ^ Jl k ii -/20 , _ Off 027 ,'. r-l XI t-> O <T - O Ol <N 1 M 0 1 —1 XI O f-l Xi rH loViw P. m -H XI C QJ •H XI O )_! O 1 O rH 01 >^ 01 XI •-21 OJ *• XI - C rH C w O " C -* O M rH p, rH rJJp. , t 'l O I 112592. ^ O vo co vD ' ' Ki-.-t-j ' 12:111 ,!• >o-.e-:) J— ' v ~ •—~~ " _„ 1 2 J •.;.'.) Till,; Figure 1. Capillary gas chromatography/clectron impact ionization mass spectrometry (CGC/EIMS) chroniatogram or the calibration standard solution required for quantitation of PCBs by homolog. This chroniatogram includes PCBs representative of each homolog, three carbon-13 labeled surrogates, and the deuterated internal standard; The concentration of a J 1 components and the CGC/EIMS parameters are presented in Tables 3, 4, 5, and 7. �TABLE 11. CHARACTERISTIC SIM IONS FOR PCBs Ion (relative intensity) Secondary Tertiary Homolog Primary Ci2H9Cl 188 (100) 190 (33) - CiaHgCls 222 (100) 224 (66) 226 (11) C12H7Cl3 256 (100) 258 (99) 260 (33) Ci2H6Cl4 292 (100) 290 (76) 294 (49) Ci2H5Cl5 326 (100) 328 (66) 324 (61) C12H4Cl6 360 (100) 362 (82) 364 (36) CiaHsCl? 394 (100) 396 (98) 398 (54) CisH^Clg 430 (100) 432 (66) 428 (87) Ci2HCl9 464 (100) 466 (76) 462 (76) Ci2Clib 498 (100) 500 (87) 496 (68) Source: Rote, J. W., and W. J. Morris, "Use of Isotopic Abundance Ratios in Identification of Polychlorinated Biphenyls by Mass Spectrometry," J. Assoc. Offic. Anal. Chem.. 56(1), 188-199 (1973). B-31 �TABLE 12. LIMITED MASS SCANNING (LMS) RANGES FOR PCBs Compound Mass range (m/z) C.ACU 186-190 C12HgCl2 220-226 L 12nyC i-3 254-260 C ^2ngC J-3 288-294 C i2n5Cl5 322-328 Ci2H4Clg 356-364 C12H3C17 386-400 C12H2Clg 426-434 C12HC19 460-468 C12C110 494-504 C12D6C14 294-300 13 192-196 13 300-306 13 438-446 C612C6H9C1 C12H6C14 C12H2C18 13 506-516 C12C110 a Adapted from Tindall, G. W., and P. E. Wininger, "Gas Chromatography-Mass Spectrometry Method for Identifying and Determining Polychlorinated Biphenyls," J. Chromatogr., 196, 109-119 (1980). B-32 �11.1.2 If one or the other of these criteria is not met, interferences may have affected the results, and a reanalysis using full scan EIMS conditions is recommended. 11.2 Full scan data 11.2.1 The peak must elute within the retention time windows set for that homolog (as described in Section 7.5). 11.2.2 The unknown spectrum must match that of an authentic PCB. The intensity of the three largest ions in the molecular cluster (two largest for monochlorobiphenyls) must match the natural ratio within ±20%. Fragment clusters with proper intensity ratios must also be present. 11.2.3 Alternatively, a spectral search may be used to automatically reduce the data. The criteria for acceptable identification include a high index of similarity. For the Incos 2300, a fit of 750 or greater must be obtained. 11.3 Disputes in interpretation - Where there is reasonable doubt as to the identity of a peak as a PCB, the analyst must either identify the peak as a PCB or proceed to a confirmational analysis (see Section 13.0). 12.0 Quantitative Data Reduction 12.1 Once a chromatographic peak has been identified as a PCB, the compound is quantitated based either on the integrated abundance of the SIM data or EICP for the primary characteristic ion in Tables 11 and 12. If interferences are observed for the primary ion, use the secondary and then tertiary ion for quantitation. If interferences in the parent cluster prevent quantitation, an ion from a fragment cluster (e.g., M-70) may be used. Whichever ion is used, the RF must be determined using that ion. The same criteria should be applied to the surrogate compounds (Table 13). 12.2 Using the appropriate analyte-internal standard pair and response factor (RF ) as determined in Section 7.3, calculate the concentration of^each peak using Equation 12-1. A M. V Concentration (yg/g) = ^ • ~ • ^ • ^ Eq. 12-1 is p e i where A = area of the characteristic ion for the analyte PCB ^ peak A. = area of the characteristic ion for the internal standard peak RF = response factor of a given PCB congener B-33 �TABLE 13. CHARACTERISTIC IONS FOR 13 C-LABELED PCS SURROGATES Primary Ion (relative intensity) Secondary 13 194 (100) 196 (33) 13 304 (100) 306 ( 9 4) 302 (78) 13 442 (100) 444 (65) 440 (89) 13 510 (100) 512 (87) 514 (50) Specific compound C612C6H9C1 C12H6C14 C12H2C18 C12C110 B-34 Tertiary �M. = mass of internal standard injected (micrograms) IS M = mass of sample extracted (grams) V. = volume injected (microliters) V = volume of sample extract (microliters) 12.3 If a peak appears to contain non-PCB interferences, which cannot he circumvented by a secondary or tertiary ion, either: 12.3.1 12.3.2 Perform additional chemical cleanup (Section 9) and then reanalyze the sample; or 12.3.3 12.4 Reanalyze the sample on a different column which separates the PCB and interf erents ; Quantitate the entire peak as PCB. Calculate the recovery of the four 13C surrogates using the appropriate surrogate-internal standard pair and response factor (RF. ) as determined in Section 7.4 using Equation 12-2. A M. Recovery ( ) = ^ • - r • ^ • 100 % |Eq. 12-2 is s s where A S = area of the characteristic ion for the surrogate peak A. = area of the characteristic ion for the internal standard 18 peak RF = response factor for the surrogate compound with respect to the internal standard (Equation 7-2) M. = mass of internal standard injected (nanograms) 3.S MS - mass of surrogate, assuming 100% recovery (nanograms) 12.5 Correct the concentration of each peak using Equation 12-3. This is the final reportable concentration. Corrected concentration (pg/g) = 12.6 . 100 Eq. 12-3 Sum all of the peaks for each homolog, and then sum those to yield the total PCB concentration in the sample. Report all numbers in pg/g. The reporting form in Table 14 may be used. If an alternate reporting format (e.g., concentration per peak) is desired, a different report form may be used. The uncorrected concentrations, percent recovery, and corrected recovery are to be reported. 12.7 Round off all numbers reported to two significant figures. B-35 �TABLE 14. ANALYSIS REPORT INCIDENTAL PCBs IN COMMERCIAL PRODUCTS OR PRODUCT WASTES Sample No. Sample Matrix Sample Source Notebook No. or File Location Volume Extracted Extraction/Cleanup Int. Std. Procedure Mass Added (pg) (Circle one) 298 4-Cl(d6) Surrogates Mass Added (pg) (Circle one) 300 Ratio 194 196 100/33 4-C1 304 306 100/49 8-C1 442 444 100/65 10-C1 510 512 100/87 B-36 Intensity 100/49 1-C1 (continued) Ratio Intensity % Recovery �TABLE 14 (continued) Qualitative Analyte 1° 2° I l° T 1 2° Ratio Theoretical 1-C1 188 190 100/33 2-C1 222 224 100/66 3-C1 256 258 100/99 4-C1 292 290 100/76 5-C1 326 328 100/66 6-C1 360 362 100/82 7-C1 394 396 100/98 8-C1 430 432 100/66 9-C1 464 466 100/76 10-C1 498 500 Quantitative Uncorr. Corr. Ion Cone. Cone. OK? Used RF (|Jg/g) (Hg/g) 100/87 Total M8/8 Uncorr. Reported by: Internal Audit: Name Name EPA Audit: Name Signature/Date Signature/Date Signature/Date Organization Organization Organization B-37 M8/8 Corr. �13.0 Confirmation If there is reason to question the qualitative identification (Section 11.0), the analyst may choose to confirm that a peak is not a PCB. Any technique may be chosen provided that it is validated as having equivalent or superior selectivity and sensitivity to GC/EIMS. Some candidate techniques include alternate GC columns (with EIMS detection), GC/CIMS, GC/NCIMS, high resolution EIMS, and MS/MS techniques. Each laboratory must validate confirmation techniques to show equivalent or superior selectivity between PCBs and interferences and sensitivity (limit of quantitation, LOQ). If a peak is confirmed as being a non-PCB, it may be deleted from the calculation (Section 12). If a peak is confirmed as containing both PCB and non-PCB components, it must be quantitated according to Section 12.3. 14.0 Quality Control 14.1 Each laboratory that uses this method must operate a formal quality control (QC) program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and the analysis of spiked samples as a continuing check on performance. The laboratory must maintain performance records to define the quality of data that are generated. After a date specified by the Agency, ongoing performance checks should be compared with established performance criteria to determine if the results of analyses are within accuracy and precision limits expected of the method. 14.2 The analysts must certify that the precision and accuracy of the analytical results are acceptable by: 14.2.1 14.2.2 14.3 The absolute precision of surrogate recovery, measured as the RSD of the integrated EIMS area (A ) for a set s • of samples^ must be ±10%. The mean recovery (R ) of at least four replicates of a QC check sample to be supplied by the Agency must meet Agency-specified accuracy and precision criteria. This forms the initial data base for establishing control limits (see Section 14.3 below). Control limits - The laboratory must establish control limits using the following equations: Upper control limit (UCL) = RC + 3 RSDc Upper warning limit (UWL) = R + 2 RSD Lower warning limit (LWL) = R - 2 RSD Lower control limit (LCL) = R - 3 RSD B-38 �These may be plotted on control charts. If an analysis of a check sample falls outside the warning limits, the analyst should be alerted that potential problems may need correction. If the results for a check sample fall outside the control limits, the laboratory must take corrective action and recertify the performance (Section 14.2) before proceeding with analyses. The warning and control limits should be continuously updated as more check sample replicates are added to the data base. 14.4 Before processing any samples, the analyst should demonstrate through the analysis of a reagent blank that all glassware and reagent interferences are under control. Each time a set of samples is analyzed or there is a change in reagents, a laboratory reagent blank should be processed as a safeguard against contamination. 14.5 Procedural QC - The various steps of the analytical procedure should have quality control measures. These include but are not limited to: 14.5.1 GC performance - See Section 7.1 for performance criteria. 14.5.2 MS performance - See Section 7.2 for performance criteria. 14.5.3 Qualitative identification - At least 10% of the PCB identifications, as well as any questionable results, should be confirmed by a second mass spectrometrist. 14.5.4 Quantitation - At least 10% of all manual calculations, including peak area calculations, must be checked. After changes in computer quantitation routines, the results should be manually checked. 14.6 A minimum of 10% of all samples, one sample per month or one sample per matrix type, whichever is greater, selected at random, must be run in triplicate to monitor the precision of the analysis. An RSD of ±30% or less must be achieved. If the precision is greater than ±30%, the analyst must be recertified (see Section 14.2). 14.7 A minimum of 10% of all samples, one sample per month or one sample per matrix type, whichever is greater, selected at random, must be analyzed by the standard addition technique. Two aliquots of the sample are analyzed, one "as is" and one spiked (surrogate spiking and equilibration techniques are described in Section 9.2) with a sufficient amount of Solution CSxxx to yield approximately 100 |Jg/g of each compound. The samples are analyzed together and the quantitative results calculated. The recovery of the spiked compounds (calculated by difference) must be 80-120%. If the sample is known to contain specific PCB isomers, these isomers may be substituted for solution CSxxx. If the concentrations of PCBs are known to be high or low, the amount added should be adjusted so that the spiking level is 1.5 to 4 times the measured PCB level in the unspiked sample. B-39 �14.8 Interlaboratory comparison - Interlaboratory comparison studies are planned. Participation requirements, level of performance, and the identity of the coordinating laboratory will be presented in later revisions. 14.9 It is recommended that the participating laboratory adopt additional QC practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates or triplicates may be analyzed to monitor the precision of the sampling technique. Whenever possible, the laboratory should perform analysis of standard reference materials and participate in relevant performance evaluation studies. 15.0 Quality Assurance Each participating laboratory must develop a quality assurance plan according to EPA guidelines.5 The quality assurance plan must be submitted to the Agency for approval. 16.0 Method Performance The method performance is being evaluated. Limits of quantitation; average intralaboratory recoveries, precision, and accuracy; and interlaboratory recoveries, precision, and accuracy will be presented. 17.0 Documentation and Records Each laboratory is responsible for maintaining full records of the analysis. Laboratory notebooks should be used for handwritten records. GC/MS data must be archived on magnetic tape, disk, or a similar device. Hard copy printouts may be kept in addition if desired. QC records should be maintained separately from sample analysis records. The documentation must describe completely how the analysis was performed. Any variances from the protocol must be noted and fully described. Where the protocol lists options (e.g., sample cleanup), the option used and specifics (solvent volumes, digestion times, etc.) must be stated. B-40 �REFERENCES 1. "Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual," Methods for Chemical Analysis of Water and Wastes, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio, March 1979, EPA 600-4/79-020. 2. Erickson, M. D., and J. S. Stanley, "Methods of Analysis for Incidentally Generated PCBs—Literature Review and Preliminary Recommendations," Interim Report No. 1, EPA Contract No. 68-01-5915, Task 51, 1982. 3. Bellar, T. A., and J. J. Lichtenberg, "The Determination of Polychlorinated Biphenyls in Transformer Fluid and Waste Oils," Prepared for U.S. Environmental Protection Agency, (1981) EPA-600/4-81-045. 4. American Society for Testing and Materials, "Standard Method for Analysis of Environmental Materials for Polychlorinated Biphenyls," pp. 877-885 in Annual Book of ASTM Standards, Part 40, Philadelphia, Pennsylvania (1980). ANSI/ASTM D 3304 - 77. 5. "Quality Assurance Program Plan for the Office of Toxic Substances," Office of Pesticides and Toxic Substances, U.S. Environmental Protection Agency, Washington, D.C., October 1980. B-41 �APPENDIX C ANALYTICAL METHOD: THE ANALYSIS OF BY-PRODUCTS CHLORINATED BIPHENYLS IN AIR C-l �THE ANALYSIS OF BY-PRODUCT CHLORINATED BIPHENYLS IN AIR 1.0 Scope and Application 1.1 This is a gas chromatographic/electron impact mass spectrometric (GC/EIMS) method applicable to the determination of chlorinated biphenyls (PCBs) in air emitted from commercial production through stacks, as fugitive emissions, or static (room, other containers, or outside) air. The PCBs present may originate either as synthetic by-products or as contaminants derived from commercial PCB products (e.g., Aroclors). The PCBs may be present as single isomers or complex mixtures and may include all 209 congeners from monochlorobiphenyl through decachlorobiphenyl listed in Table 1. 1.2 The detection and quantitation limits are dependent upon the volume of sample collected, the complexity of the sample matrix and the ability of the analyst to remove interferents and properly maintain the analytical system. The method accuracy and precision will be determined in future studies. 1.3 This method is restricted to use by or under the supervision of analysts experienced in the use of gas chromatography/mass spectrometry (GC/MS) and in the interpretation of gas chromatograms and mass spectra. Prior to sample analysis, each analyst must demonstrate the ability to generate acceptable results with this method by following the procedures described in Section 14.2. 1.4 The validity of the results depends on equivalent recovery of the analyte and 13C PCBs. If the *3C PCBs are not thoroughly incorporated in the matrix, the method is not applicable. 1.5 During the development and testing of this method, certain analytical parameters and equipment designs were found to affect the validity of the analytical results. Proper use of the method requires that such parameters or designs must be used as specified. These items are identified in the text by the word "must." Anyone wishing to deviate from the method in areas so identified must demonstrate that the deviation does not affect the validity of the data. Alternative test procedure approval must be obtained from the Agency. An experienced analyst may make modifications to parameters or equipment identified by the term "recommended." Each time such modifications are made to the method, the analyst must repeat the procedure in Section 14.2. In this case, formal approval is not required, but the documented data from Sectin 14.2 must be on file as part of the overall quality assurance program. C-2 �No. scnjcturt NO* NMoenlorooloAfWlf 1 2 1eh1oreb1pntnyli 4 5 6 7 8 9 10 11 12 13 14 15 .2' Is,'5 ,6 .3' ,4 3.4' 3.5 4,4' THc)i1erab1plnny1> 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 2,2' .3 2,2',4 2,2', 5 2.2'. 6 2,3,3' 2,3.4 2.3.4' 2.3,5 2,3,6 2. 3', 4 2,3', 5 2, 3', 6 2,4,4' 2.4.5 2.4,6 2.*' .5 2.4', 6 2'. 3,4 2'. 3.5 3.3'. 4 3,3'.5 3.4,4' 3.4.5 3.4', 5 SI 57 SI 59 10 61 62 13 M IS M 67 68 69 70 71 72 73 74 75 71 77 78 79 80 81 2,3' 2.3* 2.3' 2.3' 2,3' 2.3' 2.3' 2.3' 4,4' 4,5 4.5' 4.6 4', 5 4', 6 1 5.S 5',6 2.4.4-.S 2.4.4'.$ 2'. 3 4.5 3,3' 3,3* 3.3' 3.3' 82 83 84 as 2.3,3'. 4,4' 2,3,3', 4,5 2,3,3'. 4'. 5 2.3.3'. 4. 5' 2.3,3'. 4, 6 2.3,3', 4' .6 2.3.3' .5.5' 2.3.3'. 5.6 2.3.3'. 5'. 6 2.3,4, 4'. 5 2.3,4,4'. 6 2.3.4.5.6 2.3.4', 5,6 2.31. 4, 4' .5 2.3'. 4,4'. 6 2,3' ,4,5, 5' 2.3' ,4.5', 6 2'.3,3'.4,5 2 1 .3.4.4' ,5 2'. 3. 4.5. 5' 2'.3,4. 5.6' 3.3',4,4',5 3.3'. 4, 5,5' Htuehloreblphtnyla 4,4' 4,5 4.5' 5.5' 3.4.4' .5 2.2'. 3, 3'. 4 2.2'.3.3',5 2.2'. 3.3'. 6 2.2', 3,4,4' 2.2',3.4,5 2. 2' ,3.4.5' 2,2',3,4.6 2,2'. 3.4,6' 2,2',3,4',5 2,2'. 3, 4'. 6 2.2' ,3.5,5' 2,2'. 3, 5.6 2,2'. 3,5.6' 2.2'. 3. 5'. 8 2.2',3.6.6' 2.2'. 3'. 4. 5 2.2'.3'.4.8 2.2 1 .4.4'.S 2.2',4,4',6 2.2', 4,5.5' 2.2' .4.5.6' 2,2'. 4,5', 6 2.2'.4,«,6' NO. P«nt«cn lorottlphlnyll 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 2.2'.S.S' 2,2'. 5. 6' 2.2'.6.6' 2,3.3'. 4 2.3,3'. 4' 2,3,3', 5 2.3.3'. 5' 2.3,3'. 6 2.3.4.4' 2.3.4.5 2,3.1.6 2.3. 4' .5 2.3.4'. 6 2.3,5,6 Ptntlctll orettl phtny 1 1 88 87 88 39 90 91 92 93 94 95 Tttnrt 1 orob 1 phtfiy 1 » 98 2.2;,3 ' 97 98 99 2i2'l3 100 2,2'. 3 ' 101 2,2'. 3 102 103 2 < 2 ''4 ' 104 2> '.4 NUMBERING OF PCB CONGENERS3 MO. Structurt Tttnen 1 oreH etmiy 1 1 52 S3 54 B 2 3 TABLE 1. structure 128 129 130 137 132 133 134 135 131 137 138 139 140 141 142 143 144 14$ 141 147 148 149 150 151 152 153 154 155 151 157 1S8 159 160 2,2'.3.3'.4.4' 2.2'.3,3' .4.5 2.2',3.3',4.5' 2.2'.3.3'.4,« 2,2' .3.3' ,4.1' 2.2'.3,3'.5,5' 2,2'. 3,3'. 5,6 2.2* .3.3' ,5,1' 2,2' ,3,3'. 6,6' 2.2', 3,4, 4' .5 2,2'. 3, 4. 4 ' . £' 2,2' .3,4, 4 ' . 6 2.21, 3, 4, 4' .6' 2.2' .3, 4, 5, 5' 2,2'. 3.4. 5.6 2. 2' ,3, 4,5.6' 2,2'.3.4.5',6 2,2'.3.4, 6. 6' 2,2'. 3.4'. 5.5' 2.2*. 3,4- ,5,6 2,2' .3.4'. 5, 6' 2.2',3,4' .5', 6 2.2'. 3.4'. 6.6' 2,2',3.5,5',6 2.2', 3.5.6. 6' 2,2' ,4, 4 - , 5,5' 2,2', 4,4', 5.6' 2,2'. 4,4', 6.6' 2.3.3', 4.4- .5 2.3,3' .4, 4 ' . 5' 2.3,3', 4.4', 5 2.3,3' .4.5. 5' 2.3.3', 4.5,6 Il l 112 163 114 115 166 167 161 169 2.3,3' .4. 5'. 6 2.3. 3'. 4 ' . 5. S' 2,3.3' .4'. 5. 6 2,3. 3' .4'. 5'. 6 2.3.3'.5,5',6 2,3' .4,4'. 5,5' 2. 3'. 4. 4' ,5' .6 3.3',4.4'.5.5' Htptiehl orebf phtny 1 1 170 171 172 173 174 175 178 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 2,2'. 3. 3'. 4. 4 ' , 5 2.2' .3.3' ,4, 4 ' , 6 2, 2', 3. 3'. 4, 5. 5' 2, 2'. 3, 3'. 4, 5, 6 2, 2', 3, 3 ' . 4, 5, 6' 2,2'.3.3'.4,5',6 2,2', 3, 3 ' . 4' ,5. 6 2, 2', 3. 3', 5. 5 ' , 6 2. 2' .3, 3' ,5, 6, 6' 2,2',3,4,4',5,6 2, 2', 3, 4, 4 ' ,5,1' 2. 2' .3. 4, 4 ' . 5 ' . 5 2, 2', 3, 4, 4' ,6,6' 2,2', 3. 4,5, 5 ' . 6 2, 2', 3,4, 5, 6, 6' 2,2'.3,4',5,i l .S 2. 3, 3'. 4, 4 ' . 5,5' 2. 3, 3', 4. 4 ' . 5. 6 2.3, 3' .4. 4 ' , S ' , 5 2.3. 3'. 4,5. 5 ' . 1 2,3,3' .4'. 5,5'. 6 OetlcBlorottiphtnyli 194 195 191 197 198 199 200 201 202 203 204 205 2,2' ,3, 3' ,4.4', 5, 5' 2. 2 ' , 3. 3'. 4, 4 ' , 5, 6 2,2', 3. 3 ' , 4, 4 ' , S, 6' 2. 2', 3, 3', 4. 4 ' , 6, 6' 2. 2', 3. 3', 4, 5, 6, 6' 2,2'. 3,3' ,4. 5' .6, 6' 2.2'. 3. 3'. 4. 5, 5'. 6' 2.2' .3.3' ,5. 5 ' . 6 . 6 2.2'.3,4, 4'. 5, 5'. 6 2. 2' ,3.4. 4' .5, 6, 6' 2.3.3'. 4,4'. 5,5'. 6 Monichlorob<Pntnyli 206 207 208 2.2' .3, 3'. 4.4', 5.5', 6 2.2' .3,3* .4, 4' .5,6,1' 2.2'. 3, 3', 4, 5, 5'. 6, 6' OteieBlorottfohtnyl ' 209 •Adopt** fro* Stmcturt Htuchloroblphtnyls tollscMUr, X. ind Zcll, M., FrtMirius Z. Anal.CUM., 302. 20-31 (I960). C-3 2,2',3,3'4.4'.5,5'.6,5' �2.0 Summary 2.1 The air must be sampled such that the specimen collected for analysis is representative of the whole. Statistically designed selection of the sampling position (stack, flue, port, etc.) or time should be employed. Gaseous and particulate PCBs are withdrawn isokinetically from stacks, room air exhausts, process point exhausts, and other flowing gaseous streams using a sampling train.1 The PCBs are collected in the Florisil adsorbent tube and in the impingers in front of the adsorbent. PCBs are sampled from ambient air and other static gaseous sources onto a Florisil adsorbent tube. The sample must be preserved to prevent PCB loss prior to analysis. Storage at 4°C is recommended. 2.2 The Florisil adsorbent is extracted with hexane in a Soxhlet extractor, the aqueous condensate is extracted with hexane and the acetone/hexane impinger rinse is back-extracted with water. All three organic extracts are then combined. Optional cleanup techniques may include sulfuric acid cleanup and Florisil adsorption chromatography. The sample is concentrated to a final known volume for instrumental determination. 2.3 The PCB content of the sample extract is determined by capillary (preferred) or packed column gas chromatography/electron impact mass spectroraetry (CGC/EIMS or PGC/EIMS) operated in the selected ion monitoring (SIM), full scan, or limited mass scan (LMS) mode. 2.4 PCBs are identified by comparison of their retention time and mass spectral intensity ratios to those in calibration standards. 2.5 PCBs are quantitated against the response factors for a mixture of 11 PCB congeners using the internal standard technique. 2.6 The PCBs identified by the SIM technique may be confirmed by full scan CGC/EIMS, retention on alternate GC columns, other mass spectrometric techniques, infrared spectrometry, or other techniques, provided that the sensitivity and selectivity of the technique are demonstrated to be comparable or superior to GC/EIMS. 2.7 The analysis time is dependent on the extent of workup employed. The time required for instrumental analysis of a single sample excluding data reduction and reporting, is about 30 to 45 min. 2.8 Appropriate quality control (QC) procedures are included to assess the performance of the analyst and estimate the quality of the results. These QC procedures include the demonstration of laboratory capability: periodic analyst certification, the use of control charts, and the analysis of blanks, replicates, and standard addition samples. A quality assurance (QA) plan must be developed for each laboratory. C-4 �2.9 While several options are available throughout this method, the recommended procedure for stack gases to be followed is: 2.9.1 2.9.2 The sample is preserved at 4°C to prevent any loss of PCBs or changes in matrix which may adversely affect recovery. 2.9.3 The three sample fractions are extracted and combined. 2.9.4 The extract is cleaned up and concentrated to an appropriate volume. Internal standards are added. 2.9.5 An aliquot of the extract is analyzed by CGC/EIMS operated in the SIM mode. On-column injections onto a 15-m DB-5 capillary column, programmed (for toluene solutions) from 110° to 325°C at 10°/min after a 2 min hold is used. Helium at 45-cm/sec linear velocity is used as the carrier gas. 2.9.6 PCBs are identified by retention time and mass spectral intensities. 2.9.7 PCBs are quantitated against the response factors for a mixture of 11 PCB congeners. 2.9.8 3.0 The sample is collected using a modified Method 5 train1 according to a scheme which permits extrapolation of the sample data to the source being assessed. The total PCBs are obtained by summing the amounts for each homolog found, and the concentration is reported as micrograms per cubic meter. Interferences 3.1 Method interferences may be caused by contaminants, in sample collection media, solvents, reagents, glassware, and other sample processing hardware, leading to discrete artifacts and/or elevated baselines in the total ion current profiles. All of these materials must be routinely demonstrated to be free from interferences by the analysis of laboratory reagent blanks as described in Section 14.4. 3.1.1 Glassware must be scrupulously cleaned. All glassware is cleaned as soon as possible after use by rinsing with the last solvent used. This should be followed by detergent washing with hot water and rinses with tap water and reagent water. The glassware should then be drained dry and heated in a muffle furnace at 400°C for 15 to 30 min. Some thermally stable materials, such as PCBs, may not be eliminated by this treatment. Solvent rinses with acetone and pesticide quality hexane may be substituted C-5 �for the muffle furnace heating. Volumetric ware should not be heated in a muffle furnace. After it is dry and cool, glassware should be sealed and stored in a clean environment to prevent any accumulation of dust or other contaminants. It is stored inverted or capped with aluminum foil. 3.1.2 3.2 4.0 The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required. All solvent lots must be checked for purity prior to use. Matrix interferences may be caused by contaminants that are coextracted from the sorbent material or impingers. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the sources of samples. Safety 4.1 The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemical specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. 4.2 Polychlorinated biphenyls have been tentatively classified as known or suspected human or mammalian carcinogens. Primary standards of these toxic compounds should be prepared in a hood. Personnel must wear protective equipment, including gloves and safety glasses. Congeners highly substituted at the meta and para positions and unsubstituted at the ortho positions are reported to be the most toxic. Extrme caution should be taken when handling these compounds neat or in concentrated solution. The class includes 3,3',4'4'-tetrachlorobiphenyl (both natural abundance and isotopically labeled). 4.3 5.0 Waste disposal must be in accordance with RCRA and applicable state rules. Apparatus and Materials All specifications are suggestions only. are included for illustration only. C-6 Catalog numbers and suppliers �5.1 Stack sampling train1 - See Figure 1; a series of four impingers with a solid adsorbent trap between the third and fourth impingers. The train may be constructed by adaptation from a Method 5 train.2 Descriptions of the train components are contained in the following subsections. 5.1.1 Probe nozzle - Stainless steel (316) with sharp, tapered leading edge. The angle of taper shall be £ 30° and the taper shall be on the outside to preserve a constant internal diameter. The probe nozzle shall be of the buttonhook or elbow design, unless otherwise specified by the Agency. The wall thickness of the nozzle shall be less than or equal to that of 20 gauge tubing, i.e., 0.165 cm (0.065 in.) and the distance from the tip of the nozzle to the first bend or point of disturbance shall be at least two times the outside nozzle tubing. Other configurations and construction material may be used with approval from the Agency. 5.1.2 Probe liner - Borosilicate or quartz glass equipped with a connecting fitting that is capable of forming a leakfree, vacuum tight connection without sealing greases; such as Kontes Glass Company "0" ring spherical ground ball joints (model K-671300) or University Research Glassware SVL teflon screw fittings. A stainless steel (316) or water-cooled probe may be used for sampling high temperature gases with approval from the Agency. A probe heating system may be used to prevent moisture condensation in the probe. 5.1.3 Pitot tube - Type S, or equivalent, attached to probe to allow constant monitoring of the stack gas velocity. The face openings of the pitot tube and the probe nozzle shall be adjacent and parallel to each other but not necessarily on the same plane, during sampling. The free space between the nozzle and pitot tube shall be at least 1.9 cm (0.75 in.). The free space shall be set based on a 1.3 cm (0.5 in.) ID nozzle, which is the largest size nozzle used. The pitot tube must also meet the criteria specified in Method 22 and be calibrated according to the procedure in the calibration section of that method. 5.1.4 Differential pressure gauge - Inclined manometer capable of measuring velocity head to within 10% of the minimum measured value. Below a differential pressure of 1.3 mm (0.05 in.) water gauge, micromanometers with sensitivities of 0.013 mm (0.0005 in.) should be used. However, micromanometers are not easily adaptable to field conditions and are not easy to use with pulsating flow. Thus, other methods or devices acceptable to the Agency may be used when conditions warrant. C-7 �Thermometer Florisil Tube Probe (r^. Reverse-Type' Pitot Tube Manometer Tight /—TN Pump Control Box Figure 1. PCB sampling train for stack gases. C-8 Check Valve �5.1.5 Impingers - Four impingers with connecting fittings able to form leak-free, vacuum tight seals without sealant greases when connected together as shown in Figure 1. The first and second impingers are of the GreenburgSmith design. The final two impingers are of the Greenburg-Smith design modified by replacing the tip with a 1.3 cm (1/2 in.) ID glass tube extending to 1.3 cm (1/2 in.) from the bottom of the flask. One or two additional modified Greenburg-Smith impingers may be added to the train between the third impinger and the Florisil tube to accommodate additional water collection when sampling high moisture gases. Throughout the preparation, operation, and sample recovery from the train, these additional impingers should be treated exactly like the third impinger. 5.1.6 5.1.7 Metering system - Vacuum gauge, leak-free pump, thermometers capable of measuring temperature to within ±3°C (y 5°F), dry gas meter with 2% accuracy at the required sampling rate, and related equipment, or equivalent, as required to maintain an isokinetic sampling rate and to determine sample volume. When the metering system is used in conjunction with a pitot tube, the system shall enable checks of isokinetic rates. 5.1.8 5.2 Solid adsorbent tube - Glass with connecting fittings able to form leak-free, vacuum tight seals without sealant greases (Figure 2). Exclusive of connectors, the tube has a 2.2 cm inner diameter, is at least 10 cm long, and has four deep indentations on the inlet end to aid in retaining the adsorbent. Ground glass caps (or equivalent) must be provided to seal the adsorbent-filled tube both prior to and following sampling. Barometer - Mercury, aneroid, or other barometers capable of measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg). In many cases, the barometric reading may be obtained from a nearby weather bureau station, in which case the station value shall be requested and an adjustment for elevation differences shall be applied at a rate of -2.5 mm Hg (0.1 in. Hg) per 30 mm (100 ft) elevation increase. Static air sampling train1 - The sampling train, see Figure 3, consists of a glass-lined probe, an adsorbent tube containing Florisil, and the appropriate valving and flow meter controls for isokinetic sampling as described in Section 5.1. The sampling apparatus in Figure 3 is the same as that in Figure 1 and Section 5.1, except that the Smith-Greenburg impingers and heated probe are not used. If condensation of significant quantities of moisture prior to the solid adsorbent is expected, Section 5.1 of the C-9 �} 28/12 10cm j28/12 Figure 2. Florisil adsorbent tube. C-10 �Probe (to sample from duct) •* Glass- lined Probe Florisil Glass Wool Check Valve Vacuum Line ! Manometer - Integrated | Flow Meter I Figure 3. Air Tight Pump PCB sampling train for static air. C-ll �method should be used. Since probes and adsorbent tubes are not cleaned up in the field, a sufficient number must be provided for sampling and allowance for breakage. 5.3 Sample recovery 5.3.1 5.3.2 Teflon FEP® wash bottle - Two, 500 ml, Nalgene No. 0023A59 or equivalent. 5.3.3 Sample storage containers - Glass bottles, 1 liter, with TFE®-lined screw caps. 5.3.4 Balance - Triple beam, Ohaus Model 7505 or equivalent. 5.3.5 Aluminum foil - Heavy duty. 5.3.6 5.4 Ground glass caps - To cap off adsorbent tube and the other sample exposed portions of the train. Metal can - To recover used silica gel. Analysis 5.4.1 Glass Soxhlet extractors - 40 mm ID complete with 45/50 S condenser, 24/40 S 250 ml round-bottom flask, heating mantle for 250 ml flask, and power transformer. 5.4.2 Teflon FEP wash bottle - Two, 500 ml, Nalgene No. 0023A59 or equivalent. 5.4.3 Separatery funnel - 1,000 ml with TFE® stopcock. 5.4.4 Kuderna-Danish concentrators - 500 ml. 5.4.5 Steam bath. 5.4.6 Separatory funnel - 50 ml with TFE® stopcock. 5.4.7 Volumetric flask - 25.0 ml, glass. 5.4.8 Volumetric flask - 5.0 ml, glass. 5.4.9 Culture tubes - 13 x 100 mm, glass with TFE®-lined screw caps. 5.4.10 Pipette - 5.0 ml glass. 5.4.11 Teflon®-glass syringe - 1 ml, Hamilton 1001 TLL or equivalent with Teflon® needle. 5.4.12 Syringe - 10 (Jl, Hamilton 701N or equivalent. C-12 �5.4.13 Disposable glass pipettes with bulbs - To aid transfer of the extracts. 5.4.14 Gas chromatography/mass spectrometer system. 5.4.14.1 Gas chromatograph - An analytical system complete with a temperature programmable gas chromatograph and all required accessories including syringes, analytical columns, and gases. The injection port must be designed for oncolumn injection when using capillary columns or packed columns. Other capillary injection techniques (split, splitless, "Grob," etc.) may be used provided the performance specifications stated in Section 7.1 are met. 5.4.14.2 Capillary GC column - A 12-20 m long x 0.25 mm ID fused silica column with a 0.25 pm thick DB-5 bonded silicone liquid phase (J&W Scientific) is recommended. Alternate liquid phases may include OV-101, SP-2100, Apiezon L, Dexsil 300, or other liquid phases which meet the performance specifications stated in Section 7.1. 5.4.14.3 Packed GC column - A 180 cm x 0.2 cm ID glass column packed with 3% SP-2250 on 100/120 mesh Supelcoport or equivalent is recommended. Other liquid phases which meet the performance specifications stated in Section 7.1 may be substituted. 5.4.14.4 Mass spectrometer - Must be capable of scanning from 150 to 550 daltons every 1.5 sec or less, collecting at least five spectra per chromatographic peak, utilizing a 70-eV (nominal) electron energy in the electron impact ionizaton mode and producing a mass spectrum which meets all the criteria in Table 2 when 50 ng of decafluorotriphenyl phosphine [DFTPP, bis(perfluorophenyDphenyl phosphine] is injected through the GC inlet. Any GC-to-MS interface that gives acceptable calibration points at 10 ng per injection for each PCB isomer in the calibration standard and achieves all acceptable performance criteria (Section 10) may be used. Direct coupling of the fused silica column to the MS is recommended. Alternatively, GC to MS interfaces constructed of all glass or glasslined materials are recommended. Glass can be deactivated by silanizing with dichlorodimethylsilane. C-13 �TABLE 2. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA Mass Ion abundance criteria 197 198 199 Less than 1% of mass 198 100% relative abundance 5-9% of mass 198 275 10-30% of mass 198 365 Greater than 1% of mass 198 441 442 443 Present, but less than mass 443 Greater than 40% of mass 198 17-23% of mass 442 C-14 �5.4.14.5 A computer system that allows the continuous acquisition and storage on machine-readable media of all mass spectra obtained throughout the duration of the chromatographic program must be interfaced to the mass spectrometer. The data system must have the capability of integrating the abundances of the selected ions between specified limits and relating integrated abundances to concentrations using the calibration procedures described in this method. The computer must have software that allows searching any GC/MS data file for ions of a specific mass and plotting such ion abundances versus time or scan number to yield an extracted ion current profile (EICP). Software must also be available that allows integrating the abundance in any EICP between specified time or scan number limits. 6.0 Reagents 6.1 Sampling 6.1.1 6.1.2 Glass wool - Cleaned by thorough rinsing with hexane, dried in a 110°C oven, and stored in a hexane-washed glass jar with TFE®-lined screw cap. 6.1.3 Water - Deionized, then glass-distilled, and stored in hexane-rinsed glass containers with TFES-lined screw caps. 6.1.4 Silica gel - Indicating type, 6-16 mesh. If previously used, dry at 175°C for 2 hr. New silica gel may be used as received. 6.1.5 6.2 Florisil - Floridin Company, 30/60 mesh, Grade A. The Florisil is cleaned by 8 hr Soxhlet extraction with hexane and then by drying for 8 hr in an oven at 110°C and is activated by heating to 650°C for 2 hr (not to exceed 3 hr) in a muffle furnace. After allowing to cool to near 110°C transfer the clean, active Florisil to a clean, hexane-washed glass jar and seal with a TFE®-lined lid. The Florisil should be stored at 110°C until taken to the field for use. Florisil that has been stored more than 1 month must be reactivated before use. Crushed ice. Solvents - All solvents must be pesticide residue analysis grade. New lots should be checked for purity by concentrating an aliquot by at least as much as is used in the procedure. C-15 �6.3 Calibration standard congeners - Standards of the PCB congeners listed in Table 3 are available from Ultra Scientific, Hope, Rhode Island; or Analabs, North Haven, Connecticut. 6.4 Calibration standard stock solutions - Primary dilutions of each of the individual PCBs listed in Table 3 are prepared by weighing approximately 1-10 mg of material within 1% precision. The PCB is then dissolved and diluted to 1.0 ml with hexane. The concentration is calculated in mg/ml. The primary dilutions are stored at 4°C in screw-cap vials with Teflon cap liners. The meniscus is marked on the vial wall to monitor solvent evaporation. Primary dilutions are stable indefinitely if the seals are maintained. The validity of primary and secondary dilutions must be monitored on a quarterly basis by analyzing four quality control check samples (see Section 14.2). 6.5 Working calibration standards - Working calibration standards are prepared that are similar in PCB composition and concentration to the samples by mixing and diluting the individual standard stock solutions. Example calibration solutions are shown in Table 3. The mixture is diluted to volume with pesticide residue analysis quality hexane. The concentration is calculated in ng/ml as the individual PCBs. Dilutions are stored at 4°C in narrow-mouth, screw-cap vials with Teflon cap liners. The meniscus is marked on the vial wall to monitor solvent evaporation. These secondary dilutions can be stored indefinitely if the seals are maintained. These solutions are designated "CSxxx," where the xxx is used to encode the nominal concentration in ng/ml. 6.6 Alternatively, certified stock solutions similar to those listed in Table 3 may be available from a supplier, in lieu of the procedures described in Section 6.4. 6.7 DFTPP standard - A 50 ng/(Jl solution of DFTPP is prepared in acetone or another appropriate solvent. 6.8 Internal standard stock solution - The four 13C-labeled PCBs listed in Table 4 may be available from a supplier as a certified solution. This solution may be used as received or diluted further. 6.9 Solution stability - The calibration standard, surrogate and DFTPP solutions should be checked frequently for stability. These solutions should be replaced after 6 months, or sooner if comparison with quality control check samples indicates compound degradation or concentration change. 6.10 Quality control check samples will be supplied by the Agency. C-16 �TABLE 3. CONCENTRATIONS OF CONGENERS IN PCB CALIBRATION STANDARDS (ng/ml)a Homo log Congener no. CS1000 CS100 CS050 CS010 1 1 1,040 104 52 10 1 3 1,000 100 50 10 2 7 1,040 104 52 10 3 30 1,040 104 52 10 4 50 1,520 152 76 15 5 97 1,740 174 87 17 6 143 1,920 192 96 19 7 183 2,600 260 130 26 8 202 4,640 464 232 46 9 207 5,060 506 253 51 10 209 4,240 424 212 42 4 210 (IS) 255 255 255 255 1 211 (RS) 104 104 104 104 4 212 (RS) 257 257 257 257 8 213 (RS) 407 407 407 407 10 214 (RS) 502 502 502 502 a Concentrations given as examples only. C-17 �TABLE 4. COMPOSITION OF INTERNAL STANDARD SPIKING SOLUTION (SS100) CONTAINING 13C-LABELED PCBs3 Congener no. Compound Concentration (pg/ml) 211 (l',2l,3',4',5',6'-13C6)4-chlorobiphenyl 104 212 (13C12)3,3',4,4'-tetrachlorobiphenyl 257 213 (13C12)2,2',3,3',5,5',6,6'-octachlorobiphenyl 395 214 (13C12)decachlorobiphenyl 502 a Concentrations given as examples only. C-16 �7.0 Calibration Maintain a laboratory log of all calibrations. 7.1 Sampling train 7.1.1 Probe nozzle - Using a micrometer, the inside diameter of the nozzle is measured to the nearest 0.025 mm (0.001 in.). Three separate measurements are made using different diameters each time and obtain the average of the measurements. The difference between the high and low numbers must not exceed 0.1 mm (0.004 in.). When nozzles become nicked, dented, or corroded, they must be reshaped, sharpened, and recalibrated before use. Each nozzle must be permanently and uniquely identified. 7.1.2 Pitot tube - The pitot tube must be calibrated according to the procedure outlined in Method 2.2 7.1.3 Dry gas meter and orifice meter - Both meters must be calibrated according to the procedure outlined in APTD0581.3 When diaphragm pumps with bypass valves are used, proper metering system design is checked by calibrating the dry gas meter at an additional flow rate of 0.0057 m3/min (0.2 cfm) with the bypass valve fully opened and then with it fully closed. If there is more than ±2% difference in flow rates when compared to the fully closed position of the bypass valve, the system is not designed properly and must be corrected. 7.1.4 Probe heater calibration - The probe heating system must be calibrated according to the procedure contained in APTD-0581.3 7.1.5 Temperature gauges - Dial and liquid filled bulb thermometers are calibrated against mercury-in-glass thermometers, Thermocouples should be calibrated in constant temperature baths. 7.2 The gas chromatograph must meet the minimum operating parameters shown in Tables 5 and 6, daily. If all of the criteria are not met, the analyst must adjust conditions and repeat the test until all criteria are met. 7.3 The mass spectrometer must meet the minimum operating parameters shown in Tables 2, 7, and 8, daily. If all criteria are not met, the analyst must retune the spectrometer and repeat the test until all conditions are met. C-19 �TABLE 5. OPERATING PARAMETERS FOR CAPILLARY COLUMN GAS CHROMATOGRAPHIC SYSTEM Parameter Recommended Tolerance Liquid phase Finnigan 9610 15 m x 0.255 mm ID Fused silica DB-5 (J&W) Liquid phase thickness Carrier gas Carrier gas velocity Injector Injector temperature Injection volume Initial column temperature Column temperature program Separator Transfer line temperature 0.25 pm Helium 45 cm/sec r* On-column (J&W) c Optimum performance 1.0 (Jlc 70°C (2 min)d 70°-325°C at 10°C/mine None 280°C Other nonpolar or semipolar < 1 HID Hydrogen Optimum performance Other Optimum performance Other Other Other Glass jet or othe Optimum8 Tailing factorh 0.7-1.5 0.4-3 Peak width1 7-10 sec < 15 sec Gas chromatograph Column a Other Other Substitutions permitted with any common apparatus or technique provided performance criteria are met. b Measured by injection of air or methane at 270°C oven temperature. c For on-column injection, manufacturer's instructions should be followed regarding injection technique. d With on-column injection, initial temperature equals boiling point of the solvent; in this instance, hexane. e C^Clio elutes at 270°C. Programming above this temperature ensures a clean column and lower background on subsequent runs. f Fused silica columns may be routed directly into the ion source to prevent separator discrimination and losses. g High enough to elute all PCBs, but not high enough to degrade the column if routed through the transfer line. h Tailing factor is width of front half of peak at 10% height divided by width of back half of peak at 10% height for single PCB congeners in solution CSxxx. i Peak width at 10% height for a single PCB congener is CSxxx. C-20 �TABLE 6. OPERATING PARAMETERS FOR PACKED COLUMN GAS CHROMATOGRAPHY SYSTEM Gas chromatograph Column Tolerance Recommended Parameter Finnigan 9610 Other3 180 cm x 0.2 cm ID Other glass Column packing 3% SP-2250 on 100/ 120 mesh Supelcoport Other nonpolar or semipolar Carrier gas Helium Hydrogen Carrier gas flow rate 30 ml/min Optimum performance Injector On-column Other Injector temperature 250°C Optimum Injection volume 1.0 pi ^ 5 Ml Initial column temperature 150°C, 4 min Other Column temperature program 150°-260°C at 8°/min Other Separator Glass jet Other Transfer line temperature 280°C Optimum8 Tailing factor0 ,0.7-1.5 0.4-3 10-20 sec < 30 sec Peak widthd a Substitutions permitted if performance criteria are met. b High enough to elute all PCBs. c Tailing factor is width of front half of peak at 10% height divided by width of back half of peak at 10% height for single PCB congeners in solution CSxxx. d Peak width at 10% height for a single PCB congener is CSxxx. C-21 �TABLE 7. OPERATING PARAMETERS FOR QUADRUPOLE MASS SPECTROMETER Parameter Recommended SYSTEM Tolerance Mass spectrometer Finnigan 4023 Other3 Data system Incos 2400 Other Scan range 95-550 Other Scan time 1 sec Otherb Resolution Unit Optimum performance Ion source temperature 280°C 200°-300°C Electron energy 70 eV Optimum performance Trap current 0.2 mA Optimum performance Multiplier voltage -1,600 V Optimum performance Preamplifier sensitivity 10"6 A/V Set for desired working range a Substitutions permitted if performance criteria are met. b Greater than five data points over a GC peak is a minimum. c Filaments should be shut off during solvent elution to improve instrument stability and prolong filament life, especially if no separator is used. C-22 �TABLE 8. OPERATING PARAMETERS FOR MAGNETIC SECTOR MASS SPECTROMETER SYSTEM Parameter Recommended Tolerance Mass spectrometer Finnigan MAT 311A Other8 Data system Incos 2400 Other Scan range 98-550 Other Scan mode Exponential Other Cycle time 1.2 sec Other Resolution 1,000 > 500 Ion source temperature 280°C 250-300° Electron energy0 70 eV 70 eV Emission current 1-2 mA Optimum Filament current Optimum Optimum Multiplier -1,600 V Optimum a Substitutions permitted if performance criteria are met. b Greater than five data points over a GC peak is a minimum. c Filaments should be shut off during solvent elution to improve instrument stability and prolong filament life, especially if no separator is used. C-23 �7.4 The PCS response factors (RF ) must be determined using Equation 7-1 for the analyte homologs? A x M. RFp = A. x j -£ ^ Eq. 7-1 H r is Mp where RF = response factor of a given PCB isomer A = area of the characteristic ion for the PCB congener " peak M = mass of PCB congener injected (nanograms) A. = area of the characteristic ion for the internal standard peak M. = mass of internal standard injected (nanograras) 1S If specific congeners are known to be present and if standards are available, selected RF values may be employed. For general samples, solutions CSxxx and SSxxx or a mixture (Tables 3 and 4) may be used as the response factor solution. The PCB-surrogate pairs to be used in the RF calculation are listed in Table 9. Generally, only the primary ions of both the analyte and surrogate are used to determine the RF values. If alternate ions are to be used in the quantitation, the RF must be determined using that characteristic ion. The RF value must be determined in a manner to assure ±20% accuracy and precision. For instruments with good day-to-day precision, a running mean (RF) based on seven values determined once each day may be appropriate. Other options include, but are not limited to, triplicate determinations of a single concentration spaced throughout a day or determination of the RF at three different levels to establish a working curve. If replicate RF values differ by greater than ±10% RSD, the system performance should be monitored closely. If the RSD is greater than ±20%, the data set must be c6nsidered invalid and the RF redetermined before further analyses are done. 7.5 If the GC/EIMS system has not been demonstrated to yield a linear response or if the analyte concentrations are more than one order of magnitude different from those in the RF solution, a calibration curve must be prepared. If the analyte and RF solution concentrations differ by more than one order of magnitude, a calibration curve should be prepared. A calibration curve should be established with triplicate determinations at three or more concentrations bracketing the analyte levels. C-24 �TABLE 9. PAIRINGS OF ANALYTE. CALIBRATION, AND SURROGATE COMPOUNDS Analyte Congener3 no. Compound 1 2,3 4-15 16-39 40-81 82-127 128-169 170-193 194-205 206-208 o 209 I 2-Ci2HgCl 3- and 4-C12H9Cl Ci2HgCl2 C^HyCls C12H6C14 c 12H5Cls C12HsCl7 Ci2H2Clg Cj^HClg CiaCl10 Calibration standard Congener Compound no. 1 3 7 30 50 97 143 183 202 207 209 2 4 2,4 2,4 ,6 2,2 ',4 ,6 2,2 ',3 ',4,5 2,2 ',3 ,4,5 ,6' 2,2 ',3 ',4,4' ,5', 6 2,2 ',3 ,3',5,5', 6, 6' 3' 2,2 ',3 ,° » 4, 4' ,5,6, 6' C 12Cli 0 NJ a Ballschmiter numbering system, see Table 1. Surrogate Congener no. Compound 211 211 211 212 212 212 212 213 213 213 214 13 C6-4 c "3 e-4 i C6-4 13 C12-3,3' ,4,4' 13 Ci2-3,3' ,4,4' 13 C12-3,3' ,4,4' 13 Ci2-3,3' ,4,4' 13 C12-2,2' ,3,3' ,5,5', 6, 6' 13 q 01 C12-2,2' ,O,O ,5, 5', 6,6' 13 q 01 C12-2,2' ,J,J ,5,5', 6, 6' 13 Ci2Cll0 �7.6 8.0 The relative retention time (RRT) windows for the 10 homologs and surrogates must be determined. If all congeners are not available, a mixture of available congeners or an Aroclor mixture (e.g., 1016/1254/1260) may be used to estimate the windows. The windows must be set wider than observed if all isomers are not determined. Typical RRT windows for one column are listed in Table 10. The windows may differ substantially if other GC parameters are used. Sample Collection, Handling, and Preservation The sampling shall be conducted by competent personnel experienced with this test procedure and cognizant of the constraints of the anaytical techniques for PCBs, particularly contamination problems. 8.1 Stack sampling1 8.1.1 Pretest preparation - All train components shall be maintained and calibrated according to the procedure described in APTD-0581,3 unless otherwise specified herein. This should be done in the laboratory prior to sampling. 8.1.1.1 Cleaning glassware - All glass parts of the train upstream of and including the adsorbent tube and impingers, should be cleaned as described in Section 3.1.1. Special care should be devoted to the removal of residual silicone grease sealants on ground glass connections of used glassware. These grease residues should be removed by soaking several hours in a chromic acid cleaning solution prior to routine cleaning as described above. 8.1.1.2 Solid adsorbent tube - 7.5 g of Florisil activated within the last 30 days and still warm from storage in a 110°C oven, is weighed into the adsorbent tube (prerinsed with hexane) with a glass wool plug in the downstream end. A second glass wool plug is placed in the tube to hold the sorbent in the tube. Both ends of the tube are capped with ground glass caps. These caps should not be removed until the tube is fitted to the train immediately prior to sampling. 8.1.2 Preliminary determinations - The sampling site and the minimum number of sampling points are selected according to Method I2 or as specified by the Agency. The stack pressure, temperature, and the range of velocity heads are determined using Method 22 and moisture content using Approximation Method 42 or its alternatives for the purpose of making isokinetic sampling rate calculations. Estimates may be used. However, final results must be based on actual measurements made during the test. C-26 �TABLE 10. RELATIVE RETENTION TIME (RRT) RANGES OF PCB HOMOLOGS VERSUS d6-3,3'.4.4'-TETRACHLOROBIPHENYL PCB homolog Monochloro No. of isomers measured Observed range of RRTsa Congener no. Observed RRTa Projected range of RRTs 3 0.40-0.50 1 3 0.43 0.50 0.35-0.55 Dichloro 10 0.52-0.69 7 0.58 0.35-0.80 Trichloro 9 0.62-0.79 30 0.65 0.35-0.10 Tetrachloro 16 0.72-1.01 50 0.75 0.55-1.05 Pentachloro 12 0.82-1.08 97 0.98 0.80-1.10 Hexachloro 13 0.93-1.20 143 1.05 0.90-1.25 Heptachloro 4 1.09-1.30 183 1.15 1.05-1.35 Octachloro 6 1.19-1.36 202 1.19 1.10-1.50 Nonachloro 3 1.31-1.42 207 1.33 1.25-1.50 Decachloro 1 1.44-1.45 209 1.44 1.35-1.50 a The RRTs of the 77 congeners and a mixture of Aroclor 1016/1254/1260 were measured versus 3,3',4,4'-tetrachlorobiphenyl-de (internal standard) using a 15-m J&W DB-5 fused silica column with a temperature program of 110°C for 2 min, then 10°C/min to 325°C, helium carrier at 45 cm/sec, and an oncolumn injector. A Finnigan 4023 Incos quadrupole mass spectrometer operating with a scan range of 95-550 daltons was used to detect each PCB congener. b The projected relative retention windows account for overlap of eluting homologs and take into consideration differences in operating systems and lack of all possible 209 PCB congeners. C-27 �The molecular weight of the stack gases is determined using Method 3.2 A nozzle size is selected based on the maximum velocity head so that isokinetic sampling can be maintained at a rate less than 0.75 cfm. It is not necessary to change the nozzle size in order to maintain isokinetic sampling rates. During the run, the nozzle size must not be changed. A suitable probe length is selected such that all traverse points can be sampled. Sampling from opposite sides for large stacks may be considered to reduce the length of probes. A sampling time is selected appropriate for total method sensitivity and the PCB concentration anticipated. Sampling times should generally fall within a range of 2 to 4 hr. A buzzer-timer should be incorporated in the control box (see Figure 1) to alarm the operator to move the probe to the next sampling point. 8.1.3 Preparation of collection train - During preparation and assembly of the sampling train, all train openings must be covered until just prior to assembly or until sampling is about to begin. Immediately prior to assembly, all parts of the train upstream of the adsorbent tube are rinsed with hexane. The probe is marked with heat resistant tape or by some other method at points indicating the proper distance into the stack or duct for each sampling point. 200 ml of water is placed in each of the first two impingers, and the third impinger left empty. CAUTION: Sealant greases must not be used in assembling the train. If the preliminary moisture determination shows that the stack gases are saturated or supersaturated, one or two additional empty impingers should be added to the train between the third impinger and the Florisil tube. See Section 5.1.5. Approximately 200 to'300 g or more, if necessary, of silica gel is placed in the last impinger. Each impinger (stem included) is weighed and the weights recorded to the nearest 0.1 g on the impingers and on the data sheet. Unless otherwise specified by the Agency, a temperature probe is attached to the metal sheath of the sampling probe so that the sensor is at least 2.5 cm behind the nozzle and pitot tube and does not touch any metal. C-28 �The train is assembled as shown in Figure 1. Through all parts of this method use of sealant greases such as stopcock grease to seal ground glass joints must be avoided. Crushed ice is placed around the impingers. 8.1.4 Leak check procedure - After the sampling train has been assembled, the probe heating system(s) is turned on and set (if applicable) to reach a temperature sufficient to avoid condensation in the probe. Time is allowed for the temperature to stabilize. The train is leak checked at the sampling site by plugging the nozzle and pulling a 380 mm Hg (15 in. Hg) vacuum. A leakage rate in excess of 4% of the average sampling rate or 0.0057 m3/min (0.02 cfm) whichever is less, is unacceptable. The following leak check instruction for the sampling train described in APTD-05813 may be helpful. The pump is started with bypass valve fully open and coarse adjust valve completely closed. The coarse adjust valve is partially opened and the bypass valve slowly closed until 380 mm Hg (15 in. Hg) vacuum is reached. The direction of bypass valve must not be reversed. This will cause water to back up into the probe. If 380 mm Hg (15 in. Hg) is exceeded, either the leak check is conducted at this higher vacuum or the leak check is ended as described below and start over. When the leak check is completed, the plug is first slowly removed from the inlet to the probe and the vacuum pump is immediately turned off. This prevents the water in the impingers from being forced backward into the probe. Leak checks, shall be conducted as described above prior to each test run and at the completion of each test run. If leaks are found to be in excess of the acceptable rate, the test will be considered invalid. To reduce lost time due to leakage occurrences, it is recommended that leak checks be conducted between port changes. 8.1.5 Train operation - During the sampling run, an isokinetic sampling rate within 10%, or as specified by the Agency, of true isokinetic shall be maintained. During the run, the nozzle or any other part of the train in front of and including the Florisil tube must not be changed. For each run, the data required on the data sheets must be recorded. An example is shown in Figure 4. The dry gas meter readings are recorded at the beginning and end of each sampling time increment, when changes in flow rates are made, and when sampling is halted. Other data point readings are taken at least once at each sample point during each time increment and whenever significant C-29 �FIELD DATA PLANT. OATE_ SAMPLING LOCATION. SAMPLE TYPE RUN NUMBER OPERATOR PROBE LENGTH AND TYPE. NOZZLE ID. ASSUMED MOISTURE. "„ SAMPLE BOX NUMBER METER BOX NUMBER METER AH p C FACTOR PROBE HEATER SETTING HEATER BOX SETTING REFERENCE Ap_ AMBIENT TEMPERATURE BAROMETRIC PRESSURE . STATIC PRESSURE. (P$)_ FILTER NUMBER ($) SCHEMATIC OF TRAVERSE POINT LAYOUT READ AND RECORD ALL DATA EVERY, MINUTES TRAVERSE POINT NUMBER s ^X CLOCK hTIME LiNG r_ \Aoc K, TIMt.iim N^ ~~ GAS METER READING <Vml. It3 VELOCITY HEAD (APSI. in. H?0 —— __ ORIFICE PRESSURE DIFFERENTIAL (AHI. in. H20l DESIRED STACK TEMPERATURE |TSI.°F ACTUAL n i COMMENTS: Figure 4. EPAlDur) 2K Field data sheet, DRY GAS METER TEMPERATURE INLET (Tm mt."F OUTLET •Tm^.-'F PUMP VACUUM, in. H| SAMPLE BOX TEMPERATURE. °F IMPINGCR TEMPERATURL "F �changes (20% variation in velocity head readings) necessitate additional adjustments in flow rate. The portholes are cleaned prior to the test run to minimize change of sampling deposited material. To begin sampling, the nozzle cap is removed, the probe heater operational and temperature up, and the pitot tube and probe positions are verified (if applicable). The nozzle is positioned at the first traverse point with the tip pointing directly into the gas stream. The pump is started and the flow adjusted to isokinetic conditions. Nomographs are available for sampling trains using type S pitot tubes with 0.85 ± 0.02 coefficients (C ), and when sampling in air or a stack gas with equivalent density (molecular weight, M,, equal to 29 ± 4), which aid in the rapid adjustment of the isokinetic sampling rate without excessive computations. If C and M, are outside the above stated ranges, the nomograph cannot be used unless appropriate steps are taken to compensate for the deviations. When the stack is under significant negative pressure (height of impinger stem), the coarse adjust valve must be closed before inserting the probe into the stack to avoid water backing into the probe. If necessary, the pump may be turned on with the coarse valve closed. When the probe is in position, the openings around the probe and porthole must be blocked off to prevent unrepresentative dilution of the gas stream. The stack cross section is traversed, as required by Method I2 or as specified by the Agency. To minimize chance of extracting deposited material, the probe nozzle should not bump into the stack walls when sampling near the walls or when removing or inserting the probe through the portholes. During the test run, periodic adjustments are made to keep the probe temperature at the proper value. More ice and, if necessary, salt is added to the ice bath to maintain a temperature of less than 20°C (68°F) at the impinger/silica gel outlet, to avoid excessive moisture losses. Also, the level and zero of the manometer should be periodically checked. If the pressure drop across the train becomes high enough to make isokinetic sampling difficult to maintain, the test run should be terminated. Under no circumstances should the train be disassembled during the test run to determine and correct causes of excessive pressure drops. C-31 �At the end of the sample run, the pump is turned off, the probe and nozzle removed from the stack, and the final dry gas meter reading recorded. A leak check is performed, with acceptability of the test run based on the same criteria as in Section 8.1.4. The percent isokinetic is calculated (see calculation section) to determine whether another test run should be made. If there is difficulty in maintaining isokinetic rates due to source conditions, the Agency should be consulted for possible variance on the isokinetic rates. 8.1.6 8.2 Blank train - For each series of test runs, a blank train is set up in a manner identical to that described above, but with the nozzle capped with aluminum foil and the exit end of the last impinger capped with a ground glass cap. The train is allowed to remain assembled for a period equivalent to one test run. The blank sample is recovered as described in Section 8.3. Static air sampling3 - The sampling procedure for static air is identical to that described in Section 8.1 with the following exceptions: (a) impingers and a heatable probe are not required prior to the adsorbent tube; and (b) the PCB concentrations may dictate a longer or shorter sampling time. The selection of sampling time and rate should be based on the approximate levels of PCB residues expected in the sample. The sampling rate should not exceed 14 liter/rain and may typically fall in the range of 5 to 10 liter/rain. Sampling times should be more than 20 min but should not exceed 4 hr. 8.3 Sample recovery - Proper cleanup procedure begins as soon as the probe is removed from the stack at the end of the sampling period. When the probe can be safely handled, all external particulate matter near the tip of the probe nozzle is wiped off. The probe is removed from the train and both ends closed off with aluminum foil. The inlet to the train is capped off with a ground glass cap. The probe and impinger assembly are transfered to the cleanup area. This area should be clean and protected from the wind so that the chances of contaminating or losing the sample will be minimized. The train is inspected prior to and during disassembly and any abnormal conditions noted. The samples are treated as follows: 8.3.1 Adsorbent tube - The Florisil tube is removed from the train and capped with ground glass caps. 8.3.2 Sample Container No. 1 - The first three impingers are removed. The outside of each impinger is wiped off to remove excessive water and other debris. The impingers C-32 �are weighed (stem included), and the weight recorded on a data sheet. The contents are poured directly into Container No. 1. 8.3.3 8.3.4 8.4 Sample Container No. 2 - Each of the first three impingers are rinsed sequentially with 30-ml acetone and then with 30-ml hexane, and the rinses put into Container No. 2. Material deposited in the probe is quantitatively recovered using 100-ml acetone and then 100-ml hexane and these rinses added to Container No. 2. Silica gel container - The last impinger is removed, and the outside wiped to remove excessive water and other debris. It is weighed (stem included), and the weight recorded on the data sheet. The contents are transferred to the used silica gel can. Sample preservation - Samples should be stored in the dark at 4°C. Storage times in excess of 4 weeks are not recommended. 9.0 Sample Preparation1 9.1 Extraction 9.1.1 Adsorbent tube - The entire contents of the adsorbent tube are expelled directly onto a glass wool plug in the sample holder of a Soxhlet extractor. Although no extraction thimble is required, a glass thimble with a coarsefritted bottom may be used. The tube is rinsed with 5-ml acetone and then with 15-ml hexane and these rinses put into the extractor. The extraction apparatus is assembled and the adsorbent extracted with 170-ml hexane for at least 4 hr. The extractor should cycle 10 to 14 times per hour. After allowing the extraction apparatus to cool to ambient temperature, the extract is transferred into a KudernaDanish evaporator. The extract is evaporated to about 5 ml on a steam bath and the evaporator allowed to cool to ambient temperature before disassembly. The extract is transferred to a 50-ml separatory funnel and the funnel set aside. 9.1.2 Sample Container No. 1 - The aqueous sample is transferred to a 1,000-ml separatory funnel. The container is rinsed with 20-ml acetone and then with two 20-ml portions of hexane, adding the rinses to the separatory funnel. The sample is extracted with three 100 ml portions of hexane and the sequential extracts transferred to a Kuderna-Danish evaporator. C-33 �The extract is concentrated to about 5 ml and allowed to cool to ambient temperature before disassembly. The extract is filtered through a micro column of anhydrous sodium sulfate into a 50-ml separatory funnel containing the corresponding Florisil extract from Section 9.1.1. The micro column is prepared by placing a small plug of glass wool in the bottom of the large portion of a disposable pipette and then adding anhydrous sodium sulfate until the tube is about half full. 9.1.3 Sample Container No. 2 - The organic solution is transferred into a 1,000-ml separatory funnel. The container is rinsed with two 20 ml portions of hexane and the rinses added to the separatory funnel. The sample is washed with three 100 ml portions of water. The aqueous layer is discarded and the organic layer transferred to a KudernaDanish evaporator. The extract is concentrated to about 5 ml and allowed to cool to ambient temperature before disassembly. The extract is filtered through a micro column of anhydrous sodium sulfate into the 50-ml separatory funnel containing the corresponding Florisil and impinger extracts (Section 9.1.2). 9.2 Cleanup - Two tested cleanup techniques are described below.4 Depending upon the complexity of the sample, one or both of the techniques may be required to fractionate the PCBs from interferences. If the sample extract is colored, the Florisil column cleanup may be indicated. 9.2.1 Acid cleanup 9.2.1.1 Add 5 ml of concentrated sulfuric acid to the separatory funnel containing the sample extract and shake for 1 min. 9.2.1.2 Allow the phases to separate, transfer the sample (upper phase) with three 1 to 2 ml solvent rinses to Kuderna-Danish evaporator and concentrate to an appropriate volume. 9.2.1.3 Analyze as described in Section 10.0. 9.2.1.4 If the sample is highly contaminated, a second or third acid cleanup may be employed. 9.2.2 Florisil column cleanup 9.2.2.1 Variations among batches of Florisil may affect the elution volume of the various PCBs. For this reason, the volume of solvent required to C-34 �completely elute all of the PCBs must be verified by the analyst. The weight of Florisil can then be adjusted accordingly. 9.2.2.2 Place a 20-g charge of Florisil, activated overnight at 130°C, into a Chroraaflex column. Settle the Florisil by tapping the column. Add about 1 cm of anhydrous sodium sulfate to the top of the Florisil. Pre-elute the column with 70-80 ml of hexane. Just before the exposure of the sodium sulfate layer to air, stop the flow. Discard the eluate. 9.2.2.3 Add the sample extract to the column. Add 225 ml of hexane to the column. Carefully wash down the inner wall of the column with a small amount of the hexane prior to adding the total volume. Discard the first 25 ml. 9.2.2.4 Collect 200 ml of hexane eluate in a KudernaDanish flask. All of the PCBs should be in this fraction. Concentrate to an appropriate volume. 9.2.2.5 Analyze the sample as described in Section 10.0. 10.0 Gas Chromatographic/Electron Impact Mass Spectrometric Determination 10.1 Internal standard addition - Pipet an appropriate volume of internal standard solution SSxxx into the sample. The final concentration of the internal standards must be in the working range of the calibration and well above the matrix background. The internal standards are thoroughly mixed by mechanical agitation. Note: The volume measurement of the spiking solution is critical to the overall method precision. The analyst must exercise caution that the volume is known ±1% or better. Where necessary, calibration of the pipet is recommended. Note: This same solution is used as a surrogate standard solution in the protocols for products/product waste and for water. In this protocol, the 13C-labeled PCBs are spiked after extraction, so are used as internal standards. Alternately, another internal standard solution such as the d63,3',4,4'-tetrachlorobiphenyl used in the product/product waste and water protocols may be used, if acceptable RF precision and accuracy are shown across the homolog range. 10.2 Tables 2, and 5 through 8 summarize the recommended operating conditions for analysis. Figure 5 presents an example of a chromatogram. C-35 �W O) ,H CO CO 00 0) 4-1 l-i 3 C ffl 4-1 c o K 10U.O vO ^O T3 U rH CO 1 rH rH C £*^ C QJ C QJ J^ p., fi Q) J2 p. -H £X ^Q -H -H XI XI ^-s O O Q) M l-l 4J O O O O i H C x; CJ co rJ 1-1 C 3 M 4-1 rH >> QJ QJ 1 o o en a I I ,c ^ )S *—' <f rH >-. r^> C <f H r-f <J •H J>"i *• _O £j ^3" c QJ x: XI -H rH jj") -H XI O IM C QJ P>i p. -H It 1C rH CO rH >% C o) x: P. ca l-i 0) -H l-i a co rH 1-1 >. C QJ 4-1 QJ H x: 1 p. 4-1 O |-i 0 tH QJ H 1 vO f. 0 cO 4J O rH X: O •H Q 1 ^J i X CJ -H M H | 04" 7 "** 01 P. ,--, P . x: 0 ca XI C 0 M O O CO -H o 1 vD 0 vO ^O v£) LO rH 0 X! O - 4-> rH 1-1 O l-i O XI 0 o 1-1 QJ XI rH 1 •H cfl M O x: 1-1 U 3 cfl CO CO a CJ —' QJ Q cfl - <r M - o rH CO X O) ffl rrj 1 vO - oo p. <J *. LO _ QJ rn x: r, LO f. 4-1 O •v ~^r ^ CO LO ** • t < CO CO n *, •- -<r ^ CN ^ CN] «s CM r. 0) Q r, CN ^ " J r, CO *x CO ' , 1208 o f. I3 C ' r. CN CN i ui ||7ll ™" ^ '' 7 | rH 1 2 f. r C7 CM" 1 r T II a o x : 4-1 XI m -<r ^-^ CJ O <f •s QJ PL, | LO - <3~ Ovl 04 fQ -H , n -H — >sO c - ^J" **3" , ; vo 0-1 CIO QJ x: P, rH M C &^ c rH 1 rH p, CO O XI P. •H XI O o ^i o rH x: o o 10: (W o X: •H XI «2_.Mh.. 1 c-.rj -H X3 rO o P. -~ p. n rH XI x; C X! o ,x C QJ rH o I 2 o l-l o rH x: rH i—i x: - 6 5 QJ QJ - CX rH CJ CO C JZ O O HC i t O O o o co rH rH (30 x: x: o 112592 CN rH J>^ 1 rH 1 rH rH >•>,>> ' CO 02? r 1M0 11:20 04 ™ I H (I »;« * "t lono IB: 1D I * 1I ,,,„ i uv: j ->0: CO ^_ 1 - V r-.'f' ^ 23:?'J soA'i Till.: Figure 5. Capillary gas chromatography/electron impact ionization mass spectrometry (CGC/EIMS) chromatogram or the calibration standard solution required for quantitation of PCBs by homolog. This chromatogram includes PCBs representative of each liomolog, three carbon-13 labeled surrogates, and the deuterated internal standard. The concentration of all components and the CGC/EIMS parameters are presented in Tallies 3, 4, 5, and 7. �10.3 While the highest available chromatographic resolution is not a necessary objective of this protocol, good chromatographic performance is recommended. With the high resolution of CGC, the probability that the chromatographic peaks consist of single compounds is higher than with PGC. Thus, qualitative and quantitative data reduction should be more reliable. 10.4 After performance of the system has been certified for the day and all instrument conditions set according to Tables 2, and 5 through 8, inject an aliquot of the sample onto the GC column. If the response for any ion, including surrogates and internal standard, exceeds the working range of the system, dilute the sample and reanalyze. If the responses of surrogates, internal standard, or analytes are below the working range, recheck the system performance. If necessary, concentrate the sample and reanalyze. 10.5 Record all data on a digital storage device (magnetic disk, tape, etc.) for qualitative and quantitative data reduction as discussed below. 11.0 Qualitative Identification 11.1 Selected ion monitoring (SIM) or limited mass scan (IMS) data The identification of a compound as a given PCS homolog requires that two criteria be met: 11.1.1 (1) The peak must elute within the retention time window set for that homolog (Section 7.6); and (2) the ratio of two ions obtained by SIM (Table 11) or by IMS (Table 12) must match the natural ratio within ±20%. The analyst must search the higher mass windows, in particular M+70, to prevent misidentification of a PCB fragment ion cluster as the parent. 11.1.2 If one or the other of these criteria is not met, interferences may have affected the results and a reanalysis using full scan EIMS conditions is recommended. 11.2 Full scan data 11.2.1 The peak must elute within the retention time windows set for that homolog (as described in Section 7.6). 11.2.2 The unknown spectrum must match that of an authentic PCB. The intensity of the three largest ions in the molecular cluster (two largest for monochlorobiphenyls) must match the natural ratio within ±20%. Frequent clusters with proper intensity ratios must also be present. 11.2.3 Alternatively, a spectral search may be used to automatically reduce the data. The criteria for acceptable C-37 �TABLE 11. CHARACTERISTIC SIM IONS FOR PCBs Ion (relative intensity) Secondary Tertiary Homolog Primary ^12^9^1 188 (100) 190 (33) C^HgC^ 222 (100) 224 (66) 226 (11) Ci2H7Cl3 256 (100) 258 (99) 260 (33) C12H6C14 292 (100) 290 (76) 294 (49) C12H5C15 326 (100) 328 (66) 324 (61) £12^4^16 360 (100) 362 (82) 364 (36) C12H3C17 394 (100) 396 (98) 398 (54) Ci2H2Cl8 430 (100) 432 (66) 428 (87) Cj^HClg 464 (100) 466 (76) 462 (76) C 498 (100) 500 (87) 496 (68) 12 C llO - Source: Rote, J. W., and W. J. Morris, "Use of Isotopic Abundance Ratios in Identification of Polychlorinated Biphenyls by Mass Spectrometry," J. Assoc. Offic. Anal. Chem., 56(1), 188-199 (1973). C-38 �TABLE 12. LIMITED MASS SCANNING (LMS) RANGES FOR PCBs Compound Mass range (m/z) CX2H.CU 186-190 C12H8C12 220-226 C12H7C13 254-260 C12H6C13 288-294 Ci2H5Cl5 322-328 Ci2H4Cl6 356-364 C12H3C17 386-400 C12H2C18 426-434 C12HC19 460-468 CisCl^ 494-504 C12D6C14 294-300 13 192-196 13 300-306 C612C6H9C1 C12H6C14 13 438-446 -C12C110 506-516 C12H2C18 a Adapted from Tindall, G. W., and P. E. Wininger, "Gas Chromatography-Mass Spectrometry Method for Identifying and Determining Polychlorinated Biphenyls," J. Chromatogr.t 196, 109-119 (1980). C-39 �identification include a high index of similarity. For the Incos 2300, a fit of 750 or greater must be obtained. 11.3 Disputes in interpretation - Where there is reasonable doubt as to the identity of a peak as a PCB, the analyst must either identify the peak as a PCB or proceed to a confirmational analysis (see Section 13.0). 12.0 Quantitative Data Reduction 12.1 Once a chromatographic peak has been identified as a PCB, the compound is quantitated based either on the integrated abundance of the SIM data or EICP for the primary characteristic ion in Tables 11 and 12. If interferences are observed for the primary ion, use the secondary and then tertiary ion for quantitation. If interferences in the parent cluster prevent quantitation, an ion from a fragment cluster (e.g., M-70) may be used. Whichever ion is used, the RF must be determined using that ion. The same criteria should be applied to the internal standard compounds (Table 13). 12.2 Using the appropriate response factor (RF ) as determined in Section 7.3, calculate the mass of each PCB peak (M ) using Equation P 12-1. A , M = -E • 'M p A.is RF p is Eq. 12-1 H * where A = area of the characteristic ion for the analyte PCB " peak A. = area of the characteristic ion for the internal standard peak RF = response factor of a given PCB congener M. S = mass of internal standard injected (micrograms) ~L 12.3 If a peak appears to contain non-PCB interferences which cannot be circumvented by a secondary or tertiary ion, either: 12.3.1 12.3.2 Perform additional chemical cleanup (Section 9) and then reanalyze the sample; or 12.3.3 12.4 Reanalyze the sample on a different column which separates the PCB and interferents; Quantitate the entire peak as PCB. Sum all of the peaks for each homolog and then sum those to yield the total PCB mass, MT, in the sample. If a concentration-perpeak or concentration-per-homolog reporting format is desired, carry each value through the calculations in an appropriate manner. C-40 �TABLE 13. CHARACTERISTIC IONS FOR Specific compound C612C6H9C1 ^ Primary 13 C-LABELED PCS SURROGATES Ion (relative intensity) Secondary Tertiary 13 194 (100) 196 (33) 13 304 (100) 306 (49) 302 (78) 13 442 (100) 444 (65) 440 (89) 510 (100) 512 (87) 514 (50) C12H6C14 C12H2C18 13 C12C110 C-41 �12.5 Calculation of air sample volume1 12.5.1 Nomenclature M = Mass of PCB represented by a chromatographic peak " micrograms M~ = Total mass of PCBs in sample, micrograms C = Concentration of PCBs in air, micrograms per cubic meter, corrected to standard conditions of 20°C, 760 mm Hg (68°F, 29.92 in. Hg) on dry basis A = Cross-sectional area of nozzle, square meter (square n feet) B = Water vapor in the gas stream, proportion by volume I = Percent of isokinetic sampling MWw = Molecular weight of water, 18 g/g-mole (18 lb/ Ib-mole) P, = Barometric pressure at the sampling site, mm Hg oar /. (in. IT \ Hg) Ps = Absolute stack gas pressure, mm Hg (in. Hg) Pstd, = Standard absolute pressure, 760 mm Hg (29.92 in Hg) R = Ideal gas constant, 0.06236 mm Hg-m3/K-g-raole (21.83 in. Hg-ft3/°R-lb-mole) T = Absolute average dry gas meter temperature °K (°R) TS = Absolute average stack gas temperature °K (°R) = Standard absolute temperature, 293°K (528°R) V, = Total volume of liquid collected in impingers and silica gel, milliliters. Volume of water collected equals the weight increase in grams times 1 ml/g Vm = Volume of gas sample as measured by dry gas meter, dcm (dcf) V , ,x = Volume of gas sample measured by the dry gas meter corrected to standard conditions, dscra (dscf) C-42 �,N = Volume of water vapor in the gas sample corrected to standard conditions, son (scf) V = Total volume of sample, railliliter V = Stack gas velocity, calculated by EPA Method 2, s m/sec (ft/sec) AH = Average pressure differential across the orifice meter, mm H20 (in. H20) Pw = Density of water, 1 g/ml (0.00220 Ib/ral) 6 = Total sampling time, minutes 13.6 = Specific gravity of mercury 60 = Seconds per minute 100 = Conversion to percent 12.5.2 Average dry gas meter temperature and average orifice pressure drop - See data sheet (Figure 4). 12.5.3 Dry gas volume - Correct the sample volume measured by the dry gas meter to standard conditions [20°C, 760 mm Hg (68°F, 29.92 in. Hg)] by using Equation 12-2. ., Vstd) - T „ *std V m - P +M *bar 13.6 _ „„ = P + AH bar 1376" Eq. 12-2 V where K = 0.3855°K/mm Hg for metric units = 17.65 °R/in. Hg for English units 12.5.4 Volume of water vapor P w RTstd Vw(std) = Ic MW P 5,^ = K Ic , , ,, V, ajT- .V, v ' w std where K = 0.00134 m3/ml for metric units = 0.0472 ft3/ml for English units 12.5.5 Eq. ^ 12-3 Moisture content = -J^Iltd)E 1. 2 4 V +V m(std) w(std) If the liquid droplets are present in the gas stream, assume the stream to be saturated and use a psychrometric chart to obtain an approximation of the moisture percentage. B ws C-43 �12.6 Concentration of PCBs in stack gas - Determine the concentration of PCBs in the air according to Equation 12-5 and report in micrograms per cubic meter using Table 14. If an alternate reporting format (e.g., concentration per peak) is desired, a different report form may be used. M C a = K y—-- Eq. 12-5 m(std) where K = 35.31 ft3/m3 12.7 Isokinetic variation 12.7.1 Calculations from raw data. [K V, + (V /T ) (P, ) + AH/13.6)] 1nn Ts l 100 Ic m m bar 10 , T r i = -60s e v P A- Eq- 12' s n 3 where K = 0.00346 mm Hg-m /ml-°K for metric units = 0.00267 in. Hg-ft3/ml-°R for English units 12.7.2 Calculations from intermediate values T V f «. ,, P . . 100 T s m(std) std 1 " T , , s 6n s 60 (1-B J A P std V ws _ ,7 ' /"/ tq ,, _s Vm(std) _ T Ps Vs An 0 (1-B ws) where K = 4.323 for metric units = 0.0944 for English units 12.7.3 Acceptable results - The following range sets the limit on acceptable isokinetic sampling results: If 90% < I < 110%, the results are acceptable. If the results are low in comparison to the standards and I is beyond the acceptable range, the Agency may opt to accept the results. 12.8 Round off all numbers reported to two significant figures. 13.0 Confirmation If there is reason to question the qualitative identification (Section 11.0), the analyst may choose to confirm that a peak is not a PCB. Any technique may be chosen provided that it is validated as having equivalent or superior selectivity and sensitivity to GC/EIMS. Some candidate techniques include alternate GC columns (with EIMS detection), GC/CIMS, GC/NCIMS, high resolution EIMS, and MS/MS techniques. Each laboratory C-44 �TABLE 14. ANALYSIS REPORT INCIDENTAL PCBs IN AIR Sample No. Sample Matrix Sample Source Notebook No. or File Location m3 Volume Collected [V , fcdJ Mass of Internal Stanaara Injected, M. is pg Qualitative Analyte 1° 2° I l° T 2° Ratio Theoretical IS 298 246 100/76 1-C1 188 190 100/33 2-C1 222 224 100/66 3-C1 256 258 100/99 4-C1 292 290 100/76 5-C1 326 328 Quantitative Ion Mass OK? Used RF M (pg) P 1.000 100/66 i 6-C1 360 362 100/82 7-C1 394 396 100/98 8-C1 430 432 100/66 9-C1 464 466 100/76 10-C1 498 500 100/87 Total (MT) Concentration (C.) M£ 3 Mg/m Reported by: Internal Audit: Name Name EPA Audit: Name Signature/Date Signature/Date Signature/Date Organization Organization Organization C-45 �must validate confirmation techniques to show equivalent or superior selectivity between PCBs and interferences and sensitivity (limit of quantitation, LOQ). If a peak is confirmed as being a non-PCB, it may be deleted from the calculation (Section 12). If a peak is confirmed as containing both PCB and non-PCB components, it must be quantitated according to Section 12.3. 14.0 Quality Control 14.1 Each laboratory that uses this method must operate a formal quality control (QC) program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and the analysis of spiked samples as a continuing check on performance. The laboratory must maintain performance records to define the quality of data that are generated. After a date specified by the Agency, ongoing performance checks should be compared with established performance criteria to determine if the results of analyses are within accuracy and precision limits expected of the method. 14.2 The analysts must certify that the precision and accuracy of the analytical results are acceptable by: 14.2.1 14.2.2 14.3 The absolute precision of surrogate recovery, measured as the RSD of the integrated EIMS area (A ) for a set of samples, must be ±10%. The mean recovery (R ) of at least four replicates of a QC check sample to be supplied by the Agency must meet Agency-specified accuracy and precision criteria. This forms the initial data base for establishing control limits (see Section 14.3 below). Control limits - The laboratory must establish control limits using the following equations: Upper control limit (UCL) = R + 3 RSD Upper warning limit (UWL) = R + 2 RSD Lower warning limit (LWL) = RC - 2 RSDc Lower control limit (LCL) = R - 3 RSD These may be plotted on control charts. If an analysis of a check sample falls outside the warning limits, the analyst should be alerted that potential problems may need correction. If the results for a check sample fall outside the control limits, the laboratory must take corrective action and recertify the performance C-46 �(Section 14.2) before proceeding with analyses. The warning and control limits should be continuously updated as more check sample replicates are added to the data base. 14.4 Before processing any samples, the analyst should demonstrate through the analysis of a reagent blank that all glassware and reagent interferences are under control. Each time a set of samples is analyzed or there is a change in reagents, a laboratory reagent blank should be processed as a safeguard against contamination. 14.5 Procedural QC - The various steps of the analytical procedure should have quality control measures. These include but are not limited to: 14.5.1 GC performance - See Section 7.1 for performance criteria. 14.5.2 MS performance - See Section 7.2 for performance criteria. 14.5.3 Qualitative identification - At least 10% of the PCB identifications, as well as any questionable results, should be confirmed by a second mass spectrometrist. 14.5.4 Quantitation - At least 10% of all manual calculations, including peak area calculation, must be checked. After changes in computer quantitation routes, the results should be manually checked. 14.6 A minimum of 10% of all samples, one sample per month or one sample per matrix type, whichever is greater, must be selected at random, sampled, and analyzed in triplicate to monitor the precision of the analysis. An RSD of ±30% or less must be achieved. If the precision is greater than ±30%, the analyst must be recertified (see Section 14.2). 14.7 A minimum of 10% of all samples, one sample per month or one sample per matrix type, whichever is greater, selected at random, must be analyzed by the standard addition technique. Two aliquots of the sample are analyzed, one "as is" and one spiked with a sufficient amount of solution CSxxx to yield approximately 100 pg/ sample of each compound. The spiking compounds are thoroughly incorporated by mechanical agitation. For the liquid impinger contents, shaking for 30 sec should be sufficient. For the Florisil, 10 min tumbling is recommended. For filters where inadequate incorporation may be expected, overnight equilibration with agitation is recommended. Note: The volume measurement of the spiking solution is critical to the overall method precision. The analyst must exercise caution that the volume is known to ±1% or better. Where necessary, calibration of the pipet is recommended. C-47 �The samples are analyzed together and the quantitative results calculated. The recovery of the spiked compounds (calculated by difference) must be 80-120%. If the sample is known to contain specific PCB isomers, these isomers may be substituted for solution CSxxx. If the concentrations of PCBs are known to be high, the amount added should be adjusted so that the spiking level is 1.5 to 4 times the measured PCB level in the unspiked sample. 14.8 Sampling efficiency - The efficiency of PCB collection during sampling should be monitored. This may be achieved by adding a known amount of the 13C surrogate spiking solution (Section 6.4) sufficient to give an analytical signal well above background to the first impinger prior to sampling. The recovery of the four compounds should be > 14.9 Interlaboratory comparison - Interlaboratory comparison studies are planned. Participation requirements, level of performance, and the identity of the coordinating laboratory will be presented in later revisions. 14.10 It is recommended that the participating laboratory adopt additional QC practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates or triplicates may be analyzed to monitor the precision of the sampling technique. Whenever possible, the laboratory should perform analysis of standard reference materials and participate in relevant performance evaluation studies. 15.0 Quality Assurance Each participating laboratory must develop a quality assurance plan according to EPA guidelines.5 The quality assurance plan must be submitted to the Agency for approval. 16.0 Method Performance The method performance is being evaluated. Limits of quantitation; average intralaboratory recoveries, precision, and accuracy; and interlaboratory recoveries, precision, and accuracy will be presented. 17.0 Documentation and Records Each laboratory is responsible for maintaining full records of the analysis. Laboratory notebooks should be used for handwritten records. GC/MS data must be archived on magnetic tape, disk, or a similar device. Hard copy printouts may be kept in addition if desired. QC records should be maintained separately from sample analysis records. C-48 �The documentation roust describe completely how the analysis was performed. Any variances from the protocol must be noted and fully described. Where the protocol lists options (e.g., sample cleanup), the option used and specifies (solvent volumes, digestion times, etc.) must be stated. C-49 �REFERENCES 1. Haile, C. L., and E. Baladi, "Methods for Determining the Polychlorinated Biphenyl Emissions from Incineration and Capacitor and Transformer Filling Plants," U.S. Environmental Protection Agency, (1977) EPA-600/4-73-048. 2. U.S. Environmental Protection Agency, Federal Register, 42(160), Thursday, August 18, 1977. 3. Martin, R. M., "Construction Details of Isokinetic Source Sampling Equipment," Environmental Protection Agency, Air Pollution Control Office Publication No. APTD-0581. 4. Bellar, T. A., and J. J. Lichtenberg, "The Determination of Polychlorinated Biphenyls in Transformer Fluid and Waste Oils," Prepared for U.S. Environmental Protection Agency, (1981) EPA-600/4-81-045. 5. Quality Assurance Program Plan for the Office of Toxic Substances, Office of Pesticides and Toxic Substances, U.S. Environmental Protection Agency, Washington, D.C., October 1980. C-50 �APPENDIX D ANALYTICAL METHOD; THE ANALYSIS OF BY-PRODUCT CHLORINATED BIPHENYLS IN INDUSTRIAL WASTEWATER D-l �THE ANALYSIS OF BY-PRODUCT CHLORINATED BIPHENYLS IN INDUSTRIAL WASTEWATER i.0 Scope and Application 1.1 This is a gas chromatographic/electron impact mass spectrometric (GC/EIMS) method applicable to the determination of chlorinated biphenyls (PCBs) in industrial wastewater. The PCBs present may originate either as synthetic by-products or as contaminants derived from commercial PCB products (e.g., Aroclors). The PCBs may be present as single isomers or complex mixtures and may include all 209 congeners from monochlorobiphenyl through decachlorobiphenyl listed in Table 1. 1.2 The detection and quantitation limits are dependent upon the volume of sample extracted the complexity of the sample matrix and the ability of the analyst to remove interferents and properly maintain the analytical system. The method accuracy and precision will be determined in future studies. 1.3 This method is restricted to use by or under the supervision of analysts experienced in the use of gas chromatography/mass spectrometry (GC/MS) and in the interpretation of gas chromatograms and mass spectra. Prior to sample analysis, each analyst must demonstrate the ability to generate acceptable results with this method by following the procedures described in Section 14.2. 1.4 The validity of the results depends on equivalent recovery of the analyte and 13C PCBs. If the *3C PCBs are not thoroughly incorporated in the matrix, the method is not applicable. 1.5 During the development and testing of this method, certain analytical parameters and equipment designs were found to affect the validity of the analytical results. Proper use of the method requires that such parameters or designs must be used as specified. These items are identified in the text by the word "must." Anyone wishing to deviate from the method in areas so identified must demonstrate that the deviation does not affect the validity of the data. Alternative test procedure approval must be obtained from the Agency. An experienced analyst may make modifications to parameters or equipment identified by the term "recommended." Each time such modifications are made to the method, the analyst must repeat the procedure in Section 14.2. In this case, formal approval is not required, but the documented data from Section 14.2 must be on file as part of the overall quality assurance program. D-2 �TABLE 1. No. Structure NO. Menoeftloraoiphenylt 2 52 3 4 54 55 56 S7 IS » 60 61 (2 63 64 65 66 67 68 01chlorob<BHttiy1i a 9 10 n 12 13 14 IS 2.2' 2.3 2.3' 2.4 2.4' 2.5 2.6 3,3' 3,4 3.4' 3|5 4.4' Trlchloraolphtnyli 16 17 18 19 20 21 22 23 24 2S 26 27 28 29 JO 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 SO SI 2. 2'. 3 2.2'. 4 2. 2'. 5 2, 2', 6 2.3.3' 2,3.4 2.3.4' 2,3.5 2,3.6 2,3', 4 2, 3', 5 2,3', 6 2.4,4' 2.4,5 2.4,6 2, 4'. 5 2. 4' ,5 2', 3,4 2', 3,5 3,3', 4 3.3'.5 3,4,4' 3.4.5 3.4'. 5 NO. 69 70 71 72 73 74 75 76 77 78 79 80 81 10$ 2.3,3 ,4,4' 1 1 1 C 2 .J.J ,4,9 2,3,3 .4'. 5 2.3.3 ,4.5' 2,3.3 ,4.6 2,3.3 .4* ,6 2.3,3 ,5,5' 2,3,3 .5.6 2.3,3 .5', 6 2,3.4 4'.5 2.3,4 4' ,6 2.3,4 5,6 2.3,4', 5, 6 2,3'.4.4-.5 2.3'. 4. 4' .6 2.3'. 4, 5. 5' 2.3". 4,1 6 5', 21 .3. 3 . 4.5 2'. 3.4. 4' .5 21 .3.4.5. 52'.3.4.5,6' 3. 3'. 4. 4' .5 3,3'. 4. 5.5' 170 171 172 173 174 175 176 177 178 179 180 Htmeliloroblptitnylt 2.2'. «,S' 9* « *' 2 •* •*»• 2,2'. 5,62.3. 3'. 4 2.3.3'. 4' 2.3.3' .5 2.3.3-. S' 2.3,J'.< 2.3.4.4' 2.3.4.5 2,3.4,6 2.3. 4' .5 2,3.4-. 6 2.3,5.6 2.3', 4.4' 2.3', 4,5 2.3', 4.5" 2.3'. 4.6 2.3-.4'.5 2.3-,4-.6 .3'.S.5' ,3-.5',6 .4.4'. 5 ,4. 4', 6 '.3 4.5 .3' 4,4.3' 4,5 .3' 4,5' .3' 5.5.4.4-.S 2.2-.3.3'.4 2.2'. 3. 3', 5 2.2'.3.3',6 2. 2'. 3.4,4' 2,2' .3.4.5 2.2- .3, 4, 5' 2.2'. 3, 4,6 2,2'. 3.4,6"' 2.2'. 3, 4'. 5 2.2'. 3. 4'. 6 2.2', 3,5.5' 2.2'. 3, 5.6 2.2-.3.S.6' 2.2'. 3,5', 6 2.2-,3,6.6' 2.2-,3'.4.5 2.2'.3',4,6 2.2'. 4,4', 5 2.21,4.4'.6 2.2'. 4, 5.5' 2,2'. 4.5.5' 2.2-,4.S',6 2,2'. 4.6. S' 10 . 182 P«nt»ctil orebt phtny 1» Irtit IUO 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 125 126 127 Pmticftl arotl pHtny 1 » 82 S3 84 85 86 87 88 39 90 91 92 93 94 T«tricMorob<Bh«nyl» 95 96 97 2.2', 3.3' 2.2'. 3,4 98 2.2'. 3,499 2.2'.3,$ 100 2.2'.3.5' 101 2.2'. 3.6 10Z 2.2'.3,6' 103 2.2'. 4,4104 2,2' ,4, 5 2,2'. 4.J' 2 2 1 4 61 2.2 .4.6 structure Tttnetil arott Ph«nv1 s 1 4 5 6 7 NUMBERING OF PCB CONGENERS3 structure 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 2,2'.3.3-,4.42,2'. 3,3' .4. 2.2'.3.3',4. 2.2' .3,3'. 4. .2', 3.3'. 4, ,2'. 3, 3', 5, .2'.3,3',S. .2'.3.3'.5, ,2'. 3,3' 6, ' ,2'.3,4,4- ( 1 ,2'. 3,4. 4'. .2'. 3. 4.4' , 1 2.2". 3,4.4'. 2.2' .3,4, 5, 5 2,2'. 3,4, 5,6 2.2',3,4.5,6 2.2'. 3. 4,5'. 2.2'. 3,4, 6. 6 2,2' ,3,4'. 5. 2.2' ,3, 4', S. 2.2'.3,4'.5, 2.2', 3,4'. 5' 6 2.2', 3, 4' .5, 2.2-.3,5.5'. 2.2', 3.5.6.6' 2.2' ,4.4'. 5.5' 2.21, 4,4-. 5. S2.2',4.4'.M' 2,3,3'. 4, 4'. 5 2.3. 3' .4,4' .5' 2.3.3', 4, 4'. 6 2.3.3'. 4,5, 5' 2,3,3'. 4,i,« HtueMorobiphtnyl* 161 1X9 IK 163 164 165 166 167 168 169 tallieMttr, 181 183 184 185 186 187 188 189 190 191 192 193 2.3.3'. 4'. 5.6 2,3, 3', 4'. 5 ' , 6 2;3;3'.S.S',6 2.3.4. 4- .5,6 2,3' .4.4'. 5. 5' 2.3'. 4, 4', £'.6 3,3'.4.4'.5,5 1 2,2',3,3',4,4',5 2.2',3,3'.4,4',6 2.2', 3, 3 ' , 4, 5, 5' 2, 2'. 3, 3', 4,5,6 2. 2'. 3, 3', 4, 5,6' 2.2' .3,3' .4. 5'. 6 2,2'. 3.3', 4.6. 6' 2. 2 1 . 3,3' ,4' ,5,6 2. 2', 3,3'. 5, 5'. 6 2,2',3,3',5,6,6' 2.2-.3.4,4'.5.5' 2. 2', 3, 4, 4', 5. 6 2. 2'. 3, 4, 4', 5, 6' 2,2'. 3. 4, 4'. 5'. 6 2.2',3.4,4',j,6 1 2.2' .3. 4,5, 5' ,6 2,2' .3,4,5, 6, 6' 2,2',3,4 1 ,5.5 1 .6 2,2'. 3,4', 5. 6, 6' 2. 3, 3', 4, 4', 5,5' 2,3.3', 4. 4 ' , 5, 6 2. 3. 3' .4. 4' .5'. 6 2, 3, 3'. 4, 5,5' 6 2.3, 3'. 4' .5,5' ,6 Octiehl orobi phtny 1 s 194 195 196 197 198 199 200 201 202 203 204 205 2,2'. 3. 3', 4. 4 ' , 5,5' 2,2'.3,3'.4,4'.5,6 2,2'.3,3'.4.4',5,5' 2, 2', 3. 3'. 4, 4 ' , 6, 6' 2.2'.3.3',4,5.5'.S 2,2'. 3, 3' .4. 5,6, 6'1 2.2'.3.3 1 ,4.S'.6.6 2.2'. 3, 3'. 4. 5, 5 ' , 6' 2.2' .3. 3' ,5, 5'. 6.6' 2,2', 3, 4. 4'. 5, 5 ' . 6 2.2' .3,4,4' .5, 6, 6' 2,3.3' ,4.4'.5.5'.6 NomehlarobfohtnyM 206 207 208 2,2-.3,3'.4.4',5,5 < .S 2.2'.3.3'.4.4'.5,6,6' 2,2',3.3 I ,4,5,5'.6,6' 0«eicMorot>(pn«ityl X. ind Z«11. H., Frwnlui I. Anil. ChM., 302. 20-31 (1980). D-3 2.3. 3', 4, 5', 6 H»otieH1orattfphtnyl » 209 •Adapted 1rm structure 2.2'.3,3'4,4',$,5',6.6' �2.0 Summary 2.1 The wastewater must be sampled such that the specimen collected for analysis is representative of the whole. Statistically designed selection of the sampling position (valve, port, outfall, etc.) or time should be employed. The sample must be preserved to prevent PCB loss prior to analysis. Storage at 4°C with optional preservation at low pH is recommended. 2.2 The sample is mechanically homogenized and subsampled if necessary. The sample is then spiked with four 13C PCB surrogates and the surrogates incorporated by further mechanical agitation. 2.3 The surrogate-spiked sample is extracted and cleaned up at the discretion of the analyst. Possible extraction techniques include liquid-liquid partition and sorption onto resin columns followed by solvent elution. Cleanup techniques may include liquid-liquid partition, sulfuric acid cleanup, saponification, adsorption chromatography, gel permeation chromatography or a combination of cleanup techniques. The sample is diluted or concentrated to a final known volume for instrumental determination. The EPA Method 6081 and 6252 extraction and cleanup procedures may be used. 2.4 The PCB content of the sample extract is determined by capillary (preferred) or packed column gas chromatography/electron impact mass spectrometry (CGC/EIMS or PGC/EIMS) operated in the selected ion monitoring (SIM), full scan, or limited mass scan (IMS) mode. 2.5 PCBs are identified by comparison of their retention time and mass spectral intensity ratios to those in calibration standards. 2.6 PCBs are quantitated against the response factors for a mixture of 11 PCB congeners, using the response of the 13C surrogate to compensate for losses in workup and instrument variability. 2.7 The PCBs identified by the SIM technique may be confirmed by full scan CGC/EIMS, retention on alternate GC columns, other mass spectrometric techniques, infrared spectrometry, or other techniques, provided that the sensitivity and selectivity of the technique is demonstrated to be comparable or superior to GC/EIMS. 2.8 The analysis time is dependent on the extent of workup employed. The time required for instrumental analysis, excluding data reduction and reporting, is about 30 to 45 min. 2.9 Appropriate quality control (QC) procedures are included to assess the performance of the analyst and estimate the quality of the results. These QC procedures include the demonstration of laboratory capability: periodic analyst certification, the use of control charts, and the analysis of blanks, replicates, and standard addition samples. A quality assurance (QA) plan must be developed for each laboratory. D-4 �2.10 While several options are available throughout this method, the recommended procedure to be followed is: 2.10.1 The sample is collected according to a scheme which permits extrapolation of the sample data to the body or containers of water being sampled. 2.10.2 The sample is preserved at low pH and at 4°C to prevent any loss of PCBs or changes in matrix which may adversely affect recovery. 2.10.3 The sample is-mechanically homogenized and subsampled if necessary. 2.10.4 The sample is spiked with four 13C-PCB surrogates (4-chlorobiphenyl; 3,3',4,4'-tetrachlorobiphenyl; 2,2',3,3',5,5',6,6'-octachlorobiphenyl; and decachlorobiphenyl). 2.10.5 The sample is extracted. 2.10.6 The extract is cleaned up and concentrated to an appropriate volume. 2.10.7 An aliquot of the extract is analyzed by CGC/EIMS operated in the SIM mode. On-column injections onto a 15-m DB-5 capillary column, programmed (for toluene solutions) from 110° to 325°C at 10°/min after a 2 min hold is used. Helium at 45-cm/sec linear velocity is used as the carrier gas. 2.10.8 PCBs are identified by retention time and mass spectral intensities. 2.10.9 PCBs are quantitated against the response factors for a mixture of 11 PCB congeners. 2.10.10 The total PCBs are obtained by summing the amounts for each homolog found and the concentration is reported as micrograms per liter. 3.0 Interferences 3.1 Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware, leading to discrete artifacts and/or elevated baselines in the total ion current profiles. All of these materials must be routinely demonstrated to be free from interferences by the analysis of laboratory reagent blanks as described in Section 14.4. D-5 �3.1.1 Glassware must be scrupulously cleaned. All glassware is cleaned as soon as possible after use by rinsing with the last solvent used. This should be followed by detergent washing with hot water and rinses with tap water and reagent water. The glassware should then be drained dry and heated in a muffle furnace at 400°C for 15 to 30 min. Some thermally stable materials, such as PCBs, may not be eliminated by this treatment. Solvent rinses with acetone and pesticide quality hexane may be substituted for the muffle furnace heating. Volumetric ware should not be heated in a muffle furnace. After it is dry and cool, glassware should be sealed and stored in a clean environment to prevent any accumulation of dust or other contaminants. It is stored inverted or capped with aluminum foil. 3.1.2 The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required. All solvent lots must be checked for purity prior to use. 3.2 Matrix interferences may be caused by contaminants that are coextracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the sources of samples. 4.1 The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. 4.2 Polychlorinated biphenyls have been tentatively classified as known or suspected human or mammalian carcinogens. Primary standards of these toxic compounds should be prepared in a hood. Personnel must wear protective equipment, including gloves and safety glasses. 4.0 Congeners highly substituted at the meta and para positions and unsubstituted at the ortho positions are reported to be the most toxic. Extreme caution should be taken when handling these compounds neat or in concentration solution. The class includes 3,3',4,4'-tetrachlorobiphenyl (both natural abundance and isotopically labeled). D-6 �4.3 4.4 5.0 Diethyl ether should be monitored regularly to determine the peroxide content. Under no circumstances should diethyl ether be used with a peroxide content in excess of 50 ppm as an explosion could result. Peroxide test strips manufactured by EM Laboratories (available from Scientific Products Company, Cat. No. P1126-8 and other suppliers) are recommended for this test. Procedures for removal of peroxides from diethyl ether are included in the instructions supplied with the peroxide test kit. Waste disposal must be in accordance with RCRA and applicable state rules. Apparatus and Materials 5.1 Sampling containers - Amber glass bottles, 1-liter or other appropriate volume, fitted with screw caps lined with Teflon. Cleaned foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, samples should be protected from light using foil or a light-tight outer container. The bottle must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination. 5.2 Glassware - All specifications are suggestions only. Catalog numbers are included for illustration only. 5.2.1 Volumetric flasks - Assorted sizes. 5.2.2 Pipets - Assorted sizes, Mohr delivery. 5.2.3 Micro syringes - 10.0 pi for packed column GC analysis, 1.0 |Jl for on-column CGC analysis. 5.2.4 Chromatographic column - Chromaflex, 400 mm long x 19 mm ID (Kontes K-420540-9011 or equivalent). 5.2.5 Gel permeation chromatograph - GPC Autoprep 1002 (Analytical Bio Chemistry Laboratories, Inc.) or equivalent. 5.2.6 Kuderna-Danish Evaporative Concentrator Apparatus 5.2.6.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked. Ground glass stopper size (S19/22 joint) is used to prevent evaporation of solvent. 5.2.6.2 Evaporative flask - 500 ml (Kontes K-57001-0500 or equivalent). Attach to concentrator tube with springs (Kontes K-662750-0012 or equivalent). 5.2.6.3 Snyder column - Three ball macro (Kontes K5030000121 or equivalent). D-7 �5.3 Balance - Analytical, capable of accurately weighing 0.0001 g. 5.4 Gas chromatography/mass spectrometer system. 5.4.1 Gas chromatograph - An analytical system complete with a temperature programmable gas chromatograph and all required accessories including syringes, analytical columns, and gases. The injection port must be designed for oncolumn injection when using capillary columns or packed columns. Other capillary injection techniques (split, splitless, "Grob," etc.) may be used provided the performance specifications stated in Section 7.1 are met. 5.4.2 Capillary GC column - A 12-20 m long x 0.25 mm ID fused silica column with a 0.25 |Jm thick DB-5 bonded silicone liquid phase (J&W Scientific) is recommended. Alternate liquid phases may include OV-101, SP-2100, Apiezon L, Dexsil 300, or other liquid phases which meet the performance specifications stated in Section 7.1. 5.4.3 Packed GC column - A 180 cm x 0.2 cm ID glass column packed with 3% SP-2250 on 100/120 mesh Supelcoport or equivalent is recommended. Other liquid phases which meet the performance specifications stated in Section 7.1 may be substituted. 5.4.4 Mass spectrometer - Must be capable of scanning from 150 to 550 Daltons every 1.5 sec or less, collecting at least five spectra per chromatographic peak, utilizing a 70-eV (nominal) electron energy in the electron impact ionization mode and producing a mass spectrum which meets all the criteria in Table 2 when 50 ng of decafluorotriphenyl phosphine [DFTPP, bis(perfluorophenyl)phenyl phosphine] is injected through the GC inlet. Any GC-to-MS interface that gives acceptable calibration points at 10 ng per injection for each PCB isomer in the calibration standard and achieves all acceptable performance criteria (Section 10) may be used. Direct coupling of the fused silica column to the MS is recommended. Alternatively, GC-toMS interfaces constructed of all glass or glass-lined materials are recommended. Glass can be deactivated by silanizing with dichlorodimethylsilane. 5.4.5 A computer system that allows the continuous acquisition and storage on machine-readable media of all mass spectra obtained throughout the duration of the chromatographic program must be interfaced to the mass spectrometer. The data system must have the capability of integrating the abundances of the selected ions between specified limits and relating integrated abundances to concentrations using the calibration procedures described in this method. The computer must have software that allows D-8 �TABLE 2. DFTPP KEY IONS AND ION ABUNDANCE CRITERIA Mass Ion abundance criteria 197 198 199 Less than 1% of mass 198 100% relative abundance 5-9% of mass 198 275 10-30% of mass 198 365 Greater than 1% of mass 198 441 442 443 Present, but less than mass 443 Greater than 40% of mass 198 17-23% of mass 442 D-9 �searching any GC/MS data file for ions of a specific mass and plotting such ion abundances versus time or scan number to yield an extracted ion current profile (EICP). Software must also be available that allows integrating the abundance in any EICP between specified time or scan number limits. 6.0 Reagents 6.1 Solvents - All solvents must be pesticide residue analysis grade. New lots should be checked for purity by concentrating an aliquot by at least as much as is used in the procedure. 6.2 Stock standard solutions - Standards of the PCB congeners listed in Table 3 are available from Ultra Scientific, Hope, Rhode Island; or Analabs, North Haven, Connecticut. 6.3 Calibration standard stock solutions - Primary dilutions of each of the individual PCBs listed in Table 3 are prepared by weighing approximately 1-10 mg of material within 1% precision. The PCB is then dissolved and diluted to 1.0 ml with hexane. Calculate the concentration in mg/ml. The primary dilutions are stored at 4°C in screw-cap vials with Teflon cap liners. The meniscus is marked on the vial wall to monitor solvent evaporation. Primary dilutions are stable indefinitely if the seals are maintained. The validity of primary and secondary dilutions must be monitored on a quarterly basis by analyzing four quality control check samples (see Section 14.2). 6.4 Working calibration standards - Working calibration standards are prepared that are similar in PCB composition and concentration to the samples by mixing and diluting the individual standard stock solutions. Example calibration solutions are shown in Table 3. The mixture is diluted to volume with pesticide residue analysis quality hexane. The concentration is calculated in ng/ml as the individual PCBs. Dilutions are stored at 4°C in narrow-mouth, screw-cap vials with Teflon cap liners. The meniscus is marked on the vial wall to monitor solvent evaporation. These secondary dilutions can be stored indefinitely if the seals are maintained. These solutions are designated "CSxxx," where the xxx is used to encode the nominal concentration in ng/ml. 6.5 Alternatively, certified stock solutions similar to those listed in Table 3 may be available from a supplier, in lieu of the procedures described in Section 6.4. 6.6 DFTPP standard - A 50-ng/pl solution of DFTPP is prepared in acetone or another appropriate solvent. 6.7 Surrogate standard stock solution - The four 13C-labeled PCBs listed in Table 4 may be available from a supplier as a certified solution. This solution may be used as received or diluted further. These solutions are designated "SSxxx," where the xxx is used to encode the nominal concentration in ng/ml. D-10 �TABLE 3. CONCENTRATIONS OF CONGENERS IN PCS CALIBRATION STANDARDS (ng/ml)a Homolog Congener no. CS1000 CS100 CS050 CS010 1 1 1,040 104 52 10 1 3 1,000 100 50 10 2 7 1,040 104 52 10 3 30 1,040 104 52 10 4 50 1,520 152 76 15 5 97 1,740 174 87 17 6 143 1,920 192 96 19 7 183 2,600 260 130 26 8 202 4,640 464 232 46 9 207 5,060 506 253 51 10 209 4,240 424 212 42 4 255 255 255 255 1 211 (RS) 104 104 104 104 4 212 (RS) 257 257 257 257 8 213 (RS) 407 407 407 407 10 a 210 (IS) 214 (RS) 502 502 502 502 Concentrations given as examples only. D-ll �TABLE 4. COMPOSITION OF SURROGATE SPIKING SOLUTION (SS100) CONTAINING 13C-LABELED PCBs3 Congener no. Compound Concentration (Hg/ml) 211 104 212 (13C12)3,3' ,4,4'-tetrachlorobiphenyl 257 213 (13C12)2,2' ,3,3' ,5,5' ,6,6'-octachlorobiphenyl 395 214 a (I1 ,2' ,3' ,4' ,5' ,6'-13C6)4-chlorobiphenyl (13C12)decachlorobiphenyl 502 Concentrations given as examples only. D-12 �6.8 6.9 Solution stability - The calibration standard, surrogate and DFTPP solutions should be checked frequently for stability. These solutions should be replaced after 6 months, or sooner if comparison with quality control check samples indicates compound degradation or concentration change. 6.10 7 .0 Internal standard solution - A solution of de-3,3" ,4,4" -tetrachlorobiphenyl is prepared at a nominal concentration of 1-10 mg/ml in hexane. The solution is further diluted to give a working standard. Quality control check samples will be supplied by the Agency. Calibration 7.1 The gas chroma tograph must meet the minimum operating parameters shown in Tables 5 and 6, daily. If all of the criteria are not met, the analyst must adjust conditions and repeat the test until all criteria are met. 7.2 The mass spectrometer must meet the minimum operating parameters shown in Tables 2, 7, and 8, daily. If all criteria are not met, the analyst must retune the spectrometer and repeat the test until all conditions are met. The PCB response factor (RF ) must be determined using Equat 7-1 for the analyte homologi. where is p RF = response factor of a given PCB isomer A = area of the characteristic ion for the PCB congener P peak M = mass of PCB congener injected (nanograms) A. = area of the characteristic ion for the internal standard peak M. = mass of internal standard injected (nanograms) IS Using the same conditions as for RF , the surrogate response factors (RF ) must be determined usSng Equation 7-2. A x M. IS S where A S = area of the characteristic ion for the surrogate peak MS = mass of surrogate injected (nanograms) Other items are the same as defined in Equation 7-1. D-13 �TABLE 5. OPERATING PARAMETERS FOR CAPILLARY COLUMN GAS CHROMATOGRAPHIC SYSTEM Recommended Parameter Tolerance Gas chromatograph Finnigan 9610 Other Column 15 m x 0.255 mm ID Fused silica Other Liquid phase DB-5 Other nonpolar or semipolar Liquid phase thickness 0.25 urn < 1 |Jm Carrier gas Helium Hydrogen Carrier gas velocity 45 cm/sec Optimum performance Injector On-column (J&W) (J&W) Injector temperature Optimum performance Injection volume Other c 1.0 plc Optimum performance Other d Initial column temperature 70°C (2 min) Column temperature program 70°-325°C at 10°C/min£ Separator None Glass jet or other Transfer line temperature 280°C Optimum** Tailing factor 0.7-1.5 0.4-3 Peak width 7-10 sec < 15 sec Other Other a Substitutions permitted with any common apparatus or technique provided performance criteria are met. b Measured by injection of air or methane at 270°C oven temperature. c For on-column injection, manufacturer's instructions should be followed regarding injection technique. d With on-column injection, initial temperature equals boiling point of the solvent; in this instance, hexane. e C^Clio elutes at 270°C. Programming above this temperature ensures a clean column and lower background on subsequent runs. f Fused silica columns may be routed directly into the ion source to prevent separator discrimination and losses. g High enough to elute all PCBs, but not high enough to degrade the column if routed through the transfer line. h Tailing factor is width of front half of peak at 10% height divided by width of back half of peak at 10% height for single PCB congeners in solution CSxxx. i Peak width at 10% height for a single PCB congener is CSxxx. D-14 �TABLE 6. OPERATING PARAMETERS FOR PACKED COLUMN GAS CHROMATOGRAPHY SYSTEM Tolerances Recommended Parameter Gas chromatograph Finnigan 9610 Other3 Column 180 cm x 0.2 cm ID glass Other Column packing 3% SP-2250 on 100/ 120 mesh Supelcoport Other nonpolar or semipolar Carrier gas Helium Hydrogen Carrier gas flow rate 30 ml/min Optimum performance Injector On-column Injector temperature 250°C Optimum Injection volume 1.0 pi g 5 pi Initial column temperature 150°C, 4 min Other Column temperature program 150°C-260° at 8°/min Other Separator Glass jet Other Transfer line temperature 280°C Optimum3 Tailing factor 0.7-1.5 0.4-3 Peak widthd 10-20 sec < 30 sec p a Substitutions permitted if performance criteria are met. b High enough to elute all PCBs. c Tailing factor is width of front half of peak at 10% height divided by width of back half of peak at 10% height for single PCS congeners in solution CSxxx. d Peak width at 10% height for a single PCB congener in CSxxx. D-15 �TABLE 7. OPERATING PARAMETERS FOR QUADRUPOLE MASS SPECTROMETER SYSTEM Parameter Recommended Tolerance Mass spectrometer Finnigan 4023 Other3 Data system Incos 2400 Other Scan range 95-550 Other Scan time 1 sec Otherb Resolution Unit Optimum performance Ion source temperature 280°C 200°-300°C Electron energy 70 eV Optimum performance Trap current 0.2 mA Optimum performance Multiplier voltage -1,600 V Optimum performance Preamplifier sensitivity 10"6 A/V Set for desired working range a Substitutions permitted if performance criteria are met. b Greater than five data points over a GC peak is a minimum. c Filaments should be shut off during solvent elution to improve instrument stability and prolong filament life, especially if no separator is used. D-16 �TABLE 8. OPERATING PARAMETERS FOR MAGNETIC SECTOR MASS SPECTROMETER SYSTEM Parameter Tolerance Recommended Mass spectrometer Finnigan MAT 311A Other3 Data system Incos 2400 Other Scan range 98-550 Other Scan mode Exponential Other Cycle time 1.2 sec Otherb Resolution 1,000 > 500 Ion source temperature 280°C 250°-300°C Electron energy 70 eV 70 eV Emission current 1-2 mA Optimum Filament current Optimum Optimum Multiplier -1,600 V Optimum a Substitutions permitted if performance criteria are met. b Greater than five data points over a GC peak is a minimum. c Filaments should be shut off 'during solvent elution to improve instrument stability and prolong filament life, especially if no separator is used. D-17 �If specific congeners are known to be present and if standards are available, selected RF values may be employed. For general samples, solutions CSxxx and SSxxx or a mixture (Tables 3 and 4), with a similar level of internal standard (dg-3,3',4,4*-tetrachlorobiphenyl) added, may be used as the response factor solution. The PCB-surrogate pairs to be used in the RF calculation are listed in Table 9. Generally, only the primary ions of both the analyte and surrogate are used to determine the RF values. If alternate ions are to be used in the quantitation, the RF must be determined using that characteristic ion. The RF value must be determined in a manner to assure ±20% accuracy and precision. For instruments with good day-to-day precision, a running mean (RF) based on seven values determined once each day may be appropriate. Other options include, but are not limited to, triplicate determinations of a single concentration spaced throughout a day or determination of the RF at three different levels to establish a working curve. If replicate RF values differ by greater than ±10% RSD, the system performance should be monitored closely. If the RSD is greater than ±20%, the data set must be considered invalid and the RF redetermined before further analyses are done. 7.4 7.5 8.0 If the GC/EIMS system has not been demonstrated to yield a linear response or if the analyte concentrations are more than two orders of magnitude different from those in the RF solution, a calibration curve must be prepared. If the analyte and RF solution concentrations differ by more than one order of magnitude, a calibration curve should be prepared. A calibration curve should be established with triplicate determinations at three or more concentrations bracketing the analyte levels. The relative retention time (RRT) windows for the 10 homologs and surrogates must be determined. If all congeners are not available, a mixture of available congeners or an Aroclor mixture (e.g., 1016/1254/1260) may be used to estimate the windows. The windows must be set wider than observed if all isomers are not determined. Typical RRT windows for one column are listed in Table 10. The windows may differ substantially if other GC parameters are used. Sample Collection, Handling, and Preservation 8.1 Amber glass sample containers should have Teflon-lined screw caps. With noncorrosive samples, methylene chloride-washed aluminum foil liners may be substituted. The volume is determined by the amount of sample to be collected but will usually be 1 liter or 1 qt. The sample size is dependent on the anticipated PCB levels and difficulty of the subsequent extraction/cleanup steps. D-18 �TABLE 9. Analyte Congener no . 1 2,3 PAIRINGS OF ANALYTE, CALIBRATION, AND SURROGATE COMPOUNDS Compound 2-C12H9Cl 3- and 4-C12H9Cl 1 3 /•* TT r>~t Li2ngLl2 -f ' i £. on 1O~ jy r* TJ r*i L. 12^7 *•*-!- 3 An_fti HU O 1 p l2^6*->-'-4 u n L. 82-127 128-169 C12H5C15 C12H4C16 1"7A1OO 1/0-19J r* ur*! Li2h.3Ll7 194-205 206-208 209 C12H2C18 C12HC19 C12C110 Compound Congener no. 2 4 2,4 2,4, 6 2,2' ,4 ,6 2,2' ,3 ',4,5 2,2' ,3 ,4,5 ,6' 2,2' ,3 ',4,4', 5', 6 2,2' ,3 ,3',5, 5', 6, 6' J 2,2' ,3 ,3'» 4, 4', 5, 6, 6' /"* f L12Lli 0 211 211 211 212 212 212 212 213 213 213 214 Congener no. 4— 1 r 1j O 30 50 97 143 183 202 207 209 v£> a Surrogate Calibration standard Ballschmiter numbering system, see Table 1. Compound 13 C6-4 C6-4 13 C6-4 13 Ci2-3,3' ,4 ,4' 13 Ci2-3,3' ,4 ,4' 13 C12-3,3' ,4 ,4' 13 Ci2-3,3' ,4 ,4' 13 ,6,6' C12-2,2' ,3 ,3', 5, 5' 13 C12-2,2' ,3 ,3' , J V J 3 5 , ,6,6' 13 ,6,6' C12-2,2' ,3 ,3', 5, 5' 13 13 c12ci10 �TABLE 10. PCB homolog RELATIVE RETENTION TIME (RRT) RANGES OF PCB HOMOLOGS VERSUS d6-3,3',4.4'-TETRACHLOROBIPHENYL No. of isomers measured Observed range of RRTs3 Calibration solution Congener Observed RRT3 no. Projected range of RRTs 3 0.40-0.50 1 3 0.43 0.50 0.35-0.55 10 0.52-0.69 7 0.58 0.35-0.80 9 0.62-0.79 30 0.65 0.35-1.10 Tetrachloro 16 0.72-1.01 50 0.75 0.55-1.05 Pentachloro 12 0.82-1.08 97 0.98 0.80-1.10 Hexachloro 13 0.93-1.20 143 1.05 0.90-1.25 Heptachloro 4 1.09-1.30 183 1.15 1.05-1.35 Octachloro 6 1.19-1.36 202 1.19 1.10-1.50 Nonachloro 3 1.31-1.42 207 1.33 1.25-1.50 Decachloro 1 1.44-1.45 209 1.44 1.35-1.50 Monochloro Dichloro Trichloro a The RRTs of the 77 congeners and a mixture of Aroclor 1016/1254/1260 were measured versus 3,3',4,4'-tetrachlorobiphenyl-d6 (internal standard) using a 15-m J&W DB-5 fused silica column with a temperature program of 110°C for 2 min, then 10°C/min to 325°C, helium carrier at 45 cm/sec, and an oncolumn injector. A Finnigan 4023 Incos quadrupole mass spectrometer operating with a scan range of 95-550 daltons was used to detect each PCB congener. b The projected relative retention windows account for overlap of eluting homologs and take into consideration differences in operating systems and lack of all possible 209 PCB congeners. D-20 �8.2 Sample bottle preparation 8.2.1 8.2.2 Sample bottles are heated to 400°C for 15 to 20 min or rinsed with pesticide grade acetone or hexane and allowed to air dry. 8.2.3 8.3 All sample bottles and caps should be washed in detergent solution, rinsed with tap water and then with distilled water. The bottles and caps are allowed to drain dry in a contaminant-free area. Then the caps are rinsed with pesticide grade hexane and allow to air dry. The clean bottles are stored inverted or sealed until use. Sample collection 8.3.1 8.3.2 If possible, mix the source thoroughly before collecting the sample. If mixing is impractical, the sample should be collected from a representative area of the source. If the liquid is flowing through an enclosed system, sampling through a valve should be randomly timed. 8.3.3 8.4 The primary consideration in sample collection is that the sample collected be representative of the whole. Therefore, sampling plans or protocols for each individual producer's situation will have to be developed. The recommendations presented here describe general situations. The number of replicates and sampling frequency also must be planned prior to sampling. Fill the bottle with water, add preservative (Section 8.4), cap tightly, and shake well. To prevent the caps from working loose during storage tape the caps on with a water-insoluble tape. Sample preservation - Samples should be stored at 4°C. Since there is a possibility of microbial degradation, addition of H2S04 during collection to a pH < 2 is recommended. A test strip is used to monitor the pH. Storage times in excess of 4 weeks are not recommended. If residual chlorine is present in the sample, it should be quenched with sodium thiosulfate. EPA Methods 330.4 and 330.5 may be used to measure the residual chlorine.3 Field test kits are available for this purpose. 9.0 Sample Preparation 9.1 Sample homogenization and subsampling - The sample is homogenized by shaking, blending, or other appropriate mechanical technique, if necessary. If the density of the sample is not between 0.9 D-21 �and 1.1, the density should be determined and reported. Consideration should be given to treating the sample as a product waste (see separate protocol). Note: 9.2 Surrogate addition - An appropriate volume of surrogate solution SSxxx is pipetted into the sample. The final concentration of the surrogates must be in the working range of the calibration and well above the matrix background. Note: 9.3 The precision of the mass determination at this step will be reflected in the overall method precision. Therefore, an analytical balance must be used to assure that the weight is accurate to ±1% or better. The volume measurement of cal to the overall method exercise caution that the better. Where necessary, recommended. the spiking solution is critiprecision. The analyst must volume is known to ±1% or calibration of the pipet is Sample preparation (extraction/cleanup) - After addition of the surrogates, the sample is further treated at the discretion of the analyst, provided that the GC/EIMS response of the four surrogates meets the criteria listed in Section 7.0. The literature pertaining to these techniques has been reviewed.4 Several possible techniques are presented below for guidance only. The applicability of any of these techniques to a specific sample matrix must be determined by the precision and accuracy of the *3C PCB surrogate recoveries, as discussed in Section 14.2. 9.3.1 Extraction - The entire sample must be transferred to the extraction vessel with PCB-free water washing, if necessary, to transfer all solids. The container is then rinsed with the extraction solvent to recovery any PCBs adhering to' the container wall. The solvent rinses are combined with the extracts from below. Measure the sample volume to the nearest 0.5%. 9.3.1.1 Liquid-liquid extraction - The solvent, number of extractions, solvent-to-sample ratio, and other parameters are chosen at the analyst's discretion. A suggested extraction from water is presented in EPA Methods 60S1 and 625.2 9.3.1.2 Sorbent column extraction - PCBs may be isolated from water onto sorbent columns, although these techniques are not as widely used or thoroughly validated as liquid-liquid extraction. The selection of sorbent (XAD, Porapak, carbonpolyurethane foam, etc.) will depend on the nature of the matrix. The available methods have been reviewed.4 D-22 �9.3.2 Cleanup - Several tested cleanup techniques are described below. All but the base cleanup (9.3.2.8) were previously validated for PCBs in transformer fluids.5 Depending upon the complexity of the sample, one or more of the techniques may be required to fractionate the PCBs from interferences. For most cleanups a concentrated (1-5 ml) extract should be used. 9.3.2.1 Acid cleanup 9.3.2.1.1 Place 5 ml of concentrated sulfuric acid into a 40-ml narrow-mouth screwcap bottle. Add the sample extract. Seal the bottle with a Teflon-lined screw cap and shake for 1 min. 9.3.2.1.2 Allow the phases to separate, transfer the sample (upper phase) with three rinses of 1-2 ml solvent to a clean container and concentrate to an appropriate volume. 9.3.2.1.3 Analyze as described in Section 10.0. 9.3.2.1.4 If the sample is highly contaminated, a second or third acid cleanup may be employed. 9.3.2.2 Florisil column cleanup 9.3.2.2.1 Variations among batches of Florisil (PR grade or equivalent) may affect the elution volume of the various PCBs. For this reason, the volume of solvent required to completely elute all of the PCBs must be verified by the analyst. The weight of Florisil can then be adjusted accordingly. 9.3.2.2.2 Place a 20-g charge of Florisil, activated overnight at 130°C, into a Chromaflex column. Settle the Florisil by tapping the column. Add about 1 cm of anhydrous sodium sulfate to the top of the Florisil. Pre-elute the column with 70-80 ml of hexane. Just before the exposure of the sodium sulfate layer to air, stop the flow. Discard the eluate. D-23 �9.3.2.2.3 Add the sample extract to the column. 9.3.2.2.4 Carefully wash down the inner wall of the column with 5 ml of the hexane. 9.3.2.2.5 Add 220 ml of hexane to the column. 9.3.2.2.6 Discard the first 25 ml. 9.3.2.2.7 Collect 200 ml Kuderna-Danish PCBs should be Concentrate to of hexane eluate in a flask. All of the in this fraction. an appropriate volume. 9.3.2.2.8 Analyze the sample as described in Section 10.0. 9.3.2.3 Alumina column cleanup 9.3.2.3.1 Adjust the activity of the alumina (Fisher A540 or equivalent) by heating to 200°C for 2 to 4 hr. When cool, add 3% water (wt:wt) and mix until uniform. Store in a tightly sealed bottle. Allow the deactivated alumina to equilibrate at least 1/2 hr before use. Reactivate weekly. 9.3.2.3.2 Variations between batches of alumina may affect the elution volume of the various PCBs. For this reason, the volume of solvent required to completely elute all of the PCBs must be verified by the analyst. The weight of alumina can then be adjusted accordingly. 9.3.2.3.3 Place a 50-g charge of alumina into a Chromaflex column. Settle the alumina by tapping. Add about 1 cm of anhydrous sodium sulfate. Pre-elute the column with 70-80 ml of hexane. Just before exposure of the sodium sulfate layer to air, stop the flow. Discard the eluate. 9.3.2.3.4 Add the sample extract to the column. 9.3.2.3.5 D-24 Carefully wash down the inner wall of the column with 5 ml volume of hexane. �9.3.2.3.6 Add 295 ml of hexane to the column. 9.3.2.3.7 Discard the first 50 ml. 9.3.2.3.8 Collect 250 ml Kuderna-Danish PCBs should be Concentrate to of the hexane in a flask. All of the in this fraction. an appropriate volume. 9.3.2.3.9 Analyze the sample as described in Section 10.0. 9.3.2.4 Silica gel column cleanup 9.3.2.4.1 Activate silica gel (Davison grade 950 or equivalent) at 135°C overnight. 9.3.2.4.2 Variations between batches of silica gel may affect the elution volume of the various PCBs. For this reason, the volume of solvent required to completely elute all of the PCBs must be verified by the analyst. The weight of silica gel can then be adjusted accordingly. 9.3.2.4.3 Place a 25-g charge of activated silica gel into a Chromaflex column. Settle the silica gel by tapping the column. Add about 1 cm of anhydrous sodium sulfate to the top of the silica gel. 9.3.2.4.4 Pre-elute the column with 70-80 ml of hexane. Discard the eluate. Just before exposing the sodium sulfate layer to air, stop the flow. 9.3.2.4.5 Add the sample extract to the column. 9.3.2.4.6 Wash down the inner wall of the column with 5 ml of hexane. 9.3.2.4.7 Elute the PCBs with 195 ml of 10% diethyl ether in hexane (v:v). 9.3.2.4.8 Collect 200 ml Kuderna-Danish PCBs should be Concentrate to D-25 of the eluate in a flask. All of the in this fraction. an appropriate volume. �9.3.2.4.9 9.3.2.5 Analyze the sample according to Section 10.0. Gel permeation cleanup 9.3.2.5.1 Set up and calibrate the gel permeation chromatograph with an SX-3 column according to the Autoprep instruction manual. Use 15% methylene chloride in cyclohexane (v:v) as the mobile phase. 9.3.2.5.2 Inject 5.0 ml of the sample extract into the instrument. Collect the fraction containing the PCBs (see Autoprep operator's manual) in a Kuderna-Danish flask equipped with a 10-ml ampul. 9.3.2.5.3 Concentrate the PCB fraction to an appropriate volume. 9.3.2.5.4 Analyze as described in Section 10.0. 9.3.2.6 Acetonitrile partition 9.3.2.6.1 Place the sample extract into a 125-ml separatory funnel with enough hexane to bring the final volume to 15 ml. Extract the sample four times by shaking vigorously for 1 min with 30-ml portions of hexane-saturated acetonitrile. 9.3.2.6.2 Combine and transfer the acetonitrile phases to a 1-liter separatory funnel and add 650 ml of distilled water and 40 ml of saturated sodium chloride solution. Mix thoroughly for about 30 sec. Extract with two 100-ml portions of hexane by vigorously shaking about 15 sec. 9.3.2.6.3 Combine the hexane extracts in a 1-liter separatory funnel and wash with two 100-ml portions of distilled water. Discard the water layer and pour the hexane layer through a 8-10 cm anhydrous sodium sulfate column into a 500-ml Kuderna-Danish flask equipped with a 10-ml ampul. Rinse the separatory funnel and column with three 10-ml portions of hexane. D-26 �9.3.2.6.4 Concentrate the extracts to an appropriate volume. 9.3.2.6.5 Analyze as described in Section 10.0. 9.3.2.7 Florisil slurry cleanup 9.3.2.7.1 Place the sample extract into a 20-ml narrow-mouth screw-cap container. Add 0.25 g of Florisil (PR grade or equivalent). Seal with a Teflon-lined screw cap and shake for 1 min. 9.3.2.7.2 Allow the Florisil to settle; then decant the treated solution into a second container with rinsing. Concentrate the sample to an appropriate volume. Analyze as described in Section 10.0. 9.3.2.8 Base cleanup6 9.3.2.8.1 Quantitatively transfer the concentrated extract to a 125-ml extraction flask with the aid of several small portions of solvent. 9.3.2.8.2 Evaporate the extract just to dryness with a gentle stream of dry filtered nitrogen, and add 25 ml of 2.5% alcoholic KOH. 9.3.2.8.3 Add a boiling chip, put a water condenser in place, and allow the solution to reflux on a hot plate for 45 min. 9.8.2.8.4 After cooling, transfer the solution to a 250-ml separatory funnel with 25 ml of distilled water. 9.3.2.8.5 Rinse the extraction flask with 25 ml of hexane and add it to the separatory funnel. 9.3.2.8.6 D-27 Stopper the separatory funnel and shake vigorously for at least 1 min. Allow the layers to separate and transfer the lower aqueous phase to a second separatory funnel. �9.3.2.8.7 Extract the saponification solution with a second 25-ml portion of hexane. After the layers have separated, add the first hexane extract to the second separatory funnel and transfer the aqueous alcohol layer to the original separatory funnel. 9.3.2.8.8 Repeat the extraction with a third 25-ml portion of hexane. Discard the saponification solution, and combine the hexane extracts. 9.3.2.8.9 10.0 Concentrate the hexane layer to an appropriate volume and analyze according to Section 10.0. Gas Chrotnatographic/Electron Impact Mass Spectrometric Determination 10.1 Internal standard addition - An appropriate volume of the internal standard solution is pipetted into the sample. The final concentration of the internal standard must be in the working range of the calibration and well above the matrix background. The internal standard is thoroughly incorporated by mechanical agitation. Note: The volumetric measurement of the internal standard solution is critical to the overall method precision. The analyst must exercise caution that the volume is known to be ±1% or better. Where necessary, calibration of the pipet is recommended. 10.2 Tables 2, and 5 through 8 summarize the recommended operating conditions for analysis. Figure 1 presents an example of a chromatogram. 10.3 While the highest available chromatographic resolution is not a necessary objective of this protocol, good chromatographic performance is recommended. With the high resolution of CGC, the probability that the chromatographic peaks consist of single compounds is higher than with PGC. Thus, qualitative and quantitative data reduction should be more reliable. 10.4 After performance of the system has been certified for the day and all instrument conditions set according to Tables 2, and 5 through 8, inject an aliquot of the sample onto the GC column. If the response for any ion, including surrogates and internal standards, exceeds the working range of the system, dilute the sample and reanalyze. If the responses of surrogates, analyte, or internal standard are below the working range, recheck the system performance. If necessary, concentrate the sample and reanalyze. D-28 �tH CO cd C 0) 4J fi C Ol 0 Xi X* '""•*• i—4 f~! CJ x; x: o CJ CJ O r-l C cd M r-l O C 3 o o to rH 0 01 X! p. •H p. _r\ O M 0 •H Xi o M o rH Xi CJ O o a •rt ;s CN 1 "^ o (~) CN c <r XI O 0) *• Xi P. CO t-l o tH x: o rH iH ho rH -» ^» •* •nH G/ 5 VO 01 H 1 •- ^ C 01 X! P. <r -* 0* 01 r; 4J iH a s^ 1 1 a i C 01 X! P. •H 523 575 1 JL. GS3 10:0!) X! 11 - rH >. 0 x; o rH r^) 4-1 C 01 01 H XI 1 P. -H ^3 » 0 r-l " O " O ^ •H XI rH 01 pr* | Xi ~ o 4-1 01 0 o H 1 vo r-l O rH X! CJ •rH r-l H t Cd vO CO * if) 4-1 K C •s CO -3" 01 CN 1 CNI *. ~3~ CN - CN vO -H Xi O M M 0 rH Xi o t) <T X! P. P> •H X I rH v^- <U r*, P. -H XI 0 CO r-l C C Ol ~* .d rH O £>-. C ) ^ C 01 o x ; iH Xi CJ cfl cd O H2592. CN rH 0 CO iH 1 rH 5*"\ Xi CO O Vi ^0 p. ^ P . -H •H Q) XI 4-1 O cfl M 00 O O Xi 0 O a 1 rH .C rH Xi l-l r-l O 1 •" vo ** O CO CJ 0 3 CO 0) r! vo iO CJ - P. -H XI O M O 4J CJ vO vO rH O ^~- Ol O Ol Q cfl 4j in p. 01 *n ^ _" -* -d~ vO CO CO *v •• m *. «\ co co •• • X V CN ~3~ " CN »v CN *i CN -* co n ^ I /!v/U CNJ iiao I31G •t CN 1 "^ CN 07-1 CO -" 7-W V i—i rH cO r4 613 iii" Ji r-H(V,*< O O 0) M M 4-1 O O cfl tH rH 00 me. G 0) Xi P. •H XI 0 01 P. P. •H -H - M 1 rH C 01 Xi s>* rH ^ CO T3 1 tH rH o VO 0 CO tH 1 ^W -' vO r-l 3 V 198.0- oo 0 CN" RL C'59 13:20 [I 936 llfrl 1 fl | i JLJL_ IOSO 16:10 1178 l | |m J[ .L i l'J{-9 20: CD ' 1 I1';9 23:20 SCA'l Tllh: Figure 1. Capillary gas chromatography/electron impact ionization mass spectrometry (CGC/EIMS) chromatogram or the calibration standard solution required for quantitation of PCBs by homolog. This chromatogram includes PCBs representative of each homolog, three carbon-13 labeled surrogates, and the deuterated internal standard. The concentration of all components and the CGC/EIMS parameters are presented in Tables 3, 4, 5, and 7. �10.5 11.0 Record all data on a digital storage device (magnetic disk, tape, etc.) for qualitative and quantitative data reduction as discussed below. Qualitative Identification 11.1 Selected ion monitoring (SIM) or limited mass scan (IMS) data The identification of a compound as a given PCB homolog requires that two criteria be met: 11.1.1 11.1.2 11.2 (1) The peak must elute within the retention time window set for that homolog (Section 7.5); and (2) the ratio of two ions obtained by SIM (Table 11) or by LMS (Table 12) must match the natural ratio within ±20%. The analyst must search the higher mass windows, in particular M+70, to prevent misidentification of a PCB fragment ion cluster as the parent. If one or the other of these criteria is not met, interferences may have affected the results and a reanalysis using full scan EIMS conditions is recommended. Full scan data 11.2.1 11.2.2 12.0 The unknown spectrum must match that of an authentic PCB. The intensity of the three largest ions in the molecular cluster (two largest for monochlorobiphenyls) must match the natural ratio within ±20%. Fragment clusters with proper intensity ratios must also be present. 11.2.3 11.3 The peak must elute within the retention time windows set for that homolog (as described in Section 7.5). Alternatively, a spectral search may be used to automatically reduce the data. The criteria for acceptable identification include a high index of similarity. For the Incos 2300, a fit of 750 or greater must be obtained. Disputes in interpretation - Where there is reasonable doubt as to the identity of a peak as a PCB, the analyst must either identify the peak as a PCB or proceed to a confirmational analysis (see Section 13.0). Quantitative Data Reduction 12.1 Once a chromatographic peak has been identified as a PCB, the compound is quantitated based either on the integrated abundance of the SIM data or EICP for the primary characteristic ion in Tables 11 and 12. If interferences are observed for the primary ion, D-30 �TABLE 11. CHARACTERISTIC SIM IONS FOR PCBs Ion (relative intensity) Tertiary Secondary Homolog Primary Cj^HgCl 188 (100) 190 (33) - Ci2HgCl2 222 (100) 224 (66) 226 (11) C^HrCls 256 (100) 258 (99) 260 (33) Ci2HeCl4 292 (100) 290 (76) 294 (49) C12H5C15 326 (100) 328 (66) 324 (61) c i2H4Cle 360 (100) 362 (82) 364 (36) C12H3C17 394 (100) 396 (98) 398 (54) Ci^HfcClg 430 (100) 432 (66) 428 (87) Ci2HCl9 464 (100) 466 (76) 462 (76) CiaCljo 498 (100) 500 (87) 496 (68) Source: Rote, J. W., and W. J. Morris, "Use of Isotopic Abundance Ratios in Identification of Polychlorinated Biphenyls by Mass Spectrometry," J. Assoc. Offic. Anal. Chem., 56(1), 188-199 (1973). D-31 �TABLE 12. LIMITED MASS SCANNING (LMS) RANGES FOR PCBs Compound Mass range (m/z) Ci2H9Cli 186-190 Ci2H8Cl2 220-226 Cl2H?Cl3 254-260 Ci2H6Cl3 288-294 C12H5C15 322-328 C12H4C16 356-364 C12H3C17 386-400 Ci2H2Clg 426-434 Cl2HClg 460-468 Ci2Clio 494-504 C12D6C14 294-300 13 192-196 C612CeH9Cl 13 300-306 13 C12H2C18 438-446 13 C12Clio 506-516 C12H6C14 a Adapted from Tindall, G. W., and P. E. Wininger, "Gas Chromatography-Mass Spectrometry Method for Identifying and Determining Polychlorinated Biphenyls," J. Chromatogr., 196, 109-119 (1980). D-32 �use the secondary and then tertiary ion for quantitation. If interferences in the parent cluster prevent quantitation, an ion from a fragment cluster (e.g., M-70) may be used. Whichever ion is used, the RF must be determined using that ion. The same criteria should be applied to the surrogate compounds (Table 13). 12.2 Using the appropriate analyte-internal standard pair and response factor (RF ) as determined in Section 7.3, calculate the concentration ofpeach peak using Equation 12-1. A M. V Eq 12-1 Concentration (Mg/g) = ^ ' RF ' M^ ' \T ' is p e i where A = area of the characteristic ion for the analyte PCB peak A. = area of the characteristic ion for the internal standard peak RF = response factor of a given PCB congener M. = mass of internal standard injected (micrograms) 1S M = mass of sample extracted (grams) V. = volume injected (microliters) V 12.3 = volume of sample extract (microliters) If a peak appears to contain non-PCB interferences which cannot be circumvented by a secondary or tertiary ion, either: 12.3.1 12.3.2 Perform additional chemical cleanup (Section 9) and then reanalyze the sample; or 12.3.3 12.4 Reanalyze the sample on a different column which separates the PCB and interferents; Quantitate the entire peak as PCB. Calculate the recovery of the four 13C surrogates using the appropriate surrogate-internal standard pair and response factor (RF. & as determined in Section 7.4 using Equation 12-2. ) 1 A M. Recovery ( ) = j*- - ^- • ^ • 100 % Eq. 12-2 is s s where A S = area of the characteristic ion for the surrogate peak A. = area . the characteristic ion for the internal standard of IS peak D-33 �TABLE 13. CHARACTERISTIC IONS FOR 13C-LABELED PCS SURROGATES Primary Ion (relative intensity) Secondary 13 194 (100) 196 (33) l3 304 (100) 306 (49) 302 (78) 13 C12H2C18 442 (100) 444 (65) 440 (89) 13 Ci2Clio 510 (100) 512 (87) 514 (50) Specific compound C612C6H9C1 Ci2H6Cl4 D-34 Tertiary �RF = response factor for the surrogate compound with respect to the internal standard (Equation 7-2) M. = mass of internal standard injected (nanograms) is M s = mass of surrogate, assuming 100% recovery (nanograms) 12.5 Correct the concentration of each peak using Equation 12-3. is the final reportable concentration. Corrected concentration (pg/g) = Concentration ug/g .10Q ^re>i */ 12.6 Recovery ( ) % £ This _3 ^ 12 Sum all of the peaks for each homolog, and then sum those to yield the total PCB concentration in the sample. Report all numbers in |Jg/g. The reporting form in Table 14 may be used. If an alternate reporting format (e.g., concentration per peak) is desired, a different report form may be used. The uncorrected concentrations, percent recovery, and corrected recovery are to be reported. 12.7 Round off all numbers reported to two significant figures. 13.0 Confirmation If there is reason to question the qualitative identification (Section 11.0), the analyst may choose to confirm that a peak is not a PCB. Any technique may be chosen provided that it is validated as having equivalent or superior selectivity and sensitivity to GC/EIMS. Some candidate techniques include alternate GC columns (with EIMS detection), GC/CIMS, GC/NCIMS, high resolution EIMS, and MS/MS techniques. Each laboratory must validate confirmation techniques to show equivalent or superior selectivity between PCBs and interferences and sensitivity (limit of quantitation, LOQ). If a peak is confirmed as being a non-PCB, it may be deleted from the calculation (Section 12). If a peak is confirmed as containing both PCB and non-PCB components, it must be quantitated according to Section 12,3. 14.0 Quality Control 14.1 Each laboratory that uses this method must operate a formal quality control (QC) program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and the analysis of spiked samples as a continuing check on performance. The laboratory must maintain performance records to define the quality of data that are generated. After a date specified by the Agency, ongoing performance checks should be compared with established performance criteria to determine if the results of analyses are within accuracy and precision limits expected of the method. D-35 �TABLE 14. ANALYSIS REPORT INCIDENTAL PCBs IN WASTEWATER Sample No. Sample Matrix Sample Source Notebook No. or File Location Volume Extracted Extraction/Cleanup Procedure Int. Std. liter Mass Added (|Jg) (Circle one) 4-Cl(d6) Surrogates 298 Mass Added ()Jg) 300 Intensity 100/49 (Circle one) Ratio 1-C1 194 196 100/33 4-C1 304 306 100/49 8-C1 442 444 100/65 10-C1 510 512 100/87 (continued) D-36 Ratio Intensity % Recovery �TABLE 14 (continued) Qualitative I Analyte 1° 2° l° 1-C1 188 190 100/33 2-C1 222 224 100/66 3-C1 256 258 100/99 4-C1 292 290 100/76 5-C1 326 328 100/66 6-C1 360 362 100/82 7-C1 394 396 100/98 8-C1 430 432 100/66 9-C1 464 466 100/76 10-C1 498 500 Quantitative Uncorr Corr Ion Cone. Cone OK? Used RF (pg/4) (M8/4) 100/87 2° Ratio Theoretical Total MS/4 Uncorr. Reported by: Internal Audit: Name Name EPA Audit: Name Signature/Date Signature/Date Signature/Date Organization Organization Organization D-37 M8/4 Corr. �14.2 The analysts must certify that the precision and accuracy of the analytical results are acceptable by: 14.2.1 14.2.2 14.3 The absolute precision of surrogate recovery, measured as the RSD of the integrated EIMS area (Ag) for a set of samples, must be ±10%. The mean recovery (R ) of at least four replicates of a QC check sample to be supplied by the Agency must meet Agency-specified accuracy and precision criteria. This forms the initial data base for establishing control limits (see Section 14.3 below). Control limits - The laboratory must establish control limits using the following equations: Upper control limit (UCL) = RL. + 3 RSD V_ Upper warning limit (UWL) = R + 2 RSD Lower warning limit (LWL) = R - 2 RSD Lower control limit (LCL) = R - 3 RSD These may be plotted on control charts. If an analysis of a check sample falls outside the warning limits, the analyst should be alerted that potential problems may need correction. If the results for a check sample fall outside the control limits, the laboratory must take corrective action and recertify the performance (Section 14.2) before proceeding with analyses. The warning and control limits should be continuously updated as more check sample replicates are added to the data base. 14.4 Before processing any samples, the analyst should demonstrate through the analysis of a reagent blank that all glassware and reagent interferences are under control. Each time a set of samples is analyzed or there is a change in reagents, a laboratory reagent blank should be processed as a safeguard against contamination. 14.5 Procedural QC - The various steps of the analytical procedure should have quality control measures. These include but are not limited to: 14.5.1 GC performance - See Section 7.1 for performance criteria. 14.5.2 MS performance - See Section 7.2 for performance criteria. D-38 �14.5.3 Qualitative identification - At least 10% of the PCB identifications, as well as any questionable results, should be confirmed by a second mass spectrometrist. 14.5.4 Quantitation - At least 10% of all manual calculations, including peak area calculations, must be checked. After changes in computer quantitation routines, the results should be manually checked. 14.6 A minimum of 10% of all samples, one sample per month or one sample per matrix type, whichever is greater, selected at random, must be run in triplicate to monitor the precision of the analysis. An RSD of ±30% or less must be achieved. If the precision is greater than ±30%, the analyst must be recertified (see Section 14.2). 14.7 A minimum of 10% of all samples, one sample per month or one sample per matrix type, whichever is greater, selected at random, must be analyzed by the standard addition technique. Two aliquots of the sample are analyzed, one "as is" and one spiked (surrogate spiking and equilibration techniques are described in Section 9.2) with a sufficient amount of Solution CSxxx to yield approximately 100 (Jg/liter of each compound). The samples are analyzed together and the quantitative results calculated. The recovery of the spiked compounds (calculated by difference) must be 80-120%. If the sample is known to contain specific PCB isomers, these isomers may be substituted for solution CSxxx. If the concentrations of PCBs are known to be high or low, the amount added should be adjusted so that the spiking level is 1.5 to 4 times the measured PCB level in the unspiked sample. 14.8 Interlaboratory comparison - Interlaboratory comparison studies are planned. Participation requirements, level of performance, and the identity of the coordinating laboratory will be presented in later revisions. 14.9 It is recommended that the participating laboratory adopt additional QC practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates or triplicates may be analyzed to monitor the precision of the sampling technique. Whenever possible, the laboratory should perform analysis of standard reference materials and participate in relevant performance evaluation studies. 15.0 Quality Assurance Each participating laboratory must develop a quality assurance plan according to EPA guidelines.7 The quality assurance plan must be submitted to the Agency for approval. D-39 �16.0 Method Performance The method performance is being evaluated. Limits of quantitation; average intralaboratory recoveries, precision, and accuracy; and interlaboratory recoveries, precision, and accuracy will be presented. 17.0 Documentation and Records Each laboratory is responsible for maintaining full records of the analysis. Laboratory notebooks should be used for handwritten records. GC/MS data must be archived on magnetic tape, disk, or a similar device. Hard copy printouts may be kept in addition if desired. QC records should be maintained separately from sample analysis records. The documentation must describe completely how the analysis was performed. Any variances from the protocol must be noted and fully described. Where the protocol lists options (e.g., sample cleanup), the option used and specifics (solvent volumes, digestion times, etc.) must be stated. D-40 �REFERENCES 1. Environmental Protection Agency, Organochlorine Pesticides and PCBs— Method 608," Fed. Reg., 44, 69501-69509 (December 3, 1979). 2. Environmental Protection Agency, "Base/Neutrals, Acids, and Pesticides— Method 625," Fed. Reg., 44, 69540-69552 (December 3, 1979), and subsequent revisions. 3. "Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual," Methods for Chemical Analysis of Water and Wastes, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio, March 1979, EPA 600-4/79-020. 4. Erickson, M. D., and J. S. Stanley, "Methods of Analysis for Incidentally Generated PCBs Literature Review and Preliminary Recommendations," Interim Report No. 1, EPA Contract No. 68-01-5915, Task 51, 1982. 5. Bellar, T. A., and J. J. Lichtenberg, "The Determination of Polychlorinated Biphenyls in Transformer Fluid and Waste Oils," Prepared for U.S. Environmental Protection Agency (1981). EPA-600/4-81-045. 6. American Society for Testing and Materials, "Standard Method for Analysis of Environmental Materials for Polychlorinated Biphenyls," pp. 877-885, in Annual Book of ASTM Standards, Part 40, Philadelphia, Pennsylvania (1980). ANSI/ASTM D 3304-77. 7. Quality Assurance Program Plan for the Office of Toxic Substances, Office of Pesticides and Toxic Substances, U.S. Environmental Protection Agency, Washington, D.C., October 1980. D-41 �TECHNICAL REPORT DATA (Please read Instructions on the reverse before completing) 3. RECIPIENT'S ACCESSION NO. 2. 1. REPORT NO. EPA-560/5-82-006 4. TITLE AND SUBTITLE 5. REPORT DATE Analytical Methods for By-Product PCBs—Initial Validation and Interim Protocols 6. PERFORMING ORGANIZATION CODE October 11, 1982 7. AUTHORIS) Mitchell D. Erickson, John S. Stanley, Gil Radolovich, Kay Turman, Karin Bauer, Jon Onstot, Donna Rose, and Margaret Wickham 8. PERFORMING ORGANIZATION REPORT NO. 9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. P R O G R A M E L E M E N T NO. Midwest Research Institute 425 Volker Boulevard Kansas City, MO 64110 11. CONTRACT/GRANT NO. 12. SPONSORING AGENCY NAME AND ADDRESS 13. TYPE OF REPORT AND PERIOD COVERED MRI Project No. 4901-A51 EPA 68-01-5915, Task 51 U.S. Environmental Protection Agency Office of Toxic Substances, Field Studies Branch TS-798 Washington, DC 20460 Interim 4, 4/24-8/31/82 14. SPONSORING AGENCY CODE 15. SUPPLEMENTARY NOTES The task manager is David P. Redford; the project officer is Frederick W. Kutz. 16. A B S T R A C T This document presents proposed analytical methods for analysis of by-product PCBs in commercial products, product waste streams, wastewaters, and air. The analytical method for commercial products and product waste streams consist of a flexible approach for extraction and cleanup of particular matrices. The 13c-labeled PCB surrogates are added as part of a strong quality assurance program to determine levels of recovery. The wastewater method is based on EPA Methods 608 and 625 with revisions to include use of the 13c-labeled PCB surrogates. The air method is a revision of a proposed EPA method for the collection and analysis of PCBs in air and flue gas emissions. Capillary or packed column gas chromatography/electron impact ionization mass spectrometry is proposed as the primary instrumental method. Response factors and retention times of 77 PCB congeners relative to tetrachlorobiphenyl-d6 are presented in addition to statistical analysis to project validity of the data and extrapolation of relative response factors to all 209 possible congeners. Preliminary studies using the ISClabeled surrogates to validate specific cleanup procedures and to analyze several commercial products and product wastes indicate that the proposed analytical methods are both feasible and practical. KEY WORDS AND DOCUMENT ANALYSIS 17. DESCRIPTORS Polychlorinated biphenyls PCBs Incidentally generated Analytical protocols Air Wastewater Commercial products b.IDENTIFIERS/OPEN ENDED TERMS Commercial waste Capillary column Electron impact EIMS Response factors Relative retenti Surrogates 18. DISTRIBUTION STATEMENT EPA Form 2220-1 (R»v. 4-77) Unclassified PREVIOUS EDITION is OBSOLETE COSATI Field/Group relative response factor n times 19. SECURITY CLASS (This Report) Unclassified 20. SECURITY CLASS (This page) Unlimited c. streams gas chromatography onization mass spectromet 21. NO. OF PAGES 243 22. PRICE �United States Environmental Protection Agency Office of Toxic Substances Washington DC 20460 � Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 186 Folder The folder containing the original item. 5385 Series The series number of the original item. Series VIII Subseries I Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Erickson, Mitchell D. John S. Stanley Kay Turman Gil Radolovich Karin Bauer Jon Onstot Donna Rose Margaret Wickham Description An account of the resource <strong>Corporate Author: </strong>Midwest Research Institute Date A point or period of time associated with an event in the lifecycle of the resource October 11 1982 Title A name given to the resource Analytical Methods for By-Product PCBs - Preliminary Validation and Interim Methods ao_seriesVIII https://www.nal.usda.gov/exhibits/speccoll/files/original/00a05b74cf6b72dc5346713df5cbf713.pdf 4797df5425895601c7d659e869604c78 PDF Text Text lt.mlM.tor 0542, Author Haile ' Clarence L Corporate Author Report/Article Tltlfl Comprehensive Assessment of the Specific Compounds Present in Combustion Processes, Volume I: Pilot Study of Combustion Emissions Variability Journal/Book Title Year Month/Day Color Number of Images ° DBSCriptOn Notes Task 3 Final Re ' P°rt, EPA Contract No. 68-01-5915, MRI Project No. 4901-A(3) Friday, March 08, 2002 Page 5421 of 5427 �United States Environmental Protection Agency Office of Toxic Substances Washington DC 20460 EPA-560/5-83-004 June, 1983 Toxic Substances xvEPA Comprehensive Assessment of the Specific Compounds Present in Combustion Processes Volume I Pilot Study of Combustion Emissions Variability ^^^^TIv~^rr'r- i 4 fr^ \\ ^ 1 L \ i t ' �PILOT STUDY OF INFORMATION OF SPECIFIC COMPOUNDS FROM COMBUSTION SOURCES by Clarence L. Haile and John S. Stanley Midwest Research Institute Robert M. Lucas and Denise K. Melroy Research Triangle Institute Carter P. Nulton Southwest Research Institute and William L. Yauger, Jr. Gulf South Research Institute TASK 3 FINAL REPORT EPA Contract No. 68-01-5915 MRI Project No. 4901-A(3) Prepared for U.S. Environmental Protection Agency Office of Pesticides and Toxic Substances Field Studies Branch 401 M Street, S.W. Washington, D.C. 20460 Attn: Dr. Frederick Kutz, Project Officer Mr. David Redford, Task Manager �DISCLAIMER This document has been reviewed and approved for publication by the Office of Toxic Substances, Office of Pesticides and Toxic Substances, U.S. Environmental Protection Agency. Approval does not signify that the contents necessarily reflect the views and policies of the Environmental Protection Agency, nor does the mention of trade names or commercial products constitute endorsement or recommendation for use. �PREFACE This final report was prepared for the Environmental Protection Agency under EPA Contract No. 68-01-5915, Task 3. The task was directed by Dr. Clarence L. Haile. Substantial portions of the effort were subcontracted to Southwest Research Institute under Dr. Carter P. Nulton and to Gulf South Research Institute under Mr. William L. Yauger, Jr. This work was completed in coordination with statistical design studies conducted by Research Triangle Institute under Dr. Robert M. Lucas. This report was prepared by Dr. Clarence L. Haile and Dr. John S. Stanley with substantial contributions from Dr. Robert M. Lucas, Ms. Denise K. Melroy, Dr. Carter P. Nulton, and Mr. William L. Yauger, Jr. MIDW5ST)RESEARCH,INSTITUTE r E. Going Program Manager Approved: James L. Spigarelli, Director Analytical Chemistry Department June 1983 111 �CONTENTS Preface Figures Tables 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. iii v vi Introduction Summary Recommendations Plant Descriptions Ames Municipal Power Plant, Unit No. 7 Chicago Northwest Incinerator, Unit No. 2 Sampling Methods Flue Gas Plant Background Air Solid and Aqueous Media Continuous Monitoring Process Data Collection Analysis Methods Organics Cadmium Field Test Data Ames Municipal Power Plant, Unit No. 7 Chicago Northwest Incinerator, Unit No. 2 Analytical Results Ames Municipal Power Plant, Unit No. 7 Chicago Northwest Incinerator Analytical Quality Assurance Results Surrogate Compound Recoveries Interlaboratory Comparison Studies Emissions Results Ames Municipal Power Plant, Unit No. 7 Chicago Northwest Incinerator, Unit No. 2 Statistical Summary of Pilot Study Data Overview First Tier Summary Second Tier Summary References 1 3 5 6 6 1 9 9 12 12 1? 15 16 16 31 34 34 42 52 52 83 107 107 107 112 112 112 129 129 129 137 147 Appendix A - TRW Field Test Report for the Ames Municipal Electric System, Unit No. 7 148 Appendix B - TRW Field Test Report for the Chicago Northwest Incinerator, Unit No. 2 242 �FIGURES Number Page 1 Modified Method 5 train for organics sampling 10 2 Locations of flue gas sampling ports on a typical combustion unit 11 3 Sector schemes for sampling bottom ash 14 4 General analytical scheme 18 5 TOC1 chromatogram for Aroclor 1254 23 �TABLES Number 1 PAH Compounds Selected 16 2 Recovery of Selected PAHs and 1,2,3,4-TCDD From Ames Fly Ash. 20 3 TOC1 Analysis Parameters 22 4 HRGC Screening Parameters 24 5 Extract Compositing Scheme for Tier 2 Analyses 25 6 HRGC/MS Parameters Used for Analyses of PCDDs and PCDFs in Composite Chicago NW Flue Gas Outlet Extracts 26 HRGC/MS-SIM Parameters Used for Analysis of PCBs in Composite Flue Gas Outlet Extracts 27 PCB Compounds Used for Determinations in Composite Flue Gas Outlet Extracts 27 Ions Monitored During HRGC/HRMS Confirmatory Analysis of PCDDs and PCDFs in Composite Chicago NW Flue Gas Outlet Extracts 29 PCDD and PCDF Compounds Used for Determinations in Composite Chicago NW Flue Gas Outlet Extracts 29 HRGC/HRMS Parameters Used for Analysis of 2,3,7,8-Tetrachlorodibenzo-£-dioxin in Composite Chicago NW Flue Gas Outlet Extracts 30 Recovery of Cadmium From Fortified Samples of Fly Ash From the Chicago NW Incinerator 33 Recovery of Cadmium From Fortified Samples From the Ames Municipal Power Plant 33 Daily Data Summaries for Flue Gas Sampling, Ames Municipal Power Plant, Unit No. 7 35 Average Process Data for the Ames Municipal Power Plant, Unit No. 7 38 7 8 9 10 11 12 13 14 15 VI �TABLES (continued) Number Page 16 Fuel Combustion During Flue Gas Sampling 40 17 Daily Production and Consumption at Ames Municipal Power Plant, Unit No. 7 41 Heat Content of Fuels Used at the Ames Municipal Power Plant During Sampling Period 43 Daily Data Summaries for Flue Gas Measurements, Chicago Northwest Incinerator, Boiler No. 2 44 Means of the Means for Process Data, All Test Days, Chicago NW Incinerator, Boiler No. 2 46 Weekly Inventories of Refuse and Residue at the Chicago NW Incinerator (All Boilers) 48 Charges Fed to Boiler No. 2 on a Shift Basis Chicago Northwest Incineration Facility 49 TOC1 and Surrogate Recovery Results for the Ames Flue Gas Inlet Samples 53 TOC1 Results and Surrogate Recoveries for the Ames Flue Gas Outlet Samples. 55 TOC1 Results and Surrogate Recoveries for Ames Plant Background Air Particulate Samples 56 TOC1 Results and Surrogate Recoveries for Ames ESP Ash Samples 57 TOC1 Results and Surrogate Recoveries for Ames Bottom Ash Samples 60 28 TOC1 Results and Surrogate Recoveries for Ames Coal Samples . 63 29 TOC1 Results and Surrogate Recoveries for Ames Refuse Derived Fuel Samples 64 TOC1 Results and Surrogate Recoveries for Ames Bottom Ash Hopper Quench Water Influent Samples 67 TOC1 Results and Surrogate Recoveries for Ames Bottom Ash Hopper Quench Overflow Water Samples 68 TOC1 Results and Surrogate Recoveries for Ames Untreated Well Water 71 18 19 20 21 22 23 24 25 26 27 30 31 32 vii �TABLES (continued) Number 33 Page Compounds Quantitated in Samples From the Ames Municipal Power Plant, Unit No. 7 72 Concentrations of Polychlorinated Biphenyl Isomers in Flue Gas Outlet Samples From the Ames Municipal Power Plant, Unit No. 7 77 35 Cadmium Results for Ames - ESP Ash Samples 78 36 Cadmium Results for Ames - Bottom Ash Samples 79 37 Cadmium Results for Ames - Coal Samples 80 38 Cadmium Results for Ames - Refuse-Derived Fuel Samples. . . . 81 39 Cadmium Results for Ames - Flue Gas Outlet Particulates . . . 82 40 TOC1 Results and Surrogate Recoveries for Chicago NW Flue Gas Samples ..... 84 TOC1 Results and Surrogate Recoveries for Chicago NW Plant Background Air Samples 85 TOC1 Results and Surrogate Recoveries for Chicago NW ESP Ash Samples • 86 TOC1 Results and Surrogate Recoveries for Chicago NW Combined Bottom Ash Samples 89 TOC1 Results and Surrogate Recoveries for Chicago NW Refuse Samples 92 TOC1 Results and Surrogate Recoveries for Chicago NW Tap Water Samples 95 Compounds Quantitated in Samples From the Chicago NW Incinerator, Unit No. 2 96 34 41 42 43 44 45 46 47 48 49 Comparison of TOC1 Results From Direct TOC1 Assays Versus Calculated TOC1 From Specific Compounds Identified in Composite Chicago NW Extracts . 98 Concentrations of Polychlorinated Biphenyl Isomers in Flue Gas Outlet Samples From the Chicago Northwest Incinerator Unit No. 1 99 Concentrations of Polychlorodibenzo-o,-dioxins and Furans in Flue Gas From the Chicago Northwest Incinerator and Corresponding Emission Rates 100 viii �TABLES (continued) Number 50 Page Concentrations of 2,3,7,8-Tetrachlorodibenzo-pj-dioxin in flue Gas From the Chicago NW Incinerator 102 Cadmium Concentrations in Fly Ash From Chicago Northwest Incinerator, Unit No. 2 103 Cadmium Concentrations in Combined Bottom Ash From Chicago Northwest Incinerator, Unit No. 2 104 Cadmium Concentrations in Refuse From Chicago Northwest Incinerator 105 Cadmium Concentrations in the Flue Gas Outlet Particulates From Chicago Northwest Incinerator, Unit No. 2 106 55 Summary of Surrogate Recovery Data. . 108 56 Results of Interlaboratory TOC1 Analyses 109 57 Interlaboratory Comparison of Analytical Results for the Extraction and Analysis of Specific Compounds in Four Sets of Quality Assurance Samples 110 Interlaboratory Comparison of the Levels of PCDDs and PCDFs in Composite extracts From the Chicago NW Incinerator . . . Ill Total Organic Chlorine Inputs and Emissions - Ames Municipal Power Plant, Unit No. 7 113 Compounds Quantitated in the Primary Input and Emission Media for the Ames Municipal Power Plant, Unit No. 7 114 Flue Gas Concentrations for PCBs and Emission Rates for the Ames Municipal Power Plant, Unit No. 7. 118 Cadmium Inputs and Emissions - Ames Municipal Power Plant, Unit No. 7 119 Total Organic Chlorine Inputs and Emissions - Chicago Northwest Incinerator, Unit No. 2 120 Compounds Quantitated in Input and Emission Media Chicago NW Incinerator, Unit No. 2 122 Flue Gas Concentrations of PCBs and Emission Rates for the Chicago Northwest Incinerator Unit No. 1 124 51 52 53 54 58 59 60 61 62 63 64 65 IX �TABLES (continued) Number 66 Page Concentrations of Polychlorodibenzo-£-dioxins and Furans in Flue Gas From the Chicago Northwest Incinerator and Corresponding Emission Rates 125 67 Concentrations of 2,3,7,8-Tetrachlorodibenzo-£-dioxin in Flue Gas From the Chicago NW Incinerator and Corresponding Emission Rates 127 68 Cadmium Input and Emissions From Chicago Northwest Incinerator, Unit No. 2 128 Summary Statistics for Total Organic Chlorine Concentration Data From Ames, Iowa 132 Summary Statistics for Total Organic Chlorine Concentration Data From Chicago NW 133 Summary of Surrogate Compounds Percent Recovery for Specimens From Ames, Iowa 134 69 70 71 72 Summary of Surrogate Compound Percent Recovery for Specimens From Chicago, NW 135 73 Validity of Confidence Statements for Selected Levels of Bias 136 74 Summary of Coefficient of Variation for the Pilot Study. . . 138 75 Summary of Statistics for Compounds Quantitated in Primary Input Media at Ames, Iowa . 140 76 Summary Statistics for Compounds Quantitated in Gaseous Emissions at Ames, Iowa 141 Summary Statistics for Compounds Quantitated in Solid Emissions at Ames, Iowa 142 77 78 Summary of Total Input and Emissions From Ames, Iowa . . . . 143 79 Summary of Statistics for Compounds Quantitated in Gaseous Emissions From Chicago 144 Summary of Flue Gas Emissions of Polychlorinated Biphenyl Isomers from Ames, Iowa 145 80 81 Summary of Flue Gas Emissions of Polychlorinated Biphenyls, Dibenzo-£-dioxins, and dibenzofurans from Chicago NW . . . 146 �SECTION 1 INTRODUCTION This pilot study was conducted as a prelude to a nationwide survey of organic emissions from major stationary combustion sources. The primary objectives of the pilot study were to obtain data on the variability of organic emissions from two such sources and to evaluate the sampling and analysis methods. These data are used to construct the survey design for the nationwide survey. The compounds of interest are polynuclear aromatic hydrocarbons (PAHs) and chlorinated aromatic compounds, including polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p_-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs). Of particular interest is 2,3,7,8-tetrachlorodibenzop_-dioxin (TCDD). In addition, total cadmium was also determined in special samples from both plants to meet special Environmental Protection Agency (EPA) needs. Midwest Research Institute (MRI) was responsible for overall task management, specifying the sampling and analysis methods, assisting in the collection of samples, receiving samples at the plant sites, shipping the samples to the analysis laboratories, and conducting all sample analyses. MRI was assisted in this effort by two subcontractors. Southwest Research Institute (SwRI) assisted in sampling, exercised sample control, and conducted most of the analyses for samples from the first plant. Gas chromatographic/ mass spectrometric confirmation of PCBs, PCDDs, and PCDFs was conducted by MRI. Gulf South Research Institute (GSRI) provided similar assistance for the second plant. The statistical design of the pilot study was constructed by Research Triangle Institute (RTI). RTI also conducted statistical analysis of the resulting emissions data and constructed the design for the nationwide survey. The results of the statistical analysis are summarized in Section 9 of this report. The survey design is summarized in a report to the EPA Office of Toxic Substances.*• TRW, Inc. was responsible for conducting the field sampling and data collection. The results of TRW's efforts are described in two reports to EPA's Industrial Environmental Research Laboratory in Research Triangle Park.2'3 The body of these reports are contained in Appendices A and B. A summary of the results of this study is contained in Section 2 of this report. Section 3 presents recommendations for future work. Brief descriptions of the two combustion sources are contained in Section 4. The sampling and analysis methods are described in Sections 5 and 6. Sections 7 and 8 present the field test data and analytical results. The analytical quality �assurance results are summarized in Section 9. Section 10 presents the emissions results and Section 11 is a statistical summary of the emissions results. �SECTION 2 SUMMARY Two major stationary combustion sources, a municipal incinerator and a co-fired (refuse-derived fuel plus coal) power plant, were studied to determine the variability of organic emissions between sources and over a designated time period for each plant. The pilot study results served as a basis for structuring the survey design for a nationwide survey1 for organic emissions from stationary combustion sources. All inputs and outputs (including fuel, air, water, ash, and flue gas) that were influenced by the combustion process at each facility were sampled for a minimum of 11 days. Daily flue gas samples (20 m3) were collected concurrently at the inlet and outlet of the control devices using a modified Method 5 sampling train. The solid and aqueous inputs and outputs from each plant were collected six times per day (at roughly 4-hr intervals). The samples were extracted and analyzed for total organic chlorine (TOC1), PAHs, PCBs, PCDDs, and PCDFs. A limited number of samples were analyzed for cadmium. The TOC1 procedure (more correctly, total extractable organic halide) was developed for this study to provide a sensitive measure of the variability of chlorinated organic emissions. The TOC1 emissions from the municipal incinerator and the co-fired power plant differed and were variable within the test duration for each plant. The flue gas accounted for more than 80% of each plant's TOC1 emissions. The TOC1 emissions averaged 322 mg/hr from the municipal incinerator and 246 mg/hr from the co-fired power plant. The variability of the TOC1 results was the key element in the construction of the nationwide survey design.1 A number of specific compounds including chlorinated benzenes and chlorinated phenols were detected in the flue gas from the municipal incinerator. The sum of the organic chlorine concentrations attributable to these specific compounds is comparable to the TOC1 results. Fewer chlorinated compounds were identified in the flue gas extracts of the co-fired plant and were generally present at lower concentrations than in extracts from the municipal incinerator. Polycyclic organic compounds including PAHs, PCDDs and PCDFs were identified in the flue gas extracts from the municipal incinerator. Some PAHs and PCBs were also identified and quantitated in the flue gas from the cofired power plant, but PCDDs and PCDFs were not detected. �The mean concentration observed for total PCBs from the municipal incinerator was 42 ng/dscm (dscm = dry standard cubic meter), compared to an average of 19 ng/dscm from the co-fired power plant. However, the order of the average emission rate is reversed because of the lower flue gas flow rate of the refuse incinerator. The average PCB emission rates for the RDF/coal-fired power plant and the refuse incinerator were 6 mg/hr and 3.6 mg/hr, respectively. Because of the variability observed in the data, no significant differences between concentrations or emission rates between the two plants can be determined. The PCB isomer distribution ranged from dichlorinated to pentachlorinated compounds for the municipal incinerator and trichlorinated to decachlorinated compounds for the co-fired power plant. PCDDs and PCDFs were not identified in sample extracts from the co-fired power plant. However, several PCDDs and PCDFs were identified in composited sample extracts from the municipal incinerator. Trichloro- and tetrachlorodibenzofurans were the most abundant of the PCDDs and PCDFs in these extracts, averaging 300 ng/dscm and 90 ng/dscm, respectively. The specific PCDD isomer 2,3,7,8-tetrachlorodibenzo-£-dioxin (2,3,7,8-TCDD) was also identified in these extracts from the municipal incinerator and averaged 0.4 ng/dscm (average mass emission 34 (jg/hr). This isomer was identified in these extracts using high resolution gas chromatography/high resolution mass spectrometry. This identification was confirmed by an independent laboratory using similar instrumentation. The level of cadmium was also measured in the inputs and outputs for a limited number of sample days for each plant. The mass balance observed for the inputs and emissions of the co-fired power plant was fairly good. However, the agreement for cadmium inputs and emissions for the municipal incinerator was poor. This was likely due to the difficulties encountered in obtaining representative samples of the refuse burned at this facility. �SECTION 3 RECOMMENDATIONS The nationwide this report provide analysis procedures fired power plants, combustion study should be conducted. The results in the basis for a sound statistical design for sampling and in future programs (i.e., municipal incinerators, coaletc.). Extraction studies should be undertaken with fly ash samples that have been shown to contain PCDDs and PCDFs. Analysis of such a material could provide a better measure of recovery efficiency of these compounds than from other similar solid materials. The modified Method 5 sampling procedure used in this study is based on sound developments for particulate sampling coupled with adsorption of organic vapors on a resin of known properties. However, this sampling procedure should be rigorously evaluated for the collection efficiencies of PCDDs and PCDFs as an additional quality assurance measure. The preliminary data presented in this report surement should be further evaluated for use as an organic emissions. The development of a good TOC1 cantly reduce the costs of obtaining large amounts suggest that the TOC1 meaindicator of chlorinated measurement could signifiof combustion source data. Additional work should be conducted to improve the selective separation and detection of PCDDs and PCDFs. Current methods require labor-intensive extractions and cleanup procedures. �SECTION 4 PLANT DESCRIPTIONS AMES MUNICIPAL POWER PLANT, UNIT NO. 7 The Ames Municipal Power Plant is owned and operated by the city of Ames, Iowa, and is located within the city limits. The coal-fired utility boiler tested at this plant was Unit No. 7, one of three units that have been modified to burn processed refuse as a supplemental fuel with coal. Unit No. 7, a pulverized coal suspension fired boiler, is used under normal operating condition. The other two units are operated under peak demand or when Unit No. 7 is down. This unit was originally designed to burn either coal or natural gas as the primary fuel. It was first brought into operation in 1968 and was modified to burn refuse-derived fuel (RDF) in 1975. Unit No. 7 generally burns a mixture of Colorado coal, Iowa coal, and RDF. Generally, the ratio of the two types of coal varies, although during this particular testing period a 45 to 55% ratio of Colorado to Iowa coal was maintained in the pulverized coal mixture. Approximately 20% (by weight) of the total fuel prepared and fired at this facility was RDF and 80% was pulverized coal. The RDF is produced at a separate Ames city facility located near the power plant. Raw refuse is sorted to remove glass and metals for recycling. The remaining material (largely papers and plastics) are milled and pneumatically conveyed to a storage bin. The RDF is fed from this bin to the boiler at the required rate. The maximum RDF feed rate is 8.5 tons/hr (7.7 metric tons/hr). Pulverized coal is supplied to the furnace by tangentially orientated nozzles so that combustion is accomplished in a suspension. Approximately 20% of the total ash produced during coal-only firing is bottom ash. RDF is supplied to the furnace at a point just above the primary coal combustion zone. Moveable grates hold the residual RDF at the bottom of the coal combustion zone to enhance RDF combustion. The grates are lowered during bottom ash wasting and when RDF is not being fired. The ash and slag deposited in the hopper are removed at least three times per day. An average of 758,000 liters/day (200,000 gal./day) of well water (sluice water) is used to remove the solid waste from the furnace bottom. This waste is drained to a holding pond where the ash is dredged out and stock piled. The water from the holding pond is allowed to percolate through the soil and eventually into a nearby river. �Electrostatic precipitators (ESPs) are used to remove particulates from the stack gases. The ESPs require at least 61 kw of the maximum 35,000 kw gross output of Unit No. 7. Fly ash collected in the ESP hoppers is pneumatically conveyed (3 times/day) to the bottom ash hopper drain system. Additional information including schematics of the plant site, the flow system, Unit No. 7 design, and the solid waste recovery system is presented in the pilot test program engineering report provided by TRW (see Appendix A). Other tables in the TRW report list the boiler design data, the pulverizer specifications, the fan design performance parameters, performance characteristics of the ESP, and the predicted performance characteristics of Unit No. 7. CHICAGO NORTHWEST INCINERATOR, UNIT NO. 2 The Chicago Northwest Incinerator is one of four municipal incinerators owned and operated by the city of Chicago (Illinois) and located within the city limits. This plant has four incinerators, each having a nominal burning capacity of 400 ton/24 hr day (363 metric tons/24 hr day). Each incinerator has a charging hopper, feed chute, hydraulic powered feeders and stoker, boiler, economizer and fly ash hoppers. Draft through the furnace is provided by forced draft fans, overfire air fans, and induced draft fans. Mixed refuse from domestic sources is brought to the incinerator in trucks having a capacity of 5 tons (4,500 kg) or 25 cubic yards (19 m3). The refuse varies considerably in consistency and moisture content seasonally and from load to load. All refuse is collected in a storage pit of 9,700 cubic yard (7,400 cubic yard) capacity. The refuse is not sorted prior to storage in the pit except for large items (e.g., furniture and large appliances) which are milled prior to storage in the pit. The refuse typically contains considerable quantities of automobile tires, small appliances, and similar discarded durable goods. The refuse is removed from the pit by one of three transfer cranes and is dumped directly into the four furnace feed hoppers. Refuse in the charging hopper of each incinerator flows by gravity from the hopper to three stoker feeders through a feed chute. The stoker feeders at the bottom of the feed chute push the refuse into the stoker by a reciprocating action. Alternate lateral rows of grate steps have controlled continuous reciprocating action with the moving grate steps pushing in reverse direction to the flow of refuse. This action moves a portion of the burning refuse under the unignited material and thereby effects an agitation and blending of the whole burning mass. Combustion air entering from below the grates cools the grates, helps to agitate the burning refuse and supplies the oxygen which produces a maximum burn-out in the shortest length of grate travel. The combustion air combines with the burning refuse to generate heat and raise the temperature of the flue gas to as high as 2000°F (1100°C). At rated burning capacity and based on 50% excess air (dry) the flue gas flow rate at 550°F (290°C) is estimated to be 142,300 actual cubic feet per minute (acfm) or 4,030 m3/min. The flue gas passes upward through the'furnace, through the boiler passes and finally through the economizer to the electrostatic precipitator. As it passes through the boiler it transfers heat to the water. �At the inlet to the electrostatic precipitator the temperature is reduced to approximately 500°F (260°C) because of the above heat exchange. During the passage of the flue gas through the boiler passes and economizer the heavier fly ash particles drop out. Hoppers are provided below the boiler and economizer for the collection of the particulates. In order to obtain maximum combustion efficiency, the depth of the refuse bed is controlled by automatic discharge or clinker rollers located at the end of the grate. As the residue reaches this point it is dumped into an ash discharger and is quenched in water. The residue is pushed up an inclined slope that permits draining and produces a residue of less than 15% moisture. In addition to quenching, the ash discharger also serves as a water seal for the furnace and prevents infiltration of air into the furnace. The furnace operates under slight negative pressure. The residue leaving each incinerator ash discharger passes through a hydraulically operated chute to one of two residue conveyors. The residue is screened to separate material larger than 2 in. (5 cm) in diameter. Hydraulic powered chutes are used to direct the flow of the residue away from the rotary screens and into a by-pass hopper. The residue conveyors also receive and transport stoker grate sittings and fly ash accumulations from the boiler hoppers, economizer hoppers, and the electrostatic precipitators. Stoker grate siftings collect in six hoppers under each of the three stoker grate sections. Residue from the hoppers is removed from the plant by trucks. The weight of the residue leaving the plant is measured and recorded at the weighing station. The boiler fly ash is collected in four hoppers, two of which discharge to the stoker grates. The other two hoppers are discharged directly through a common pipe to the residue conveyor. The fly ash from the economizer hoppers passes through a common pipe connected to the-discharge end of a conveyor handling fly ash from the two electrostatic precipitator hoppers. The fly ash is deposited directly into the residue discharge chute. The flue gas exiting the ESPs is vented to a 250-ft (76 m) high stack via an induced draft fan. Flue gases from two identical units are discharged from a single stack via a breaching. A more detailed description of the plant operation and schematics of the plant site, the flow system, and the flue gas and grab sampling locations is presented in the TRW pilot test program engineering report (see Appendix B). �SECTION 5 SAMPLING METHODS FLUE GAS Flue gas sampling for organic compounds was accomplished concurrently at points both inlet and outlet to the electrostatic precipitators using two modified Method 5 sampling trains (shown in Figure 1) at each location. Figure 2 shows the locations of sampling ports on a typical unit. The sampling crew collected 10 m3 (10 ± 1 m3) samples with each sampling train by extracting the flue gas at rates approximating the flue gas velocity for each plant. Cadmium was sampled at the ESP outlet using a single Method 5 sampling train. The standard train was operated the same as depicted in Figure 1, but without condenser and the XAD-2 sorbent trap. EPA Method 5 Procedures4 for particulate sampling were followed for both organic and inorganic sampling procedures, except that 10 m3 was sampled with each organic train. Detailed descriptions of the Method 5 calibration and actual sampling procedures for specific ducts and stacks at the Ames Municipal Power Plant and Chicago Northwest Incinerator have been presented in the respective field data reports (Appendices A and B). Additional details on the pretest preparation and sample recovery procedures are described in a methods manual for the nationwide combustion source survey.5 The flue gas sampling at the Ames facility was conducted both on the duct just before the electrostatic precipitator and on the stack. Sampling for organics was to be performed for 14 consecutive days with an additional 3 days sampling for particulate cadmium. However, due to extreme weather conditions only 11 days of concurrent inlet and outlet samples were collected. Eight additional inlet samples were also collected. The flue gas sampling at the Chicago plant was conducted at the duct inlet to the electrostatic precipitator and at the duct leading from the precipitator to the stack. Despite boiler down time and equipment malfunction, 11 days of organic samples (including concurrent inlet and outlet flue gas) were taken. A complete sampling train, including resin trap filter and impinger solutions was set up as a train background (blank) at each plant. The train was taken to normal operating temperature and allowed to remain at this temperature for 1 hr. Upon completion of testing, the sampling equipment was brought to a clean laboratory area for recovery. Each sampling train was kept in a separate area to prevent sample mixup and cross contamination. The individual sample train components were recovered as follows: �Cyclone (optional) Condenser & Resin Cartridge Thermocouple Reverie-Type Pitot Tube Console Impingers 1,3 and 4 are of (he Modified Greenburg-Smllh Type Impinger 2 is of I lie Greenburg-Smith Design Impinger I and 2 Contain 100 ml Water Impinger 3 Empty Impinger 4 Contains 200-300 Grams Silica Gel Figure 1. Modified Method 5 train for organics sampling. 10 �ESP Inlet Ports Stack Platform and Ports Figure 2. Locations of flue gas sampling ports on a typical combustion unit. 11 �Dry particulate in cyclone - cyclone flasks were transferred to cyclone catch bottle. • Probe was wiped to remove all external particulate matter near probe ends. Filters were removed from their housings and placed in proper containers. • After recovering dry particulate from the nozzle, probe, cyclone, and flask, these parts were rinsed with distilled water to remove remaining particulate. They were subsequently rinsed with glass distilled acetone and cyclohexane and put into a separate container. All rinses were retained in an amber glass container. Sorbent traps were removed from the train, capped with glass plugs, and given to an on-site MRI representative. Condenser coil, if separate from the sorbent trap, and the connecting glassware to the first impinger was rinsed into the condensate catch (first impinger). • First and second impingers were measured, volume recorded and retained in an amber glass storage bottle. The impingers were then rinsed with small amounts of distilled water, acetone and cyclohexane. These rinsings were combined with the condensate catch. Rinse volumes were also recorded. • The volumes of the third and fourth impingers were measured and recorded. Solutions were discarded. Silica gel was weighed, weight gain recorded and regenerated for further use. To maintain sample integrity, all containers were amber glass, with TFElined lids. PLANT BACKGROUND AIR A high volume air sampler was used to collect organic compounds and cadmium associated with particulates in the air used for combustion. The samples were collected on 8 in. x 10 in. (20 cm x 25 cm) glass fiber filters. A high volume sampler was placed on the roof of each facility to obtain a representative background of outside ambient air, rather than sampling air inside the building that could have been contaminated or influenced by the combustion process. SOLID AND AQUEOUS MEDIA Solid and aqueous samples that directly contact the combustion process were collected several times during each 24-hr period according to schedules 12 �provided by RTI. Four solid sample types were collected from the Ames plant, coal, ESP hopper ash, bottom ash, and RDF. ESP ash, refuse, and combined ash were sampled at the Chicago plant. Combined ash includes mixed ESP ash and bottom ash since the design of the Chicago ash handling system did not allow separate access to bottom ash. All solid samples were collected six times per day at roughly 4-hr intervals. Some solid samples were accessible from more than one nominally equivalent point in the plant. In these cases, samples were taken from specific points according to a randomized scheme provided by RTI. Hence, coal was sampled from two feed streams, RDF was sampled from four feed streams, and ESP ash was sampled from two collection hoppers at the Ames plant based on this scheme. Similarly, bottom ash from the Ames plant and bottom ash and refuse from the Chicago plant were sampled from specific sectors of the exposed material according to the randomized scheme. Figure 3 shows the sector systems used in sampling bottom ash from the Ames and Chicago plants. Raw refuse was sampled at the Chicago incinerator from the two sides of the feed hopper. The aqueous streams sampled at Ames included cooling tower blowdown water, well water, and bottom ash quench overflow. Only city tap water (plant intake water) was sampled at the Chicago facility. Liquid streams that did not flow continuously were allowed to purge for 3 min prior to obtaining samples. Sample containers were rinsed three times with sample liquid prior to being filled with that liquid. The streams sampled and frequency of sampling were as follows : • Bottom ash quench overflow water was sampled twice per shift, for a total of six samples per 24-hr period. Cooling tower blowdown feed for the bottom ash quench system was sampled once per day. Three well water samples were collected over the testing period. City tap water was sampled once per day. CONTINUOUS MONITORING The continuous monitoring data collected for the two different plants included: (1) oxygen [03] concentrations, (2) carbon dioxide [C02] concentrations, (3) carbon monoxide [CO] concentrations, (4) hydrocarbon concentrations [THC] [GI through C6] and (5) ambient temperatures. On-line monitoring was performed at the inlet of the electrostatic precipitators (ESP) at both plants and in the duct leading from the exit side of the ESP to the induced draft fan at the Chicago Northwest Incinerator and at the 100 ft (30 m) level on the stack at the Ames Municipal Power Plant. A stainless steel filter connected to a 3-ft (91-cm) probe was inserted into the sample port for each sample location. Heat traced line was run from the sample port to a gas conditioner. Vacuum pumps were used to draw the inlet and outlet sample gas from the sample ports through the gas conditioner 13 �' / E F C D A B North Hopper Door Ames Municipal Electric System, Unit No. 7 Bottom Ash Hopper A B C D F Chicago Northwest Incinerator, Unit No. 2 Residue Discharge Chute Figure 3. Sector schemes for sampling bottom ash. 14 �and to the analytical instruments. An automatic timer switched the continuous monitoring equipment from inlet to outlet every 15 rain. The average values for 02, C02) CO and THC recorded during each test period are presented in Section 8 of this report with a summary of the flue gas testing parameters. A more detailed description of the continuous monitoring data is presented in Appendices A and B. PROCESS DATA COLLECTION In order to fully characterize the operation of the two different combustion facilities and to designate periods of dramatic changes in the performance of a particular unit, numerous operating parameters were recorded throughout the flue gas sampling periods, as well as on a 24-hr basis. This information included mass flow data for fuels (coal, fuel oil, and RDF), periods of soot blowing, unit downtime, steam flow rate, steam pressure, steam temperature, feedwater flow rate, feedwater temperature, combustion air flow rate, combustion air temperature, percent excess oxygen, induced and forced fan pressures, furnace draft, furnace temperature, flue gas temperature, and ambient temperature and ambient pressure. The process data averages based on 24-hr periods and the flue gas test durations are presented in Section 7 of this report. Data for these parameters taken on an hourly basis are presented in detail in the Appendices. 15 �SECTION 6 ANALYSIS METHODS ORGANICS The analysis methods for organics were designed to provide qualitative and quantitative determinations of several specific analytes and to provide semiquantitative information on any additional polychlorinated aromatic compounds identified. The specific analytes included eight PAH compounds (listed in Table 1), PCBs, PCDDs, and PCDFs. Special emphasis was placed on highly selective and sensitive procedures for determining 2,3,7,8-TCDD. TABLE 1. PAH COMPOUNDS SELECTED Benzo[a]pyrene Pyrene Fluoranthene Phenanthrene Chrysene Indeno[l,2,3-cd]pyrene Benzo[£,h,ijperylene Anthracene Samples were also assayed for total organic chlorine (TOC1) to provide a general measure of the variability of chlorinated emissions. Since it was anticipated that concentrations for many specific compounds would be near minimum detectable levels, the variabilities observed for specific compounds may be more representative of measurement error than emission variabilities. The sensitivity of the TOC1 procedure should allow more reliable detection of the variability of emissions for chlorinated organics. 16 �A tiered scheme was used to economize on the total number of analyses required. The tier 1 operations, schematically shown in Figure 4, included sample extraction, TOC1 assays, capillary gas chromatographic (HRGC) screening for halogenated compounds and hydrocarbons, and PAH analysis by capillary gas chromatography/mass spectrometry (HRGC/MS). Extract analysis by capillary gas chromatography with Hall electrolytic conductivity and flame ionization detectors (HRGC/Hall-FID) provided a sensitive screen for halogenated compounds that was used to aid the identification of specific halogenated compounds in the HRGC/MS data. Some of the individual grab samples were composited to form daily and shift composite samples prior to extraction for tier 1 analysis. The sample compositing scheme was provided by RTI. The tier 2 analyses, also shown in Figure 4, focused on very sensitive and selective determinations of PCBs, PCDDs, and PCDFs. Extracts were analyzed by HRGC/MS operated in selected ion monitoring mode (HRGC/MS-SIM). Suspected responses for PCDDs and PCDFs were confirmed by using high resolution mass spectrometry (HRGC/HRMS-SIM). In addition, three extracts were submitted to the EPA laboratory at Research Triangle Park for collaborative confirmation of PCDDs and PCDFs. The analytical quality assurance program included analyses of method spikes, method blanks, and field blanks in addition to the use of stable isotope-labelled surrogate compounds spiked into all samples to provide some analytical recovery data for all samples. Scanning HRGC/MS analyses were conducted using a stable isotope-labelled internal standard, dio~anthracene. HRGC/HRMS-SIM analyses for TCDD employed 37Cl4-2,3,7,8-tetrachlorodibenzo-£dioxin. In addition, two sets of check samples, one set for TOC1 and one set for specific chlorinated aromatic compounds, were sent to the two laboratories conducting the tier 1 analyses. The analytical methods used are described in detail in the subsections that follow. Additional details of the analytical procedures are described in methods manual for the nationwide combustion source survey.5 Tier 1 Methods Sample Preparation and Compositing-Flue gas samples—The contents of the two modified Method 5 sampling trains used at each sampling point on each day were analyzed as a single sample. That is, the four trains used each sampling day (except for several days at the Ames site on which outlet flue gas was not sampled) comprised daily samples for outlet and inlet flue gas. Hence, the corresponding sample components from both trains were extracted together, i.e., filters, cyclone catch, train rinsings, and resin cartridges. All extracts resulting from the two trains were then combined. All filters and cyclone catches were weighed prior to extraction to allow estimation of particulate emissions. However, the filters were not desiccated to constant weight according to the Method 5 procedures in order to maintain sample integrity for subsequent organic analyses. Hence, the particulate emissions estimates may not be valid. 17 �Sample Extract Short Packed Column GC/Hall (TOCI) TIER 1 HRGC/Hall-FIDor HRGC/FID Screen Add Internal Standard Anthracene - d]g HRGC/MS (Scanning) Surrogates + Pol/cyclic Organic Compounds Add Internal Standard 37, 2,3,7,8-Tetrachlorodibenzo-p-dioxinHRGC/MS-SIM Chlorinated Polycyclic Organic Compounds (Biphenyls, Dioxins, Furans) ••Hold TIER 2 HRGC/HRMS-SIM Confirmation ••Hold Interlaboratory Verification HRGC/HRMS-SIM Figure 4. General analytical scheme. 18 �Grab samples--Portions of the ash, fuel, and aqueous samples were composited according to a schedule provided by RTI to form daily and shift composites for each sample type for selected sampling days. Fly ash, bottom ash, and coal from the Ames site were prepared prior to compositing by pulverizing in a ceramic ball mill with stainless steel balls. Plant background air samples—The single combustion air sample collected each day was extracted and analyzed individually. Prior to extraction, the filters were weighed to allow estimation of the total particulate catch. Sample Extraction— Solid samples—In order to determine the most appropriate extraction procedure, a number of solvent and extraction systems were evaluated using samples of Ames fly ash spiked with selected PAH's and 1,2,3,4-TCDD. Chlorinated solvents were avoided in order to minimize the possibility of producing chlorinated species during the extraction. Preliminary evaluations of simple sample-solvent contact techniques added by mechanical or ultrasonic agitation produced low recoveries. Subsequent evaluations were focused on Soxhlet and reflux procedures. Table 2 summarizes the results of evaluations of seven sample pretreatment and solvent system combinations using Ames fly ash spiked with selected PAHs and 1,2,3,4-TCDD. Pretreatment with water and Soxhlet extraction with benzene provided the highest recovery for all spiked compounds. The average recovery for the nine compounds was 81%. The range of recoveries obtained with this procedure was 56 to 107%. The influence of pretreatment with water on the extractability of the target compounds is not clear. However, a general improvement in recoveries was observed for extractions with acetone/cyclohexane azeotrope when water was added to the ash prior to extraction. Similar effects have been reported for soil and sediment extraction by many researchers. Possibly, the water hydrates cations in the ash that tend to associate with the mobile n-cloud of polynuclear species so that they are more easily extractable. Some researchers have reported good recoveries with procedures involving pretreatment with aqueous acid and extraction with aromatic solvents, e.g., pretreatment with 1 N HC1 and extraction with toluene.6 However, this procedure was determined to be unsatisfactory for several reasons. Acid pretreatment may encourage degradation of some compounds. Reflux or Soxhlet extraction with toluene must be conducted at a higher temperature than for benzene (the boiling points of toluene and benzene are 111 and 80°C, respectively) so that thermally unstable and relatively volatile compounds may be lost. In addition, toluene extracts cannot be conveniently concentrated using Kuderna-Danish evaporation over a steam or hot water bath. All solid samples were Soxhlet extracted with benzene for 8 to 16 hr. The entire sample was extracted for the flue gas train components. Twentygram aliquots of coal, refuse, refuse-derived fuel (RDF), bottom ash, and fly ash were extracted. The fly ash was mixed with 10 ml of prepurified water just prior to analysis. All samples were spiked with the two surrogate spiking compounds, dg-naphthalene and d12-chrysene, just prior to extraction. However, since the extracts for various flue gas components were later combined, only one component for each flue gas sample was selected for surrogate 19 �TABLE 2. RECOVERY OF SELECTED PAHs AND 1,2,3,4-TCDD FROM AMES FLY ASH % Recovery D E F G 62 46 102 63 49 42 107 65 68 60 25 94 60 65 68 64 24 86 72 54 74 75 72 67 81 Chrysene 38 40 NSa NS 38 15 73 Benzo [ a ] py rene 26 28 35 52 26 8 69 Indeno[l,2,3-c,d]pyrene 15 20 27 40 15 0 58 Benzo [ g , h , i ] pery lene 17 24 25 41 17 0 56 Average 45 48 50 59 44 25 81 Compound A B C Phenanthrene 62 76 60 63 Anthracene 49 67 48 Fluoranthene 60 61 Pyrene 64 1,2,3,4-TCDD Note: A. B. C. D. E. Soxhlet 16 hr, cyclohexane, dry fly ash (20 g). Same as A except 5 ml H20 + 5 ml acetone added to fly ash. Soxhlet 16 hr, acetone/cyclohexane azeotrope (67% acetone). Same as C except 5 ml H20 added to fly ash (80% cyclohexane). Soxhlet 16 hr, cyclohexane/ethanol azeotrope + 10 ml water on fly ash (20 g). F. Reflux 4 hr with 250 ml H20 + 50 ml toluene. G. Soxhlet 16 hr with benzene + 10 ml H20 added to 20 g fly ash. a NS = No chrysene in spike. 20 �spiking. The component selected was varied so as to provide some recovery data for all components. The extracts from coal, refuse, and RDF were washed with three 100-ml portions of prepurified water to remove polar interferences. The extracts from all solid samples were dried by passage through short columns of preextracted anhydrous sodium sulfate before concentration to 2 to 10 ml in Kuderna-Danish evaporators. The extracts were further concentrated under a gentle stream of dry nitrogen. The final extract volume was typically 1.0 ml. However, some extracts were analyzed at volumes ranging from 0.20 to 10.0 ml. All extracts were spiked with the internal standard for scanning HRGC/MS, djo-anthracene, prior to analysis. Aqueous samples—All aqueous samples, i.e., flue gas rinses, first impinger waters, overflow waters, raw waters, etc., were batch extracted in separatory funnels with three 60-ml portions of cyclohexane. As in the case of the solid samples, the aqueous samples were spiked with the surrogate spiking compounds just prior to analysis. The resulting extracts were dried and concentrated to 0.20 to 1.0 ml according to the procedures described for solid samples. TOC1 Assay-The TOC1 contents of all extracts were determined using a simplified GC/ Hall procedure. A short packed column and a rapid temperature program were used to elute all chromatographable compounds with volatilities equal to or greater than dichlorobenzene as a single peak. The TOC1 contents of sample extracts were determined by comparing the area response of the peak with that obtained for chlorinated standards. TOC1 results were expressed as chloride. The specific parameters used by SwRI and GSRI for TOC1 assays of the Ames and Chicago samples, respectively, are shown in Table 3. A sample TOC1 chroraatogram for an Aroclor 1254 PCB standard (GSRI procedure) is shown in Figure 5. HRGC/Hall-FID Screening-Sample extracts were screened by HRGC/Hall-FID prior to HRGC/MS analysis to provide a preliminary indication of their halogenated and hydrocarbon contents. In addition, the Hall responses were used to help identify elution times on which to focus examination of the subsequent mass spectral data for halogenated compounds. The specific parameters used by SwRI and GSRI are shown in Table 4. Fused silica capillary columns were used with Grob-type capillary injection systems operated in the splitless mode. GSRI did not have a fused silica column effluent splitter available; hence, extracts from the Chicago plant were screened using FID detection only. Scanning HRGC/MS-Sample extracts were analyzed by HRGC/MS to determine the target PAH compounds and to allow identification and quantitation of specific chlorinated compounds. The primary determinations of surrogate spiking compound recoveries were made from the HRGC/MS data. The chromatographic parameters utilized were essentially identical to those used for the HRGC/Hall-FID screening. 21 �TABLE 3. TOC1 ANALYSIS PARAMETERS Parameter SwRI (Ames samples) GSRI (Chicago NW samples) Column 0.9 m x 4 nun ID, glass 1.0 m x 2 mm ID, glass Packing 2.5 cm of 10% SP-2100 UltraBond 3.8 cm of 2.5% SE-30 on 80/100 mesh Chromosorb G, rest of column filled with 80/100 mesh glass beads Carrier gas He at 60 ml/min He at 30 ml/min Column temperature 60°C for 3 min, then to 230°C at 40°C/min 60°C for 3 min, then to 250°C at 40°C/min External standard compound chlorobiphenyl Aroclor 1254 22 �25 ng Aroclor 1254 Attenuation - 500 V) a> ID V ex. Vent Valve Closed 4 8 12 Time (Minutes) Figure 5. TOC1 chromatogram for Aroclor 1254. 23 16 �TABLE 4. HRGC SCREENING PARAMETERS Parameter GSRI (Chicago NW samples) SwRI (Ames samples) Column 30 m fused silica, wall coated with SE-30 30 m fused silica, wall coated with SE-30 Column temperature 100°C for 5 min, then to 300°C at 10°C/min 60°C for 2 min, then to 300°C at 10°C/min Detectors Hall-FID, 1:1 split FID During the runs, the spectrometer was repetitively scanned over the range m/e 35 to 550 at 1.0 sec/scan. The PAH compounds, including the surrogates, were identified using three extracted ion current plots (EICPs). The criteria for compound identification are coincident peaks in all EICPs at the appropriate retention time with the characteristic response ratios. Compounds identified were quantitated by comparing the EICP response for the most abundant ion with that for the same compound in a mixed standard solution. Tier 2 Methods Following completion of the tier 1 chemical analyses, RTI conducted a statistical analysis of the TOC1 results and constructed a preliminary design for the nationwide survey based on the observed TOC1 variabilities. The preliminary survey design specified sampling programs of 5 and 3 days duration for coal-fired and refuse-fired plants, respectively. Hence, in order to allow inclusion of the pilot study data in the survey data set, the extracts were composited prior to further analysis to simulate a 5-day test at the Ames plant and a 3-day test at the Chicago plant. The compositing scheme, provided by RTI, is shown in Table 5. The composite extracts for each composite day were prepared by combining equal volumes of daily composites from the designated sample days. This necessitated the preparation of daily composites from shift composite extracts or individual sample extracts for many samples and sample days. 24 �TABLE 5. EXTRACT COMPOSITING SCHEME FOR TIER 2 ANALYSES Composite day I II III IV V Sample days combined Ames samples Chicago samples 3/2, 3/15 3/13, 3/22 3/14, 3/19 3/17, 3/20 3/3, 3/23 5/6, 5/9, 5/16 5/7, 5/10, 5/12 5/11, 5/13, 5/15 The composite extracts were screened by HRGC/Hall-FID or HRGC/FID prior to analysis for PAH compounds by scanning HRGC/MS, and for PCBs, PCDDs, and PCDFs by HRGC/MS-SIM. Only extracts for which positive responses were obtained for PCDDs and PCDFs were analyzed by HRGC/HRMS-SIM. HRGC/Hall-FID and HRGC/FID Screening— The composited extracts were screened by HRGC/Hall-FID (Ames samples) or HRGC/FID (Chicago samples) by the procedures described for Tier 1 screening except that fused silica capillary columns wall-coated with SE-54 were used. Scanning HRGC/MS Analysis— The HRGC/MS procedures employed for the composite extracts were essentially the same as was used for tier 1 analyses. The target PAH compounds were determined and any other compounds observed were identified by manual and computer-assisted spectral interpretation. Quantitative estimates for all compounds identified were based on responses versus responses for the same or similar compounds in standard solutions. HRGC/MS-SIM AnalysisAll composite extracts were screened for the presence of PCDDs and PCDFs by HRGC/MS-SIM. The chromatographic parameters used by SwRI and GSRI for the Ames and Chicago extracts, respectively, were the same as were used for scanning HRGC/MS analyses. The ions selected for detection were the two most abundant ions in the molecular cluster for each compound. No positive responses were detected in any of the Ames extracts. Positive responses were detected in composite flue gas extracts from the Chicago plants. However, interfering materials in the extracts hindered reliable identifications. Three composite flue gas extracts from the Chicago plant were cleaned by a vigorous base treatment, an acid treatment, and an alumina chromatographic procedure specifically developed for PCDD and PCDF assays. The composited extracts were split into two fractions each. One fraction was spiked with l,2,3,4-tetrachlorodibenzo-£-dioxin and octachlorodibenzo-£-dioxin, and the other fraction was not spiked. The extracts were stirred with 45% aqueous KOH solution at ambient temperature for 3 hr. The mixture was extracted with hexane and the extract was washed with concentrated sulfuric acid until the washes remained colorless. The extract was concentrated and chromatographed on an alumina column using dichloromethane as the eluting solvent. 25 �The cleaned extracts were analyzed at MRI by HRGC/MS-SIM. The instrumental parameters are listed in Table 6. These analyses were conducted using a high resolution mass spectrometer operated at 1,000 resolution (10% valley). Positive PCDD and PCDF responses were detected in all extracts. Since low resolution mass spectrometric analysis of PCDDs and PCDFs in environmental extracts may be obscured by the presence of similar chlorinated aromatic compounds (e.g., PCB's), these extracts were held for analysis by capillary gas chromatograpy/high resolution mass spectrometry using selected ion monitoring (HRGC/HRMS-SIM). TABLE 6. HRGC/MS PARAMETERS USED FOR ANALYSES OF PCDDs AND PCDFs IN COMPOSITE CHICAGO NW FLUE GAS OUTLET EXTRACTS Column 18 m fused silica wall-coated with SE-54 Column temperature 110°C for 2 min, then to 325°C at 10°C/ min Injector J&W on-column Spectrometer resolution 1,000 (10% valley) Scan rate 1-2 sec/scan (3-5 ions/scan) Ions selected (m/e) Trichlorodibenzo-£-dioxin Tetrachlorodibenzo-£-dioxin Pentachlorodibenzo-£-dioxin Hexachlorodibenzo-£-dioxin Heptachlorodibenzo-£-dioxin Octachlorodibenzo-£-dioxin 285.9, 319.9, 353.9, 389.8, 423.8, 457.7, 287.9 321.9 355.9 391.8 425.8 459.7 Trichlorodibenzofuran Tetrachlorodibenzofuran Pentachlorodibenzofuran Hexachlorodibenzofuran Heptachlorodibenzofuran Octachlorodibenzofuran 269.9, 303.9, 337.9, 373.8, 407.8, 441.7, 271.9 305.9 339.9 375.8 409.8 443.7 The Ames and Chicago composite flue gas outlet extracts were also analyzed at MRI for PCBs by HRGC/MS-SIM. The instrumental parameters and ions selected are shown in Table 7. The focused ions were switched several times during a single HRGC/MS run so that all PCB compounds could be analyzed in two runs, one for odd chlorine substitutions and a second for even chlorine substitutions. PCBs were quantitated by comparing the total area response for all 26 �TABLE 7. HRGC/MS-SIM PARAMETERS USED FOR ANALYSIS OF PCBs IN COMPOSITE FLUE GAS OUTLET EXTRACTS Column 15 m fused silica, wall-coated with DB-5 (a specially bonded SE-54 coating) Column temperature 60°C for 2 min, then to 265°C at 8°C/min Injector Grob-type, splitless Spectrometer resolution 1,000 (10% valley) Scan rate 1-2 sec/scan (2-4 ions/scan) Ions selected (m/e) Dichlorobiphenyl Trichlorobiphenyl Tetrachlorobiphenyl Pentachlorobiphenyl Hexachlorobiphenyl Heptachlorobiphenyl Octachlorobiphenyl Nonochlorobiphenyl 221.9, 255.9, 291.9, 323.9, 357.8, 393.8, 427.7, 461.7, 223.9 257.9 293.9 325.9 359.8 395.8 429.7 463.7 compounds identified for a specific chlorine substitution with the area response for a specific isomer of the same chlorine substitution number. For example, total trichlorobiphenyls were quantitated against 2,5,2'-trichlorobiphenyl. The PCB isomers used for quantitation are listed in Table 8. TABLE 8. PCB COMPOUNDS USED FOR DETERMINATIONS IN COMPOSITE FLUE GAS OUTLET EXTRACTS 2,2'-Dichlorobiphenyl 4,4'-Dichlorobiphenyl 2,5,2'-Trichlorobiphenyl 2,4,2',4'-Tetrachlorobiphenyl 2,4,2',5'-Tetrachlorobiphenyl 2,3,4,5,6-Pentachlorobiphenyl 2,4,6,2',4',6'-Hexachlorobiphenyl 2,3,4,2',3',4'-Hexachlorobiphenyl 2,3,4,5,6,2',5'-Heptachlorobiphenyl 2,3,4,5,2',3',4',5'-Octachlorobiphenyl Decachlorobiphenyl 27 �HRGC/HRMS-SIM Confirmatory Analysis of PCDDs and PCDFs-PCDDs and PCDFs were identified and quantitated in the composite Chicago flue gas outlet extracts by HRGC/HRMS-SIM. The instrumental parameters employed were the same as for low resolution screening at MRI except that the spectrometer was operated at 10,000 resolution (10% valley). The selected ions monitored are listed in Table 9. In order to achieve maximum sensitivity while minimizing the number of HRGC/HRMS-SIM runs, ions for a specific chlorine substitution for both dioxins and furans were monitored in a single run. For example, trichlorodibenzo-p_dioxins and trichlorodibenzofurans were analyzed in the same run. However, the tetra-substituted compounds were analyzed in separate runs to provide even better sensitivity for the most toxic PCDDs and PCDFs. The PCDD and PCDF compounds identified were quantitated by comparing the total area response for all compounds of a specific chlorine substitution with the area response for a specific isomer of the same chlorine substitution number. The specific PCDD and PCDF isomers used for quantitation are listed in Table 10. Compounds for which no corresponding authentic compound was available were quantitated against the most similar compound. Hence, hexachlorodibenzofurans were quantitated against hexachlorodibenzo-£-dioxin. The response factor used for pentachlorodibenzodioxins was the average of responses for tetra- and hexa-isomers. Tetrachlorodibenzo-p_-dioxins were quantitated using 37Cl4-2,3,7,8-tetrachlorodibenzo-£-dioxin as an internal standard. Since discrete isomers were not identified, only totals were determined for each chlorine substitution. A separate HRGC/HRMS-SIM analysis with a 60-m Carbowax column was used to determine 2,3,7,8-tetrachlorodibenzo-g-dioxin. The instrumental parameters are shown in Table 11. The Carbowax column, although providing good separation of specific tetra-isomers, required longer analysis times and caused signficant peak broadening. Hence, it was not used for general PCDD and PCDF analyses. The internal standard method employing 37Cl-labeled compound was used for quantitation. Quality Assurance Procedures The analytical quality assurance program consisted of the use of surrogate spiking compounds in all samples; the use of internal standards for most GC/MS analyses; analyses of field blanks and method blanks; and interlaboratory comparison studies for selected determinations. Surrogate spiking compounds were used as the primary analytical quality indicators. The two stable isotope labeled surrogates, dg-naphthalene and dj2~chrysene, were spiked immediately prior to extraction into all samples at 5 to 10 times the limits of detection. The surrogate concentrations were determined using scanning HRGC/MS data. The surrogate compound recoveries provide indications of overall quality of the extraction and extract concentration procedures. All scanning HRGC/MS analyses were conducted using dio~anthracene as the internal standard. Tetrachlorodibenzo-£-dioxin analyses by HRGC/HRMS-SIM were conducted using 37Cl4-2,3,7,8-tetrachlorodibenzo-D-dioxin. 28 �TABLE 9. IONS MONITORED DURING HRGC/HRMS CONFIRMATORY ANALYSIS OF PCDDs AND PCDFs IN COMPOSITE CHICAGO NW FLUE GAS OUTLET EXTRACTS Compound m/e Trichlorodibenzo-£-dioxin Tetrachlorodibenzo-£-dioxin 37 Cl4-2,3,7,8-Tetrachlorodibenzo-£-dioxin (internal standard) enacorenzo-£-oxn Pentachlorodibenzo-£-dioxin Hexachlorodibenzo-£-dioxin -Heptachlorodibenzo-£-dioxin Octachlorodibenzo-£-dioxin 285.9355, 287.9325 319.8965, 321.936 327.8847 joj.ooo/, 353.8887, 389.8157, 423.7688, 457.7377, 333.0020 355.8858 391.8127 425.7659 459.7347 Trichlorodibenzofuran Tetrachloridibenzofuran Pentachlorodibenzofuran Hexachlorodibenzofuran Heptachlorodibenzofuran Octachlorodibenzofuran 269.9406, 303.9017, 337.8938, 373.8208, 407.7739, 441.7428, 271.9376 305.8987 339,8909 375.8178 409.7710 443.7398 TABLE 10. PCDD AND PCDF COMPOUNDS USED FOR DETERMINATIONS IN COMPOSITE CHICAGO NW FLUE GAS OUTLET EXTRACTS 1,2,4-Trichlorodibenzo-£-dioxin 1,2,3,4-Tetrachlorodibenzo-£-dioxin 2,3,7,8-Tetrachlorodibenzo-£-dioxin Hexachlorodibenzo-£-dioxin (isomer unknown) Octachlorodibenzo-£-dioxin 2,3,7,8-Tetrachlorodibenzofuran Octachlorodibenzofuran 29 �TABLE 11. HRGC/HRMS PARAMETERS USED FOR ANALYSIS OF 2,3,7,8-TETRACHLORODIBENZO-R-DIOXIN IN COMPOSITE CHICAGO NW FLUE GAS OUTLET EXTRACTS Column 60 m fused silica, wall-coated with Carbowax 20M Column temperature 110°C for 2 min, then to 220°C at 10°C/min Injector J&W on-column (1 pi injection) Spectrometer resolution 10,000 (10% valley) Scan rate 1 sec/scan (3 ions) Ions selected 319.8965, 321.8936 Tetrachlorodibenzo-g-dioxin 37 C142,3,7,8-Tetrachloro-£dioxin (internal standard) 327.8847 Analyses of field blanks and method blanks (i.e., laboratory blanks) provided indications of possible sample contamination due to contact with the sampling and analysis equipment as well as general sample and extract handling. Field blanks comprised 10 to 15% of the total samples and included unused components of the flue gas sampling train, a complete sampling train for each plant (as described in Section 5), unused sample containers, and aliquots of solvents used for sample recovery at the plant. Method blanks were extracts prepared in the same manner as sample extracts although no samples were extracted. Since the tier 1 analyses were conducted by two laboratories (SwRI and GSRI), interlaboratory comparison studies were conducted to check the comparability of the resulting data. Three such studies were conducted. Comparability of TOC1 results was investigated by a set of TOC1 check extracts prepared by MRI and by an exchange of selected sample extracts between SwRI and GSRI. Check samples of fly ash spiked with selected chlorinated compounds were also prepared by MRI and analyzed by SwRI and GSRI using HRGC/Hall and scanning HRGC/MS. In addition, extracts in which positive responses were observed for PCDDs and PCDFs by HRGC/HRMS-SIM were submitted to Robert Harless at EPA's Environmental Monitoring and Support Laboratory in Research Triangle Park for collaborative analysis. The results of these analyses are described in Section 9. 30 �CADMIUM Samples of fly ash weighing 0.1 g or samples of bottom ash weighing 0.1 to 1 g were placed in 150-ml beakers that had been precleaned with nitric acid. Ten milliliters of aqua regia were initially added to each ash sample. The samples were gently heated and allowed to reflux until the evolution of yellow fumes subsided. An additional 5 ml of aqua regia was then added, and the ash was allowed to continue digesting. Another 5 ml of aqua regia was added to all samples, and the samples were allowed to digest for at least 20 more min. The samples were permitted to cool, and all of the material was transferred to 50-ml plastic centrifuge tubes. Centrifugation was accomplished at 2,500 rpm for approximately 5 min. The supernatant liquid was transferred by Pasteur pipets to the original beakers. Deionized water was added to the residue in the centrifuge tubes, the mixtures were agitated, the tubes were once again centrifuged, and the supernatant was added to that in the original beakers. This washing procedure was repeated again. The residue remaining in the centrifuge tube was then washed three times with a 5% (v/v) nitric acid solution. For each washing, 5 ml of the acid solution was added to each sample, and the samples were centrifuged and processed as described above. The final solutions in the beakers (approximately 85 ml) were returned to the hot plate and heated gently until the volume of the solution was reduced to 20 ml. The solutions were allowed to cool, filtered through Whatman No. 4 filter paper, and diluted to 50 ml with deionized water. A modification of this procedure was used for the digestion of refuse and filter samples. Fifteen milliliters of aqua regia and 10 ml of deionized water were added to 1-g portions of refuse or to the entire air filter. Tap water and probe-rinse water were digested by adding 3 ml of concentrated nitric acid and 1 ml of concentrated hydrochloric acid to 200 ml of sample and heating gently until the volume was reduced to less than 50 ml. The digested sample was diluted to 50 ml with deionized water. Solutions prepared by digestion of solid samples were analyzed by flame atomic absorption spectrophotometry (AAS) using an air-acetylene flame. Water samples were analyzed by heatedgraphite atomization AAS. A comprehensive QA/QC control program was conducted for cadmium analyses. The program included analysis of the National Bureau of Standards coal fly ash standard reference material, aqueous solutions of cadmium prepared in-house, fortified and duplicate samples, and reagent blanks. Samples were usually digested and analyzed in groups of eight: four distinct samples, a duplicate of one of the original four which had been fortified with 10 pg of cadmium, a duplicate of another of the original four which was unaltered, a quality-control sample, and a reagent blank. The fresh dilutions of a standard solution of cadmium were prepared on each day of analysis and were used to calibrate the AAS. The precision and accuracy of the analytical method used by GSRI were determined by analysis of a coal fly ash standard reference material from the National Bureau of Standards (NBS) and fortified fly ash from the Chicago 31 �Northwest Incinerator. The average and standard deviation of the percentage of cadmium recovered by analysis of four replicate samples of the NBS coal fly ash was 98 ± 11. Analysis of seven replicate samples of incinerator fly ash showed the cadmium concentration to be 260 M8/8- The recovery of cadmium from the incinerator fly ash was determined by analysis of samples fortified with cadmium. The results of the recovery study are presented in Table 12. An average of 95 ± 15% of the cadmium was recovered from the fortified samples. SwRI provided QA measures in terms of analysis of all sample types spiked at the levels shown in Table 13. 32 �TABLE 12. RECOVERY OF CADMIUM FROM FORTIFIED SAMPLES OF FLY ASH FROM THE CHICAGO NW INCINERATOR Cadmium determined in fortified sample (|Jg/g) Cadmium added to sample (Mg/g) Percent cadmium recovered Sample Cadmium in original sample (Hg/g)3 1 260 100 330 70 2 260 99 370 111 3 260 100 360 100 4 260 97 350 93 5 260 100 360 100 6 260 100 370 110 7 260 100 340 80 Mean recovery 95 Standard deviation 15 a Average of seven replicate analyses. TABLE 13. RECOVERY OF CADMIUM FROM FORTIFIED SAMPLES FROM THE AMES MUNICIPAL POWER PLANT Sample type Spike level Fly ash 0.5 Mg/g 97 Bottom ash 0.5 Mg/g 93 Refuse 0.1 Mg/g 98 Coal 0.5 Mg/g 94 Aqueous 4 (Jg/100 ml 33 Recovery 110 �SECTION 7 FIELD TEST DATA AMES MUNICIPAL POWER PLANT, UNIT NO. 7 The field test activity at the Ames Municipal Power Plant took place from February 25, 1980 to March 28, 1980. All required tests were completed and all recovered samples were sent to SwRI for analysis. A summary of the reduced data for flue gas sampling on a daily basis as calculated from the field data sheets is presented in Table 14. The following abbreviations are used throughout this report: DSCF = dry standard cubic feet, DSCM = dry standard cubic meters, ACFM = actual cubic feet per minute, DSCFM = dry standard cubic feet per minute, and DSCMM = dry standard cubic meters per minute. The data listed are corrected to standard conditions, i.e., 20°C (68°F) and a barometric pressure of 29.92 in. of mercury (1.0 atm). Percent isokinetic is the sampling velocity expressed as percent of the gas velocity in the stack or duct at the sampling points. Events that may have created uncertainties as to the quality of the flue gas sampling procedures are noted. Due to severe weather conditions, flue gas outlet samples were not collected on test days 3 to 11. Process data was monitored on an hourly basis during the entire testing period. Table 15 presents a summary of the pertinent process data as averages for daily 24-hr plant operation and operation during the flue gas sampling durations. The process data gathered indicated that the operating conditions fluctuated in patterns related to the amount of electricity generation demand placed on the boiler, and on the type of fuel being burned to meet that demand. Overall fluctuation consisted of two components. The first component was the daily variation. The load peaked in the afternoon and fell to a minimum before dawn. The second type of variation was caused by sudden operational changes, which was due to reduced power generation for various reasons such as the buying of cheaper power from a private utility, or the reduction in flow of RDF to the boiler. Unit No. 7 was generally operated between a range of 16 to 35 MW. Production over 35 MW placed considerable wear on the unit, and was avoided whenever possible. Production under 16 MW introduced instability and the possibility of large transient swings in operating conditions. Usually the boiler was operating close to one of these limits. It operated at 35 MW during peakloads because the load of the serviced community was over 35 MW. Production was reduced to 16 MW when off-peak power could be bought more cheaply from neighboring utilities. 34 �TABLE 14. DAILY DATA SUMMARIES FOR FLUE GAS SAMPLING, AMES MUNICIPAL POWER PLANT, UNIT HO. 7 Date Test (1980) no. Sampling location Inlet 3-2 3-3 1 2 North0 Soutjh Outlet 263d 4 3-6 5 3-7 6 3-8 7 3-9 8 3-10 9 3-11 10 3-12 11 Stack THC temperature pp. °F Molecular weight Moisture Velocity ft/sec 4.48 4.48 6.34 6.34 12.79 12.79 11.31 11.31 18.00 18.00 15.00 15.00 < < < < 2 2 2 2 334.31 311.78 320.93 309.92 29.01 29.35 29.30 29.31 9.95 7.15 6.32 6.24 33.55 29.09 22.69 24.79 Northe 173.54 North* 126.93 South* 212.05 South 101.52 ISA 324.36 2&3 307.31 4.92 3.60 6.01 2.88 9.19 8.70 4.38 4.33 4.33 4.33 5.87 5.87 13.80 13.80 13.80 13.80 12.44 12.44 . 12.00 12.00 11.00 11.00 11.00 < < < < < < 2 2 2 2 2 2 351.55 373.36 234.83 369.90 342.38 336.94 29.34 29.32 29.41 29.39 29.31 29.31 8.39 8.59 7.81 7.97 7.45 7.48 37.78 42.94 46.61 37.15 26.00 26.10 North South 14 &8 2&3* 184.21 252.78 5.22 4.43 7.16 4.43 14.41 14.41 17.00 < 2 17.00 < 2 370.46 352.55 29.56 29.30 7.43 9.48 North South 1&4I* 2S3h 256.88 246.73 7.28 6.99 4.41 4.41 14.56 14.56 18.00 < 2 18.00 < 2 361.09 349.23 29.49 29.38 Inlet North South 367.65 323.17 10.41 9.15 4.35 4.35 13.79 13.79 18.00 18.00 < 2 < 2 363.83 347.46 Inlet North South 368.68 365.42 10.44 4.59 10.35 4.59 13.92 13.92 16.00 < 2 16.00 < 2 Inlet North South 351.42 333.61 9.95 9.45 4.79 4.79 13.60 13.60 28.00 28.00 Inlet North1 North1 South3. Souttr" 74.03 294.81 121.92 140.22 2.10 8.35 3.45 3.97 7.1 7.1 7.1 7.1 11.6 11.6 11.6 11.6 Inlet North!* South 130.81 193.61 3.70 5.48 3.7 3.7 Inlet North South 394.09 383.01 11.16 10.85 4.7 4.7 Inlet , Gas flow ACFM DSCFM DSCMM North" South Inlet Outlet Inlet 3-5 Gas composition C02 CO ppm 5.80 7.43 6.06 6.88 Inlet 3 °2 204.62 262.52 214.10 243.02 Outlet 3-4 Sanple volume DSCM DSCF Outlet Isokinetic rate % 247,700 147,000 4,162 gg'oj 296,000 182,000 5,153 ™m*° _ 650,300 376,000 10,650 gjj'^g 107.14 324,600 190,600 5,397 gg'^ 45.10 43.72 346,200 193,100 5,467 *'^ || 8.14 9.03 43.20 41.09 333,300 189,800 5,375 ,gj'jo 29.28 29.18 8.93 9.72 42.92 43.48 341,600 200,300 5,671 ''4 ^5 351.00 335.86 28.14 29.27 18.32 9.18 43.61 44.01 346,400 187,400 5,307 'gjj'gj < 2 < 2 377.55 359.83 29.19 29.16 9.56 9.75 39.62 39.28 312,000 171,460 4,855 JQJ'J* 25.00 25.00 25.00 25.00 < < < < 316.83 364.73 344.38 315.88 29.19 29.16 29.20 29.17 7.79 8.05 7.78 8.02 30.27 30.38 36.43 27.38 492,300 286,000 8,098 ,gj ''j 13.9 13.9 25.00 25.00 < 2 < 2 352.09 330 . 65 29.31 28.25 8.59 17.13 45.23 43.77 351,900 196,200 5,555 gg'^g 13.5 13.5 22.0 22.00 < 2 < 2 374.75 356.59 29.49 29.30 6.98 8.48 45.68 44.20 355,400 201,000 5,692 jpj'jg 2 2 2 2 95.60 50.55 (continued) �TABLE 14 (continued) Date Test (1980) no. Sampling location Inlet 3-13 12 Outlet Inlet 3-14 13 Outlet Inlet 3-15 14 Outlet Inlet 3-17 15 Outlet Inlet 3-18 16 Outlet Inlet 3-19 17 Outlet Inlet 3-20 18 Outlet Inlet 3-22 19 Outlet Inlet 3-23 20 Outlet Sample volume DSCM DSCF Gas composition C02 CO ppm X % 02 Stack THC temperature ppi. °F Molecular weigl.t Moisture X Velocity ft/sec North South 1&4" 2&3 350.46 369.82 158.98 305 . 29 9.92 3.34 10.47 3.34 4.50 5.17 10.35 5.17 15.56 15.56 13.97 13.97 21.00 21.00 18.00 18.00 < < < < 2 2 2 2 361.78 340.61 339.44 315.08 29.53 29.54 29.56 29.28 8.63 8.54 7.10 9.37 42.45 41.41 25.85 26.58 North South 1&4 2&3 374.34 352.11 367.77 351.36 10.60 3.70 14.81 9.97 3.70 14.81 10.42 5.31 13.18 9.95 5.31 13.18 28.00 28.00 30.00 30.00 < < < < 2 2 2 2 384.68 375.70 365.94 358.75 29.31 29.30 29.14 29.15 9.67 9.70 9.60 9.50 43.48 41.49 24.34 24.84 North South 1&4 2&3 276.77 268.37 319.13 307 . 00 6.31 12.59 22.00 6.31 12.59 22.00 8.37 10.67 19.00 8.37 10.67 19.00 < < < < 2 2 2 2 368.23 357.65 319.42 356.65 29.27 28.32 29.09 29.10 8.14 7.68 7.88 7.83 North South 1&4 2&3 359.80 390.47 406.86 391.84 10.19 11.06 11.52 11.10 3.73 3.73 5.43 5.43 14.40 14.40 12.90 12.90 < < < < 2 2 2 2 371.23 348.41 354.56 345.31 29.35 29.44 29.21 29.25 North South 1&4 2&3 369.16 371.50 392.69 353.25 10.45 10.52 11.12 10.00 3.82 14.39 3.82 14.39 5.42 13.00 5.42 13.00 23.00 < 2 23.00 < 2 24.00 < 2 24.00 < 2 381.96 354.96 360.06 357.50 North South 1&4 2S3 349 . 7 1 9.90 3.60 14.40 368 . 75 10.44 3.60 14.40 374.30 10.60 5.30 13.00 360.58 10.21 5.30 13.00 2 2 2 2 North South0 ISA 2&3 347.89 368 . 08 356.20 388.52 9.85 3.80 13.80 22.00 < 2 10.42 3.80 13.80 22.00 < 2 10.09 6.00 12.50 17.00 < 2 11.00 6.00 12.50 17.00 < 2 North South 1&4 2&3 363.46 348.60 402.14 401.16 10.29 3.60 14.20 9.87 3.00 14.20 11.39 5.30 12.70 11.36 5.30 12.70 North South 1&4 2&3 336.53 330.73 301.61 358.98 9.53 9.37 8.54 10.17 7.83 7.60 9.04 8.69 6.00 12.60 6.00 12.60 9.70 10.00 9.70 10.00 22.00 22.00 22.00 22.00 24.00 24.00 26.00 26.00 38.00 38.00 38.00 38.00 < < < < Gas flowb ACFM DSCFH Isokinetic rate Dscrm 332,100 187,100 5,298 326,700 193,600 5,481 336,000 185,400 5,250 306,506 170,300 4,822 30.85 29.96 20.00 21.31 240,400 135,400 3,834 257,500 152,100 4,307 8.83 8.17 8.71 8.43 41.89 42.84 26.01 27.27 335,000 189,000 5,351 332,100 191,500 5,423 29.29 29.37 29.24 29.18 9.36 8.73 8.62 9.09 43.06 41.89 27.12 25.60 335,900 186,300 - 5,274 328,600 187,800 5,319 380.28 361.59 373.12 365.94 29.29 29.37 29.03 29.24 9.68 8.68 10.28 8.59 41.87 43.42 26.75 26.92 337,300 184,300 5,218 334,500 185,300 5,246 350.96 342.65 338.12 342.81 29.33 29.39 29.29 29.21 8.31 7.86 7.79 8.44 42.13 42.11 24.63 26.91 333,100 191,000 5,408 321,200 188,400 5,334 < < < < 2 2 2 2 348.64 342.09 340.00 330.60 29.36 29.41 29.19 29.24 8.54 8.07 8.61 8.23 41.65 39.63 26.26 26.81 321,400 185,000 5,239 330.700 195,500 5,537 < < < < 2 2 2 2 364.41 355.41 354.13 338.13 29.26 28.69 28.82 29.28 8.16 12.74 9.73 5.87 28.65 27.26 16.63 19.70 221,100 121,500 3,440 226,400 132,800 3,761 X 102.35 102.23 77 .72 91.73 101.27 107.20 99.80 96.74 102.11 108.67 104.05 96.83 1 06 . 85 99.99 107.18 95.48 100.17 108.07 99.82 93.81 107.21 97.16 101.03 92.62 92.21 104.31 95.09 97.71 105.17 96.42 104.10 99.03 103.54 115.99 110.45 102.66 (continued) �TABLE 14 (concluded) Test Date (1980) no. 3-24 21 3-25 22 3-26 23 Sampling location Outlet 1,2, 3S4 North1" Southp Outlet 1,2, 3&4 Sample volume DSCF DSCM 02 % Gas composition C02 CO THC % ppm ppm 130.42 3 6 . 9 5.4 13.2 122.79 3.48 5.4 Stack Isokinetic temperature < 2 Molecular °F Moisture Velocity % ft/sec weight 365.47 29.15 9.53 25.76 Gas flow ACFM 160.500 DSCFM rate DSCMM 90,170 2,553 % 103.72 T , Inlet North South Outlet 1,2 3S4 Inlet 326.82 344.98 138.67 13.2 9.26 6 0 12.60 . 0 9.77 6 0 12.60 . 0 3.93 4 8 13.70 . 0 < 2 356.40 29.10 9.92 24.58 < 2 <2 < 2 380.80 382.45 364.38 29.13 29.14 29.24 9.17 9 0 . 9 9.26 37.23 37.40 26.42 153,200 87,030 2,464 101.06 , fi 106.24 1 2 5 0 6 4 6 2 ' '0 ' 0 118.43 164,700 93,240 2,640 106.64 2 5 1 0 9 0 a Average values for duration of test. b Sun of flow through total inlet and total outlet. c Low volume collected due to high leak rate at end. Volume was corrected for leak rate. Test quality fair. d Low volume collected due to freezing of impingers. e At 250 rain, noted nozzle pointed in wrong direction. Switched nozzle from 0.312 to 0.250 in. diameter tip to maintain isokinetic flow. Test quality was good for gas and fair for particulate. f Switched nozzle from 0.312 to 0.237 in. diameter tip to maintain isokinetic flow. g Due to snow and icy conditions, no sample was obtained. h Cancelled per instructions of EPA until 3/13/80. i Switched nozzle from 0.250 to 0.310 in. diameter tip to maintain isokinetic flow. j Switched nozzle from 0.310 k Probe found broken at 140 min, no samples retained. conditions. Test quality was fair. 1 No solutions retained due to backup of H202 into all impingers. • QA test cancelled after 240 min due to leak at one of the probe tips. n Test stopped at 296 min due to continual freezing of the train components. o Problems with the Batelle trap freezing and leaks in the Teflon line were encountered. Test quality was fair to good. p QA test only. Test quality was good. to 0.240 with diameter tip to maintain isokinetic flow. Test restarted with a new probe but only one half the duct was traversed due to freezing The resin, cyclone and filters were retained. Test quality was fair. Test quality was fair to poor. The filter and traps were replaced to solve leak problems. No samples were saved because nozzle was in the wrong direction nnd the test would not be duplicate. �TABLE 15. AVERAGE PROCESS DATA FOR THE AMES MUNICIPAL POWER PLANT, UNIT NO. 7 24-hr Process data Standard deviation Mean Flue gas test duration process data Standard deviation Mean Steam flow rate (1,000 Ib/hr) 255 35 289 50 Steam pressure (psig) 852 3 853 3 Steam temperature 892 3 896 5 Feedwater flow rate (1,000 Ib/hr) 263 37 298 51 Feedwater temperature 366 16 377 19 (°F) Fuel feed rate 1 (1,000's Ibs/hr) 2 30.4 30.6 3.2 3.4 33.1 Fuel oil (gal./hr) 10.7 11.2 - - I.D. fans amps 45 1 46 2 I.D. fans pressure (psig) F.D. fans amps 5.5 0.7 1 29 5.9 30 4.2 1.0 1.1 F.D. fans pressure (psig) 4.0 0.6 4.5 0.9 Furnace draft (psig) 0.6 - 0.6 0.1 Flue gas temperature Boiler exit3 ESP inlet3 Ambient temperature (°F) 667 323 (°F) Ambient pressure in. Hg 24 15 31 13 29.01 a Not total time means. 38 0.13 674 326 39a 29.01 31 18 20 0.13 �The daily mean of gross electrical output (24-hr basis) was typically between 29 and 32 MW due to boiler operation at full output for a large portion of the day. In fact, the hourly readings indicated that output was rarely below 35 MW between the hours of 8 AM and 10 PM or longer. During non-peak hours the boiler operated between 16 and 25 MW, depending on load and the amount of power being purchased from neighboring utilities. Fuel consumption varied directly with the amount of electricity produced. Of the three types of fuels used in Unit No. 7 (coal, RDF, and fuel oil), coal was used in the largest quantity. The amount of RDF burned was limited to approximately 17% in terms of the total heat produced. This was because RDF, due to its lower heating value, cannot sustain sufficient temperatures to maintain required boiler efficiency and steam quality. Also, RDF requires a longer residence time in the boiler for complete combustion, and this places another physical restriction on the amount of RDF in the fuel mixture. Fuel oil is used sparingly, and only as an igniter to insure flame continuity during soot blowing. The large variations in fuel oil consumption noted in Table 15 were more related to operating practices than to the boiler requirements. The means and standard deviations for coal consumption follow those of the gross electrical output. This indicates that coal consumption is closely related to electrical output, as expected. However, these daily averages mask out one important effect. The amount of coal burned depends on whether there is RDF in the mixture or not. All other things being equal, the flow of coal will always go up or down, depending on whether RDF is being removed or introduced into the mixture, respectively. Data for the steam cycle in the boiler are also listed in Table 15 on an average basis. Examination of the data on a daily basis indicated that the steam and feedwater flow rates fluctuate in a daily cycle, with means and standard deviations following the gross electrical output. However, the values for steam temperature and pressure remain fairly constant. The feedwater temperature also varied. It was higher on days of high electricity production, and lower on days of low production. The induced and forced draft fan measurements listed in Table 15 are of limited significance, since they did not respond to increases in production with greater airflows and correspondingly greater current consumption. The furnace draft data indicated little or no correspondence to any of the other measured data. Most of the flue gas and ESP inlet temperature readings were incomplete as they did not cover the entire 24-hr day. Most of this information was recorded during peak operation, and may therefore be considered representative for peak operation conditions. Both the flue gas and ESP inlet temperatures decreased during off-peak periods. The continuous supply of RDF to the boiler during the test was found to be unreliable. The RDF conveyors which feed Unit No. 7 were prone to jamming and required frequent maintenance. Often the RDF supply ran out because the solid waste recovery plant was experiencing mechanical problems, or had run out of refuse to process. The durations of RDF-firing during the flue gas sampling periods are shown in Table 16 along with the mean coal feed rates. 39 �TABLE 16. FUEL COMBUSTION DURING FLUE GAS SAMPLING Date Test period Mean coal feed rate (1,000 Ib/hr) 3/2/80 3/3/80 3/4/80 3/5/80 3/6/80 3/7/80 3/8/80 3/9/80 3/10/80 3/11/80 3/12/80 3/13/80 3/14/80 3/15/80 3/17/80 1120-2000 0920-1855 0900-1800 0900-1820 0840-2140 0850-2220 0840-2215 0830-2211 0810-1733 0825-2235 0910-1315 0835-2147 0840-2255 0905-2206 0849-2225 0900-2325 0843-2407 33.5 32.6 3/20/80 3/22/80 3/23/80 3/24/80 3/25/80 3/26/80 0905-1625 0947-1412 0927-1410 1110-1547 1120-1546 0922-1406 None 1100-1530 Entire run 1020-finish 0900-finish 1230-finish 0900-finish None 1512-finish Entire run Entire run 1608-finish Entire None 1010-1105 1340-finish Entire run Start-1310 1610-finish 1100-1135 Start-1212 None Entire run Entire run Start-1330 34.9 36.2 34.3 35.5 35.4 35.7 32.1 25.2 36.3 33.8 35.1 38.6 34.4 23.0 35.1 3/18/80 3/19/80 RDF feed period 33.3 33.2 21.4 33.1 33.8 35.1 Mean RDF density (lb/ftS) . 5 4.7 5 4.3 4 3.7 4 4 4.3 4.3 4.5 NAa 3.7 4 3.5 4 3.8 3.3 a NA = not available. Out of 23 days of sampling, RDF was burned during the entire test run for only 7 days. On 12 days RDF was burned part of the time, and on 4 days it was not burned during the flue gas sampling. Routine activities such as ash removal and soot blowing were performed at times designated in the test plan. RDF was observed to have a substantially higher ash content than coal, and this characteristic was reflected by longer ash removal periods, and more periodic soot blowing. Both activities decreased substantially when RDF was not being burned. Table 17 contains information on daily production and consumption at the Ames Municipal Power Plant, Unit No. 7 recorded by the power plant operators 40 �TABLE 17. DAILY PRODUCTION AND CONSUMPTION AT AMES MUNICIPAL POWER PLANT, UNIT NO. 7 Date 3/2/80 3/3/80 3/4/80 3/5/80 3/6/80 3/7/80 3/8/80 3/9/80 3/10/80 3/11/80 3/12/80 3/13/80 3/14/80 3/15/80 3/17/80 3/18/80 3/19/80 3/20/80 3/22/80 3/23/80 3/24/80 3/25/80 3/26/80 a Power production (kwh) gross net Thermal energy (Btu/kwh) net gross 681,000 709,000 761,000 759,000 7000 4,0 735,000 648,000 494,000 693,000 739,000 7000 5,0 742,000 729,000 5800 0,0 699,000 759,000 748,000 753,500 7600 0,0 426,000 710,000 700,000 726,000 11,186 11,296 11,396 11,697 11,693 11,652 11,602 11,524 10,955 11,440 11,348 11,544 11,537 11,434 11,170 10,855 10,794 11,368 11,077 11,311 10,841 11,080 10,949 623,902 648,682 700,072 698,461 679,858 674,470 590,057 443,496 635,037 678,629 6846 8,5 681,889 668,119 457,939 639,942 696,494 682,596 689,205 647,644 382,263 650,039 642,011 664,973 12,210 12,346 12,388 12,711 12,728 12,697 12,742 12,836 11,985 12,458 12,362 12,562 12,588 12,684 12,201 11,829 11,829 12,388 12,075 12,605 11,841 12,081 11,954 Steam production (Ib/kwh) 9.57 9.59 9.53 9.73 9.50 9.64 9.54 9.47 9.54 9.57 9.62 9.68 9.51 9.50 9.59 9.52 9.51 9.56 9-55 9.49 9.61 9.52 9.60 Iowa coal (Ibs) 339,988 418,330 412,290 434.538 432,096 427,127 358,286 301,888 486,980 334,328 408,980 432,270 412,440 322,448 412,335 417,010 414,315 445.392 410,520 269,610 629,920 610,880 612,960 This value is derived from the average Btu content of each fuel, b This is only a rough measure of RDF weight. Fuel consumption L RDF" Colorado coal (Ibs) (Ibs) 432,712 342,270 351,210 370.162 339,504 378,773 317,720 267,712 262,220 392,472 334,620 368,230 324,060 253,352 337,365 341,190 338,985 379,408 335,880 220,590 157,480 152,720 153,240 0 113,000 226,800 192,375 213,200 130,800 168,460 26,000 81,200 229,600 229,075 144,075 230,400 22,050 97,650 154,874 134,816 63,700 92,000 0 51,600 93,000 134,970 Oil (gal.) 60 160 70 60 90 100 130 150 100 270 290 50 90 910 70 60 100 490 640 800 490 680 40 Sluice water for bottom and fly ash Removal (gal.) 250,000 340,000 320,000 380,000 450,000 320,000 360,000 314,908 386,716 403,172 413,644 422,620 418,132 335,104 396,000 473,000 477,000 320,000 250,000 180,000 300,000 430,000 540,000 Water input to evaporator (gal.) 8,300 9,000 2,200 6,800 9,200 2,500 1,120 8,500 6,300 5,800 3,500 9,100 0 5,700 11,100 15,200 6,000 7,300 5,400 16,600 4,500 4,000 18,500 �on a daily basis. The total gross and net power production was recorded directly from meters inside the plant. The total steam produced divided by the gross power production gave a good indication of boiler efficiency. Separate meters were used for measuring the water used for ash removal and the total input to the evaporators. The days of highest sluice water use corresponded with days of prolonged use of RDF in the fuel mixture. The evaporators eventually feed into the working fluid cycle of the boiler, and gave a fair indication of make-up water required, except that there was a water reclamation system attached to the boiler. Hence, these values indicated new input to the system, but did not account for total make-up water requirements. Most of the fuel types were very accurately measured. Coal was measured through a weight integrating system, and fuel oil was similarly measured through a volume integrating system. However, no accurate measurement of the RDF was possible. The values listed were derived from volumetric readings and a very rough measurement of the RDF density, taken once every shift. Although rough estimates of the RDF content were made, there was no effective means for obtaining a representative sample of the refuse mixture. The variability of the RDF in the total pulverized mixture is reflected in the results for TOC1 and inputs and emissions of cadmium from this plant. The BTU contribution of each fuel was then calculated by doing calorimetric analyses. This was done periodically, and the values used for the duration of this test program are given in Table 18. By summing the Btu contribution of each fuel, a value for total heat production was found. This value was then divided by either the gross or net electricity production to express thermal energy as it related to the power production of the day. CHICAGO NORTHWEST INCINERATOR, UNIT NO. 2 The field test activity took place from April 30, 1980 to May 23, 1980. All required tests were completed and all recovered samples were sent to GSRI for analysis. A summary of the reduced flue gas data (inlet and outlet) on a daily basis as calculated from the field data sheets is presented in Table 19. Events that may influence the quality of the tests are also noted on this table. The process parameters considered to be important to the operation of Boiler No. 2 included the steam flow rate, steam pressure, feedwater flow rate, feedwater temperature, combustion air flow rate, combustion air temperature, % oxygen, I.D. fan pressure, F.D. fan pressure, furnace draft and furnace temperature. Most of this data was available from instrumentation in the control room. Table 20 summarizes this plant process data in terms of the average values of the typical sampling date operations. This data is presented in terras of 24-hr plant operation and the flue gas test period durations. Although there are some slight variations, the values are readily comparable for the two time intervals. A comparison of the daily process data with the average of the data collected indicates that the Chicago Northwest Incineration facility operated in essentially the same mode 24 hr a day, 7 days a week. Although major changes in steam production were noted to occur over short time intervals (less than 1 hr) no significant variation in steam production occurred day to day indicating a rather consistent fuel feed rates during the duration of the tests. 42 �TABLE 18. HEAT CONTENT OF FUELS USED AT THE AMES MUNICIPAL POWER PLANT DURING SAMPLING PERIOD Duration of test Heat content for each fuel type Colorado Fuel oil coal RDF Iowa coal (Btu/gal.) (Btu/lb) (Btu/lb) (Btu/lb) 3/2/80 thru 3/16/80 8,946 10,556 5,587 138,603 3/17/80 thru 3/26/80 9,035 10,298 6,128 138,603 �TABLE 19. DAILY DATA SUMMARIES FOR FLUE GAS MEASUREMENTS, CHICAGO NORTHWEST INCINERATOR, BOILER NO. 2 Date Test (1980) No. Sampling location Sample volume DSCM DSCF North0 256.84 South6 135.20 Outlet North 317.86 South 324.14 Inlet 5-4 1 2 3 4 5 6 7 8 9 10 2 2 2 2 459.47 444.88 432.76 451.27 28.26 28.52 28.33 28.41 11.56 9.57 11.56 10.87 20.17 21.27 36.40 39.33 111,400 56,500 102,200 51,830 Isokinetic rate % 1,600 1,468 459.04 445.78 442.00 451.04 28.53 28.56 28.45 29.58 12.24 12.03 12.47 2.95 20.62 18.42 38.21 40.60 104,300 51,300 1,453 106,400 55,310 1,566 North South Outlet North South 324.36 400.66 403.32 407.07 9.19 11.34 11.42 11.53 9.4 9.4 9.4 9.4 9.8 9.8 9.7 9.7 185 185 189 189 < < < < 2 2 2 2 445.55 431.46 459.04 457.78 28.34 28.36 28.39 28.41 13.43 13.26 12.86 12.75 19.90 21.23 36.70 38.87 110,900 54,930 1,555 102,000 49,780 1,410 North South, Outlet North South 331.52 370.83 427.50 457.50 9.39 10.50 12.11 12.96 9.9 9.9 10.4 10.4 9.5 9.5 8.9 8.9 142 < 142 < 169 < 169 < 2 2 2 2 445.36 460 . 60 454.20 464.32 28.57 28.50 28.82 28.47 11.27 11.85 8.60 11.60 19.34 19.96 38.39 41.69 105,600 52,770 1,494 108,100 54,430 1,541 North* SouthJ North Outlet South 342.70 367.81 371.55 383.75 9.77 10.42 10.52 10.87 7.9 7.9 8.1 8.1 10.5 10.5 10.7 10.7 61 61 59 59 < < < < 2 2 2 2 423.77 460.80 449.64 437.76 28.30 28.20 28.17 28.24 14.14 14.94 15.46 14.89 17.71 17.31 32.99 32.48 93,900 45,870 1,299 88,400 42,770 1,211 North South. K Outlet North South 320.56 347.61 367.97 412.06 9.08 9.84 10.42 11.67 8.8 10.3 8.8 10.3 9.4 9.7 9.4 9.7 1 1 1 1 < < < < 2 2 2 2 452.59 457.63 448.92 452.28 28.37 28.34 28.50 28.33 13.62 13.83 11.94 13.40 18.12 17.86 35.43 39.50 96,530 46,250 1,310 101,200 49,320 1,397 North South 1 Outlet North " South™ 344.80 378.50 299.62 459.63 9.76 10.72 8.49 13.02 9.8 9.8 9.8 9.8 9.0 9.0 9.5 9.5 1 1 1 1 < < < < 2 2 2 2 463.29 462.48 462.53 447.47 28.19 28.15 28.37 28.30 13.86 14.24 12.91 13.52 19.12 18.51 38.99 38.13 101.000 48,280 1,367 103,900 50,470 1,429 North South Outlet North South 316.55 373.03 376.48 391.17 8.96 10.56 10.66 11.08 8.7 8.7 10.4 10.4 9.7 9.7 9.0 9.0 1 1 1 1 < < < < 2 2 2 2 456.24 468.33 442.84 452.88 28.40 28.38 28.41 28.42 12.57 12.79 12.21 12.08 17.58 19.11 36.73 39.17 98,830 47,970 1,358 102,500 50,800 1,438 North South Outlet North South 308.73 364.16 366.28 388.73 8.74 10.31 10.37 11.01 9.7 9.7 9.1 9.1 9.6 9.6 9.8 9.8 1 1 1 1 < < < < 2 2 2 2 465.61 468.65 457.16 453.52 28.19 28.19 28.25 28.20 14.57 14.52 14.10 14.54 16.42 17.82 36.85 39.39 92,240 43,330 1,227 102,900 49,060 1,389 North 338.45 South 376.86 Outlet North" 377.44 South 396.28 9.59 10.67 10.69 11.22 10.2 10.2 9.6 9.6 9.4 9.4 9.7 9.7 111° 111 98 98 < < < < 2 2 2 2 465.43 458.88 459.56 463.68 28.29 28.27 28.88 28.24 13.60 13.75 8.89 14.22 18.05 17.67 35.47 38.49 95,870 46,760 1,324 99,850 49,810 1,410 Inlet 5-15 < < < < 2 2 2 2 Inlet 5-13 172d 172 156 156 < < < < Inlet 5-12 7.4 7.4 7.7 7.7 159 159 171 171 Inlet 5-11 11.2 11.2 11.3 11.3 10.1 10.1 9.5 9.5 Inlet 5-10 7.27 3.83 9.00 9.20 9.6 9.6 10.4 10.4 Inlet 5-9 DSCMM 11.57 10.74 11.85 12.97 Inlet 5-8 ACFM Gas flowb DSCFM 408.46 379.18 418.43 457.89 Inlet 5-7 Stack temperature Molecular Moisture Velocity weight »F ft/sec % North South Outlet North 8 South Inlet 5-6 Gas composition 02 C02 CO THC % % PP» ppm (continued) 90.82 79.24 94.61 97.96 96.25 98.32 98.85 93.23 98.17 97.71 100.75 96.29 100.22 97.28 96.59 100.04 99.85 101.90 105.57 107.99 108.82 105.61 98.61 96.51 100.85 100.82 99.20 102.22 98.95 94.93 102.67 100.42 105.23 102.11 104.01 102.82 102.87 102.67 102.40 106.30 �TABLE 19 (continued) Date Test (1980) No. Sampling location North South Outlet North South 353.83 357.30 404.61 416.58 Inletp North South Outletp 324.92 331.75 218.81 Inlet 5-16 11 5-17 12 5-18 13 Inlet North South Outlet 5-19 -PLn ,4 Sample volume DSCF DSCM I-l=t Outlet ACFM Gas flow DSCFM DSCMM Isokinetic rate % 465.32 467.67 455.72 460.24 28.49 28.42 28.35 28.38 11.15 11.69 11.79 11.59 18.79 18.22 99,300 49,200 1,395 '93 'ol 40^83 117,500 58,310 1,651 {oi'<;2 80 < 2 80 < 2 84 < 2 474.80 475.00 451.00 28.27 28.37 28.16 13.47 13.70 14.38 17.25 16.85 39.27 91,430 106,000 43,540 51,350 1,233 1,454 *£•*£ 103.01 r 463.00 28.25 13.91 44.37 119,800 57,360 1,624 92.45 r 465.60 28.36 11.65 44.53 120,200 59,140 1,675 98.36 8.5 8.5 7.9 7.9 9.20 10.3 9.40 10.3 6.20 10.7 10.0 10.0 9.0 6.20 10.7 9.2 102 6.81 12.7 7.2 304 88° 88 98 98 < < < < Velocity ft/sec 2 2 2 2 11.1 11.1 11.8 11.8 10.02 10.12 11.46 11.80 , Moisture q 219.36 North South Gas composition3 Stack 02 C02 CO THC temperature Molecular ppm ppoi °F weight q 240.61 a b c d e f g h i j k 1 m n Average during test period. Sum of the North and South train measurements. Test was run for 350 nin. Test was discontinued because of unsuccessful leak checks after filter replacement. High due to excessive instrument drift. Test ran for only 193 nin due to plant shut down because of a boiler leak. Only 21 of the required 24 points were traversed. Test quality was poor due to crack in the probe. Low moisture obtained because of cracked probe. Sampling time increased from 20 to 25 min per point after 180 min. Test quality was good. Sampling time increased from 20 to 25 min per point after 267 min. Test quality was good. Test was halted one point from completion due to stormy water. Test quality was good. Analyzer taken off line (see d). Due to excessive leak rate in the north tracer, 60% of the sample was collected with the south tracer, 40% with the north. Probe was found with a cracked tip. Based on 8.9% moisture versus 12% moisture for the other tests, it was determined that only the last 10 points were traversed with the broken probe. Test quality was fair. o Results ± 10% due to drift, p Inlet QA test, outlet 1st day cadmium test, q Inlet sample not required for cadmium test, r THC data not required for cadmium test. �TABLE 20. MEANS OF THE MEANS FOR PROCESS DATA, ALL TEST DAYS, CHICAGO NW INCINERATOR, BOILER NO. 2* Parameter Steam flow rate (Ibs/hr) Disc recorder Chart recorder Digital integrator Steam pressure (psig) Feedwater flow rate (Ibs/hr) Chart recorder Digital integrator Feedwater temperature (°F) Combustion air flow rate (ft3/hr) Chart recorder Digital integrator Combustion air temperature (°F) 24-hr process data Standard Mean deviation Flue gas test duration process data Standard deviation Mean 99,000 103,000 99,000 4,500 4,500 3,600 100,000 104,000 100,000 8,100 8,300 10,300 282 4 287 2 99,000 97,000 4,800 5,400 101,000 100,000 8,400 11,000 221 1 221 1 79,000 72,000 2,000 2,600 78,000 70,000 2,700 2,200 663 21 673 23 I.D. fans pressure (inches HgO) 2 .6 0.2 2.5 0.3 F.D. fans pressure (inches HgO) 14 .1 0.4 14.1 0.6 Furnace draft (inches ^ ) 0 Furnace temperature (°F) a 0.23 1,160 From Appendix B. 46 0.06 42 0.22 1,198 0.8 67 �Additional information collected for daily process tables included the times of soot blowing, fuel input to Boiler No. 2, down time on Boiler No. 2, daily barometric pressure and miscellaneous comments concerning the boiler operation. Soot blowing was to follow a set schedule of three times per day, although deviations from this schedule were observed. Barometric pressure was obtained once per day from nearby Midway airport and deviations from typical plant operation were noted from the operator's log book. The measurement of fuel input posed a somewhat more difficult problem. All refuse and residue hauling trucks entering and leaving the incinerator plant were carefully weighed. This facilitated the accurate characterization of overall inputs and outputs. However, there was no accurate way of proportioning these materials between specific boilers for a given period of time. Attempts to determine the fuel burned or ash discharged from Boiler No. 2 were approximations. Chicago Northwest Incinerator maintains inventory sheets listing inputs and outputs from the facility on a weekly basis. Relevant data from these sheets are reproduced in Table 21. The weight of refuse received was measured on scales before and after the refuse trucks released their loads. The volume of refuse received was determined by multiplying the number of truck loads by the volume of each truck (19.5 cubic yards). Density of the refuse was estimated using these two measurements, and is therefore the density of refuse inside the trucks. In order to quantify the amount of refuse burned, the number of loads, or charges, handled by the grab bucket cranes were noted for each boiler. The total number of charges to Boiler No. 2 for daily operations are given in Table 22. To approximate the amount of refuse burned in Boiler No. 2, it was necessary to determine an average weight per charge. When refuse trucks enter the plant, they discharge their contents into a large storage pit. Although the weight of refuse added to the pit is well characterized for each weekly period, the carry-over of material from week to week cannot be accurately measured. Furthermore, this carry-over is quite variable over the length of time being considered. It is necessary to quantify the carry-over in terms of weight, so that the total weight of refuse burned, and hence, the average weight per charge, can be approximated. The calculation of the average weight per charge involves using visual measurements of the pit volume taken at the end of each week. This "pit estimate" can then be used in association with the density of the incoming garbage to approximate the weight of refuse in the pit. The average weight per charge can be determined by the following equation: Average wt per charge _ (pit estimate for previous week - pit estimate + refuse delivered) total number of charges All terms in parenthesis must be expressed as weights. This method, however, has a drawback in that the density in the pit is probably not the same as the density inside the refuse trucks, since the refuse inside the trucks is compacted and is liable to expand somewhat as the trucks are unloaded. 47 �TABLE 21. WEEKLY INVENTORIES OF REFUSE AND RESIDUE AT THE CHICAGO NW INCINERATOR (ALL BOILERS) 4/28/80 to 5/4/80 Refuse received By weight (tons) By volume (cu yd) Density (lbs/yd3) Storage pit condition At beginning of week (% full) At end of week ( full) % Refuse consumed No. charges burned Average weight per charge (Ibs) Total weight (tons) Total volume (cu yd) Residue Fine ash fraction (tons) Fine ash fraction (cu yd) Metal fraction (tons) Metal fraction (cu yd) Total ash (tons) Total ash (cu yd) 5/5/80 to 5/11/80 5/12/80 to 5/18/80 5/19/80 to 5/25/80 6,747 24,490 551 9,152 29,618 618 7,902 26,561 595 8,720 28,778 606 84 65 61 42 65 61 42 42 5,205 2,771 5,710 3,240 5,952 2,812 4,714 3,700 7,212 28,562 9,250 36,634 8,367 33,138 8,720 34,535 2,511 3,100 949 5,423 3,460 8,523 2,500 3,086 750 4,286 3,250 7,372 1,815 2,240 1,514 18,651 3,329 10,891 2,904 3,585 629 3,594 3,533 7,179 Volume reduction thru incineration 70% 80% 67% 79% Weight reduction thru incineration 52% 65% 60% 60% 48 �TABLE 22. CHARGES FED TO BOILER NO. 2 ON A SHIFT BASIS CHICAGO NORTHWEST INCINERATION FACILITY No. of Date, shift charges No. of Date, shift charges No. of Date, shift charges No. of Date, shift charges 4-28, 5-12, 2nd 3rd 99 99 5-19, 2nd 3rd 110 105 2nd 3rd 98 99 5-5, 4-29, 1st 2nd 3rd 100 94 101 5-6, 1st 2nd 3rd 68 112 5-13, 1st 2nd 3rd 100 100 60 5-20, 1st 2nd 3rd 104 118 110 4-30, 1st 2nd 3rd 90 94 101 5-7, 1st 2nd 3rd 99 84 100 5-14, 1st 2nd 3rd 96 5-21, 1st 2nd 3rd 100 106 90 5-1, 1st 2nd 3rd 94 49 98 5-8, 1st 2nd 3rd 81 101 100 5-15, 1st 2nd 3rd 104 106 108 5-22, 1st 2nd 3rd 80 105 100 5-2, 1st 2nd 3rd 100 98 101 5-9, 1st 2nd 3rd 100 98 100 5-16, 1st 2nd 3rd 106 97 110 5-23, 1st 2nd 3rd 107 107 102 5-3, 1st 2nd 3rd 100 102 99 5-10, 1st 2nd 3rd 99 101 100 5-17, 1st 2nd 3rd 112 97 114 5-24, 1st 2nd 3rd 98 105 94 5-4, 1st 2nd 3rd 97 96 12 5-11, 1st 2nd 3rd 102 101 105 5-18, 1st 2nd 3rd 108 104 118 5-25, 1st 2nd 3rd 101 105 107 5-5, 1st 5-12, 1st 103 5-19, 1st 105 5-26, 1st 105 Total for week 1,823 2nd 3rd - 1,754 1,943 49 2,159 �It seems likely that the level of compression would have a more pronounced effect upon the refuse density than the actual characteristics of the refuse. Since the compaction inside the pit is always similar, one would also expect the density in the pit to be reasonably constant. The plant personnel indicated that the typical refuse density was 505 Ib/cu yd. Therefore, this value can be used as an assumed density, and the pit estimates used in the equation: Volume of refuse in pit = P*t estimate ( of tota^volume) x total pit volume % total pit volume = 9,700 cu yd Weight of refuse in pit = volume of refuse in pit x refuse density in pit assumed refuse density = 505 Ib/cu yd Weight of refuse incinerated per week = (weight of refuse in pit at beginning of week - weight of refuse in pit at end of week + weight of refuse delivered) . ,. , total weight of refuse incinerated A Average weight per charge = total number of charges Volume of refuse incinerated = weight of refuse incinerated assumed refuse density The amounts of fine ash and metal fractions produced by the incinerator during the test period are listed in Table 21. It should be noted that these are the amounts leaving the plant during this time period, and are not necessarily the same as the ash being produced during this period. Since no account has been taken of any carry-over from week to week, it can only be assumed the carry-over is similar each week. In order to obtain total ash, the metal and fine ash fractions were summed together. The ash volumes were calculated using the following densities: Density of fine ash fraction = 1,620 Ib/cu yd (960 kg/m3) Density of metal fraction = 350 Ib/cu yd (210 kg/m3) These values were based on previous analyses done by the plant, and have been assumed to be typical. Since all of the combined ash was subjected to a water quench, these weights incorporate a rather large moisture content. However, no better characterization was available. The volume and weight reductions achieved through incineration have been calculated as an indication of how efficiently the boilers were operating. Due to the heterogeneous nature of the refuse used to fuel this plant, it was very difficult to obtain representative samples for laboratory analyses for organic compounds and cadmium. The previous discussion of the approximation of refuse burned in Unit No. 2 reflects an additional problem in previding accurate information for the levels of the analytes introduced as inputs to this combustion source. Both the variabilities of TOC1 and cadmium 50 �and the agreement of cadmium between the inputs and emissions from the plant were highly affected by the difficulty of obtaining representative refuse samples. 51 �SECTION 8 ANALYTICAL RESULTS AMES MUNICIPAL POWER PLANT, UNIT NO. 7 Organics The results of TOC1 determinations in flue gas inlet and outlet samples from the Ames plant are shown in Tables 23 and 24, respectively, along with the recoveries observed for the surrogate spiking compounds. The results for plant background air particulates, ESP ash, bottom ash, coal, RDF, bottom ash quench influent water (cooling tower blowdown), bottom ash quench overflow water, and untreated well water (plant intake water) are shown in Tables 25 to 32. These results, as well as all other results in this report, are shown uncorrected for surrogate recoveries. The coal extracts apparently contained very high levels of hydrocarbons. Hence, the Hall detector used for TOC1 assays required cleaning after only one to two analyses. Hence, TOC1 assays were completed on only six coal extracts. Organic chlorine was not detected by the TOC1 procedure in any of the field blanks, method blanks, or flue gas first impinger extracts. In general, the surrogate recoveries were good in all samples. The recoveries for dg-naphthalene (typically 50-80%) were generally lower than for djg-chrysene (typically 70-100%). This is likely due to the much higher volatility of naphthalene compared to chrysene. Hence, naphthalene losses may be partially attributed to volatility losses during extract concentration. The results of determinations of PAH compounds and additional compounds identified in the composite extracts are shown in Table 33. In addition to PAH compounds, chlorinated benzenes and phenols were identified in some samples. Notably, phenol was detected at parts-per-million concentrations in the coal extracts. Phthalate esters were also identified in RDF and ash samples. As anticipated, phthalate levels were high in the RDF extracts. Low levels of phthalate esters were also identified in the composite flue gas extracts, although the levels were similar to those observed in the flue gas train blanks. The levels of phthalate esters in the train blank ranged from 0.3 to 4 pg/dscm. The results of HRGC/MS-SIM analysis of the composite Ames flue gas outlet extracts for PCBs are shown in Table 34. These results are similar to those obtained by Richard and Junk7 for the Ames Unit No. 7. The primary chlorobiphenyl compounds identified were tetra- through hexachloro-substituted. 52 �TABLE 23. TOC1 AND SURROGATE RECOVERY RESULTS FOR THE AMES FLUE GAS INLET SAMPLES TOC1 Sample volume (dscm) Mass (ng) Cone, (ng/dscm) Surrogate recovery dl2~Chrysene dg-Naphthalene () % () % Test day Date 1 3-2 13.23 3,210 243 2 3-3 17.41 20,000 1,150 63, 85 100, 100 3 3-4 12.38 9,480 766 61, 82 98, 79 4 3-5 14.27 6,480 454 31 33 5 3-6 19.56 18,600 951 57 58 6 3-7 20.79 8,560 412 51 82 7 3-8 19.40 7,110 367 43 60 8 3-9 17.87 7,350 411 44, 48 76, 74 9 3-10 9.18 7,650 833 55 81 10 3-11 22.01 12,400 562 42 63 11 3-12 12 3-13 20.39 11,600 568 59 76 13 3-14 20.57 11,500 559 54 81 14 3-15 15.43 6,320 410 49 87 u> 0 85 Test scrubbed (continued) �TABLE 23 (concluded) TOC1 Test day Date Sample volume (dscm) Mass (n«) Cone, (ng/dscm) Surrogate recovery di2-Chrysene dg -Naphthalene ( W () % 15 8,170 394 120 86 3-18 20.97 22,600 1,080 45 39 17 3-19 20.34 6,390 314 63 60 18 3-20 20.27 13,100 647 54 52 19 3-22 20.16 6,330 314 103 87 20 .p- 21.25 16 Ul 3-17 3-23 18.90 4,780 253 50 55 �TABLE 24. TOC1 RESULTS AND SURROGATE RECOVERIES FOR THE AMES FLUE GAS OUTLET SAMPLES TOC1 Sample volume (dscm) Mass (ng) Cone, (ng/dscm) Surrogate recovery dg-Naphthalene d^-Chrysene () % () % Test day Date 1 3-2 12.94 2,020 156 53 92 2 3-3 17.89 21,600 1,210 60 78 12 3-13 14.85 4,920 332 59 98 13 3-14 20.37 34,200 1,680 64 76 14 3-15 17.73 4,230 238 24 64 15 3-17 22.62 21,500 948 43 85 16 3-18 21.12 18,100 855 43 84 17 3-19 20.81 21,800 1,050 49 105 18 3-20 21.09 4,330 205 46 89 19 3-22 22.75 2,830 124 35 77 20 3-23 18.71 2,930 157 41 98 3-lla U1 Ul a No flue gas outlet samples collected due to severe weather. �TABLE 25. TOC1 RESULTS AND SURROGATE RECOVERIES FOR AMES PLANT BACKGROUND AIR PARTICULATE SAMPLES Test Day Date Volume On3) TOC1 (ng) TOC1 (ng/m3) Surrogate Recovery d8 -Naphthalene d^-Chrysene () % () % 1 2 3 4 5 3-2 3-3 3-4 3-5 3-6 500 540 510 550 800 2,930 3,920 3,150 3,190 4,940 5.9 7.3 6.2 5.8 6.2 23 3 24 26 41 85 110 100 96 100 6 7 8 9 10 3-7 3-8 3-9 3-10 3-11 700 600 870 750 830 3,240 3,160 3,460 3,750 5,110 4.6 5.3 4.0 5.0 6.2 56 24 45 39 36 110 73 88 93 93 11 12 13 14 15 3-12 3-13 3-14 3-15 3-17 600 960 930 910 910 4,180 3,260 2,980 4,530 3,820 7.0 3.4 3.2 5.0 4.2 48 59 59 32 80 140 130 140 92 79 16 17 18 19 20 3-18 3-19 3-20 3-22 3-23 950 960 1,110 840 1,040 5,090 6,580 4,620 2,690 1,880 5.4 6.9 4.2 3.2 1.8 68 65 73 51 73 110 77 89 120 83 Filter Blank Filter Blank 4,260 2,110 95 45 120 57 Calculated from the sampling time and the flowmeter reading on the Hi-Vol sampler. 56 �TABLE 26. TOC1 RESULTS AND SURROGATE RECOVERIES FOR AMES ESP ASH SAMPLES Surrogate recovery Test day 0 Date 3-1 Time Hopper code 0300 0430 0830 1230 1630 B A B A A B 2030 1 2 3-2 3-3 0030 0430 0830 1230 1630 2030 TOC1 (ng/g) dg-Naphthalene () % d12-Chrysene () % 1.8 36 100 5.9 6.3 5.8 0.3 4.5 5.3 78 38 60 91 61 73 140 140 87 69 73 95 x ' B B A B B B 0030 0430 A B \ f 4.1 57 84 0830 1230 A A \ ] 2.2 59 58 1630 2030 B \ f 1.1 46 88 5.1 8.7 1.1 10.6 5.4 8.0 40 46 71 61 70 71 110 65 110 78 69 90 B 3 3-4 0030 0430 0830 1230 1630 2030 B B A B B B 4 3-5 0030 0430 A B J j 2.7 52 98 0830 1230 B B \ ] 8.5 54 90 \ f 4.4 54 71 \ f 3.4 1 100 \ f 2.5 5 83 1630 2030 5 3-6 B 0030 0430 A 0830 1230 B B B B (continued) 57 �TABLE 26 (continued) Test day Date Time Hopper code 5 3-6 1630 2030 B A 6 3-7 0030 0430 A A 0830 1230 A A 1630 2030 TOC1 (ng/g) Surrogate recovery da-Naphthalene di2~Chrysene () % () % 9 3-10 10 3-11 2.4 0 90 3.0 60 98 B B I } 4.0 65 89 2330 0330 B B I 210 9 90 A A 3.7 41 100 A I } 5.2 59 99 2330 0330 0730 1130 1530 1930 A A B B A B 8.1 2.5 1.9 3.2 3.6 6.4 47 53 33 20 34 56 53 83 69 69 66 90 2330 0330 B B } 9.8 52 110 A B } 5.7 57 110 1530 1930 3-9 100 0730 1130 8 28 1530 1930 3-8 2.2 0730 1130 7 I } A A I 2.1 35 110 2330 0330 0730 1130 1530 1930 A A B A A B 3.0 3.8 1.9 0.9 2.9 3.7 54 1 45 1 59 8 120 140 110 110 110 73 B (continued) 58 �TABLE 26 (concluded) Surrogate recovery dg-Naphthalene 12 3-13 13 3-14 22 3-25 A B A B B B 3.2 2330 0330 B B 2.6 60 A A 2.1 103 B B 2.1 100 2330 0330 A A 2.1 130 B B 4.4 38 120 1530 1930 3-12 2330 0330 0730 1130 1530 1915 0730 1130 11 Time 1530 1930 Date TOC1 (ng/g) 0730 1130 Test day Hopper code B A 2.6 69 120 0001 0400 0800 1200 1600 2000 A B A A B A 1.7 71 130 59 90 130 �TABLE 27. TOC1 RESULTS AND SURROGATE RECOVERIES FOR AMES BOTTOM ASH SAMPLES Test day 0 Date 3-1 TOC1 (ng/g) Time Sector code 0105 0530 0930 1330 D B D D D v B J 1730 2130 30.3 31 77 67 85 52 110 0.2 75 68 362 92 110 11.1 30 130 79.0 114 26.3 60.0 52.5 81 52 53 41 57 47 69 21 79 47 84 95 72.0 67 50 22.7 72 92 \ " 13.8 50 96 E A \ 1 66.5 58 89 C B } > 55.0 68 110 0130 0530 0930 1300 1730 2130 D E C C D C 2 3-3 0130 0530 C j A F !• j 1730 2130 D B \ • 1 0130 0535 0930 1300 1730 2130 D E F E A E 0130 0530 C I 0930 1330 B | 1730 2130 F 0130 0530 0930 1330 4 5 3-4 3-5 3-6 130 31 42 57 85 39 43 3-2 0930 1330 65 9.0 13.0 0.6 3.3 1.6 99.5 1 3 Surrogate recovery d8-Naphthalene d12-Chrysene () % () % F 251 J (continued) 60 �TABLE 27 (continued) Date Time 5 3-6 1730 2130 C E 6 3-7 0130 0530 C A 0930 1300 TOC1 (ng/g) Sector code Test day Surrogate recovery dg-Naphthalene di2~Chrysene () % () % 10 3-11 39 81 34.0 19 83 C F I 81.0 38 103 0030 0430 E C I 35.9 65 79 B C I 4.9 63 20 A A I 57.5 54 46 0030 0430 0830 1230 1630 2030 B B D D F A 1.3 8.0 0.8 6.2 77 56 12 29 51 6 70 76 46 48 31 49 0030 0430 E E } 3.6 77 63 C F } 92.5 87 120 2030 3-10 51.0 E F I } 1445 1630 9 3-9 90 1630 2030 8 55 0830 1230 3-8 11.6 1730 2130 7 I B 16.4 11 120 0030 0430 0830 1230 1630 2030 D A A D D A 5.7 86 53 77 44 79 66 97 87 160 130 130 120 127 5.8 38.6 136 85.5 97.0 316 (continued) 61 �TABLE 27 (concluded) Surrogate recovery d8-Naphlhalene d12-Chrysenc () % () % Test day Date Time Sector code8 11 3-12 0030 0430 0830 1230 1630 2030 C D A E E A 57.0 61 120 0030 0430 A A 43.3 62 100 0830 D 76.0 54 110 1630 2030 A F 59 100 0030 0430 F C 32.3 59 80 0830 1230 B B 15.8 51 96 1630 2030 A B 64.5 62 110 0100 0500 0900 1300 1700 2100 A D B F B E 14.8 68 70 12 13 22 3-13 3-14 3-25 TOC1 (ng/g) 349 a The accessible portion of the hopper was divided into six sectors which were sampled according to a randomized selection scheme. 62 �TABLE 28. TOC1 RESULTS AND SURROGATE RECOVERIES FOR AMES COAL SAMPLES Date Time 3-1 Test day Feed stream code 0300 0700 1100 1500 1900 2300 A A A B B B 0300 0700 1100 1500 2300 B B A B A 3-2 TOC1 (ng/g) Surrogate recovery d g-Naphthalene 92 4 7 4 5 4 97 97 110 87 92 61 110 96 83 97 59 a Two coal feed lines were sampled according to a randomized selection scheme. �TABLE 29. TOC1 RESULTS AND SURROGATE RECOVERIES FOR AMES REFUSE - DERIVED FUEL SAMPLES Test day 0 Date Time Food stream code8 3-1 0225 0630 1030 1430 B D D A 1430 TOC1 (ng/g) ) ( ( > Surrogate recovery d8-Naphthalene dxa'Chrysene () % () % 3-3 42 61 C 10,800 58 80 1830 2230 2 5,550 B ) B / 29,500 54 160 3 3-4 0230 0630 1030 1430 1830 2230 A A C C A C 5,500 370 19,000 23,600 4,400 2,800 45 75 50 41 66 64 82 120 98 56 120 110 4 3-5 0230 B 480 61 140 1030 1440 D ) D f 5,100 76 150 1830 2250 D \ C J 5,000 71 120 0230 0630 B \ B f 9,500 80 140 1030 1430 A \ c f 13,300 62 110 1830 2230 C \ B f 1,900 55 110 0230 1430 A B 4,250 18,500 77 50 100 110 1830 2230 B t A J 7,050 63 5 6 3-6 3-7 64 170 (continued) �TABLE 29 (continued) Test day Date Time Food stream code8 7 3-8 0130 B 0930 1330 TOC1 (ng/g) Surrogate recovery dg -Naphthalene di2~Chrysene «) «) 22,000 88 98 D\ D j 4,300 68 110 1730 2130 D ] C J 9,900 55 120 8 3-9 0130 B 5,000 71 110 9 3-10 1730 2130 C A 7,350 3,150 64 42 120 68 10 3-11 0130 0530 0930 1330 1730 2130 A C A A D A 4,950 21,100 23,200 8,600 9,550 10,300 73 86 68 35 64 55 150 130 93 120 130 69 11 3-12 0130 0530 0900 1330 1730 2130 D , B D D C C * 19,900 88 130 0130 0530 D) D ] 10,900 66 84 1730 2130 D) C J 8,200 91 98 0130 0530 B\ C J 16,500 77 150 0930 1330 B) C J 4,300 57 84 1730 2130 A) C} 46,300 84 98 (continued) 12 13 3-13 3-14 65 �TABLE 29 (concluded) Test day Date Time Food stream code* 22 3-25 1000 1400 1800 2200 A B C D TOC1 (ng/g) 13,100 Surrogate recovery dg -Naphthalene d12-Chrysene () % () % 83 130 a Four RDF feed lines were sampled according to a randomized selection scheme. 66 �TABLE 30. TOC1 RESULTS AND SURROGATE RECOVERIES FOR AMES BOTTOM ASH HOPPER QUENCH WATER INFLUENT SAMPLES Surrogate recovery dg-Naphthalene d12-Chrysene Date Time TOC1 (ng/A) 1 3-2 2400 239 47 87 3 3-4 0400 271 51 120 5 3-6 1400 441 80 100 8 3-9 2100 339 82 100 10 3-11 0800 369 89 130 13 3-14 0300 576 64 130 Test day 67 �TABLE 31. TOC1 RESULTS AND SURROGATE RECOVERIES FOR AMES BOTTOM ASH HOPPER QUENCH OVERFLOW WATER SAMPLES Surrogate recovery dg-Naphthalene d^-Chrysene () % () % TOC1 (ng/1) Test day Date Time 0 3-1 0100 > 0500 0900 1300 1700 2100 ' NDa'b 90 698 656 680 494 626 528 47 25 44 b NDD 35 28 80 82 120 56 97 92 518 19b 79 50 524 89 1 3-2 0100 0500 0900 1300 1700 2100 2 3-3 0100 0500 \ 0900 1300 | 1700 2100 } 706 3 4 3-4 72 76 488 558 274 294 678 0100 0500 0900 1255 1700 2100 64 30 57 51 37. K NDb 28 54 66 50 22 78 96 825 37 98 49 110 1,180 3-6 I | 1700 2100 5 0100 0500 0900 1300 3-5 } 691 38 94 0100 0500 i 301 ND 24 0900 1300 1 427 ND 889 68 55 (continued) �TABLE 31 (continued) TOC1 (ng/1) Surrogate recovery dg -Naphtha lene ffU \ Test day Date Time 5 3-6 1700 2100 I 947 87 100 6 3-7 0100 0500 J 819 2 80 0900 1300 } 866 80 55 1700 2100 | 81 852 98 2400 0400 | 94 863 120 0800 1200 | 74 94 1600 2000 2400 | ? 1,040 ' 71 94 0400 0800 1200 1600 2000 2400 776 1,050 984 516 496 376 42 63 53 24, D NDb 120 110 87 140 130 120 0 85 80 605 120 7 8 3-8 3-9 3-10 0400 776C \ fa/ 1,100 Mil Ni/i_ 0800 1200 1600 2000 \ 795 46 100 2400 3-11 | 776C 0 85 0400 0800 1200 1600 2000 2400 870 806 778 864 880 728 c 130 110 90 17 57 120 120 86 88 83 (continued) �TABLE 31 (concluded) Surrogate recovery dg-Naphthalene d^-Chrysene Date Time 3-12 0400 0800 1200 1600 2000 2400 603 0400 0800 892 1200 1600 916 44 84 2000 2400 613 ND 57 0400 0800 458 34 78 1200 1600 770 42 97 2000 Test day TOC1 (ng/1) 1,060 42 80 0030 0430 0830 1230 1630 2030 638 36 110 3-13 3-14 3-25 81 a ND = not detected. b Extract was inadvertently evaporated to dryness. c Samples collected at 0400 and 2400 on 3-10 were inadvertently composited. d This sample was not spiked with the surrogate compounds. e This extract was lost prior to analysis for surrogate recoveries. 70 �TABLE 32. TOC1 RESULTS AND SURROGATE RECOVERIES FOR AMES UNTREATED WELL WATER TOC1 (ng/JK) Surrogate recovery di2~Chrysene d8 -Naphthalene () % () % Test day Date Time 0 3-1 0200 33 NDa 68 5 3-6 2200 65 65 99 23 3-26 1615 62 66 97 a Extract was inadvertently evaporated to dryness. 71 �TABLE 33. COMPOUNDS QUANTITATED IN SAMPLES FROM THE AMES MUNICIPAL POWER PLANT, UNIT NO. 7 Concentration Compound Composite day Coal (ng/g) Refuse-derived fuel (ng/g) Plant background air (ng/dscn) Flue gas inlet (ng/dsen) Flue gas outlet (ng/dscn) ESP ash (ng/g) Botton ash (ng/g) Botton ash hopper quench water overflow (|Jg/«) Bottoa ash hopper quench water overflow (Kg/*) Well a water (Mg/» Target PAH compounds Phenanthrene Anthracene Fluoranthene 1 2 3 4 5 7,550 900 ,9 15,400 8,500 18,600 1 2 3 4 5 1,570 1,840 1,260 2,120 4,110 1 1,190 1,640 3,320 2 0.29 1,400 940 948 828 296 5 3,210 Pyrene 1 2 3 4 5 1,340 1,960 3,810 1,070 400 ,4 552 436 282 372 Chrysene 1 2 370 425 434 3 4 5 Benzofalpyrene 1 2 3 4 5 Indeno) 1 ,2,3-c,dJpyrene J 2 3 4 5 90 0 1,060 238 1,300 0.32 0.17 0.16 0.19 0.36 984 271 306 198 3 4 0.6 0.8 0.8 0.7 0.7 1.0 0.5 0.36 0.7 0.7 1.1 0.5 0.29 04 .0 0.37 0.60 03 .8 0.07 0.17 0.11 0.09 0.07 270 420 660 640 200 390 59 57 77 89 100 49 77 78 46 77 70 240 140 87 94 40 97 28 130 220 8SO 480 230 330 320 37 480 21 64 120 19 63 0.2 0.2 0.2 32 250 140 43 500 24 130 10 52 30 46 450 110 96 9.0 64 29 6.0 420 250 66 330 0.3 3.5 28 9.6 2.8 0.3 320 2.7 170 13 28 0.02 (continued) �TABLE 33 (continued) Concentration Compound Composite day Benzo[g,h,i]perylene Coal (ng/g) Refuse-derived fuel (ng/g) 1 2 3 4 5 Plant background air (ng/dscn) Flue gas inlet (ng/dscm) Flue gas outlet (ng/dscm) ESP ash (ng/g) Bottom ash (ng/g) Bottom ash hopper quench water overflow ((Jg/«) Bottom ash hopper quench water overflow (Ug/«) Well water (Mg/*) 3.3 22 4.6 0.09 Additional compounds identified Dichlorobenzene 1,2,4-Trichlorobenzene 1 2 3 4 5 0.07 3.3 1,300 1,200 520 430 1 2 3 4 5 25 79 24 0.07 5 25 0.02 0.01 99 180 110 69 85 OJ Hexachlorobutadiene 1 2 3 4 5 Tetrachlorobenzene 1 2 3 4 5 103 1 2 3 4 5 Pentachlorophenol 0.02 0.07 1,300 24 690 (continued) �TABLE 33 (continued) Concentration Compound Phenol 2,4-DiMthylphenol Composite day 1 2 3 4 5 Coal (ng/g) Fluorene Benz I a ) anthracene Benzofluoranthrene Benzol ejpyrene 3.3 1.3 0.8 1.5 1.8 1,0 000 12,000 280 ,0 23,000 2,0 900 Flue gas inlet (ng/dsn) 4,700 400 ,0 1,0 300 5,100 9,500 1 2 3 4 5 6,400 7,700 300 ,0 6,000 6,200 ESP ash (ng/g) 220 190 380 Botton ash (ng/g) 980 1,600 1,800 360 730 Botton ash hopper quench water overflow (ug/t) Bottom ash hopper quench water overflow (pg/4) Well water (ug/£) 00 .6 0.06 27 8 2,100 1 2 3 4 5 1,400 1,100 1,800 1,800 2,700 1 2 3 3,500 3,100 560 ,0 3,300 7,000 1 2 3 4 5 1 2 3 4 5 Flue gas outlet (ng/dsca) 1,000 1,200 1,300 4 5 Naphthalene Refuse -de rived fuel (ng/g) Plant background air (ng/dso) 2,200 1,500 1,500 0.28 0.22 0.32 0.28 0.13 60 0 450 380 320 02 .2 0.32 02 .8 0.13 36,000 470 960 260 1,200 620 1,800 740 650 550 81 300 850 0.17 15 0.02 360 110 29 0.18 0.5 0.14 0.44 0.53 0.55 0.38 261 710 1,000 0.42 0.67 0.63 0.65 0.51 14 120 7.2 9.9 6.5 2.7 12 6.9 0.03 17 1 2 3 4 5 29 (continued) 0.02 �TABLE 33 (continued) Concentration Compound Acenaphthene Acenaphthylene Composite day Coal (ng/g) 1 2 3 A 5 650 970 1,600 1,400 1,500 1 2 3 4 5 220 240 560 400 450 Trichlorobenzene Bottom ash (ng/g) Well water9 (fig/*) 0.7 1.0 120 75 10 100 130 20 26 1 2 3 4 5 Dimethylphthalate ESP ash (ng/g) 1 2 3 4 5 j>-Chloro-n~cresol Flue gas outlet (ng/dscm) 1,200 1 2 3 4 5 2 , 4-Dichlorophenol Flue gas inlet (ng/dscn) Bottom ash hopper quench water overflow (fig/I) Bottom ash hopper quench water overflow (pg/Jt) 0.07 Refuse-derived fuel (ng/g) Plant background air (ng/dso.) 1 2 3 Ui 36 77 24 0.04 0.30 3.0 A 5 Diet hylphtha late 730 1 2 3 4 5 9,100 250 1,400 11,000 0.20 11 0.5 2.0 37 16 (continued) �TABLE 33 (concluded) Concentration Composite Compound Di-n-butylphthalate day 4 S Flue gas inlet (ng/dscm) 18,000 14,000 640 ,0 14,000 4 S ESP ash (ng/g) 15 3.0 40 . Bottom ash (ng/g) 4.0 42 12 35 170 32 51 49,000 22,000 1 2 3 Flue gas outlet (ng/dscm) 6.0 1 2 3 4 5 Bii(2-ethylhexyl)phthalate Refuse-derived fuel (ng/g) 1 2 3 Butylbenzylphtbalate Coal (ng/g) Plant background air (ng/dscm) 3000 5,0 4,0 400 35,000 22,000 » All extracts fro* these samples were combined for a single composite extract, b Specific isomer not determined. 6.0 3.0 2.0 8.0 90 8 1,200 480 810 Bottom asb hopper quench water overflow (pg/t) Bottom ash hopper quench water overflow (Mg/«) Well water9 (Mg/«) �TABLE 34. CONCENTRATIONS OF POLYCHLORINATED BIPHENYL ISOMERS IN FLUE GAS OUTLET SAMPLES FROM THE AMES MUNICIPAL POWER PLANT, UNIT NO. 7 Compound identified 1 Composite day (Concentration, ng/dscm) 2 3 4 6.4 Trichlorobiphenyl Tetrachlorobiphenyl 2.2 3.0 6.4 1.1 4.1 Hexachlorobiphenyl 4.3 Heptachlorobiphenyl 9.8 3.6 10.1 25.0 17.0 2.9 Decachlorobiphenyl 22.0 3.8 11.0 4.5 Pentachlorobiphenyl 5 2.9 Total chlorobiphenyl 5.2 27.0 23.0 PCDDs and PCDFs were not detected in the Ames samples. The detection limit for PCDD and PCDF compounds in the composite flue gas extracts was 0.1 to 0.25 ng/dscm. Cadmium The results for cadmium analysis of samples of fly ash, bottom ash, coal and refuse-derived fuel for test days 11 to 14 and 21 to 23 are presented in Tables 35 to 39. The fly ash samples contained the highest concentrations of cadmium ranging from approximately 1.5 to 11 pg/g, while the cadmium concentration in bottom ash samples varied from approximately 0.5 to 4 |Jg/g. The concentration of cadmium in the coal samples was generally less than 1 pg/g while values of 1 to 5 pg/g were recorded for refuse-derived fuel. In general, the cadmium concentration for all water samples was below the detection limit (0.6 pg/liter) of the analysis method. Table 35 presents the cadmium concentrations for the flue gas outlet particulate samples for test days 21 to 23. The concentrations of cadmium in flue gas particulates for the three test days did not vary markedly. The mean concentration was 25.3 pg/dscm with a standard deviation of 2.7 pg/dscm. 77 �TABLE 35. CADMIUM RESULTS FOR AMES - ESP ASH SAMPLES Test day Date Time Hopper code3 11 12 3/12 3/13 3/13 3/13 3/13 3/13 3/13 3/14 3/14 3/14 3/14 3/14 3/14 3/15 3/15 3/15 3/15 3/15 3/16 3/16 3/16 3/16 3/16 3/16 3/24 3/24 3/24 3/24 3/24 3/24 3/25 3/25 3/25 3/25 3/25 3/25 3/26 3/26 3/26 3/26 3/26 3/26 2330 0330 0730 1130 1530 1930 2330 0330 0730 1130 1530 1930 2330 0330 0730 1130 1530 1930 2330 0330 0730 1130 1530 1930 0001 0400 0800 1200 1600 2000 0001 0400 0800 1200 1600 2000 0001 0400 0800 1200 1600 2000 B B A A B A A A B B B A B A B B A B A B A B B B B A A B B A A B A A B A A A B A A B 13 14 21 22 23 Cadmium (M8/g) 9.01 10.3 10.8 8.14 9.89 3.67 7.36 8.42 8.16 9.11 9.96 6.78 6.84 8.47 4.39 3.43 8.00 2.88 5.55 2.35 1.94 1.65 2.97 2.93 3.29 2.16 2.16 3.53 7.89 5.69 4.53 5.11 3.36 8.93 9.70 6.41 5.76 5.73 6.86 8.03 9.19 9.70 a Two hoppers were sampled according to a randomized selection scheme. �TABLE 36. CADMIUM RESULTS FOR AMES BOTTOM ASH SAMPLES Test day Date Time Sector o code Cadmium (M8/g) 12 3/13 3/13 3/13 3/13 3/13 3/14 3/14 3/14 3/14 3/14 3/14 3/15 3/15 3/15 3/15 3/15 3/15 3/16 3/16 3/16 3/16 3/16 3/16 3/24 3/24 3/24 3/24 3/24 3/24 3/25 3/25 3/25 3/25 3/25 3/25 3/26 3/26 3/26 3/26 3/26 3/26 0030 0430 0830 1630 2030 0030 0430 0830 1230 1630 2030 0130 0430 0830 1230 1630 2030 0030 0430 0830 1230 1630 2030 0100 0500 0900 1300 1700 2100 0100 0500 0900 1300 1700 2100 0100 0500 0900 1300 1700 1200 A A D A F F C B B A B D A A D D A C D A G E A E C C C A A D D B F B E B A C C B C 3.92 1.86 2.24 0.25 1.28 1.66 3.28 2.96 1.90 1.90 1.46 4.36 7.15 0.74 0.78 0.96 0.46 0.62 0.78 0.48 1.08 0.90 1.00 1.02 2.82 0.60 1.64 0.76 1.34 0.78 3.68 3.24 3.76 1.94 2.78 2.00 2.20 2.28 2.84 2.02 2.48 13 14 21 22 23 a The accessible portion of the hopper was divided into six sectors which were sampled according to a randomized selection scheme. �TABLE 37. CADMIUM RESULTS FOR AMES - COAL SAMPLES Feed stream code Test day Date Time 12 3/13 3/13 3/13 3/13 3/13 3/14 3/14 3/14 3/14 3/14 3/14 3/15 3/15 3/15 3/15 3/15 3/15 3/16 3/16 3/16 3/16 3/16 3/16 3/24 3/24 3/24 3/24 3/24 3/24 3/25 3/25 3/25 3/25 3/25 3/25 3/26 3/26 3/26 3/26 3/26 3/26 0600 1000 1400 1800 1800 0200 00 60 1000 1400 1800 2200 0200 0600 1000 1400 1800 2200 0200 0600 1000 1400 1800 2200 0230 0630 1030 1430 1830 2230 0230 0630 1030 1430 1830 2230 0230 0630 1030 1430 1830 2230 13 14 21 22 23 A 8 A B B B B B B A B A A A A A B B B A B A B A B A B B B B A B A A A B A B B A B Cadmium (M8/g) 0.124 0.024 0.068 0.116 4.04 0.043 007 .8 0.219 0.159 0.128 0.176 0.210 0.293 000 .4 0.153 0.055 0.075 0.138 0.027 0.094 0.099 0.367 0.141 0.157 0.104 0.129 0.241 0.090 0.173 0.122 0.045 0.079 0.055 0.084 0.286 0.193 0.109 0.055 0.222 0.166 0.641 a Two coal feed lines were sampled according to a randomized selection scheme. 80 �TABLE 38. CADMIUM RESULTS FOR AMES - REFUSE-DERIVED FUEL SAMPLES Test day Date Time 12 3/13 3/13 3/13 3/13 3/14 3/14 3/14 3/14 3/14 3/14 3/15 3/24 3/25 3/25 3/25 3/25 3/26 3/26 3/26 3/26 3/26 0130 0530 1730 2130 0130 0530 0930 1330 1730 2130 0130 1400 1000 1400 1800 2200 0200 0600 1000 1800 2200 13 14 21 22 a Feed stream code D D D C B C B C A C A C A B C D B B B A A Cadmium (Mg/g) 2.84 1.99 2.41 1.14 2.31 2.96 4.85 2.79 2.37 3.68 5.30 2.63 3.71 3.72 2.37 1.73 1.59 1.69 6.26 3.60 0.94 Four RDF feed lines sampled according to a randomized selection scheme. 81 �TABLE 39. CADMIUM RESULTS FOR AMES - FLUE GAS OUTLET PARTICULARS Mass (MS) Cadmium Concentration (Mg/dscra) Test day Date Volume (dscm) 21 3/24 3.69 83.2 22.6 22 3/25 3.48 97.3 28.0 23 3/26 3.93 100.0 25.5 �CHICAGO NORTHWEST INCINERATOR Organics The results of TOC1 analyses of flue gas inlet and outlet samples from the Chicago incinerator are shown in Table 40 along with the corresponding surrogate recovery data. TOC1 and surrogate results for plant background, air particulates, ESP ash, combined bottom ash (i.e., bottom ash plus ESP ash), refuse, and tap water (plant intake water) are shown in Tables 41 to 45. Organic chlorine was not detected by the TOC1 procedure in any of the field blanks, method blanks, or flue gas first impinger extracts. These results, as well as all other results in this report, are shown uncorrected for surrogate recoveries. In general, the surrogate recoveries were poor. As with the Ames results, dg-naphthalene recoveries (typically 10-50%) were lower than di2~chrysene recoveries (typically 30-60%). Although a portion of the apparent losses may be attributed to difficult sample matrices, the cause of consistently lower recoveries is not known. The results of determinations of PAH compounds and additional compounds identified in the composite Chicago extracts are shown in Table 46. Composite refuse extracts were not analyzed due to extremely high levels of interfering materials and the likely nonrepresentatative nature of the refuse sample collection. A large number of chlorinated benzene and phenolic compounds were identified. Dibenzofuran was identified in the flue extracts. As noted for the Ames samples, only very low levels of phthalate esters were identified in the flue gas blank extracts. Interestingly, the compound specific determinations compare very favorably with the TOC1 results for the same extracts. Table 47 shows a comparison of the TOC1 results for selected composite extracts (i.e., those in which significant levels of chlorinated compounds were identified) calculated from the TOC1 concentrations in the component extracts with those calculated from the sums of chlorinted compounds identified. The percent deviation from the mean for these pairs is 14%. The results of analysis of the composite Chicago flue gas outlet extracts for PCBs are shown in Table 48. In contrast to the results from the Ames extracts, the PCS contents of the Chicago flue gases were largely di- through pentachloro-substituted. The results of HRGC/HRMS analyses of the composite Chicago incinerator extracts for PCDDs and PCDFs are shown in Table 49. The mean recoveries for 1,2,3,4-tetrachlorodibenzo-j>-dioxin and octachlorodibenzo-|>-dioxin through the extract cleanup were 60 and 25%, respectively. Although a number of PCDD and PCDF compounds were identified, trichlorodibenzofurans were found at the highest concentrations. Table 50 shows the results of specific analyses for 2,3,7,8-tetrachlorodibenzo-£-dioxin. This compound was detected in all three extracts, although the concentrations measured were substantially less than 1 ng/dscm. No PCDD or PCDF isomers were detected in any blank extracts. 83 �TABLE 40. TOC1 RESULTS AMD SURROGATE RECOVERIES FOR CHICAGO NW FLUE GAS SAHPLES TOC1 Test day Date Volume (s. dc) Resin Mass (ng) Particulates Total cone, (ng/dscn) Surrogate recovery diz-Chrysene dg-Naphthalene () I Particulates Resin Particulates Resin (W Flue Gas Inlet 1 2 3 4 5 6 7 8 9 10 11 5-4 5-6 5-7 5-8 5-9 5-10 5-11 5-12 5-13 5-15 5-16 11.10 22.31 20.53 19.89 20.19 18.92 2.8 04 19.52 19.05 20.26 20.22 17,500 33,900 12,300 13,900 22,600 10,700 11,900 11,700 11,000 12,100 33,200 14,400 5,0 220 26,700 21,330 19,700 23,900 1,0 090 36,300 3,0 040 17,400 22,500 Flue Gas 1 2 5 4 5 6 7 8 9 10 11 5-4 18.20 5-6 5-7 5-8 5-9 24.82 22.95 5-10 5-11 5-12 5-13 5-15 5-16 25.07 21.39 2.9 20 21.51 21.74 21.38 21.91 23.26 1,0 680 69,100 32,700 3900 0,0 3,0 220 6,0 320 4,0 790 3,0 940 19,100 4,0 450 3,0 060 37 80 49 54 38 9 17 30 22 25 92 280 ,0 3,860 1,900 1,770 2,090 1,830 1,110 2,470 2,170 1,460 2,753 38 20 41 62 54 27 16 13 46 27 13 40 19 52 16 48 27 17 36 24 28 13 340 ,6 1,100 7 3,140 1,760 13,500 19 7.720 2,0 400 7,070 590 ,4 400 ,6 200 ,7 3,310 2,540 2,920 1.230 230 ,0 1,490 62 58 45 100 47 56 68 25 41 77 29 Outlet 8,780 28,600 12,000 9,940 6,750 67 140 90 110 100 96 58 89 70 67 140 0 16 5 38 44 6 64 64 18 58 58 0 4 35 77 99 54 120 80 82 44 40 130 23 120 50 40 70 68 66 36 �TABLE 41. TOC1 RESULTS AND SURROGATE RECOVERIES FOR CHICAGO NW PLANT BACKGROUND AIR SAMPLES TOC1 (ng) TOC1 (ng/m3) Surrogate recovery d8-Naphthalene djg-Chrysene () % () % Test day Date Volume (m3) 2 5-6 660 1,510 2.3 58 45 3 5-7 490 1,400 2.9 67 74 4 5-8 570 1,840 3.2 46 71 5 5-9 590 1,730 3.0 23 55 6 5-10 510 < 30 < 0.1 7 1 7 5-11 590 430 0.7 55 170 8 5-12 390 < 30 < 0.1 0 0 9 5-13 580 540 0.9 34 33 10 5-15 490 890 1.8 26 28 11 5-16 710 1,240 1.7 37 44 5-17 520 760 1.5 11 24 5-19 320 590 1.8 2 66 a Calculated from the sampling time and the flowmeter reading on the HiVol sampler. 85 �TABLE 42. TOC1 RESULTS AND SURROGATE RECOVERIES FOR CHICAGO NW ESP ASH SAMPLES Test Day TOCI (ng/g) Date Time 0 5-3 0200 0600 1000 1400 1800 2200 1 5-4 0200 0600 1 Surrogate Recovery d8-Naphthalene di2-Chrysene fty \ V fb/ 5-6 41 36 0 44 45 18 68 63 46 80 72 35 59 8 35 1000 1400 2 226 203 68 89 143 54 I « 28 52 1400 62 8 24 ?6 7 39 1800 2200 } 192 58 97 } 49 20 15 1800 2200 5-7 0200 0600 1000 1400 3 } / 95 0 0 4 5-8 0200 0600 1000 1400 1800 2200 370 150 15 14 23 49 60 28 0 18 5 44 83 24 12 7 18 31 5 5-9 0200 0600 1000 1400 1800 2200 130 340 41 210 160 38 40 56 44 37 28 26 28 14 32 21 20 30 6 5-10 0400 0800 1200 111 84 57 37 19 9 32 35 32 (continued) 86 �TABLE 42 (continued) Surrogate Recovery dj2~Chrysene dg-Naphthalene Time TOC1 (ag/g) 5-10 1600 2000 59 65 39 8 40 76 0000 76 23 57 66 21 54 30 38 2000 0000 31 13 0 0400 0800 | 40 36 1200 1600 I « 36 21 2000 0000 | 30 32 0400 0800 \ 65 40 35 1200 1600 6 Date 5-11 Test Day \ 150 30 30 76 26 26 20 12 16 220 203 70 159 < 1 0 52 28 23 0 48 49 25 0 (continued) 7 0400 0800 1200 1600 5-12 8 5-13 9 5-14 \ 108 } 1600 2000 0000 10 5-15 0400 0800 1200 1600 2000 I 132 38 37 �TABLE 42 (concluded) Test Day TOC1 (ng/g) Date Time 5-16 0000 0400 0800 1200 1600 2000 137 211 78 173 15 154 5-17 0100 0900 1300 1700 2100 12 11 12 88 Surrogate Recovery rig-Naphthalene 22 24 39 50 9 0 14 49 59 57 17 39 26 �TABLE 43. TOC1 RESULTS AND SURROGATE RECOVERIES FOR CHICAGO NW COMBINED BOTTOM ASH SAMPLES TOC1 Surrogate Recovery d12~Chrysene d8-Naphthalene < 1 18 23 5-3 0300 0700 1100 1500 1900 2300 E E E A < < < < < < 1 1 1 1 1 1 39 33 18 31 56 52 35 26 23 20 21 25 0300 0700 A A \ J < 1 12 0 D 1 < 1 34 7 1500 A < 1 29 52 C A \ / 6 34 32 0300 0700 A E » / < 1 0 26 B E ) J 6 38 58 1900 2300 3 A 1100 1500 2 2300 1900 2300 1 Time 1100 1500 0 Date 5-2 Test day Sector code D B ) f 3 46 52 5-4 5-6 5-7 (ng/g) B 4 5-8 0700 1100 1500 1900 1900 2300 B B D E C B < 1 < 1 < 1 124 < 1 < 1 8 22 19 37 13 0 24 26 20 64 8 0 5 5-9 0300 0700 1100 1500 1900 2300 B C D C B A 7 76 5 3 < 1 38 11 75 48 72 47 85 5 9 11 78 13 10 (continued) 89 �TABLE 43 (continued) Sector code8 TOC1 (ng/g) 7 16 Test day Date Time 6 5-10 0100 0500 0900 1300 1700 2100 A 0100 0500 E E I 0900 1300 E D } 1700 2100 B C 0100 0500 E B 0900 1300 A B 1700 2100 B E 0100 0500 D D 0900 1300 C A 1700 E 5-14 1700 2100 A A 5-15 0100 0500 0900 1300 7 8 9 10 5-11 5-12 5-13 Surrogate Recovery dg-Naphthalene d12~Chrysene () % 13 42 34 41 34 33 11 43 34 <l 31 25 } < l 36 36 } <> 8 13 1 28 17 25 I » 37 26 I 57 100 I » 60 12 < 1 28 7 > 2 19 0 A E } 18 34 8 C C \ 2 35 7 E B C E E < 1 < 1 < 1 49 • 3.8 7 8 8 11 12 (continued) 90 �TABLE 43 (concluded) Test day Sector j codea TOC1 (ng/g) Surrogate Recovery dg-Naphthalene d12-Chrysene () % () % Time 5-15 11 Dae 1700 2100 E c\ I < 1 21 5 5-16 0100 0500 0900 1300 1700 2100 E C C E B D < 1 26 26 50 44 6 24 6 8 7 6 6 6 7 < < < < 1 1 1 1 The accessible portion of the bottom ash discharge hopper was divided into five sectors which were sampled according to a randomized selection scheme. 91 �TABLE 44. TOC1 RESULTS AND SURROGATE RECOVERIES FOR CHICAGO NW REFUSE SAMPLES 3 0100 0515 0900 1300 1700 2100 A B B B A B 1,780 9,940 0100 0500 A B A 0900 1300 A B A B 2110 1 5-3 1700 2100 0 Time Sector code TOC1 Date 0900 Test day 5-4 5-7 Surrogate recovery d -Naphthalene d12~Chrysene 8 12,300 15 12 12 5 28 15 15 12 0 5 18 15 221 0 0 < 1 0 0 \ f 14 0 0 \ f 1,350 0 0 A < 1 25 0 961 62 778 \ > 4 5-8 0100 0500 0900 1300 1700 2100 A B A B A B 84 165 38 583 27 567 8 12 19 9 0 9 4 15 32 26 0 9 5 5-9 0100 0500 0900 1300 1700 2100 B A A B B A 1,550 36 5 0 14 2 0 120 5 0 10 0 0 246 41 607 1,670 273 (continued) �TABLE 44 (continued) Test day 6 Sector code Date Time 5-10 0300 0700 1100 1500 1900 2300 B A B A B A 0300 0700 TOC1 (ng/g) Surrogate recovery d8-Naphthalene d12-Chrysene 9 5-13 0 0 B \ A| 599 2 0 B \ B J 95 0 0 0300 0700 B A \ I < 1 0 0 A } 1 389 8 3 1900 2300 5-12 < 1 1100 1500 8 B \ A ( 1900 2300 5-11 0 1 0 6 38 0 1100 1500 7 167 11 54 0 9 0 6 46 0 B B \ f < 1 0 0 0300 0700 A } J < 1 0 0 1100 1500 B \ A I < i o o B A 108 467 < 1 (continued) �TABLE 44 (concluded) TOC1 (ng/g) Surrogate recovery d12-Chrysene d g -Naphtha lene () % () % Test day Date Time Sector code 10 5-14 1500 1900 B A < 1 2,700 0 5 50 10 5-15 0300 0700 1100 1500 1900 2300 A A B B A B 22 8,070 < 1 < 1 < 1 < 1 68 30 0 0 0 4 68 32 0 0 0 5 5-16 0300 0700 1100 1500 1900 A B A A B 26 < 1 45 < 1 < 1 16 0 0 17 6 15 0 0 1 6 5-17 0000 B < 1 6 0 11 The accessible portion of refuse was divided into two sectors which were sampled according to a randomized selection scheme. �TABLE 45. TOC1 RESULTS AND SURROGATE RECOVERIES FOR CHICAGO NW TAP WATER SAMPLES Surrogate recovery di2~Chrysene dg-Naphthalene /O> \ \ A>/ () % Test day Date TOC1 (ng/£) 5 5-9 < 30 14 16 6 5-10 < 30 0 0 7 5-11 5-14 < 30 < 30 68 12 24 10 95 �TABLE 46. Compound COMPOUNDS QUANTITATED IN SAMPLES FROH THE CHICAGO NV INCINERATOR, UNIT HO. 2 Composite day Plant backbround air particulates concentration (ng/dsca) Flue gas inlet concentration (ng/dscn) Flue gas outlet concentration (ng/dsoi) Combined ash concentration (ng/g) 120 32 28 200 110 340 110 27 18 39 27 51 17 300 140 57 92 91 77 12 Target PAH Compounds Phenanthrene 1 2 3 Fluoranthene 1 2 3 Pyrene 1 2 3 1.0 0.28 0.82 0.18 9.4 7.8 Additional Compound* Idendified 1 ,3-Dichlorobenzene 1 2 3 130 130 18 1 ,4-Dicblorobenzene 1 2 3 96 98 14 1 ,2-Dichlorobenzene 1 2 3 140 120 20 1,2, 3-Trichlorobenzene 1 2 3 140 81 27 48 57 150 1,2,4-Trichlorobenzene 1 2 3 550 380 160 200 220 560 1 ,3,5-Trichlorobenzene 1 2 3 490 280 120 190 180 460 Tetrachlorobenzene* 1 2 3 1,400 1,000 1,400 790 630 (continued) ESP Ash concentration (ng/g) �TABLE 46 (concluded) Plant backbround air particulates concentration (ng/dscm) Flue gas inlet concentration (ng/dsm) Flue gas outlet concentration (ng/dscn) 1 2 3 too 39 12 Dichlorophenol' 1 2 3 560 240 190 1 2 3 2,100 140 ,0 1,200 1,900 1 2 3 2,200 1,100 1 2 3 130 64 190 160 430 Dibenzofuran 1 2 3 86 28 23 100 67 140 Dine thy Iphthalate 1 2 3 Hexachlorobenzene Tetrachlorophenol" Pentachlorophenol Diethylphthalate 1 2 3 Butylbenzylphthalate 1 2 3 60 0 1,500 1,100 1,700 83 4.8 50 1 2 3 Bis(2-ethylhexyl)phthalate 970 600 1 2 3 Di-n-butylphthalate a ESP Ash concentration (ng/g) 240 280 630 Tri chloropheno 1a Combined ash concentration (ng/g) 110 48 260 Compound Composite day Specific isoner not determined. 15 6.1 32 130 47 370 170 230 89 �TABLE 47. COMPARISON OF TOC1 RESULTS FROM DIRECT TOC1 ASSAYS VERSUS CALCULATED TOC1 FROM SPECIFIC COMPOUNDS IDENTIFIED IN COMPOSITE CHICAGO NW EXTRACTS Composite day TOCI assay Sum of compounds identified Flue gas inlet 1 2 3 130 mg/hr 88 mg/hr 67 mg/hr 200 mg/hr 110 mg/hr 56 mg/hr Flue gas outlet 1 2 3 97 mg/hr 110 mg/hr 86 mg/hr 120 mg/hr 96 mg/hr 190 mg/hr 98 ng/g 93 ng/g Sample type ESP Ash 98 �TABLE 48. CONCENTRATIONS OF POLYCHLORINATED BIPHENYL ISOMERS IN FLUE GAS OUTLET SAMPLES FROM THE CHICAGO NORTHWEST INCINERATOR UNIT NO. 2 Compound identified Composite day (Concentration, ng/dscm) 1 3 2 Dichlorobiphenyl 5.8 6.0 40 Trichlorobiphenyl 7.6 4.3 36 Tetrachlorobiphenyl 4.2 1.5 13 Pentachlorobiphenyl 2.3 1.0 4.5 Total chlorobiphenyl 19.9 12.8 93.5 99 �TABLE 49. CONCENTRATIONS OF POLYCHLORODIBENZO-P-DIOXINS AND FURANS IN FLUE GAS FROM THE CHICAGO NORTHWEST INCINERATOR Concentrations (ng/dscm) Total trichlorodibenzo-p-dioxins Day 1 2 3 Mean S.D. 15 12 11 13 2.1 Total trichlorodibenzofurans Day 1 2 3 Mean S.D. 350 280 270 300 44 Total tetrachlorodibenzo-p-dioxins Day 1 2 3 Mean S.D. 7.2 5.4 6.2 6.3 0.90 Total tetrachlorodibenzofurans Day 1 2 3 Mean S.D. 89 84 96 90 6.0 Total hexachlorodibenzo-p-dioxins Day 1 2 3 Mean S.D. 14 21 14 16 4.0 (continued) 100 �TABLE 49 (concluded) Concentrations (ng/dscm) Total hexachlorodibenzofurans Day 1 2 3 Mean S.D. 43 84 59 62 21 Total heptachlorodibenzo-p-dioxins Day 1 2 3 Mean S.D. 7.2 7.8 7.7 7.6 0.32 Total heptachlorodibenzofurans Day 1 2 3 Mean S.D. 7.2 7.2 8.0 7.5 0.46 Octachlorodibeuzo-p-dioxin Day 1 2 3 Mean S.D. 2.6 2.2 2.8 2.5 0.39 Octachlorodibenzofuran Day 1 2 3 Mean S.D. 0.72 0.63 0.46 0.60 0.13 101 �TABLE 50. CONCENTRATIONS OF 2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN IN FLUE GAS FROM THE CHICAGO NW INCINERATOR Concentration (ng/dscm) Day 1 0.35 2 0.36 3 0.52 Mean 0.41 S.D. 0.10 Cadmium The results for cadmium analysis of samples of fly ash, bottom ash, and refuse for test days 8 to 14 are presented in Tables 51 to 53. The fly ash samples contained the highest concentrations of cadmium, ranging from 86 to 560 (Jg/8- The concentration of cadmium in bottom ash was approximately one order of magnitude lower than that of the fly ash samples. The cadmium content of refuse samples ranged from less than 0.12 to 1.4 (Jg/8- Cadmium was not detected in the tap water from this plant. The concentrations of cadmium in the flue gas outlet samples are listed in Table 54. Also included in these tables are results for the recoveries of spiked samples, which was part of the QA program discussed in the analysis methods. The recovery of cadmium averaged 91% from both the combined ash and the refuse and 114% from the fly ash. 102 �TABLE 51. CADMIUM CONCENTRATIONS IN FLY ASH FROM CHICAGO NORTHWEST INCINERATOR, UNIT NO. 2 Test day Date Time 9 5/13 0000 0400 5/14 10 5/15 0800 1200 1600 1700 2000 0400 0800 1200 Cadmium (Mg/g) 283 201, 212 209, 217, 222 376 458 391 86.1, 82.3 250 1600 200 225 209, 218 380, 392 419, 425, 440 361 560 Spike recovery () %a 139 109 124, 118, 114 11 5/16 0000 0400 0800 1200 1600 306 325, 325 237 250 216 135 12 5/17 0100 0500 0900 1300 1700 2100 230 279, 348 289 290 313 328, 323 94 0100 0500 309 326 13 5/18 97 ± 9° Spiked distilled water a 100 Spiked with 10 (Jg total cadmium. b Spiked with 10 pg total cadmium and analyzed with the sample digests. c Mean and standard deviation for eight determinations. 103 �TABLE 52. CADMIUM CONCENTRATIONS IN COMBINED BOTTOM ASH FROM CHICAGO NORTHWEST INCINERATOR, UNIT NO. 2 Test day Cadmium (Mg/g) Spike recovery () %3 11 5/13 0100 0500 0900 1300 1700 8.20 23.4 8.30, 7.34 36.1, 31.2 15.1 95 61 1700 2100 5.40 30.8, 27.8 88 5/15 0100 0500 0900 1300 1700 2100 15.9, 9.20 31.7 48.8 7.3 17.1 18.5, 49.4 31.7, 60.5 81, 106 0100 0500 0900 1300 2000 2100 10 Time 5/14 9 Date 7.88, 28.7, 6.80 27.8 13.3 10.7, 8.64 12.1 7.5 5/16 12 5/17 0200 0600 1000 1400 1800 2200 5/18 0200 0600 1000 1400 1800 2200 5/19 0200 0600 1000 1400 120 105 6.35 8.00 21.7 4.60 71 3.60 14 67 14.5 10.4 6.00 14.3 13.1, 14.8 17.6 13 98 13.1 46.9 7.85 14.3 93 ± 6C Spiked distilled water a Spiked with 10 pg total cadmium. b Spiked with 10 )Jg total cadmium and analyzed with the sample digests. c Mean and standard deviation for six determinations. 104 �TABLE 53. CADMIUM CONCENTRATIONS IN REFUSE FROM CHICAGO NORTHWEST INCINERATOR Test day 8 10 11 12 13 14 Date Time 5/12 5/13 5/13 5/13 5/13 5/14 5/14 5/14 5/15 5/15 5/15 5/15 5/15 5/15 5/16 5/16 5/16 5/16 5/16 5/17 5/17 5/17 5/17 5/17 5/17 5/18 5/18 5/18 5/18 5/19 5/19 5/19 5/19 2300 0300 0700 1100 1500 1500 1900 2300 0300 0700 1100 1500 1700 2300 0300 0700 1100 1500 1900 0000 0400 0800 1200 1600 2000 0000 1200 1600 2000 0000 0400 0800 1200 Cadmium (Mg/K) 1.45 0.50, 1.25 0.85 0.28 0.45 0.63 1.07 0.95, 1.02 0.67 0.14 0.85 < 0.12 0.20 1.10, 1.04 1.07 0.83, 0.80 < 0.12 < 0.12, < 0.12 0.63 1.10 0.68 < 0.12 0.18 0.16 0.60 0.57 0.25 1.04, 0.94 0.55 1.25 9.85, 8.44 0.79 8.13 Spike recovery () %3 91 72 95 106 105 94 78 ± 22C Spiked distilled water a Spiked with 10 (Jg total cadmium. b Spiked with 10 (Jg total cadmium and analyzed with the sample digests. c Mean and standard deviation for seven determinations. 105 �TABLE 54. CADMIUM CONCENTRATIONS IN THE FLUE GAS OUTLET PARTICULARS FROM CHICAGO NORTHWEST INCINERATOR, UNIT NO. 2 Cadmium Concentration (ng/dscm) Date Volume (dscm) Mass (pg) 12 5/17 6.20 520 84 13 5/18 6.20 1,490 240 14 5/19 6.81 1,850 272 Test day 106 �SECTION 9 ANALYTICAL QUALITY ASSURANCE RESULTS The principal quality assurance indicators used for this study were the recoveries for surrogate compounds spiked into all samples prior to extraction and the results of three interlaboratory comparison studies. SURROGATE COMPOUND RECOVERIES The surrogate recoveries determined for all samples from both plants are summarized in Table 55. As indicated in the previous section, the recoveries observed for naphthalene are generally lower than those for chrysene. Since the compounds of primary interest in this study are less volatile than naphthalene, the naphthalene recoveries likely indicate the maximum losses attributable to volatilization. The chrysene recoveries likely provide a more accurate indication of the recoveries of the principal analytes related to extraction efficiency and general extraction handling. The apparent analytical accuracy and precision as indicated by the recoveries and standard deviations of surrogates observed for each media was likely influenced by the dilution of extracts prior to analysis. Many of the more complex extracts required dilution such that the concentrations of the surrogate compounds in the diluted extracts were near the analytical detection limits. In general, the surrogate recoveries observed for the Ames samples were higher than those observed for the Chicago samples. This is likely attributable, at least in part, to the complexity of the Chicago samples. INTERLABORATORY COMPARISON STUDIES TOC1 Two interlaboratory comparison studies were conducted to check the comparability of TOC1 assay as conducted by SwRI and GSRI. In the first study, selected extracts from the two plants were submitted for TOC1 assay by the other laboratory. A second set of TOC1 extracts was prepared at MRI by mixing several extracts of organic chemicals manufacturing wastewaters. The results of these two studies are shown in Table 56. Although some significant discrepancies are apparent, the data from the two laboratories are generally comparable. 107 �TABLE 55. SUMMARY OF SURROGATE RECOVERY DATA Plant Sample type Determinations Surrogate recovery dg Naphthalene d12-Chrysene () % () % Flue gas outlet 11 47 ± 12 86 ± 12 Flue gas inlet 22 57 ± 24 73 ± 19 Plant background air particulates 21 48 ± 23 98 ± 22 ESP ash 51 44 ± 25 96 ± 22 Bottom ash 51 55 ± 20 85 ± 31 6 90 ± 16 90 ± 18 36 65 ± 15 110 ± 28 Bottom ash hopper quench water influent 6 69 ± 17 110 ± 18 Bottom ash hopper quench water overflow Ames 50 42 ± 32 88 ± 25 44 ± 38 88 ± 17 Coal RDF Well water Chicago Flue gas outlet 11 (resin) 11 (filter) 26 ± 23 29 ± 13 61 ± 37 62 ± 34 Flue gas inlet 11 (resin) 11 (filter) 41 ± 26 32 ± 17 93 ± 28 55 ± 22 Plant background air particulates 12 31 ± 23 51 ± 45 ESP ash 53 26 ± 18 35 ± 22 Bottom ash 51 33 ± 18 21 ± 20 Refuse 51 9 ± 13 10 ± 21 4 24 ± 30 13 ± 10 Tap water a The resin and filter catch portions of the Chicago flue gas samples were spiked, extracted, and analyzed separately for the surrogate compounds, 108 �TABLE 56. RESULTS OF INTERLABORATORY TOC1 ANALYSES TOC1 (ng/extract) SwRI results GSRI results Sample Chicago flue gas outlet (5/15) resin3 Chicago flue gas inlet (5/7) particulate Ames Ames Ames Ames Ames Ames bottom ash (3/7, bottom ash (3/9, flue gas outlet flue gas outlet RDF (3/4, 0230) RDF (3/3, 1430) Synthetic Extract I II III IV a Prepared by SwRI. c Resin and particulate combined. d 11,300 10,900 13,800 12,400, 16,200 Prepared by GSRI. b 1,020 124 4,230 18,100 109,000 215,000 7,300 10,700 7,600 10,400 0130 + 0530)b 2030) (3/15)C (3/18)° 23,000 19,200 39,300 42,800 10,020 31,400 227 91.8 702 443 78,800 181,000 Chicago flue gas outlet (5/12) resin Chicago flue gas outlet (5/9) particulate Chicago flue gas outlet (5/6) particulate Chicago flue gas outlet (5/11) resin 44,500 26,700 39,400 12,000 8,780 47,900 Prepared by MRI. Specific Compound Analysis An interlaboratory study was also conducted using spiked fly ash aliquots spiked with specific compounds. Mixed fly ash from the Ames and Chicago plants was divided into 20-g aliquots. The aliquots were spiked by MRI with six chlorinated compounds and submitted to GSRI and SwRI for analysis by the same extraction, HRGC and scanning HRGC/MS procedures used for the plant samples. Four pairs of duplicate fly ash aliquots were submitted to each laboratory. The results of these analyses are shown in Table 57 along with the surrogate recoveries. Most compounds were identified in the spiked samples by both laboratories. Exceptions were pentachlorophenol in most samples and decachlorobiphenyl in one sample by SwRI. 109 �TABLE 57. INTERLABORATORY COMPARISON OF ANALYTICAL RESULTS FOR THE EXTRACTION AND ANALYSIS OF SPECIFIC COMPOUNDS IN FOUR SETS OF QUALITY ASSURANCE SAMPLES I Compound Spike level (ng/g) II Concentration9 (ng/g) GSRI SwRI Spike level (ng/g) IV III a Concentration (ng/g) SwRI GSRI Concentration (ng/g) GSRI SwRI Spike level (ng/g) 1 ,2-Dichlorobenzeoe 0 NDb ND 585 90, 125 952 , 1,130 2,930 940 , 430 1 ,2,4-Trichlorobenzene 0 ND ND 560 100, 170 1,170 , 1,220 4,200 1,660 , 865 Hexaehlorobenzene 0 ND ND 550 45, 65 295 , 150 2,750 790 , 365 2,4,6-Trichlorophenol 0 ND ND 2,850 ND, 45 1,040 , 748 570 75 , ND " 112 , ND, ND C tr, tr 535 ND , ND tr , tr 1,230 6,050 , 2,890 Spike level (ng/g) Concentration (ng/g) SwRI GSRI 20,200, 4,410 7,420, 6,300 4,390 700, 1,010 11,700, 10,200 2,800 720, 855 7,660, 8,420 85, 75 170, 103 4,280 355, 840 3,690, 2,040 tr, tr 4,020 ND, ND tr, tr 403, 566 2,450 8,650, 6,800 2,460, 1,280 1,630, 1,680 275 Pentarhlorophenol 0 ND ND 2,680 Decachlorobiphenyl 0 ND ND 490 Naphthalene-da 38, 2 88, 88 25, 40 89 , 88 59 ,30 98, 84 34, 42 101, 89 Chrysene-d,2 49, 23 73, 84 41, 40 88 , 76 50 , 38 75, 71 45, 45 111, 103 425, 970 Surrogate Compound Recovery ( ) * a Concentration values reported for two identical samples prepared by MRI. b ND = not detected. c tr = trace. �PCDD and PCDF Analysis The results of the interlaboratory comparison of PCDD and PCDF analyses conducted on Chicago flue gas outlet extracts by MRI and R. Harless at EPA's Research Triangle Park laboratory are shown in Table 58. Both the qualitative and quantitative results from the two laboratories were quite comparable. There were no qualitative discrepancies. The agreement in quantitation is reasonable, particularly in view of the facts that: (1) the two laboratories utilized different gas chromatographic systems and different selected ion monitoring procedures (computer controlled ion selection by MRI and hardware controlled ion selection by EPA) and (2) that the levels were near the limits of detection. TABLE 58. INTERLABORATORY COMPARISON OF THE LEVELS OF PCDDs AND PCDFs IN COMPOSITE EXTRACTS FROM THE CHICAGO NW INCINERATOR Composite Total mass in sample (ng) EPA3 results MRI results Parameter 14 1 24 2 2,3,7, 8-Tetrachlorodibenzo-p-dioxin 24 7.0 3 2,3,7, 8-Tetrachlorodibenzo-p-dioxin 34 9.4 4 Total tetrachlorodibenzo-p-dioxin 500 1,200 5 Total tetrachlorodibenzo-p-dioxin 360 740 6 Total tetrachlorodibenzo-p-dioxin 400 660 7 Total tetrachlorodibenzofuran 5,600 1,640 8 a 2,3,7, 8-Tetrachlorodibenzo-p-dioxin Total hexachlorodibenzo-p-dioxin 1,400 280 Calculated from data in Reference 8. 111 �SECTION 10 EMISSIONS RESULTS AMES MUNICIPAL POWER PLANT, UNIT NO. 7 The TOC1 input and emission rates determined for the Ames plant during the test period are shown in Table 59. These results were calculated from the daily mean levels of TOC1 in coal, RDF, and ash from Section 8 and the mass and volume flow rates from the engineering and process data in Section 7. Since TOC1 is not a conservative parameter, it the mean TOC1 destruction rate is greater than 99%. data indicate that flue gas was responsible for the emissions, 83%. Bottom ash and fly ash contributed tively, of the total emissions. is not surprising that Interestingly, these largest fraction of TOC1 only 11 and 5%, respec- Table 60 shows the input and emission rates for the target PAHs and other compounds identified in the composited Ames extracts. The mass and volume flow data used for the input and emission calculations are averages for the sampling days comprising the composite days. The emission rates for PCBs in Table 61. Only the composited flue PCBs by HRGC/MS-SIM. PCBs may have sions media at concentrations below the Ames flue gas samples are shown in gas outlet extracts were analyzed for been present in other inputs and emisthe limit of detection of scanning HRGC/MS. A summary of the cadmium inputs and emissions for the test days investigated at the Ames Municipal Power Plant is presented in Table 62. The total inputs and emissions represent a good mass balance. CHICAGO NORTHWEST INCINERATOR, UNIT NO. 2 The calculated TOC1 inputs and emissions are shown in Table 63. The apparent mean TOC1 destruction rate (97%) is slightly lower than was observed for the Ames plant. However, the difficulty experienced in taking representative samples of raw refuse hinders accurate destruction efficiency determinations. The contribution of flue gases to total TOC1 emissions is remarkably similar, 87% for the Chicago incinerator relative to 83% for Ames power plant. 112 �TABLE 59. TOTAL ORGANIC CHLORINE INPUTS AND EMISSIONS - AHES MUNICIPAL POWER PLAHT, UKIT Nn Inputs Coal TOC1 RDF Date Load feed Feed () 1 ( ) (kg/hr) I 3/2 3/3 3/4 3/5 36 / 3/7 3/8 3/9 3/10 3/11 3/12 3/13 3/14 3/15 3/17 3/18 3/19 3/20 3/22 3/23 86 86 90 91 8 9 87 80 60 83 8* 89 89 87 62 84 91 89 87 84 52 0 13 23 19 2 2 14 20 4 10 24 21 16 24 4 12 17 15 7 11 0 14,600 14,400 1,0 440 15,200 1,0 460 15,200 12,800 1,0 080 14,200 13,700 1,0 600 14,100 13,900 1,0 090 1,0 420 1,0 430 1,0 420 1,0 560 14,100 9,250 Decemin•tions 20 20 20 Mean 83 14 13,800 Standard 11 deviation 7.7 1,700 (gg n/) TOC1 (t/r ».h) Emissions Refuse-derived fuel tOCl TOC1 (kg/hr) (ng/g) (gh) ./r Total TOC1 ( / r « h ) Botto* ash TOC1 (gh) k/r' 5 73 5 5 5 5 5 5 5 5 5 5 5 5 72 72 76 73 76 64 54 71 6. 85 8. 00 7. 05 6. 95 2.130 4,290 3,640 400 ,3 2,470 3,180 491 1,530 430 ,4 430 ,2 2,720 4,350 5 5 5. 45 71 417 1,850 5 5 71.5 71 2,930 2,550 78 70.5 4. 63 1,200 1,740 0 (gh) ./r 500 400 5 5 5 (ng/g) tOCl 200 350 250 350 100 20 5 HI) 20 6» 8.4 0 toil 20 100 20,100 9,300 350 ,0 820 ,0 9,900 12,100 500 ,0 530 ,0 1,0 300 1,0 990 960 ,0 2,0 200 42,900 39,900 12,700 3,5 300 2,0 450 38,500 2,500 8,100 5,0 640 8,0 600 26,100 95,700 12 12 4,0 300 4,0 000 12,800 3,0 310 2,0 460 3,0 860 260 ,0 820 ,0 5,0 650 8,0 610 2,0 620 9,0 580 12 5.5 0.55 350 550 450 550 400 500 200 300 550 500 400 550 124 97 36 44 55 33 4.4 38 113 57 156 38 43 53 16 24 22 17 0.88 11.4 67 29 62 21 20 13 13 2,312 11,500 3,0 890 3,0 900 380 62 28 1,570 620 ,0 2,0 880 28,800 150 47 21 Mass (kg/hr) ESP ash TOC1 (dscn/hr) Flue ga«" TOC1 TOC1 Total 1UC1 Percent of ttx.1 e«is»io»» (ng/d.«)_ («s/hr) (a.g/hr) 4 7 2.5 6.5 5.2 2.7 3.1 56 3.5 5.2 2.6 5.6 3.0 7.8 6.2 3.2 3.7 67 4.2 6.2 3.1 3920 0,0 323,800 3800 2,0° 322,500C 3030 4.0° 318,400C 29I.300C 2290; 4,0) 3330 3,0° 341,500C 156 1,210 766 454 951 412 367 411 833 562 48.2 392 251 146 324 131 107 100 278 192 54.4 438 312 168 351 156 191 105 296 257 1 10 17 10 7 14 9 1 4 24 10 1 3 3 1 2 35 4 2 1 89 89 80 87 92 84 56 95 94 75 '20 ,0 ,0 20 ,0 20 ,0 20 ,0 20 200 20 0 ,0 20 200 2^3 3.0 3.8 3.6 3890 2,0 289,300 2840 5,0 3540 2,0 319,100 314,800 3000 2,0 332,200 225.700 332 1,680 238 90 5 855 1,050 25 0 124 157 109 486 61.5 39 0 273 331 6. 56 41.2 35.4 174 511 36 4 2 1 62 95 20 13 ND («/hr) Mass ,0 20 ,200 ,0 20 ,200 ,0 20 ,200 ,0 20 ,0 20 ,0 20 ,0 20 1,200 («/«> TOC1 13 19 19 19 M_rA g>s_ _ 12 12 _ 12 12 7.7 9.2 308,700 616 194 246 11 5 83 14.6 17.4 32,900 425 134 138 10 10 13 a Estimated from Mass Missions data collected during 1978. Douglas Fiscus, Midwest Research Institute, personal conminication. b Flue gas sampled at the outlet of the ESP except where indicated. c Flue gas outlet samples were not collected on this day. The mass emission* and TOCl concentration data are for flue gas inlet samples collected on this day. Flue gas TOCl emissions are corrected for the TOCl to the ESP ash. �TABLE 60. COMPOUNDS QUANTITATED IN THE PRIMARY INPUT AND EMISSION MEDIA FOR THE AMES MUNICIPAL POWER PLANT, UNIT NO. 7 Inputs Compound Composite day Refuse-derived Coal fuel Input Input Cone, rate Cone. rate ( g h ) (ng/g) («ft/hr) •/r (ng/g) Plant background air Input rate Cone, (ng/dscn) (•R/hr) Flue gas inlet Emission Cone. rate (ng/dse.) («g/hr) Emissions Flue gas outlet ESP ash Emission Emission Cone. rate Cone. rate (ng/dscn) (»g/hr) (ng/g) («g/hr) Botton ash Enission Cone. rate (ng/g) («g/hr) Target PAH compounds Pyrene 110,000 1000 3,0 210,000 110,000 2000 7,0 1 2 3 4 5 1,570 1,840 1,260 2,120 4,110 2,0 300 2,0 600 1,0 800 2,0 800 59,000 1 2 3 1,190 1,640 3,320 900 3,210 17,000 2,0 300 4,0 600 1,0 200 4,0 600 984 271 306 198 1,300 1,200 580 420 1 2 1,340 1,960 3 Fluoranthene 7,550 900 ,9 15,400 8,500 18,600 3,810 4 Anthracene 1 2 3 4 5 4 5 Phenantbreoe 1,070 400 ,4 2,0 000 2,0 800 5,0 300 1,0 400 5,0 800 552 436 282 372 1,500 1,900 530 790 434 1,200 Chrysene Benzo[a]pyrene 1 2 3 4 5 370 425 1,060 238 1,300 1 2 3 4 5 5,400 600 ,0 15,000 3,200 19,000 76 140 200 200 54 390 320 320 37 480 0.17 0.16 0.19 008 .2 004 .2 0.030 59 57 77 89 100 16 18 22 28 28 49 77 78 3,100 4,100 1, 0 80 1,800 296 810 0.05 0.11 0.11 0.16 0.07 70 240 140 87 94 20 78 42 28 26 46 0.7 0.7 1.1 0.5 0.05 0.12 0.11 0.17 0.07 220 850 480 230 330 64 280 140 74 90 0.29 0.40 0.37 0.60 0.38 0.04 0.07 0.06 0.09 0.05 0.01 0.28 0.016 0.015 008 .0 0.02 0.4 14 26 24 14 22 0.07 0.17 0.11 0.09 0.07 5 270 420 660 640 200 110 0.32 0.04 0.09 0.11 0.13 0.044 0.003 0.29 140 ,0 940 948 828 0.6 0.8 0.8 0.36 0.7 0.7 1.0 0.5 0.36 3.5 28 0.76 77 40 97 28 130 110 96 250 66 330 96 12 13 21 64 120 19 63 0.2 0.2 0.2 0.2 0.2 0.2 Benzo[g,h,i]perylene 1 2 3 4 5 46 10 52 30 1.0 21 17 36 450 160 32 32 74 22 90 9.0 64 29 6.0 420 26 16 1.9 150 0.3 0.90 0.4 3.2 6.0 22 38 6.2 17 2.7 170 0.76 13 3.8 28 6.0 3.3 0.015 13 130 ' 0.09 140 43 500 3.2 99 78 14 180 24 Indeno [ 1 , 2 , 3-c , d Jpy rene 1 2 3 4 5 32 250 13 13 30 8.8 1.0 8.0 9.6 2.8 46 0.3 100 0.96 22 4.6 6.6 1.5 (continued) 58 �TABLE 60 (Continued) Compound Composite day Inputs Refuse-derived Plant Coal fuel background air Input Input Input Cone. rate Cone. rate Cone. rate (ng/g) (mg/hr) (ng/g) (mg/hr) (ng/dscm) (mg/hr) Flue gas inlet Emission rate Cone, (ng/dscm] (mg/hr) 1 Emissions Flue gas ESP ash Bottom ash outlet Emission Emission Emission Cone. rate Cone. rate rate Cone, (ng/dscm) (mg/hr) (ng/R) (mg/hr) (ng/g) (mg/hr) Additional compounds identified Dichlorobenzene 1,2,4-Trichlorobenzene Hexachlorobutadiene 3.3 1 2 3 4 5 1,300 1,200 520 430 25 79 1 2 3 4 5 1.0 24 8.2 24 25 3,500 5,200 980 920 5 1 2 3 002 .08 0.0016 0.02 002 .04 0.07 0.08 1.5 99 180 32 52 110 34 69 0.02 0.01 9.6 6.8 0.07 19 85 24 103 30 6,400 7,700 3,000 6,000 6,200 1,800 2,600 1,000 1,200 1,300 300 400 400 2,100 580 0.010 4 5 Tetrachlorobenzene 1 2 3 5 Pentachlorophenol Phenol 2 , 4-Dinethylphenol 1 2 3 4 5 1 2 3 4 5 1 2 3 4 5 1,300 3,500 24 690 10,000 12,000 2,800 23,000 29,000 150,000 170,000 39,000 310,000 420,000 7.2 1,500 3.3 1.3 0.8 1.5 1.8 0.46 0.21 0.11 0.23 0.25 4,700 4,000 13,000 5,100 9,500 1,300 1,300 4,000 1,600 2,600 220 260 190 380 230 460 98 640 990 110 260 27 920 1,900 1,700 980 1,600 1,800 360 730 11 8 (continued) 2.5 �TABLE 60 (Continued) Inputs Compound Naphthalene Fluorene Benz [a ] anthracene Benzofluoranthrene Benzo[e Jpyrene Acenaphthene Acenaphthylene Trichlorobenzene Composite day Plant Refuse-derived background air Coal fuel Input Input Input Cone, rite Cone. rate Cone, rate (og/g) (•g/hr) (ng/g) («g/hr) (ng/dsca) (•g/hr) 1 2 3 4 5 1,400 1,100 1,800 1,800 2,700 1 2 3 4 5 3,500 50,000 43,000 3,100 5,600 78,000 3,300 45,000 7,000 100,000 710 1,000 620 1,800 740 200 340 190 560 200 0.22 0.32 0.28 0.13 0.037 0.048 0.045 0.017 120 34 0.020 0.073 0.079 0.089 0.052 0.42 0.67 0.63 0.65 0.51 1,600 1,900 712 677 0.040 0.037 0.048 0.045 0.017 0.53 0.55 0.38 600 450 380 320 0.28 0.22 0.32 0.28 0.13 0.14 0.44 20,000 16,000 3 , 0 9 , 0 600 800 25,000 2,200 9,600 24,000 1,500 2,800 39,000 1,500 3,200 1 2 3 4 S 1 2 3 4 5 Emissions Flue gas Flue gas Bottoa ash inlet outlet ESP ash Emission Emission Emission Emission rate Cone. rate Cone. rate Cone. rate Cone, (ng/dsn) («g/hr) (ng/dscn) (•g/hr) (ng/g) (iig/hr) (ng/g) («g/hr) 000 .6 0.11 0.095 0.1 0.070 7.2 3.2 960 260 1,200 3,800 6,600 13,000 3,400 18,000 1 2 3 4 5 650 970 1,600 1,400 1,500 9,500 14,000 22,000 18,000 22,000 1 2 3 4 5 220 240 560 400 450 3,200 3,400 7,700 5,300 6,500 0.17 0.2 0.18 0.22 15 360 110 29 1.5 140 61 9.2 14 17 6.5 2.7 12 6.9 7.7 1.9 0.88 3.6 2.2 29 261 470 8.8 2.3 1 2 3 4 5 1 2 3 4 5 190 180 24 98 240 2.2 9.9 650 550 81 300 850 1,200 3,200 1.0 20 24 120 75 10 100 130 6.6 7.2 36 77 24 10.2 26 7.2 (continued) 0.55 12 30 5.5 32 47 �TABLE 60 (concluded) Compound Dime thy Ipht ha late Diethylphthalate Di-n-butylphthalate Butylbenzylphthaalte Composite day 1 2 3 4 5 a Specific isomer not Emissions Flue gas Flue gas Bottom ash inlet outlet ESP ash Emission Emission Emission Emission Cone. rate Cone. rate Cone. rate Cone. rate (ng/dscm) (mg/hr) (ng/dscm) (ng/hr) (ng/g) (mg/hr) (ng/g) (mg/hr) 3.0 0.20 730 1 2 3 4 5 11 0.5 9,100 25 ,000 290 1 ,300 1 ,400 2,700 11 , 0 23 , 0 00 00 18 ,000 49 ,000 14 ,000 61 ,000 6,400 12 ,000 14 ,000 28 ,000 1 2 3 4 determined. 2.0 0.48 26 1.20 37 48 16 5 .1 4.0 42 12 35 170 0.40 16 .8 6.6 11 58 32 3 .2 15 3.0 36 7.2 4.0 9.6 6.0 14 51 59 ,000 110 ,000 22 ,000 46 ,000 1 2 3 4 5 350 ,000 44 ,000 35 ,000 22 ,000 0.30 1 ,600 1 2 3 4 5 5 Bis(2-ethylhexyl)phthalate Inputs Refuse-derived Plant Coal fuel background air Input Input Input rate Cone. rate Cone. rate Cone, (ng/g) (mg/hr) (ng/g) (nig/hr) (ng/dscm) (mg/hr) 970 ,000 190 ,000 66 ,000 46 ,000 6.0 Ib 28 14 3.0 2.0 8.0 980 7.2 4.8 1,200 480 810 19 9.8 470 260 260 �TABLE 61. FLUE GAS CONCENTRATIONS OF PCBs AND EMISSION RATES FOR THE AMES MUNICIPAL POWER PLANT, UNIT NO. 7 Total PCBs Concentrations Emission rate (ng/dscm) (mg/hr) Ames composite day 1 5.2 1.4 2 27 9.0 3 23 6.8 4 25 8.2 5 17 4.8 Mean 19 6.0 S.D. 8.8 118 3.0 �TABU 62. CADMIUM INPUTS AKD EMISSIONS - AHES MUNICIPAL POVtR PLANT, UNIT NO. 7 Input Test day Date Load () I RDF (I) Mass flow (kt/hr) RDF Coal Cd cone. (MK/I) Cd input (mg/hr) Mass flow (kg/hr) Cd cone. (M8/8) Cd input (mg/hr) Total Cd input (mg/hr) Bottom ash (BA) Mass Cd Cd floo cone. emissions (kg/hr) (mg/hr) (MB/I) Emissions ESP ash (FA) Voluse Cd Mass Cd flow flow cone. emissions (dscm/hr) <m*/hr) (kg/hr) (Ug/g) Flue gas Cd Cd cone. emissions (Uf/dscm) (mg/hr) Total emissions (mg/hr) Percent of total emissions Flue BA FA gas 11 3/12 89 23.5 1.0 390 1,200 9.01 10,800 12 3/13 89 15.3 15.010 0.736 11,050 2,700 2.10 5,670 16,700 400 1.91 760 1,200 8.36 10,030 164,000 13 3/14 87 23.8 13,800 0.135 1,860 4,300 3.16 13,600 15.500 550 2.19 1,200 1,200 8.21 9.850 145,000 14 3/15 3/16 62 3.69 10,800 0.138 0.144 1,490 410 5.30 2,170 360 .6 150 2.41 0.876 360 1,200 1,200 5.43 2.90 6,520 3,480 129,000 21 3/24 85 6.15 14,800 0.149 2,200 970 2.63 2,550 4,750 200 1.36 270 1,200 4.12 4,940 153.000 22.55 3,450 8,660 3 57 22 3/25 84 10.9 14,300 0.112 1,600 1.740 2.88 5,010 6,610 300 2.70 810 1,200 6.34 7,600 148.000 27.95 4,140 12.600 6.5 60 . 5 33 23 3/26 87 15.0 14,400 920 1,200 7.54 9.050 1800 4.0 25.46 3,770 13,700 7 66 27 8 8 6 3 3 3 3 3 3 1,200 6.48 7,780 148,000 61 33 2.2 2,630 11,400 Determinations Mean Standard deviation 550 4,300 0.231 3.320 2.530 2.82 7.130 1.0 050 40 0 7 7 7 7 6 7 6 6 6 7 83 14 13,900 0.235 3,590 2,420 3.15 6,020 9,620 360 1.96 720 1,420 0.224 3.720 1,510 1.11 4,160 5,540 160 0.64 350 9.5 7.8 7 6 8 25.3 2.70 3,790 11,600 S.5 350 2,650 2.2 4.5 40 6.5 �TABLE 63. Date 5/3 5/4 5/6 5/7 5/8 5/9 5/10 5/11 5/12 5/13 5/15 5/16 5/17 Refuse input Feed TOC1 TOC1 rate cone, input (kg/hr) (ng/g) (8h) •/r 15,800 15,200 20,300 17,300 17,300 18,200 18,400 18,900 16,000 15,800 16,900 16,600 17,200 Mass emissions (dsc»/hr) < 1 < 1 3 2.9 21 21 12 2.2 15 10 6.6 < 1 < 5.5 < 5.3 16 14 87 103 60 11 53 34 24 < 3.6 12 12 . 88,080 93,960 84,600 92,460 72,600 83,820 85,740 86,280 83,340 84,600 99,060 - 1,100 3,140 1,760 13,500 2,070 3,310 2,540 2,920 1,230 2,300 1,490 - 11 11 11 11 Total TOC1 emissions (•g/hr) Percent of TOC1enissions Cooibined ash Flue gas (X) U) . 5 5 9 6 41 18 5 17 25 1.1 3 - . 95 95 91 94 59 82 95 83 75 89 97 - 5,500 5,290 5,490 4,680 4,680 4,920 4,970 5,110 3,470 3,430 3,670 3,600 3,730 13 12 13 17,200 590 9,800 4,500 8.1 35 86,780 3,200 285 327 13 87 Standard 1,440 deviation 1,180 18,700 800 7.6 34 6,830 3,500 327 345 12 12 Mean o Emissions Flue gasa TOC1 TOC1 cone. emissions (ng/dsc«) ("g/hr) Combined ash TOC1 Mass TOC1 emissions flow cone, (8h) ./r (kg/hr) (ng/g) 67,900 1,670 0 8,100 4,500 13,300 2,390 4,350 2,100 < 16 22,800 200 < 17 Deterain- 13 ations ro 4,300 110 0 470 260 730 130 230 130 < 1 1,350 12 < 1 TOTAL ORGANIC CHLORINE INPUTS AND EMISSIONS - CHICAGO NORTHWEST INCINERATOR, UNIT NO. 2 a Flue gas collected at the outlet of the ESP. 97 295 149 1,250 150 277 218 252 103 195 148 - 102 311 163 1,337 253 337 229 305 137 219 152 11 11 �The input and emission rates for target PAHs and other compounds identified in the composited Chicago extracts are shown in Table 64. Since the refuse extracts contained very high levels of extracted organics and were very difficult to analyze, composite refuse extracts were not prepared. Hence, the data were not available for the target PAHs and other compounds in the primary input medium for these composite days. The emission rates for PCBs in the Chicago flue gas samples are shown in Table 65. As in the case of the Ames data, only flue gas data was available although PCBs may have been present in other media at low concentrations. The emission rates for PCDDs and PCDFs in the Chicago flue gas samples are shown in Table 66. The mean emission rates for total PCDDs and PCDFs are 3,900 and 38,600 |Jg/hr, respectively. Table 67 shows the flue gas emission rates for 2,3,7,8-tetrachlorodibenzo-p_-dioxin. The mean emission rate is 34 pg/hr. A summary of the cadmium inputs and emissions for the test days investigated is presented in Table 68. The agreement between the total cadmium inputs and emissions is poor and reflects the problems encountered in obtaining representative samples of the refuse materials and resulting ashes. 121 �TABLE 64. Compound Composite day COMPOUNDS QUANTITATED IN INPUT AND EMISSION MEDIA CHICAGO NV INCINERATOR, UNIT NO. 2 Plant background air Conr. Input rate (ng/dscn) (ng/hr) Flue gas inlet Cone, Emission rate (ng/dscn) (•g/hr) Flue gas outlet Cone. Emission rate (ng/dsc«) (ing/hr) Combined ash Cone. Emission rate (ng/g) (mg/hr) Target PAH compounds Phenanthrene Fluoranthene 1 2 3 1 120 32 28 1.0 11 2.8 2.4 200 110 340 17 9.2 28 004 .4 no 9.8 2.4 1.6 39 27 51 2.2 0.012 27 18 2 3 Pyrene 1 0.28 0.82 0.035 2 3 0.18 008 .0 300 140 57 26 12 4.8 3.4 4.4 8.0 92 91 77 6.6 17 9.4 12 1 , 3-Dichlorobenzene 1 2 3 130 130 18 7.8 12 11 1.6 1,4-Dichlorobenzene 1 2 3 96 98 14 8.2 8.2 1.2 1 ,2-Dichlorobenzene 1 2 3 140 120 20 12 10 17 1,2, 3-Trichlorobenzene 1 2 3 140 81 27 12 7.0 2.2 48 57 150 4.0 4.8 12 1,2,4-Trichlo robenzene 1 2 3 550 380 160 46 32 13 200 220 560 17 19 48 1 ,3,5-Trichlorobenzene 1 2 3 490 280 120 44 24 10 190 180 460 16 15 40 Tetrachlorobenzene* 1 2 3 1,400 1,000 120 86 40 790 630 68 54 120 1 2 3 100 39 12 1 0 S3 Hexach lo robenzene 470 9.0 3.4 1.0 1,400 110 48 260 38 56 7.8 Additional compounds identified ,_. 78 9.0 4.0 22 (continued) 32 �TABLE 64 (Concluded) Compound Dichlorophenol Trichlorophenol Conposite day 1 2 3 1 2 3 Plant background air Cone. Input rate (ng/dscn) (ng/hr) Flue gas inlet Cone, Emission rate (ng/dscm) (mg/hr) 560 240 190 2,100 970 600 Flue gas outlet Cone, Emission rate (mg/hr) (ng/dscni) 40 20 16 180 82 52 240 280 630 22 24 1,400 1,200 1,900 120 98 160 1,500 1,100 1,700 130 96 140 16 36 8.8 5.8 11 1 2 3 2,200 1,100 600 190 90 52 1 2 3 130 11 64 5.4 190 160 430 Dibenzofuran 1 2 3 86 28 23 7.4 2.4 2.0 100 67 140 DiMthylphthalate 1 2 3 Tetrachlorophenol Pentachlorophenol 1*0 Diethylphthalate 1 2 3 Buty Ibenzy Iphtha late 1 2 3 14 4.8 50 42 400 15 6.1 32 144 54 260 1 2 3 Bis(2-ethylhexyl)- 54 1 2 3 Di-n-butylphthalate a Specific isomer not determined. Combined ash Cone. Emission rate (ng/g) (ng/hr) 130 47 370 1,200 420 3,000 86 83 �TABLE 65. FLUE GAS CONCENTRATIONS OF PCBs AND EMISSION RATES FOR THE CHICAGO NORTHWEST INCINERATOR UNIT NO. 1 Concentrations (ng/dscm) Emission rate (mg/hr) Composite day 1 20 1.7 2 13 1.1 3 93 7.8 Mean 42 3.5 S.D. 45 3.7 124 �TABLE 66. CONCENTRATIONS OF POLYCHLORODIBENZO-P-DIOXINS AND FURANS IN FLUE GAS FROM THE CHICAGO NORTHWEST INCINERATOR AND CORRESPONDING EMISSION RATES Concentrations (ng/dscm) Emission rate 15 12 11 13 2.1 1,300 Total trichlorodibenzo-p-dioxins Day 1 2 3 Mean S.D. 920 1,100 200 Total trichlorodibenzofurans Day 1 2 3 Mean S.D. 350 280 270 300 44 30,000 24,000 22,000 25,000 4,000 Total tetrachlorodibenzo-p-dioxins Day 1 2 3 Mean S.D. 7.2 5.4 6.2 6.3 0.90 620 460 520 530 81 89 84 96 90 6.0 7,600 7,200 8,000 7,600 400 14 21 14 16 4.0 1,200 1,800 1,200 1,400 350 Total tetrachlorodibenzofurans Day 1 2 3 Mean S.D. Total hexachlorodibenzo-p-dioxins Day 1 2 3 Mean S.D. (continued) 125 �TABLE 66 (concluded) Concentrations (ng/dscm) Emission rate (M8/hr) Total hexachlorodibenzofurans Day 1 2 3 Mean S.D. 43 84 59 62 21 3,800 7,200 5,000 5,300 1,700 Total heptachlorodibenzo-p-dioxins 7.2 7.8 7.7 7.6 0.32 Total 620 660 660 650 23 7.2 7.2 8.0 7.5 0.46 620 620 680 640 34 2.6 2.2 2.8 2.5 0.39 220 190 240 220 25 0.72 0.63 0.46 0.60 0.13 Day 1 2 3 Mean S.D. 62 54 40 52 11 heptachlorodibenzofurans Day 1 2 3 Mean S.D. Octachlorodibenzo-p-dioxin Day 1 2 3 Mean S.D. Octachlorodibenzofuran Day 1 2 3 Mean S.D. 126 �TABLE 67. CONCENTRATIONS OF 2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN IN FLUE GAS FROM THE CHICAGO NW INCINERATOR AND CORRESPONDING EMISSION RATES Concentration (ng/dscm) Day 1 0.35 Emission rate (pg/hr) 3.0 . *"~" i» 2 0^36 30 3 0.52 44 Mean 0.41 34 S.D. 0.10 127 8.0 ^ �TABLE 68. CADMIUM INPUT AND EMISSIONS FROM CHICAGO NORTHWEST INCINERATOR, UNIT NO. 2 Emissions Date Refuse input Mass Cd feed cone, (kg/hr) (pg/g) 8 5/12 16,000 1.45b 9 5/13 17,500 10 5/15 11 Test day Cd input (gh) •/r Combined ash Mass Cd emissions cone. (kg/hr) (Mg/g) Cd emissions (8h) •/r Volume emissions (dscm/hr) Flue gasa Cd cone. (pg/dscm) Cd emissions (mg/hr) Total Cd emissions (mg/hr) Percent of total emissions •Flue Combined gas ash () X 23,200b 3,470 0.54 9,450 3,800 17.6 66,900 16,900 0.47 7,940 3,670 26.6 97,600 5/16 16,600 0.52 8,630 3,600 14.5 52,200 12 5/17 17,200 0.48 8,260 3,730 12.8 47,700 87,200 285 24,900 72,600 66 34 13 5/18 17,500 0.59 10,300 380 ,0 32,500 97,500 240 23,400 55,900 58 42 14 5/19 2,0 240 60b .2 1500 3,0b 740 ,6 1300 5,0 1050 0,0 273 2,0 740 1040 8,0 85 15 5 7 6 3 3 3 Determinations Hean I™4 ro co Standard deviLation 7 5 8.55 2. 05 6 3 3 3 17,700 0.52 8,920 4,220 16.8 75,000 95,100 266 25,200 103,000 70 30 2,100 0.05 960 1,430 6.3 44,100 7,000 23 2,020 67,600 14 14 a Flue gas collected at the outlet of the ESP. b Not included in determinations of mean and standard deviation. �SECTION 11 STATISTICAL SUMMARY OF PILOT STUDY DATA OVERVIEW This section summarizes the data obtained from the chemical analysis of specimens collected in the pilot study. The chemical analysis was performed in two phases or tiers. In the first tier, the total organic chlorine (TOC1) concentration was measured in nearly all of the specimens collected. Some compositing of specimens was performed before chemical analysis to reduce cost. In the second tier, many more specimens were composited because of the greater expense at this level of analysis. Also, only specimens from selected media were analyzed. For the first tier chemical analysis data, the mean, coefficient of variation (CV) and nominal 95% confidence intervals for the TOC1 concentration are calculated for each sampling location at both combustion sites. The mean and CV are calculated for the concentrations of compounds quantified in the second tier analysis. In addition, the total mass flow rate and its CV are calculated. The mass flow rate is calculated by weighting the measured concentration of the compounds by the total mass flow rate associated with each measurement. The summary statistics are presented below with brief descriptions of the calculation methods. FIRST TIER SUMMARY Total Organic Chlorine For the sampling locations where each specimen was chemically analyzed independently (no compositing) the arithmetic mean (X) was calculated using the equation n X = Z X./n where X. is the TOC1 concentration of the i specimen and n is the number of specimens. The CV is calculated by first calculating the sample variance (S2) 129 �S2 = I (X. - X)2/(n - 1) The CV = S/X. The nominal 95% confidence intervals are calculated by (X - t Q5(df) S/S/n" , X + t Q5(df) where t 05(df) is obtained from tables of Student's t distribution9 and df denotes 'tne appropriate number of degrees of freedom, which is equal to the number of independent chemical analyses minus one. For several media many specimens were collected. To minimize the cost of chemical analysis for these media while retaining sufficient statistical information, a complex compositing protocol was developed for the sample locations where more than one specimen per day was collected. The compositing varied for the samples collected each day. On some days all were composited, on others the two within a shift were composited, and on others none were composited. These locations were fly ash, bottom ash, coal, RDF and OW at Ames and fly ash, combined ash and refuse at Chicago, NW. No compositing was done for the specimens collected at the other sample locations. To modify the calculations for X and S2 to compensate for the compositing, each chemical determination was assigned a weight equal to the number of specimens composited. Then the weighted mean Y was calculated by m m Y = 1 W. Y. / I W. , W i=l x x 1=1 x where Y. is the i chemical determination, W. is the number of specimens composited for the i chemical determination^nd m is the number of chem m determinations. Because I W. = n and, on average, m n I W. Y. = I X., then Y equals X, on average. I w i=l * 130 �To estimate S2 from the composited data, calculate m m 2 Sw = ._- W1 (Y. - Yw )2 /I W. I 2 1 ._- i m where W., Y., Yw, and m are the same as above. Because I W? (Y. - Y )2 i i i i w i=1 n approximately equals £ (X. - X)2 on average, S2 approximately equals S2 on average. Hence the CV (S/X) is estimated by S /Y . The technique above gives a method to estimate X and S2 as if no compositing were done. A theoretical justification of these techniques is given in Appendix C of Lucas et al.1 Tables 69 and 70 display the statistical summary of the TOC1 concentrations measured in the pilot study. Chemical Analysis Measurement Errors To assess the measurement errors in the chemical analysis, a method of standard additions was employed. Known amounts of two surrogate compounds, dg-naphthalene and di2~cnrysene, were added to the composited specimens before the chemical analysis. The mean percent recoveries of the surrogate compounds and their CVs are given in Tables 71 and 72. If the percent recoveries in these tables are indicative of the recovery rate for TOC1, then the concentrations of TOC1 are underestimated. This underestimation would be greater for the specimens from Chicago than those from Ames. However, the summary statistics reported in Table 66 and 67 above are not adjusted for the percent recovery. Biases of this type can affect the true confidence of a nominal 95% confidence interval. For example, in Table 68 the mean percent recovery of the surrogate compounds of the flue gas inlet is 59%. If this indicates a negative bias in estimating the true mean concentration of TOC1 of 41%, the true confidence of the nominal 95% confidence interval can be estimated using Table 73. To calculate the ratio of the bias (BIAS) and standard error (SE), use BIAS/SE = 4l/(49/Vl9) = 3.7 , where 41 is the absolute percent bias, 49 is the CV in Table 69, and 19 is the number of specimens analyzed. Table 73 indicates the true confidence of the nominal 95% confidence interval in Table 66 is less than 6%. Table 73 also includes the impact of other levels of bias (relative to the SE) on the true confidence of a nominal 95% confidence interval. 131 �TABLE 69. SUMMARY STATISTICS FOR TOTAL ORGANIC CHLORINE CONCENTRATION DATA FROM AMES, IOWA a Media (units) Number of specimens Mean Degrees Coefficient of of variation ( ) freedom % Nominal 95%b confidence interval Gaseous (ng/dscm) Flue gas inlet Flue gas outlet Ambient air 19 11 20 562 632 * 49 85 18 10 (426, 698) (254, 1,010) 90 (89) 88 11 62 8.3 3.6 58.6 4.4 11,900 536 81 183 23 116 50 (49) 50 5 36 (-1.0, 17.6) (2.9, 4.2) (35.1, 82.1) (3.5, 5.3) (8,342, 15,470) 91 6 664 373 70 33 51 5 (570, 760) (231, 514) 54 32 2 (1.4, 107) Solid (ng/g) Fly ash (c) Bottom ash Coal Refuse-derived fuel Liquid (ng/liter) OWd Quench water influent Well water a Number of independent chemical analyses minus one. b Nominal value based on normal probability distribution theory. c Numbers in ( ) are estimates excluding the maximum value of 210 ng/g. This value is 21 times larger than the next largest value. Both sets of summary statistics are included to illustrate the impact of the one extreme value on the estimates. d Bottom ash hopper quench water overflow. * Measured values in field specimens not significantly different from blanks. 132 �Table 70. SUMMARY STATISTICS FOR TOTAL ORGANIC CHLORINE CONCENTRATION DATA FROM CHICAGO NW Q Media (units) Number of specimens Mean 11 11 (10) 12 2,200 3,220 (2,190) 1.67 72 67 61 93.6 9.9 902 4 30 Nominal 95%b confidence interval Coefficient Degrees of of variation ( ) freedom % Gaseous (ng/dscm) Flue gas inlet Flue gas outlet (c) Ambient air 34 109 ( 36) 64 10 (1,698, 2,702) 10 (862, 5,578) ( 9) (1,330, 3,040) 11 (-.68, 4.02) Solid (ng/g) Fly ash Combined ash Refuse 85 162 251 52 50 50 (71.7, 115.6) (5.8, 13.9) (283.8, 1,520) Liquids (ng/liter) City tap water * 0 Not calculated because there was no variability in the data. a Number of independent chemical analyses minus one. b Nominal value based on normal probability distribution theory. c Numbers in ( ) are estimates excluding the maximum value of 13,500 ng/dscm. This value is 4 times larger than the next largest value. Both sets of summary statistics are included to illustrate the impact of the one extreme value on the summary statistics. 133 �TABLE 71. SUMMARY OF SURROGATE COMPOUNDS PERCENT RECOVERY FOR SPECIMENS FROM AMES, IOWA di2~Chrysene dft-Naphthalene Media No. of analyses Mean % recovery Coefficient of variation ( ) % No. of analyses Mean % recovery Coefficient of variation ( ) % 18 11 56 47 45 25 19 11 71 86 26 14 51 42 6 37 44 55 90 65 56 36 18 22 51 49 6 37 96 85 90 111 24 37 19 25 40 6 2 51 69 66 54 25 1 48 6 3 88 111 88 29 16 20 Gaseous Flue gas inlet Flue gas outlet Solid u> •P- Fly ash Bottom ash Coal Refuse-derived fuel Liquid ow* Quench water influent Well water a Bottom ash quench water overflow. b Specimens that were inadvertently evaporated to dryness were excluded. �TABLE 72. SUMMARY OF SURROGATE COMPOUND PERCENT RECOVERY FOR SPECIMENS FROM CHICAGO, NW Media dg-Naphthalene di2~Chrysene Number Mean Coefficient Number Mean Coefficient of percent of of percent of analyses recovery variation ( ) analyses recovery variation ( ) % % Gaseous Flue Gas Inlet Flue Gas Outlet Ambient Air 11 11 12 37 27 31 84 98 75 11 11 12 74 62 51 48 82 88 53 33 44 26 35 9 68 57 51 52 33 44 36 22 12 61 105 193 3 27 131 3 13 92 Solid Fly Ash Combined Ash Refuse Liquid City Tap Water 135 �TABLE 73. VALIDITY OF CONFIDENCE STATEMENTS FOR SELECTED LEVELS OF BIAS True confidence level* for the x ± 1.96 SE interval a BIAS/SE 0 0.5 0.92 1.0 0.83 1.5 0.68 2.0 0.48 2.5 0.29 3.0 0.15 3.5 0.06 4.0 * 0.95 0.02 Calculated according to the integral of the 1.96 + BIAS/SE ;V e"^ dx -1.96 + BIAS/SE a BIAS/SE is used because the true confidence depends on the relative magnitude of the bias with respect to the SE, not the absolute magnitude. Here, BIAS denotes the absolute average deviation of the estimate from the true value and SE denotes the standard error of the estimate and is equal to the standard deviation (s) divided by the square root of the sample size 136 �Table 74 summarizes the estimates of the CVs (S/X) for both the sampling and measurement (as indicated by the surrogate recovery data) component. One should note that the measurement CVs for Ames are uniformly less than those for Chicago. In fact, for some sampling locations at Chicago NW, the measurement component dominates the total variability giving negative estimates of the sampling component. This is not unexpected for the ambient air and city tap water because at these two locations one would expect the media to be rather homogeneous. However, this is unexpected at the flue gas inlet. SECOND TIER SUMMARY In the second tier of chemical analysis the concentrations of many compounds were measured. Because of the expense at this level of chemical analysis, much compositing of specimens was done before the analyses were performed. At Ames, five pairs of days were randomly selected. For each sampling location, all specimens collected during the pair of days were composited for one chemical determination. This gave a total of five independent chemical determinations in this tier for each sample location from Ames except RDF, where only four chemical determinations were performed. At Chicago, three sets of three days were randomly selected. For the selected sampling locations, all specimens collected during the three days were composited for one chemical determination. This gave a total of three independent chemical determinations in this tier for the selected sample locations at Chicago. To statistically summarize the second tier data, the arithmetic mean (X) and CV (S/X) were calculated for the concentration measurements. Also, to estimate the mass flow rates, the variable Y. was defined as Y. = r. X. ' i i i, where X. is the concentration for the i .chemical determination and r. is the mass flow rate associated with the i chemical determination. The arithmetic mean Y and CV (S/Y) were calculated to summarize the flow rates. In calculating the mean concentrations and flow rates, all trace values were assumed to be zero. This will result in an underestimate of the true values. The number of quantifiable values are also included in the summaries. The magnitude of underestimation resulting from substituting zero for trace values depends upon the number of traces and the levels of quantifiable values compared to the minimum quantifiable level. Because of the relatively few composites measured for each compound, the presence of trace values, and the relative large variability in the data (large CVs), no confidence intervals are included in the data summaries. 137 �Table 74. SUMMARY OF COEFFICIENT OF VARIATION FOR THE PILOT STUDY Media Sampling Ames Measurement Sampling Chicago, NV Measurement Gaseous Flue gas inlet Flue gas outlet Ambient air 25 13 a c 85 c 68 68 87 535 (78) 179 24 38 56 64 143 76 12 114 19 18 194 159 42 84 a Solid Fly ash Bottom ash Combined ash Coal Refuse-derived fuel Refuse Liquid OW Quench water influent City tap water 58 17 38 28 132 a Not calculated because specimen amounts were not significantly different from blanks. b Number in ( ) are estimates excluding the maximum value of 210 ng/g. This value is 21 times larger than the next largest value. Both summary statistics are included to illustrate the impact of the one extreme value on the estimate. c The estimates of these values were negative and were excluded because the CV must be non-negative. * The measurement CVs presented above are a weighted average of the CVs in Tables 68 and 69. They were calculated by CV = (S| + Sf2)^/(X8 + X12), where the subscripts 8 and 12 denote dg-naphthalene and d12-chrysene, respectively. 138 �The second tier chemical analysis data is summarized in Tables 75 through 81. These tables include summaries of the primary input and emissions media at Ames. These are coal, refuse-derived fuel, combustion air, flue gas inlet, flue gas outlet, fly ash and bottom ash. The secondary input and emission media, bottom ash hopper quench water influent, well water, and bottom ash water quench water overflow, were excluded because of the sparsity of the data. These tables also include the summaries for the flue gas inlet and outlet from Chicago. The combustion air, combined ash, and fly ash are excluded because of the sparsity of the data. No second tier chemical analysis was done on the refuse from Chicago. 139 �TABLE 75. SUMMARY STATISTICS FOR COMPOUNDS QUAUTITATED IN PRIMARY INPUT MEDIA AT AMES, IOWA Compound Coal Concentration Number olf (ng/g) detectioiis Mean CV (X) Input rate (•g/hr) Mean CV (X) Refuse-derived fuel Input rate Concentration Number of (ng/g) (•g/hr) detections Mean Mean cv (X) CV (X) Phenanthrene Anthracene Fluoranthene Pyrene Chrysene 5 5 5 5 Benzo[a]pyrene 0 0 4 1 4 4 1 0 0 0 Dichlorobenzene 0 1,2,4-Trichloro- 0 4 0 2b 41 52 56 57 69 1600 6,0 30,800 28,800 34,600 9,720 43 53 56 57 71 1,030 74 440 411 109 25 200 83 28 200 2,700 202 875 1,180 300 41 200 50 53 200 0.56 0.10 0.65 0.67 0.41 0.10 0.004 44 92 37 42 28 41 224 0.083 0.016 0.10 0.10 0.06 0.066 0.001 48 95 42 45 31 182 224 4C 0 IndenoT.1,2,3c.dj-pyrene BenzoTg.h,!]- 5 11,830 2,180 2,050 2,440 679 Combustion air Input rate Concentration (•g/hr) Nunber of (ng/g) Mean detections Mean CV (X) CV (X) 0.02 224 0.003 224 0. 3d 5 3 5 5 5 5. perylene 863 52 2,650 79 0.006 149 0.0009 145 b 0.004 224 0.0005 224 b 0.01 224 0.002 224 5 1.7 0.25 0.19 0.41 54 30 67 40 0.25 0.037 0.029 0.063 51 33 69 44 5 0.58 19 0.087 24 benzene Hexachlorobutadiene 0 0 2 Pentachlorophenol 0 2 498 Pentachlorobi- 0 2 a 0 4 4 0 10,300 438 126 1,250 133 2 0 phenyl Phenol Naphthalene Flourene Benzo(a] anthracene Benzofluoranthrene 5 5 5 0 15,360 1,760 4,500 5 630 68 8,960 71 0 Acenaphthene 5 5 1,220 374 33 38 17,100 5,220 32 37 4 0 Acenaphthylene 68 34 38 217,800 24,800 63,200 68 35 39 300 166 28 200 28,400 1,220 80 0 164 51 200 5 5 4 0 0 * CV denotes the coefficient of variation and is calculated by dividing the standard deviation by the mean. a Only trace values were detected, hence no quantification was attempted. b One specimen contained a quantifiable level and one a trace. The trace is always asstned to be zero to calculate the wan c One specimen contained a quantifiable level and three were traces. d Two specimens contained a quantifiable level and one a trace. and CV. �TABLE 76. SUMMARY STATISTICS FOR COMPOUNDS QUANTITATED IN GASEOUS EMISSIONS AT AMES, IOWA Compound Flue gas inlet Concentration Number of (ng/g) detections Mean CV ( ) % Phenanthrene Anthracene Fluoranthene Pyrene Chrysene Benzolajpyrene Benzojg.h.i]perylene Dichlorobenzene 1,2,4-Trichlorobenzene Hexachlorobutadiene Tetrachlorobenzene Pentachlorophenol Phenol 2,4-Dinethyphenol Naphthalene Fluorene Benzf a] anthracene Benzofluoranthrene Benzo[e]pyrene Acenaphthylene Trichlorobenzene Emission rate (mg/hr) CV ( ) % Mean Number of detections Flue gas outlet Concentration Emission rate (mg/hr) (ng/g) CV ( ) % Mean CV ( ) % Mean 5 5 5 5 5a 5 0 438 76.4 126 422 8.8 57.4 48 24 55 62 129 72 134 22 39 130 2.6 18 51 25 60 68 125 74 5 5 5 5 5^ 3d 3 309 65.4 68.2 170 0.54 8.2 6.0 54 25 64 67 224 151 154 66 20 20 50 0.15 2.0 1.8 74 28 60 60 224 143 153 3 3 25.8 69.6 125 108 7.8 20 126 108 2 3 1.7 39 142 139 0.50 12 141 140 1 20.6 224 6.0 224 0 ' | - lb 0 1 4.8 224 5 0 7,260 53 5 1 1 974 24 1.4 50 224 224 2 5.4 0 2 0 8.8 224 0 54 5 4 5,860 1,120 30 67 1,780 336 33 63 298 6.8 0.44 53 224 224 5 0 0 486 62 146 58 145 1.1 140 5a 5.6 81 1.7 80 224 1.8 224 2.8 135 1 0 3 5.8 138 27 116 8.7 123 1.4 2,160 * CV denotes the coefficient of variation and calculated by dividing the standard deviation by the mean. a Four specimens contained quantifiable levels and one a trace. All trace values are assumed to be zero when calculating the mean and CV. b One specimen contained a trace. c One specimen contained a quantifiable level and four contained traces. d Two specimens contained quantifiable levels and one a trace. �TABLE 77. SUMMARY STATISTICS FOR COMPOUNDS QUANTITATED IN SOLID EMISSIONS AT AMES, IOWA Compound Fly ash Concentration Number of (ng/g) detections Mean CV ( ) % Phenanthrene 5a 0 Anthracene 0 Fluoranthrene Pyrene 0 '1 Chrysene Dichloro1 benzene Phenol 3 0 2,4-Dimethylphenol 2 Naphthalene Fluorene 0 0 Acenaphthene 0 Acenaphthylene 0.2 Emission rate (mg/hr) Mean CV ( ) % Bottom ash Concentration Number of (ng/g) CV ( ) % detections Mean 5 2 4 5 lb 3b 193 31 108 106 34 4.8 102 5 4C 1,094 7.0 137 5a 1 1 5 103 3 0.2 87 61 0.2 71 0.1 0.01 224 224 0.1 0.02 224 224 158 102 190 0.07 137 0.08 Emission rate (mg/hr) Mean CV ( ) % 75 12 40 39 12 1.9 96 169 170 162 224 224 55 167 420 2.7 92 176 146 224 224 55 42 1.5 0.11 25 142 224 224 66 100 183 177 168 224 224 * -Pro CV denotes the coefficient of variation and is calculated by dividing the standard deviation by the mean. a Four specimens contained quantifiable levels and one a trace. calculating the mean and CV. b One specimen contained a quantifiable level and two a trace, c Two specimens contained quantifiable levels and two a trace. Trace values are always assumed to be zero when �TABLE 78. SUMMARY OF TOTAL INPUT AND EMISSIONS FROM AMES, IOWA Compound Phenanthrene Anthracene Fluoranthene Pyrene Chrysene Benzo[a]pyrene IndenoTl,2,3-c,d]pyrene Benzo[g,h,i]perylene Dichlorobenzene 1,2, 4-Trichlorobenzene Hexachlorobutadiene Tetrachlorobenzene Penta chl o ropheno 1 Pentachlorobiphenyl Phenol 2 , 4-Dimethylphenol Naphthalene Fluorene Benz [ a ] anthracene Benzofluoranthrene Benzo[ejpyrene Acenaphthene Acenaphthylene Trichlorobenzene Total input rate (mg/hr) CV ( ) % Mean 169,000 31,000 29,700 35,800 10,020 0.066 0.001 0.003 2,650 0.0009 0.0005 nd 1,250 tr 217,800 nd 53,200 64,400 .063 8,960 nd 17,900 5,220 nd 42 53 54 55 69 182 224 224 79 145 224 133 68 89 38 44 71 32 37 Total emission rate (mg/hr) cv (%) Mean 141 32 60 89 12.2 2.0 nd 1.8 2.4 12 nd nd nd nd 2,390 339 188 1.5 nd 1.7 1.8 0.11 25 8.7 nd denotes not detected, tr denotes trace. * CV denotes coefficient of variation and is calculated by dividing the standard deviation by the mean. 143 62 66 115 79 219 143 153 178 140 31 63 55 224 80 224 224 66 123 �TABLE 79. SUMMARY STATISTICS FOR COMPOUNDS QUANTITATED IN GASEOUS EMISSIONS FROM CHICAGO Compound Number of detections Phenanthrene Fluoranthene Pyrene 1,3-Dichlorobenzene 1 ,4-Dichlorobenzene 1,2-Dichlorobenzene 1,2,3-Trichlorobenzene 1,2,4-Trichlorobenzene 1,3,5-Trichlorobenzene Tetrachlorobenzene Hexachlorobenzene Dichlorophenol Trichlorophenol Tetrachlorophenol Pentachlorophenol Dibenzofuran * Flue gas inlet Emission rate Concentration (mg/hr) (ng/g) Mean CV ( ) % CV ( ) % Mean Number of detections 3 3 3 3 60 52 166 93 87 98 75 70 5.4 4.6 14 8.4 90 98 76 71 3 3 3 0 3 69 69 5.9 69 Flue gas outlet Emission rate Concentration (»g/hr) (ng/g) Mean CV ( ) % Mean CV ( ) % 217 39 87 53 31 10 18 3.3 7.5 52 33 10 0 3 93 69 8.0 69 0 3 83 68 7.1 69 3 85 66 6.9 64 3 363 54 30 55 3 327 62 28 62 3 297 63 26 66 3 277 57 24 60 3 957 49 82 49 3 940 43 81 43 3 50 90 4.5 92 3 139 78 12 80 3 3 330 1,220 61 64 25 105 51 64 3 3 383 1,500 56 24 33 126 54 25 3 1,300 63 111 64 3 1,430 21 122 19 2 65 101 5.5 101 3 260 57 22 55 3 46 77 3.9 76 3 102 36 8.5 31 CV denotes the coefficient of variation and is calculated by dividing the standard deviation by the mean. �TABLE 80. SUMMARY OF FLUE GAS EMISSIONS OF POLYCHLORINATED BIPHENYL ISOMERS FROM AMES, IOWA Emission rate (mg/hr) CV ( ) % Mean Compound Concentration (ng/dscm) cv (%) Mean Dichlorobiphenyl nd Trichlorobiphenyl 1.5 185 0.48 189 Tetrachlorobiphenyl 2.9 63 0.94 64 Penta chlo rob ipheny 1 9.0 87 2.8 80 Hexachlorobiphenyl 5.1 104 1.7 104 Heptachlorobiphenyl 0.6 224 0.2 224 Decachlorobiphenyl 0.6 224 0.2 224 19.4 46 6.1 47 Total Chlorobiphenyl CV denotes the coefficient of variation and is calculated by dividing the standard deviation by the mean. 145 �TABLE 81. SUMMARY OF FLUE GAS EMISSIONS OF POLYCHLORINATED BIPHENYLS, DIBENZO-£-DIOXINS, AND DIBENZOFURANS FROM CHICAGO NW Concentration (ng/dscm) cv (%) Mean Compound Emission rate (mg/hr) cv (%) Mean Dichlorobiphenyl 17.3 114 4.4 113 Trichlorobiphenyl 16.0 109 4.1 108 Tetrachlorobiphenyl 6.2 96 1.6 95 Pentachlorobiphenyl 2.6 68 1.6 67 Total chlorobiphenyl 42.1 105 10.7 104 Total trichlorodibenzo-j>-dioxins 13 16 1.1 19 300 15 Total trichlorodibenzofurans Total tetrachlorodibenzo-p_-dioxins 6.3 27 11 14 0.53 15 Total tetrachlorodibenzofurans 90 7 7.6 5 Total hexachlorodibenzo-£-dioxins 16 25 1.4 25 Total hexachlorodibenzofurans 62 33 5.3 32 Total heptachlorodibenzo-£-dioxins 7.6 4 0.65 4 Total heptachlorodibenzofurans 7.5 6 0.64 5 Octachlorodibenzo-£-dioxin 2.5 12 0.22 12 Octachlorodibenzofuran 0.60 22 0.05 21 * CV denotes the coefficient of variation and is calculated by dividing the standard deviation by the mean. 146 �REFERENCES 1. Lucas, R. M., D. K. Melroy, "A Survey Design for Refuse and Coal Combustion Process," from Research Triangle Park to EPA/EED/OTS/Washington, DC, EPA Contract No. 68-01-5848, June 1981. 2. TRW Environmental Engineering Division, RTW, Inc., "Pilot Test Program, Ames Municipal Power Plant, Unit No. 7," from TRW, Inc., to EPA/IERL/ ORD, Research Triangle Park, NC, under EPA Contract No. 68-02-2197, April 1980. 3. Bakshi, P. S., T. L. Sarro, D. R. Moore, W. F. Wright, W. P. Kendrick, and B. L. Riley, "Pilot Test Program, Chicago Northwest Incinerator, Boiler No. 2," from TRW Environmental Engineering Division to EPA/ IERL/ORD, Research Triangle Park, NC, under EPA Contract No. 68-022197, June 1980. 4. Federal Register. 41(111), 23060-23090, 1976. 5. Stanley, J. S., C. L. Haile, A. M. Small, and E. P. Olson, "Sampling and Analysis Procedures for Assessing Organic Emissions from Stationary Combustion Sources in Exposure Evaluation Division Studies," from Midwest Research Institute to EPA/OPTS/Washington, DC, under Contract No. 68-01-5915, Report No. EAP-560/5-82-014, August 1981. 6. Lustenhouwer, J. W. A., K. Olie, and 0. Hutzinger, "Chlorinated Dibenzo£-dioxins and Related Compounds in Incinerator Effluents: A Review of Measurements and Mechanisms of Formation," Chemosphere, 9, 501, 1980. 7. Richard, J. J., and G. A. Junk, "Polychlorinated Biphenyls and Effluents from Combustion of Coal/Refuse," Environmental Science and Technology, 15, 1095, 1981. 8. Memorandum from R. Harless, Analytical Chemistry Branch, ETD, IERL/RTP to Dr. A. Dupuy, EPA/Toxicant Analysis Center, "Collaborative Analysis for Chlorinated Dibenzo-p_-dioxins and Dibenzofurans in Combustion Source Extracts," August 10, 1981. 9. Snedecor, G. W., and W. G. Cochran, Statistical Methods, The Iowa State University Press, Ames, Iowa, 1980, 507 pp. 147 �APPENDIX A TRW FIELD TEST REPORT FOR THE AMES MUNICIPAL ELECTRIC SYSTEM. UNIT NO. 7 148 �PILOT TEST PROGRAM AMES MUNICIPAL POWER PLANT UNIT NO. 7 TRW ENVIRONMENTAL ENGINEERING DIVISION TRW, INC. 28 April 1980 EPA Contract .68-02-2197 EPA Project Officer: Michael C. Osborne Industrial Environmental Research Laboratory Office of Research and Development U.S. Environmental Protection Agency Research Triangle Park, N.C. 27711 149 �CONTENTS Figures Tables iv 1. Introduction 2. Summary 2.1 Sampling and Analysis 2.2 Process Data 2.3 Continuous Monitoring Data 1-1 2-1 2-1 2-1 2-23 3. System Description 3.1 Boiler Description ..... 3.2 Electrostatic Precipitator 3-1 3-1 3-12 i 4. Sampling Locations. . 4-1 5. Sampling 5.1 Gas Sampling . 5.2 Solid Sampling 5.3 Liquid Sampling -. . 5.4 Hi Volume Sampler 5.5 Quality Assurance 5.6 Sampling Train Background 5.7 Sample Recovery 5.8 Problems Encountered During Recovery 5-1 5-1 5-5 5-5 5-6 5-6 5-6 5-8 5-8 6. Calibration 6.1 Method Five Calibration Data 6.2 Instrument Calibration 6-1 6-1 6-3 7. Technical Problems and Recommendations 7.1 Problems 7.2 Recommendations 7-1 7-1 7-1 Appendices A. B. C. D. Continuous Monitoring Data Field Data Sheets Solid and Liquid Sampling Schedule. Process Data Sheets It 150 , •. A-l B-l C-l D-l �FIGURES Number 2-1 3-1 3-2 3-3 3-4 4-1 4-2 4-3 4-4 5-1 5-2 5-3 5-4 6-1 Page Oxygen in the gas before and after the air preheater. . . . 2-31 Layout of plant site 3-2 Flow diagram for unit #7 at Ames Municipal power(piant. . . 3-4 Schematic of Ames Municipal power plant boiler 17 3-7 Solid waste recovery system 3-11 Unit #7 flow diagram and measurement locations 4-2 Cross section of stack showing traverse point locations . . 4-3 Inlet duct - showing port locations 4-4 Inlet traverse point locations 4-5 ESP inlet sampling train 5-2 Stack sampling train 5-3 EPA Method 5 particulate sampling train 5-4 Ambient air sampler , 5-7 Calibration equipment set-up procedures 6-4 iii 151 �TABLES Number 2-1 2-2 2-3 2-7 2-8 2-9 3-1 Daily Organic Sampling Summary Daily Data Summaries 24 Hour Process Data for the Ames Municipal Power Plant, Unit No. 7 Test Duration Process Data for the Ames Municipal Power Plant, Unit No. 7 Daily Production and Consumption at Ames Municipal Power Plant, Unit No. 7 Heat Content of Fuels Used at the Ames Municipal Power Plant During Sampling Period Continuous Monitoring Data Excess Air Readings Air Preheater Continuous Monitoring Data Boiler Design Data 3-2 Design Specification for Raymond Bowl Pulverizers 3-3 3-4 Fan Design Performance 3-8 Predicted Performance Characteristics of Unit #7 at Ames Municipal Power Plant 3-9 Performance Characteristics of the American Standard ESP. . 3-13 Sampling Locations 4-1 2-4 2-5 2-6 3-5 4-1 1v 152 2-2 2-12 2-14 2-17 2-24 2-25 2-27 2-29 2-30 3-3 3-5 �1. INTRODUCTION This document describes the sampling and monitoring activities at the Ames Municipal Power Plant, boiler unit No. 7. The sampling and field measurement work performed was part of an overall pilot scale test program sponsored by the Office of Pesticides and Toxic Substances in cooperation with the Office of Research and Development, of the U.S. Environmental Protection Agency. The ultimate objective of the pilot scale test program is to develop an optimum sampling and analysis protocol to characterize polychlorinated organic compounds which may be emitted in trace quantities through conventional combustion of fossil fuels and refuse. The genesis of the program is an industrial study by Dow Chemical Company and two groups of European investigators reporting emissions of polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and biphenyls (PCB) from stationary conventional combustion sources. The immediate objective of the sampling and field measurements program (for a fossil-fuel 17% RDF-fired utility boiler) is the specification of procedures and equipment to obtain sufficient multimedia samples for the subsequent analytical protocol, and to satisfy the program statistical design requirements. In this respect, the TRW Environmental Engineering Division of TRW, Inc., was one of three contractors participating in the overall EPA program. These contractors, their key individuals and respective roles are: 1. Research Triangle Institute Research Triangle Park, North Carolina Statistical design of the overall test program Mr. R. M. Lucas, Task Manager 2. TRW Environmental Engineering Division, TRW, Inc. Redondo Beach, California Acquisition of samples and field measurements Mr. B. J. Matthews, Project Manager 3. Midwest Research Institute Kansas City, Missouri Laboratory analysis of all field samples Dr. C. L. Haile, Task Manager 1-1 153 �The sampling was oriented toward acquiring multimedia samples for organic compound analysis by Midwest Research Institute (MRI). Compounds of particular interest included: i Benzo [a] pyrene Chrysene Pyrene Indeno [1,2,3-cd] pyrene Fluoranthene Benzo [g_5h.»l] perylene Phenanthene Anthracene In addition, MRI is to make a determination of total organic chlorine emissions from the acquired samples. Potentially, selected samples are to be analyzed for dibenzo-p-dioxins, dibenzofurans and biphenyls. Instrumentation for on-line combustion gas stream monitoring was part of the test program. In addition, utility boiler process information (including RDF data) was also gathered. This information together with the monitoring data were acquired to assist in evaluating and interpreting chemical analysis results. This report contains all the field data for the Ames Municipal Power Plant pilot test program conducted in March 1980. Data provided include the following: • Chlorinated hydrocarbon collection using a modified EPA Method 5 train and Method 5 sampling methodology, • Gas velocities using EPA Method 2, • Continuous monitoring for CO^, CL, and CO and THC, • Particulate collection for inorganic analysis utilizing EPA Method 5. • Process data. The test program followed was described in the Pilot Test Program, Ames Municipal Power Plant, Unit No. 7 site test plan. Deviations from this program are documented and explained in their respective sections of this report. 1-2 154 �2. SUMMARY 2.1 Sampling and Analysis The field test activity took place from February 25, 1980 to March 28, 1980. All required tests were completed and all recovered samples were sent to Southwest Research Institute (SRI)'for analysis. MRI had subcontracted this part of their assignment to SRI. A summary of tests conducted including any significant commentary is presented in Table 2-1. A summary of the reduced data on a daily basis as calculated from the field data sheets is presented in Table 2-2. Data listed are corrected to standard conditions, i.e., 20°C and a barometric pressure of 29.92 inches mercury. Sampling and calibration procedures are described in Sections 4, 5 and 6. Hourly data is provided in the appendices. Appendix A contains continuous monitoring data; Appendix B contains field data; and Appendix C contains the solid and liquid sampling schedule. 2.2 Process Data Process data was monitored on an hourly basis. A summary of the averaged daily process data is provided in Table 2-3. The process data was also averaged for the time duration of actual testing performed. This data is presented in Table 2-4. The process data gathered indicated that the operating conditions fluctuated in patterns related to the amount of electricity generation demand placed on the boiler, and on the type of fuel being burned to meet that demandT~ Overall fluctuation consisted of two components. The first component was the Daily variation - the load peaked in the afternoon and fell a minimum before dawn. The second type of variation was caused by sudden operational changes, which was due to reduced power generation for various reasons such as the buying of cheaper power from a private utility, or the reduction in flow of RDF to the boiler. 2-1 155 �TABLE 2-1. DAILY ORGANIC SAMPLING SUMMARY Date Test 1980 No. Sampling locations 3/2 Inlet North Test started at 1120 and ran for 520 minutes. Low volume collected due to high leak rate at end. Volumes corrected for leak rate. If leak occurred over the entire test period then, at worst case, the results are 50% low. Test quality fair. (Port 13 to be dropped due to absence of flow). Inlet South Test started at 1125 and ran for 520 minutes. Low volume collected trying to stay within 12 hour time limit. Test quality good. (Port 1 to be dropped due to absence of flow.) Outlet Ports 2 and 3 Loss of 3 hours start due to freezing of pumps. Stopped test 360 minutes into test due to freezing of impingers. All of Port 3 traversed and only 1/2 of Port 2 - low volume collected but test quality is good due tp the evenness of flow in stack. Outlet - Ports 1 and 4 Started at 1200, ran for 390 minutes - stopped due to freezing of impingers and equipment - low volume due to stoppage - impingers backed up due to freezing of impinging solutions. Resin in Impingers 1 and 2 also due to freezing. Test quality fair. Hi Volume Sampler Test started at 1115 and off 1939. Continuous monitors Started at 1300 hrs and off at 1930 - lost start time due to gas conditioner being frozen. Unable to maintain heat line temperature due to cold weather and moisture condensing in heat line possibly scrubbing hydrocarbons, hydrocarbon results low. Test quality good. Hydrocarbon fair. Inlet North Dropped port 13 from test. Test started at 0925 and ran for 550 minutes. At 250 minutes nozzle was found to be facing in the wrong direction, reversed nozzle direction continued test. Particulate catch and size distribution will be approximately 25% low. No effect on Battelle trap. Switched to smaller diameter nozzle to maintain vsokinetic flow rate. Test quality for participate fair, for gas good. Inlet SOIR.. Test started at 0945 and ran for 550 minutes. Switched to smaller diameter nozzle to maintain isokinetic flow rate. Test quality good. Dropped port 1 from test. 1 Ul I\J 3/3 Test comments Test quality good. �TABLE 2^1. (Continued) Date Test 1980 No. Sampling Locations 3/3 Outlet Ports 2 and 3 Test started at 0945 and ran for 480 minutes. Test quality good. Outlet Ports 1 and 4 Test started at 0945 and ran for 480 minutes. Test quality good. Hi Volume Sampler Started at 1032 ended at 1915. Test quality good. Test comnents Continuous Monitors Started at 0930 ended at 1900. Test quality good except hydroCarbon values being low and hydrocarbon quality fair. Test started at 0905 and ran 417 minutes. At 75 minutes Battelle trap plugged and replaced with new one. At 250 minutes Battelle trap replaced due to leak and points (total of 2) retested. Switched to 10 minutes a point traverse rather than 25 minutes to complete test. All 3 Battelle traps should be composited due to lower volume sampled during 10 minute/ point traverse. Test quality fair - total volume 50% of required. Test started 0900 ran for 550 minutes. Test quality good. Outlet Ports 2 and 3 Ports 1 and 4 Test started 0938 ran for 15 minutes. Cancelled due to snow and icy conditions. No samples retained. Hi Volume Sampler ro i co Inlet North Inlet South 3/4 Started at 0930 ended at 1800. Filter covered with snow. Test quality fair due to snow blanket. \ Continuous Monitors Gas conditioner frozen until 1230. Started at 1230 ended at 1800. Test quality good. Hydrocarbon results fair. 3/5 Inlet North Test started 0900 and ran for 560 minutes. Test quality good. Inlet South Test started at 0900 and ran for 550 minutes. Test quality good. �TABLE 2-1. (Continued) Date Test 1980 No. Sampling Locations 3/5 Outlet - All Points Cancelled per instructions of EPA until 3/13/80. Hi Volume Sampler Test Comments Started at 1025 ended at 1940. Test quality good. Continuous Monitors Started at 0945 ended at 1150 am. Stopped due to freeze up of lines:Test quality good for data collected. Inlet North Test started at 0850 and ran for 770 minutes. At 11 minutes Into test Battelle trap plugged and was replaced. Test restarted from beginning. Test quality good. Inlet South Test started at 0840 and ran for 770 minutes. Test quality good. Hi Volume Sampler 3/6 Test started at 0852 and ended at 2220 Hrs, Test quality good,. Continuous Monitors Only inlet tested due to outlet freeze up. Test started at 1230 and ended 2045. Two hours late start and shut down 2 hours early to overlap sampling time. Test quality good. Hydrocarbons still fair. V3 3/7 Inlet North Test started at 0930 and ran for 770 minutes. Due to increased amount of water collected, impingers needed changing and during changeout resin flowed into first impinger. Trap replaced and test resumed. Test quality good. Inlet South Test started at 0850 and ran for 770 minutes. Test quality good. Hi Volume Sampler Test started at 1038 and ended at 2225. Construction welding going on nearby. Test quality expected to be good. Continuous Monitors Test started at 1315 hrs and shut down at 2100 hours. Overlap of Inlet test. Test quality good. Hydrocarbons fair. �TABLE 2-1. (Continued) Date Test 1980 No. Sampling Locations 3/8 Inlet North Test started at 0855 and ran for 770 minutes. 10 minute power failure no problems caused by this. Test quality good. Inlet South Test started 0840 and ran for 770 minutes. 30 minute power failure on this side - no problems. Probe broken at end of test during removal from port. Approximately 2% of probe catch lost. Test quality good. HI Volume Sampler Test started at 1335 and ended at 2330. Test quality good. Test Comments Continuous Monitors Test started at 1215 and ended 2030 hrs. Data not taken at inlet during 1300 hrs. to 1400 hours due to change out of probe filters. Test quality good. Hydrocarbon data fair. Test started at 0900 and ran for 770 minutes. Point 8D was run for 70 minutes to correct sampling time lost on point 11A not being sampled after nozzle change. Test quality good. Test started at 0830 and ran for 770 minutes. Changed to larger nozzle to maintain 1sok1net1c flow rate. Due to severe leak, that occurred during last portion of test, this test 1s questionable. HI Volume Sampler 8 Inlet North Inlet South 3/9 Test started at 0908 and ended at 2320 hrs. Test quality good. IM cn Test started at 1245 and ended at 2320 hrs. Test quality good. Hydrocarbon data fair. 3/10 Inlet North Test started at 0825 and ran for 140 minutes. Probe found to be broken and test restarted, no samples retained. Restarted at 1155 ran until 1745. Test stopped, with only 1/2 the duct traversed, due to cold, freeze ups and power failures. Resin, cyclone, filter, 1st impinger saved. Test quality fair. Inlet South Test started at 0810 ran for 515 minutes. Power failures and freeze ups happening cancelled test with the North side. No solutions retained from South due to H20z backup Into all impingers - resin, cyclone and filters retained. Test quality fair. �TABLE 2^1, (Continued) Date Test 1980 No. Sampling Locations 3/10 Hi Volume Sampler Test Comments Test started at 1050 and ended at 2235 hrs. Test quality good. Continuous Monitors Test started at 1130 am and ended at 1730 hours. Stopped with inlet. Test quality good. Hydrocarbon fair. Test started at 0825 and ran 770 minutes. Battelle trap replaced at 220 minutes. 2nd Battelle trap resin broke through and was replaced. 3 Battelle traps used. Test quality good. Test started at 0830 and ran for 770 minutes. Filter clogged and replaced. Test quality good. Hi Volume Sampler 10 Inlet North Inlet South 3/11 Test started at 0920 and ended at 2375 hrs. Test quality good. Continuous Monitors Test started at 1200 and ended at 2030 hrs. Test quality good. Hydrocarbon fair. o\ ro o i o> 11 QA Test Test cancelled after 240 minutes - a leak was found at one of the probe tips-unable to repair and no sample had been drawn through the train. Hi Volume Sampler 3/12 Test started at 0955 stopped at 1955. Test quality good. Continuous Monitors Test started at 0830 stopped at 1430 hrs. Test quality good. Hydrocarbon fair. 3/13 12 Inlet North Test started at 0915 and ran for 770 minutes. Power failures occurredno effect on test. Filter changed due to clogging. Test quality good. Inlet South Test started at 0835 and ran for 770 minutes. Power failure occurred no effect on test. Test quality good. Outlet Ports 2 & 3 Test started at 1210 and ran for 560 minutes. Lost startup due to freezing of equipment and traps - thawing took 1-2 hours. Test quality good. �TABLE 2-1. (Continued) Date Test 1980 No. Sampling Locations 3/13 Outlet Ports 1 & 4 Test started at 1125 and ran for 296 minutes. Stopped due to continual freezing of train components. One port completely traversed. Only 16 minutes of the second. Test quality - fair to poor. H1 Volume Sampler Test started at 0950 and ended 0130. Test quality good. 12 Test Comments Continuous Monitors Test started at 1145 and ended at 1845 hours. Test quality good. Hydrocarbons fair. 3/14 13 Inlet North Test started 0845 and ran for 770 minutes. Filter clogged and was replaced. Test quality good. Inlet South Test started at 0840 and ran for 770 minutes. Test quality good. Outlet Ports 2 & 3 Test started at 0945 and ran for 560 minutes. Test quality good. Outlet Ports 1 & 4 Test started at 1010 and ran for 560 minutes. Probe broken during port change - replaced and test continued. Test quality good. Hi Volume Sampler Test started at 0905 and ended at 2355 hrs. Test quality good. Continuous Monitors Test started at 0900 and ended at 2045 hrs. No data from 1330 to 1515 hrs due to feeeze up. Test quality good. Hydrocarbon fair. 3/15 14 Inlet-North Test started at 0909 and ran for 770 minutes. Test quality good. Inlet South Test started at 0905 and ran for 770 minutes. Test quality good. Outlet Ports 2 & 3 Test started at 0958 and ran for 560 minutes. Test quality good. Outlet Ports 1 & 4 Test started at 1025 and ran for 560 minutes. Test quality good. HI Volume Sampler Test started at 0850 and ended at 2341 hrs. Test quality good. Continuous Monitors Test started at 0845 and ended at 2000 hrs. Test quality good. Hydrocarbon data fair. �TABLE 2-1. (Continued) Date Test 1980 No. Sampling Locations 3/17 Inlet North Test started at 0849 and ran for 770 minutes. Test quality good. Inlet South Test started at 0900 and ran for 770 minutes. Test quality good. Outlet Ports 2 & 3 Test started at 1000 and ran for 560 minutes. Test quality good. Outlet Ports 1 & 4 Test started at 1010 and ran for 560 minutes. Test quality good. HI Volume Sampler Test started at 0926 and ended at 0020 hrs. Test quality good. 15 Test Comments Continuous Monitors Test started at 1030 and ended 2015 hrs. Test quality good. Hydrocarbon data fair. Test started at 0900 and ran for 770 minutes. Test quality good. Test started at 0930 and ran for 560 minutes. Test quality good. Outlet Ports 1 & 4 Test started at 0940 and ran for 560 minutes. Probe broke during port change - switched to 5 ft glass probe to traverse first 6 points of second part. After 10 ft probe of ports 2 and 3 had been recovered and cleaned, it was sent to the stack to finish remaining 2 points of ports 1 and 4. Test quality good. HI Volume Sampler ro oo Test started at 0939 and ran for 770 minutes. Test quality good. Outlet Ports 2 & 3 16 Inlet North Inlet South 3/18 Test started at 1033 and ended 0200 hours. Test quality good. Continuous Monitors Test started at 0845 and ended at 1945 hrs. Test quality good. Hydrocarbon data fair. 3/19 17 Inlet North Test started at 0859 and ran for 770 minutes. Test quality good. Inlet South Test started at 0843 and ran for 770 minutes. Test quality good. Outlet Ports 2 & 3 Test started at 0945 and ran for 560 minutes. Test quality good. �TABLE 2-1. Date Test 1980 No. Sampling Locations 3/19 Outlet Ports 1 & 4 17 H1 Volume Sampler (Continued) Test Conments Test started at 0940 and ran for 560 minutes. Test started with 5 foot probe until new 10 ft arrived. Finished Test with 10 ft probe. Test quality good. Test started at 1006 and ended at 0120 hrs. Test quality good. Continuous Monitors Test started at 0845 and ended at 1915. Test quality good. Hydrocarbon data fair. Test started at 0905 and ran for 770 minutes. Filter clogged and was replaced. Test quality good. Test started at 0914 and ran for 770 minutes. At 1850 hrs. Battelle trap froze and was thawed with warm water. Leak developed in Teflon heat line • retarded leak rate with Teflon tape but leak was still 0.11 cfm. At 2250 Battelle trap froze up and was replaced. It was later found that the filter had separated from the housing and participate had gotten down to the Battelle first. Both filter and trap were replaced and points were retraversed. Test quality good.to fair. Outlet Ports 2 & 3 Test started at 1000 and ran for 560 minutes. Test quality good. Outlet Ports 1 & 4 Test started at 0930 and ran for 560 minutes. Test quality good. HI Volume Sampler 18 Inlet-North Inlet South 3/20 Test started at 1117 and ended at 0540 hrs. Test quality good. ro i <o Continuous Monitors Test started at 1130 and ended at 2030 hrs. Test quality good. Hydrocarbon data fair. 3/22 19 Inlet North Test started at 0947 and ran for 770 minutes. Test quality is good. Inlet South Test started at 1001 and ran for 770 minutes. replaced. Test quality is good. Outlet Ports 2 & 3 Test started at 1000 and ran for 560 minutes. Test quality is good. Filter clogged and was �TABLE 2-1. Date Test 1980 No. (Continued) Test Comments Sampling Locations 19 Outlet Ports 1 & 4 Test started at 1030 and ran for 560 minutes. Test quality is good. Hi Volume Sampler 3/22 Test started at 1422 and ended at 0415 hrs. Test quality is good. Continuous Monitors Test started at 1145 and ended 2115 hrs. CO drift problems. CO taken off line until 1445 hrs. Test quality good. Hydrocarbon data fair. Test started at 0927 and ran for 990 minutes, lower plant out put. Increased time due to Test started at 0935 and ran for 990 minutes lower plant output. Test quality good. Increased time due to Outlet Ports 2 & 3 Test started at 1005 and ran for 640 minutes, Increased time due to lower plant output. Test quality good. Outlet Ports 1 & 4 Test started at 1027 and ran for 640 minutes. Increased time due to lower plant output. Impinger 3 backed up into impinger 2 - not saved. Test quality good. Hi Volume Sampler Test started at 1034 and ended at 0350. Test quality good. Continuous Monitor 20 Inlet North Inlet South 3/23 Test started at 1100 and ended at 0800 hrs. Electronic source balancing problem on CO analyzer. Analyzer (CO) taken off line. No outlet data gas conditioner not in cycle mode. Test quality good for inlet, hydrocarbon data fair. . _. Blank Blank test started at 1200 and ran for 60 minutes at temperature. quality good. Outlet Test started at 1110 and ran for 192 minutes. Test quality good. Hi Volume Sampler Off line Continuous Monitors Test started at 1030 and ended at 1530 hrs. Outlet only for inorganic sampling. No CO on line. Test quality good hydrocarbon data fair. ro 3/24 21 - QA Test to outlet stream. Test quality good. Test �TABLE 2-1. (Continued) Date Test 1980 No. Sampling Locations 3/25 Inlet North and South - QA Test Test started. No solids or liquids taken for QA. QA test only. Test scrubbed, no samples saved because nozzle was in wrong direction and test would not be duplicate. Outlet Ports 1,2, 3 and 4 Test started at 1120 and ran for 192 minutes. Test quality good. 22 Test Comments Continuous Monitors Test started at 1115 and ended at 2106 hrs. Test quality good. Hydrocarbon data fair. Hi Volume Sampler 3/26 23 Test started at 1030 and ended at 2320 hrs. Filter covered with coal dust. Test quality fair. Inlet North QA test started at 1510 and ran for 770 minutes. Test quality good. Inlet South QA test started at 1515 and ran for 770 minutes. Test quality good. Outlet Ports 1,2, 3 and 4 Test started at 0922 and ran for 192 minutes. Test quality good. Continuous Monitors Test started at 1100 and ended at 0830 hrs. No outlet data due to failure of gas conditioner to switch to outlet stream. Test quality good. Hydrocarbon data fair. �TABLE 2-2. DAILY DATA SUMMARIES Gas Composition Sample Volume Data (1930) 3-2 Test No. 1 Sampling Location ""« ES ouu. £ 3-3 2 North* ""«' Out,e, 3-4 3 £$ SouthD «g '- ££ Ou,.e, 3-6 4 5 Inlet North South 0,,,,e, CT> ro i ro 3-7 6 Ou,,e, 3-8 7 s^ln Oullet 3-9 ">"« South' £$ feu.. 3-10 9 10 11 9.95 7.15 6.32 624 29.01 2935 29.30 29.31 33.55 28.09 2? 59 2479 132673.22 116016.35 141428.G2 154523.14 7654988 70423.17 86285.62 95704.38 334.31 311.78 320.93 30992 4.4S 4.48 6.34 6.34 12.79 12.79 11.31 11.31 1800 13.00 1500 1500 -^2 <2 <2 <2 6383 8901 8620 9399 173.544 126.934 212.049 101.519 324.358 307.313 4.92 3.60 6.01 288 9.19 870 839 8.59 781 7.97 7.45 7.48 29.34 29.32 2941 29.39 2931 29.31 37.78 4?.94 46.61 37.16 26.00 26.10 149381.62 169792.93 184280.23 146887.30 162012.17 162637.08 85761.77 95782.34 108410.17 86004.68 94569.98 90037.93 351.55 37336 234.83 369.90 3-12.38 33694 4.38 4.33 4.33 433 5.87 5.87 13.80 13.80 1380 13.80 12.44 12.44 12.00 12.00 11.00 11.00 11.00 <2 <2 <2 <2 <2 <2 9573 6098 107 14 9633 9033 184.208 252.780 5.22 7.16 7.43 9.48 2956 29.30 4S.10 43.72 173312.05 9C6B4.71 172866.82 96380.09 Test Scru 3bod Test Scrut>bed 370.46 352.55 4.43 4.43 14.41 14.41 17.00 17.00 <2 <2 95.59 92.25 256.375 246.727 7.28 6.99 8.14 9.03 29.49 29.38 43.20 41.09 97049.64 17080285 162455.25 92751.96 Test Scrul )bed Test Scrutibed 361.09 349.23 4.41 441 14.56 14.5G 18.00 18.00 <2 <? 9143 104.10 367.648 323.174 10.41 9.15 893 9.72 29.28 29.18 42.92 43.48 169692 43 102970.06 9729597 171937.31 Mot Test cd Not Test ed 363.83 347.46 4.35 4.35 13.79 13.79 1800 1800 <2 <2 9728 90.54 363.684 365.424 1044 10.35 18.32 9.18 28.14 29.27 43.61 44.01 17242559 8743205 173994.36 99965.91 Not Tesi ed Not lest >xl 351.00 335.86 4.59 4.59 13.92 13.92 16.00 16.00 <2 <2 10593 99.65 351.419 333.613 995 9.45 956 9.75 29.19 29.16 3962 3928 85266.27 156073.06 155327.60 86179.64 Not Tested Not Test cd 377.55 359.83 4.79 4.79 1360 1360 2800 28.00 <2 <2 1C3M 105.53 74.033 234.807 121.924 140223 2.10 8.35 3.45 397 7.79 8.05 778 8.02 29.19 29.16 29.20 2917 3027 30.38 36.43 27.38 119C9800 7132576 120108.29 67223.13 144173.75 82977.48 108274.04 64436.72 Not Tcsi od Not Tested 31683 364.73 344.23 315.88 7.1 7.1 7.1 7.1 11.6 11.6 11.6 11.6 2500 25.00 25.00 25.00 <2 <2 <2 <2 95.60 9851 106.23 B0.56J 130811 193613 3.70 548 859 17.13 2931 28.25 45.23 43.77 17885320 103205.95 17304512 92980.29 Not Tcsi ed Not Test ed 352.C9 33065 3.7 3.7 139 13.9 25.00 2500 <2 <2 8884 £958 39-5091 3fa300C 11.16 1085 6.98 8.40 29.49 29.iO 45.63 44.20 18061964 01867.66 174783.47 99143.40 No! Tesi i:d Not Test ed 37475 356.59 4.7 47 13.5 13.5 22.00 22.00 <2 <2 97 17 10529 •*• 361.78 340.61 339.44 315.08 3.34 3.34 5.17 5.17 1556 15.56 13.97 13.&7 21 00 21.00 1800 1800 <2 <2 <2 <2 102 3S 10?.23 7? 72 91.73 «J N s :;f Out* 3-13 5.80 7.43 606 688 £« '-• ££ Out,e, 3 12 204.617 262.517 214098 243024 «*« """ ££ Ou,,et 3-11 Velocity «ps 2l3 NorthF 8 """ Ouu, S i £«" Gas Flow dscfm Isokinelics X Test Scrubbed Test Scrubbed Not Tested Not 1 esled JM 12 THC ppm Molecular Weight £\ """ CO ppm Moisture % £« ""« s^ii; CO? X M3 >2< ""*< £S $ SCF »3! Outlet 35 Stack Temp °F Ga« Flow acfm 350.455 369 B24 158.9M 3.~,5 290 9.92 10.47 4.50 10.35 8.63 8.54 7.10 937 2953 2954 29.56 29.28 42.45 41.41 2585 2658 163079.96 164036 17 161102.3'J 165622.22 93473.48 93628.05 9514681 98426.04 �TABLE 2-2. (Continued) Gat Composition Sample Volume Dale (19801 Tetl No. 3-14 Sampling Location 13 SCF M3 374.335 352.110 367.772 351.364 10.60 ""« i% ou,,., ST.!: 276.767 268.37 31913 307.00 — 555 ou,,., s^ """ £2 <*«•• 2*3 3-15 3-17 3-18 14 15 16 — ££ o- ffi 3-19 17 Inlet nlet Outlet 3 20 18 3-22 19 to North Eoulh «»» — ££ *- % «- £* OutM 3-23 20 JM ,„, , '"'" North Scum out* £« 3-24 21 Outlal 3-25 22 Intel ""* South 1.2.38.4 — ££i Outlet 3-26 23 ">"• ££ Oiillrl A 8 C 0 E F G H 1 J K L 1.2.3&4 1.2.3&4 Moisture % Molecular Weight Gn Velocity Ipt Gai Flow acini Flow dscfm " 43.48 41.49 24.34 24.84 171904.76 164048.73 151720.16 154819.20 94404.58 91011.47 83869.92 86429.91 Stack Temp 02 « CO? % CO ppm THC ppm Isokineties \ 38468 375.70 365.94 358.75 3.70 14.81 14.81 13.18 13.18 2800 28.00 30.00 30.00 <2 <2 <2 <2 101.27 10720 9980 96.74 68088.12 67307.85 75394.82 76705.48 368.23 357.65 319.42 356.65 6.31 6.31 12.59 12.59 10.G7 10.67 2200 22.00 19.00 19.00 <2 <2 <2 <2 102.11 10867 10405 9683 14.40 14.40 2200 2200 22.00 2200 <2 <2 <2 <2 10685 9909 107.18 95.48 23.00 2300 2400 24.00 <2 <2 <2 <2 10017 10807 9982 93.81 <2 <2 <2 <2 10721 97.16 10103 9262 OF 9.67 9.70 9.60 9.50 2931 7.83 7.60 9.04 8.69 814 7.68 7.88 7.83 29.27 2832 2909 29.10 30.85 2996 20.00 2131 121975.44 118444.95 12466269 132801.77 359800 390.474 406855 391.B36 10.19 11.06 11.52 11.10 8.83 8.17 8.71 8.43 29.35 2944 29.21 29.25 41.89 42.84 26.01 2727 1G'j622.66 169381.86 162117.20 169966.05 91774.43 9721069 93334.49 98183.52 371.23 348.41 354.56 34531 3.73 373 543 543 1200 309.159 3/1 .197 392.686 353.252 10.45 9.36 8.73 8.62 9.09 29.29 29.37 29.24 29.18 ! 43.06 41.89 27.12 2560 170259.70 165639.94 169022.81 159531.72 92573.11 93691.77 96719.62 91103.75 381.96 35496 360.06 357.50 3.82 14.39 382 1439 5.42 5.42 1300 41.87 4342 26.75 26.92 165560.57 171695.37 166699.92 167752.85 88914.41 95341.29 9108057 94194.67 36028 361.53 373.12 365.94 9.97 10.42 9.95 1052 11.12 1000 29.30 29.14 29. IS 12.90 13.00 14.40 1440 530 5.30 13.00 13.00 24.00 7400 26.00 2600 350.96 342.65 338.12 312.81 3.80 3.80 6.00 6.00 13.80 13.80 12.50 12.50 22.00 22.00 17.00 17.00 <2 <2 <2 <2 92.21 10431 9509 97.71 94207.94 90821.39 95997 17 9954908 348.64 34209 340.00 33060 360 300 14.70 14.20 12.70 12.70 38.00 38.00 3800 38.00 <2 <2 <2 <2 105.17 85.42 104 10 9903 C3470.17 58005.38 58763 10 74046.56 364.41 355.41 354.13 338.13 6.00 6.00 9.70 9.70 1260 L 12.60 10.00 10.00 <2 <2 <2 <2 10354 11599 11045 10266 365.47 5.4 132 <2 10372 13.2 <2 101.06 <2 <2 <2 10524 11843 106.64 968 10.60 10.21 10.28 8.59 29.29 29.37 29.03 29.24 347.892 368079 356.204 388.522 985 10.42 10.09 11.00 8.31 7.86 7.79 8.44 29.33 2939 29.29 29.21 42.13 42.11 74.63 2G.91 1665/0.31 166487.56 153481.74 18772585 94786.10 96189.05 90622.79 97760.61 363.462 348597 402.144 401.160 10.29 29.36 4165 2941 11.39 11.36 B.54 8.07 8.61 8.23 29.19 29.24 33.63 26.26 26.81 164688.40 156677.09 163656.04 167077.26 33G.525 330.733 301.612 368.976 9.53 9.37 8.54 12.74 973 10.17 5.87 2926 28.69 28.82 2928 28.65 27.28 16.63 19.70 113282.76 107773.49 103679 07 122765.69 8.16 837 837 360 9.90 1044 9.B7 5.31 5.31 3.60 349.709 368.751 374.299 360578 8.68 370 5.30 5.30 130.420 3.69 9.53 29.15 25.76 Blank H un Blank R llll 160547.70 90172.96 122.788 3.48 9.92 2910 24.58 153166.31 8/02b.45 356.40 5.4 326 820 344.976 138673 926 977 9.17 9.09 37.23 37.40 ?6.42 1472C0.78 147872.05 16467985 81800.81 8073346 93244.39 380.80 382.45 364.38 6.00 1260 926 29.13 29.14 20,24 600 3.03 12.60 13.70 Test Scru •bed With.312no»le With .250 nozzle changed to maintain flow With.312nozzle With .237 nozzle changed In maintain (low No sampl3 ietaim.il XViih .no nozzle Wuh .310 nozzle changed 10 maintain How With .240 nozzle With .309 nozzle changed to maintain flow Hesulls questionable dlM> lo l"dteak'ate Teu. .miti'ied due to cold weather. Sample laved Monitor not woiking 4.80 �TABLE 2-3. 24 HOUR PROCESS DATA FOR THE AMES MUNICIPAL POWER PLANT, UNIT NO. 7 3-2-80 Date Mean 3-3-80 Mean a Mean a Mean o Mean o Mean 5.19 4.93 31.9 29.72 4.76 4.44 31.7 28.88 5.55 5.30 30.5 28.24 7.51 7.21 27.85 25.66 6.01 5.79 252.2 36.49 268.8 284.87 56.59 289.58 48.47 279.79 56.73 274.8 74.9 Steam pressure (psig) 857.7 4.16 852.71 4.66 850.63 5.95 848.54 5.61 847.33 7.22 Steam temperature (°F) 899.63 8.53 890.1 891.46 14.63 895.6 10.97 895.33 9.89 Feedwater flow rate (1000's Ibs/hr) 261.17 37.94 278.38 71.65 290.79 52.98 300.42 46.6 291.7 54.23 Feedwater temperature (OF) 366* 7.38* 380.81 2.14 389.7 7.63 382.8 17.36 377.5 Fuel feed rate 1 (1000's Ibs/hr) 2 31.7 32.2 7.07 31.93 31.69 31.03 31.81 5.37 32.45 33.53 6.09 35.38 32.15 Fuel oil (gallons/hr) 4.6 OO Excess air X 22 3-9-80 o 31.58 29.25 Steam flow rate (1000's Ibs/hr) ro a 3-8-80 30.1 7.31 32.04* 0.98* Gross Met Mean 3-7-80 3-6-60 30.19* 2.8* 26.25* 1.51* MU o 3-5-80 3-4-80 71.48 24.01 7.32 2.1 22.08 8.28 20.33 2.35 20.17 3.92 22.21 o5.31 5.12 239.33 61.67 178 46.7 850.21 5.21 851.04 6.08 854 12.3 891.8 893 12.93 888 15.5 286.33 76.82 251.4 62.96 181 59.3 21.03 378.75 26.6 360.2 25.81 338 24.0 1.53 31.65 33.6 32.03* 28.17 1.17* 24.8 23.7 5.75 3.75 2.5 2.9 4.6 Mean 20.9 18.9 15.19 8.23 6.3 25.25 6.25 5.4 4.2 11.2 25.48 10.9 34 12.6 44 1.6 ID fans amps 46.42 1.1 45.75 2.15 46.04 1.76 46.75 1.11 46.2 1.6 46.46 2.41 45 1.72 ID fans pressure (psig) 5.15 O.B9 5.67 1.40 6.17 1.14 6.09 1.04 6.08 0.89 6.06 1.4 5.21 1.07 4.2 0.76 FD fans amps 30.29 1.12 29.91 1.79 29.54 1.41 30.46 1.35 30.3 1.5 30.67 1.79 29.44 0.97 28 1.5 FO fans pressure (psig) 4.26 0.77 3.94 1.13 4.32 0.78 4.32 1.06 4.5 1.3 4.54 1.41 3.54 1.03 3.1 1.05 Furnace draft (psig) 0.60 0.20 0.59 0.18 0.59 0.15 0.62 0.15 0.6 0.13 0.63 0.12 0.53 0.10 0.59 0.092 Flue gas temp (°F) Boiler exit ESP inlet 9.78* 647* 318.5* 6.69* 688* 17.51* 687* 341* 9.19* 3.16* 695* 6.67* 345.5* 1.58* 688* 340* 6.3* 0* 699* 342* 3.94* 4.22* 662* 327* 10.33* 8.23* 629* 305* 20.2* 21.2* Ambient temperature (OF) 16.06 7.58 27.39* 10.39* 24.08 6.81 7.63 5.22 19.79 9.19 24.58 4.29 28.17 4.99 37 7.5 Ambient pressure Inches Hg 29.34 0.18 28.89* 0.11* 28.88* 0.06* Z9.17 0.08 29.04 0.1 28.97 0.048 29.01 0.06 * Hot basted on 24 hour readings 1 2 Based on tachometer type gauge Based on weight type gauge 28.89 0.097 (Continued) �TABLE 2-3. 3-10-80 Date Mean o 3-11-80 Hean . o (Continued) 3-13-BO 3-12-80 Hean o Hean o 3-14-60 Mean a 3-15-80 Mean o 3-18-80 3-17-80 Mean o Mean o 29.1 26.7 8.77 S.43 30.8 28.0 6.10 6.20 31.2 27.1 6.26 7.99 31.2 28.3 6.11 6.16 30.5 28.0 6.25 6.01 21.7 19.6 5.95 5.68 29.5 27.2 7.74 7.58 31.8 29.3 3.84 3. 65 Steaa flow rate (1000's Ibs/hr) 254 80.2 277 62.8 255 94.0 268 82.2 270 62.8 186 55.06 259 76.1 283 40.0 Stead pressure (pslg) 853 9.1 ass 6.24 855 5.8 853 8.6 852 7.0 850 8.6 850 5.3 850 6.3 . Stea« temperature (°f ) 892 11.5 894 11.2 893 11.0 893 12.2 894 12.5 888 11.1 892 9.4 890 16.2 Feedwater flow rate (1000's Ibs/hr) 266 83.1 277 78.5 279 80.2 286 71.0 281 61.3 194 54.0 268 74.5 295 38.1 Feedwater temperature (OF) 362 34.9 372 23.6 370 25.2 371 23.4 371 21.8 330 69.4 367 26.3 375 11.7 Fuel feed rate 1 (1000's Ibs/hr) 2 28.8 31.2 9.03 29.1 30.3 7.08 30.5 31.0 7.13 31.9 33.4 9.81 30.4 30.7 6.64 24.2 24.0 6.6 30.9 31.2 7.23 32.0 31.6 3.84 Fuel oil (gallons/hr) 4.17 Excess air I 24 12.9 20 5.1 20 5.9 23 9.8 24 11.3 39 12.5 26 13.3 21 3.6 ID fans i«ps 45 2.5 46 3.1 46 1.8 46 1.5 45 1.5 42 4.0 46 1.6 46 0.98 5.8 0.77 MU Gross Net 11.25 2.08 12.08 37.9 3.75 2.92 2.50 ID fans pressure (pslg) 5.4 1.32 6.0 1.18 6.2 1.20 6.0 0.91 5.9 1.01 4.3 0.81 5.0 1.00 FD fans amps 30 1.3 30 1.1 28 6.2 30 1.5 29 1.5 28 1.4 30 1.6 30 1.0 FD fans pressure 4.0 1.18 4.6 1.12 4.4 1.46 4.2 1.20 3.7 1.12 3.0 1.00 4.1 1.09 4.1 0.97 Furnace drift (pslg) 0.60 0.036 0.58 0.024 0.61 0.042 0.63 0.024 0?62 0.044 0.74 0.092 0.59 0.074 0.59 0.1 Flue gas te»p (°F) Boiler exit ESP Inlet 685* 340* 5.3* 0* 664* 323* 37.3* 27.1* 675* 327* 31.1* 14.6* 686* 324* 37.5* 20.1* 669* 326* 30.2* 16.0* 625* 295* 27.3* 20.2* 669* 319* 48.9* 21.3* 676* 326* 24.0* 9.5* Ambient temperature 27 7.5 25 7.9 30 1.6 28 2.6 37 12.6 51 11.2 34 4.9 49 12.8 Ambient pressure inches Hg 28.91 0.195 29.14 0.061 28.88 0.08 28.89 0.13 29.11 0.02 28.98 0.10 29.09 0.04 29.06 (Continued) (psig) 0.07 �TABLE 2-3. Date 3-19-80 Mean a 3-20-80 Mean o (Continued) 3-22-80 Mean a 3-23-80 Mean o 3-25-BO 3-24.80 Mean o Mean o 3-26-80 Mean a 31.0 27.2 5.01 6.96 30.6 26.8 5.88 7.68 29.4 27.1 5.16 4.95 18.1 16.2 1.98 1.80 29.7 27.4 7.77 7.55 29.5 27.2 7.54 7.21 30.5* 27.7* 6.17* 6.29* Steam flow rate (1000's Ibs/hr) 277 52.1 273 59.8 260 51.3 153 16.2 264 73.5 262 71.9 258 79.1 Steam pressure (psig) 853 7.0 851 5.0 853 7.4 852 5.7 858 4.9 852 4.8 854 4.4 Steam temperature (°F) 888 12.1 891 12.3 891 11.8 884 10.0 891 11.2 892 10.7 890 16.6 Feed water flow rate (1000's Ibs/hr) 287 50.6 222 US. 4 270 50.5 162 17.8 273 72.5 272 71.4 283 61.6 Feedwater temperature 375 16.5 372 16.8 365 18.9 325 7.1 367 25.4 364 27.6 369 20.9 Fuel feed rate 1 (1000's Ibs/hr) 2 31.1 31.4 5.74 33.6 34.4 7.06 31.3 31.1 8.32 20.8 20.4 1.71 32.3 32.8 8.26 31.8 31.8 7.66 29.6 31.9 7.16 Fuel oil (gallons/hr) 4.17 Excess air t 20 5.9 27 7.7 22 3.8 42 11.0 25 10.8 27 14.3 22 4.8 10 fans amps 45 1.3 46 1.8 45 1.7 42 0.7 46 2.2 46 1.6 45 1.3 ID fans pressure (psig) 5.7 0.85 5.9 0.9 5.3 0.9 3.8 0.22 6.1* 0.27* 5.7 1.14 5.6 1.24 FO fans amps 29 1.5 29 6.4 29 1.5 27 0.6 29 1.7 30 1.3 29 1.5 3.9 1.37 HU Gross Net 33.33 26.67 20.4 1.67 28.33 20.4 FD fans pressure (psig) 3.9 1.18 4.8 1.32 4.1 0.99 2.3 0.3 4.1 0.92 4.2 0.84 Furnace draft (psig) 0.6 0.10 0.6 0.09 0.59 0.1 0.59 0.057 0.53 0.07 0.57* 0.11* 0.53 0.09 Flue gas tenp (°F) Boiler exit ESP inlet 666* 328* 30.2* 15.9* 681* 324* 32.8* 12.7* 659* 320* 30.4* 12.2* 599* 280* 3.9* 0* 660* 322* 36.1* 23.1* 670* 323* 31.6* 2.03* 664 315 37.1 16.6 Anblent temperature (OF) 56 9.3 44 9.2 04 5.9 37 1.6 36 1.0 38 6.3 40 4.1 Ambient pressure inches Hg 28.81 0.09 28.92 0.085 29.04 0.134 28.97 0.04 29.04 0.08 29.17 0.024 29.17 0.05 �TABLE 2-4. TEST DURATION PROCESS DATA FOR THE AMES MUNICPAL POWER PLANT, UNIT NO. 7 Date 3-2-60 Hean 3-3-80 a Hean 3-4-80 a 3-5-80 a Mean 3-6-80 o 3-8-80 3-7-80 o 0800 to 2300 Hean o 0800 to 2300 Hean o 0800 to 2300 1100 MM 31 NS 2.31 34.8 32.3 0.3 0.3 35.2 32.7 0.3 0.2 35.0 32.6 0.2 0.2 34.6 32.2 0.8 0.8 35.3 32.8 1.0 1.0 31.3 NS 29 2.2 2.1 Steam flow rate 1000' s Ibs/hr 278.2 21.5 315.9 5.2 324 3.0 319.1 3.8 315.4 10.3 322.8 11.9 275.6 23.7 Steam pressure psig 859.5 3.5 852.1 4.0 850.5 3.5 850.5 3.5 848.8 6.2 852.2 4.5 851.9 7.3 Steam temperature F 903.6 6.4 902.5 6.2 900.5 3.5 902.3 6.8 897.8 10.2 895.1 12.1 895.3 12.2 288.5 24.1 Gross Net 0900 to 1900 0900 to 1900 Hean Duration of Test to 2100 0900 to 2000 Hean Feedwater flow rate 1000's Ibs/hr 24.6 321.8 5.8 325.5 9.1 328.1 6.0 325.4 11.7 336.5 Feeduater temperature °F j__ 287.5 13.6 NS NS 381.3 2.3 390.5 6.1 394.1 3.0 388.8 3.4 390.1 6.9 375 7.3 Fuel feed rate (coal) 34.9 2.6 36.2 2.1 34.3 0.8 35.5 3.0 35.4 1.5 35.7 5.5 32.1 1.1 Excess air X 22.1 1.6 18.3 4.7 20.1 1.8 18.7 1.3 18.9 1.4 19.3 1.1 19.5 1.0 ID fans amps 47.3 0.5 46.9 0.8 47.2 0.4 47.2 0.4 47.1 0.6 47.9 0.9 46 0.8 ID fans pressure psig 5.6 0.8 6.6 0.4 7.0 0.2 6.7 0.2 6.5 0.6 6.9 0.3 5.84 0.5 0.6 30.0 0.3 Fuel oil gallons/hr FD fans »nps 30.8 1.2 30.8 0.8 30.4 0.5 30.9 0.7 31.2 0.8 31.8 FD fans pressure psig 4.6 0.8 4.5 0.7 4.7 0.3 4.4 0.6 5.2 0.8 5.3 0.7 4.1 0.7 Furnace draft psig 0.7 0.1 0.6 0.1 0.6 0.07 0.62 0.11 0.57 0.1 0.65 0.07 0.5 0.07 Flue gas temp (°F) Boiler exit ESP inlet NS NS HS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS NS Ambient temperature °F 23 3.1 NS NS 24.2 3.6 10.9 4.1 25.3 5.4 26.9 3.2 30.1 4.9 0.04 29.05 0.02 Ambient pressure Inches Hg NS - Not Sufficient Data 29.22 0.09 NS NS 28.85 0.03 29.23 0.01 28.98 0.05 28.94 (Continued) �TABLE 2-4. (Continued) Sampling Day 3-10-80 3.9.80 Hean o Hean a 3-11-80 Hean o 3.12-80 Hean o 3.13.80 Hean a 3.14.80 Hean a 3.15.80 Hean o 3-17-80 Hean o 21.0 19.1 5.14 4.94 35.0 32.3 0 0.04 35.0 32.4 0 0.09 35.5 32.8 0.58 0.61 35.0 32.4 0 0.10 34.4 31.8 1.12 1.11 19.6 18.2 6.59 6.56 34.8 32.4 0.24 0.62 Steam flow rate 177 46.6 310 5.0 320 5.5 325 0 320 0 309 14.5 182 66.8 312 3.8 Steam pressure 849 2.3 858 5.6 857 4.7 855 0 855 3.2 855 5.7 851 3.7 853 3.8 Steam temperature 892 12.2 896 11.9 898 8.6 905 5.8 899 5.1 896 12.3 889 12.5 895 8.4 13.8 184 64.2 321 4.8 HH Gross Net Feedwater flow 47.8 323 3.5 330 3.2 332 5.0 330 0 Feedwater temperature 340 21.9 390 0 388 2.6 390 0 385 1.4 384 3.1 336 24.9 383 2.5 Fuel feed rate (coal) 1000' s Ibs/hr 25.2 6.04 36.3 2.27 33.8 1.18 35.1 0.25 38.6 2.82 34.4 2.03 23.0 7.34 35.1 1.71 Fuel oil gallons/hr CD 188 319 6.25f NA 4.17f NA 11.25t NA 12.08t NA 2.08t NA 3.75t NA 37.92f HA 2.92f HA Excess air 34 12.1 16 0.8 18 18 18 1.1 17 1.5 41 14.1 18 1.6 41 4.8 46 0.6 ID fans amps 44 1.9 47 0.9 47 1.0 0.7 48 2.9 0.6 47 0.5 46 0.8 0.30 6.4 0.50 4.0 0.80 S.S 0.82 ID fans pressure 4.2 O.B1 6.2 0.25 6.8 0.29 7.4 0.48 6.4 FD fan amps 28 1.8 30 0 30 0.5 30 0 31 0.51 30 0.7 28 1.5 30 0.51 FD fan pressure 2.9 1.01 4.8 0.36 5.3 0.45 6.0 0.71 4.9 0.71 4.2 0.86 2.7 1.00 4.7 0.60 Furnace draft 0.59 0.078 0.61 0.033 0.58 0.024 0.60 0.071 0.63 0.015 0.62 0.047 0.70 0.035 0.58 0.071 Boiler flue gas temp 632* 18.6* 686 5.3 688* 13.7* 690 11.6 709 11.1 685 15.0 618 30.4 695* 35.6* ESP Inlet temperature 309* 16.9* 340 0 340* 0* 335 0 335 1.4 334 1.8 289 21.3 331* 2.2* 4.2 37 4.7 0.048 29.12 0.030 Ambient temperature 42 4.4 22 1.6 31 4.0 30 0.5 30 1.5 46 5.8 10 •Ambient pressure 28.82 0.023 28.96 0.091 29.11 0.053 28.85 0.022 28.92 0.123 29.11 0.018 28.92 Sampling duration 8:30A-10:11P 8:10A-5 :33P 8:25A-10:35P 9:10A-1 :15P 8:35A-9 :47P 8:40A-10:55P B:49A- 10:25P 9:05A- 10:06P (rontlnued) . �TABLE 2-4. Sampling Day 3-18-80 Mean HU Gross Net Steam flow rate a 3-19-80 Mean 0 (Continued) 3-20-flO Mean 3-22-80 a Hean 0 3-23-80 Hean 34.0 31.4 1.90 1.91 33.0 30.4 4.30 4.15 31.8 28.8 5.45 5.42 29.4 26.9 6.93 6.66 18.5 16.6 307 19.5 297 44.1 281 57.6 260 66.3 155 o 1.51 1.36 3-24-80 Hean 3-26-80 3-25-80 0 o Hean 34.6 32.2 0.48 0.57 2.5 311 5.8 851 34.8 32.7 0.29 0.76 11.9 311 855 Hean o 35.0 32.5 0.6 0.6 3.0 310 0.9 4.8 852 2.7 Steam pressure 6.8 853 3.8 851 7.5 856 894 11.1 888 13.9 892 12.5 889 13.6 886 7.7 899 11.8 892 9.6 902 14. B 318 20.5 307 44.1 292 55.8 270 66.2 156 38.2 321 4.8 324 2.4 327 3.9 Feedwater temperature 383 4.2 382 12.7 372 19.8 365 25.7 328 7.9 384 2.5 384 2.5 380 0 Fuel feed rate Coal (1000's Ibs/hr) 113 852 Feeduater flow W 6.0 Steam temperature to 851 4.8 33.3 33.2 7.92 21.4 1.28 33.1 1.03 33.8 0.50 35.1 2.84 2.26 32.6 6.16 8.20 33.5 Excess air 20 1.8 19 6.0 24 3.4 26 13.0 38 10.6 16 1.7 18 1.0 18 0.6 ID fans amps 46 0.5 45 0.9 46 2.4 45 1.3 42 0.6 48 1.0 48 0 46 0 ID fans pressure 6.2 0.46 4.5 0.99 5.8 1.09 5.4 1.02 3.8* 0.24* 6.2 0.17 4.8 1.82 6.6 0.34 FD fan amps 30 0.4 30 1.5 30 1.9 30 1.6 27 0.4 30 0 30 0 30 0 FD fan pressure 4.4 0.61 4.4 1.01 6.5 6.60 4.1 1.14 2.3 0.36 4.5 0.10 4.8 0.51 4.7 0.80 Furnace draft 0.60 0.107 0.60 0.109 0.81 1.019 0.61 0.056 0.58 0.057 0.52 0.093 0.59 0.075 0.53 0.065 Boiler flue gas temp 687* 7.8* 686* 8.6* 695* 15.9* 679* 9.8* 598* 4.6* 674 U.I 676 U.I 689 16.0 0 325 3.5 Fuel oil gallons/hr ESP inlet temperature 330* 3.6* 338* 2.5* 330* 4.8* 328* 2.6* 280* 0* 335 0 335 4.2 37 1.5 37 1.5 44 0.8 43 2.6 0.078 28,98 0.024 29.05 0.012 29.16 0.018 29.17 0.041 Ambient temperature 58 6.8 62 6.3 42 6.2 42 Ambient pressure 29.02 0.056 28.75 0.042 29.03 0.106 28.95 Sampling duration 9:OOA-U:25P * Hot a total time man. 8:43A-12:07A 9:05A-4 :25A 9:47A-2 :12A 9:27A-2 :10A 11:10A-3:47P 11:20A-3:46P 9:22A-2 :06P �Unit No. 7 generally operated between a range of 16 to 35 MW gross, (refer to daily process data tables provided in Appendix D). Production over 35 MW placed considerable wear on the unit, and was avoided whenever possible. Production under 16 MW introduced instability and the possibility of large transient swings in operating conditions. Usually the boiler was operating close to one of these limits. It operated at 35 MW during peakloads because the load of the serviced community was over 35 MW. Production was reduced to 16 MW when off-peak power could be bought more cheaply from neighboring utilities. Examination of Table 2-3 indicates that the daily mean of gross electrical output (24 hour basis) is typically between 29 and 32 MW due to boiler operation at full output for a large portion of the day. In fact, the hourly readings provided in Appendix D indicate that output is rarely below 35 MW between the hours of 8 AM and 10 PM or longer. During non-peak hours, the boiler operated between 16 and 25 MW, depending on load and the amount of power being purchased from neighboring utilities. Comparison of the daily cycles of power production with the standard deviations (24 hour basis) given in Table 2-3, indicates that the standard deviations range between 5 and 7 for days representative of typical operation. Values not lying in this range are indicative of abnormalities such as the buying of cheaper power through the peak hours, or unusually high off-peak loads. The standard deviations in Table 2-3 show that these abnormalities happen most often on weekends, especially Sundays. Weekday operation is fairly consistent, due to uniformly high loads and the resultant high cost of power. Net power output follows identical trends, since the pov/er demand of the auxiliary equipment associated with Unit No. 7 is fairly constant. Fuel consumption varied directly with the amount of electricity produced. Of the three types of fuels used in Unit No. 7 (coal, RDF, and fuel oil), coal was used in the largest quantities. The amount of RDF burned was limited to approximately 17% in terms of the total heat produced. This was because RDF, due to its lower heating value, cannot sustain sufficient temperatures to maintain required boiler efficiency and steam quality. Also, RDF requires a longer residence time in the boiler for complete combustion, and this places another physical restriction on the amount of RDF in the fuel mixture. Fuel oil is used sparingly, and only as an igniter to insure flame continuity dur2-20 174 �ing soot blowing. Different firemen have different procedures for its use, and the large variations in fuel oil consumption shown in Table 2-3 are more related to operating practices than to what was happening in the boiler. The continuous supply of RDF to the boiler during the test was found to be unreliable. Practical experience during the test indicated that RDF supply was very unreliable. The RDF conveyors which feed Unit No. 7 were prone to jamming and required frequent maintenance. Often the RDF supply ran out because the solid waste recovery plant was experiencing mechanical problems, or had run out of refuse to process. Out of 23 days of sampling, only on 6 was RDF burned continuously. On 15 days RDF was burned part of the time, and on 2 days it was not burned at all (refer to Appendix D). The means and standard deviations for coal consumption given in Table 2-3 follow those of the gross electrical output. This indicates that coal consumption is closely related to electrical output, as expected. However, these daily averages mask out one important effect. Referring to the tables in Appendix D, one can see that the amount of coal burned depends on whether there is RDF in the mixture or not. All other things being equal, the flow of coal will always go up or down, depending on whether RDF is being removed or introduced into the mixture, respectively. 2.2.1 Operating Parameters Data for the steam cycle in the boiler are also listed in Table 2-3. Examination of the data indicates that the steam and feedwater flow rates fluctuate in a daily cycle, with means and standard deviations following the gross electrical output. However, the values for steam temperature and pressure remain fairly constant. The feedwater temperature also varied. It was higher on days of high electricity production, and lower on days of low production. Excess air is one of the most important parameters for describing conditions inside the combustion chamber. Unit No. 7 is designed to operate at about 20% excess air. Data in Table 2-3 indicates that on the average this is true. However, the hourly data (refer to Appendix D) indicates wide fluctuations. Excess air tended to increase as the boiler load decreased. 2-21 175 �This was possibly due to the operater not decreasing the intake air with the reduction in fuel supply. On nearly each night the excess air reading was greater than 50% (the maximum readable value on the meter). The standard deviations of the mean excess air values indicate no direct relationshop to the deviations of gross power output. Consequently, excess air is not a function of power output alone. Unlike most other parameters, the excess air setting was subject to the whim of the operator, and changes from work shift to work shift could have introduced important variations. The induced and forced draft fan measurements listed in Table 2-3 are of limited significance , since they did not respond to increases in production with greater airflows and correspondingly greater current consumption. The furnace draft data indicated little or no correspondence to any of the other measured data. Most of the flue gas and ESP inlet temperature readings were incomplete as they did not cover the entire 24 hour day. Most of this information was recorded during peak operation, and may therefore be considered representative for peak operation conditions. Both the flue gas and ESP inlet temperatures decreased during off-peak periods. Routine activities such as ash removal and soot blowing was performed at times designated in the test plan. RDF was observed to have a substantially higher ash content than coal, and this characteristic was reflected by longer ash removal periods, and more periodic soot blowing. Both activities decreased substantially when RDF was not being burned. 2.2.2 Test Duration Data Table 2-4 contains means and standard deviations for all of the parameters given in Table 2-3 on a test duration basis. They are derived from the same hourly data given in Appendix D, but the averages are taken over shorter periods of time than the 24 hour means discussed previously. These values are included only to indicate what operating conditions existed during the hours of each test. They are not, however, indicative of overall boiler performance. For instance, some tests were performed only over peak hours. These means would be indicative only of peak conditions, and the corresponding standard deviations would be very small, since the parameters remained fairly constant during this period. 2-22 176 �2.2.3 Daily Production and Consumption Data Table 2-5 contains information recorded by the power plant on a daily basis. The total gross and net power production was recorded directly from meters inside the plant. The total steam produced divided by the gross power production gave a good indication of boiler efficiency. Separate meters are used for measuring the water used for ash removal and the total input to the evaporators. The days of highest sluice water use corresponded with days of prolonged use of RDF in the fuel mixture. The evaporators eventually feed into the working fluid cycle of the boiler, and gave a fair indication of make-up water required, except that there was a water reclamation system attached to the boiler. Hence, these values indicated new input to the system, but did not account for total make-up water requirements. Most of the fuel types were very accurately measured. Coal was measured through a weight integrating system, and fuel oil was similarly measured through a volume integrating system. However, no accurate measurement of the RDF was -possible. The values listed were derived from volumetric readings and a very rough measurement of the RDF density, taken once every shift. The Btu contribution of each fuel was then calculated by doing calorimetric analyses. This was done periodically, and the values used for the duration this test program are given in Table 2-6. By summing the Btu contribution of each fuel, a value for total heat production can be found. This value was then divided by either the gross or net electricity production to express thermal energy as it related to the power production of the day. 2.3 Continuous Monitoring Data Table 2-7 presents the daily averages of 02, C02, CO, and total hydrocarbon monitoring on approximate test duration basis. Occasionally the continuous monitors were allowed to run longer than the actual test, but the data can still be considered to be representative of the test duration. Hydrocarbon values were always found to be lower than 2 ppm, the sensitivity limit of the instrumentation used. 2-23 177 �TABLE 2-5. DAILY PRODUCTION AND CONSUMPTION AT AMES MUNCIPAL POWER PLANT, UNIT NO. 7 Power Production (kwh) Thermal Energy* (Btu/kwh) Oil (gallons) Sluice Uater for Bottoa and Fly Ash Removal (gallons) Uater Input to Evaporator (gallons) Fuel Consunptlon Steam Production (Ib/kwh) Iowa Coal (Ibs) Colorado Coal (Ibs) RDF* (Ibs) Date 681 000 623 902 11 186 12 210 9.57 339 9 8 8 432 712 0 60 250 000 8 300 ' 3-3-80 709 000 648 682 11 296 12 346 9.59 418 330 342 270 113 000 160 340 000 9 000 3-4-80 761 000 700 072 11 396 12 388 9.53 412 290 351 210 226 800 70 320 000 2 200 3-5-80 759 000 698 461 11 697 \2 711 9.73 434 538 370 162 192 375 60 380 000 6 800 3-6-80 740 000 679 858 11 693 12 728 9.50 432 0% 339 504 213 200 90 450 000 9 200 3-7-80 735 000 674 470 11 652 12 697 9.64 427 127 378 773 130 BOO 100 320 000 2 500 3-8-80 648 000 590 057 11 602 12 742 9.54 358 286 317 720 168 460 130 360 000 1 120 3-9-80 494 000 443 496 11 524 12 836 9.47 301 888 267 712 26 000 150 314 908 8 500 3-10-80 00 Net 3-2-80 ro I £ Gross 693 000 635 037 10 955 11 985 9.54 486 980 262 220 81 200 100 386 716 6 300 3-11-BO 739 000 678 629 11 440 12 458 9.57 334 328 392 472 229 600 270 403 172 5 800 3-12-80 750 000 688 456 11 348 12 362 9.62 408 980 334 620 229 075 290 413 644 3 500 3-13-80 742 000 681 889 11 S44 12 562 9.68 432 270 368 230 144 075 50 422 620 9 100 3-14-80 729 000 668 119 11 537 12 588 9.51 412 440 324 060 230 400 90 . 41B 132 0 3-15-80 508 000 457 939 11 434 12 684 9.50 322 448 253 352 22 050 910 335 104 5 700 3-17-80 699 000 639 942 11 170 12 201 9.59 412 335 337 365 97 650 70 396 000 11 100 3-18-80 759 000 696 494 10 855 11 829 9.52 417 010 341 190 154 874 60 473 000 15 200 3-19-80 748 000 682 596 10 794 11 829 9.51 414 315 338 985 134 816 100 477 000 6 000 3-20-80 753 500 689 205 11 368 12 388 9.56 445 392 379 408 63 700 490 320 000 7 300 3-22-80 706 000 647 644 11 077 12 075 9.55 410 520 335 880 92 000 640 250 000 5 400 3-23-80 426 000 382 263 11 311 12 605 9.49 269 610 220 590 0 800 180 000 16 600 490 300 000 4 500 Gross Net 3-24-80 710 000 650 039 10 841 11 841 9.61 629 920 157 480 51 600 3-25-80 700 000 642 Oil 11 080 12 081 9.52 610 880 152 720 93 000 680 430 000 4 000 3-26-80 726 000 664 973 10 949 11 954 9.60 612 960 153 240 134 970 40 540 000 18 500 •This Is only a rough Measure of RDF weight. This value is derived from the average Btu content of each fuel. �TABLE 2.6, HEAT CONTENT OF FUELS USED AT THE AMES MUNICIPAL POWER PLANT DURING SAMPLING PERIOD Heat Content for each Fuel Type niiM-nnn Dur 1on ^ Test Iowa Coal (Btu/lb) Colorado Coal (Btu/lb) RDF (Btu/lb) Fuel Oil (Btu/gallon) 3-2-80 thru 3-16-80 8946 10,556 5587 138,603 3-17-80 thru 3-26-80 9035 10,298 6128 138,603 2-25 179 �Fluctuations in the 02, C02, and CO levels are usually indicative of process conditions in the boiler. The means for these components at Ames were fairly uniform, as can be seen from Table 2-7. The only unusual days were March 9, 15, and 23, as evidenced by high 02 levels and low levels of C02 and CO. From Table 2-4, it can be seen that these were days of low electrical output and correspondingly high levels of excess air. Furthermore, these were the only days that were typical in this regard. Although excess air was monitored in the plant's control room, it has also Been calculated on a theoretical basis for comparison using the following expression 02 - CO/2 % excess air = 1QO x 1 4 N'2 - (02 - CO/2)] ^6 where the. gaseous components are expressed as percentages. The results of these calculations are given in Table 2-8, along with the values of excess air measured in the control room. The calculated values are consistently smaller, and the same anomalies appear (i.e., large values on the 9.th, 15th, and 23rd). In this case, the measured values are larger because these were taken after the air preheater to the boiler. Evidently, there is some air leakage in the preheater. 2.3.1 Air Preheater Leakage Oxygen in the flue gas at the inlet and outlet to the preheater was monitored on March 8, 1980 to determine air preheater leakage. Continuous monitoring results are presented in Table 2-9. The oxygen readings were also plotted and are shown in Figure 2-1. Examination of the plots in Figure 2-1 indicates that the increases and decreases in oxygen at the boiler exit are closely followed by similar increases and decreases in oxygen at the ESP inlet which is located downstream of the boiler. Since the variable oxygen readings at the inlet and outlet were taken on an intermittent basis, at 15 minute intervals, it was difficult to relate the data points at the boiler exit and the ESP inlet on a same time basis. However, from the graph the similar trends of the two curves can be easily observed. 2-26 180 �TABLE 2-7. CONTINUOUS MONITORING DATA Sampling Location Date (1980) °2 (*) Mean o Mean 2 (t) o CO (ppm) Mean o THC (PP«) a Mean ESP Inlet ESP Outlet 4.6 6.3 0.34 0.53 12.7 11.4 0.44 0.53 17.9 16.5 1.61 1.57 <2 <2 . Inlet Cutlet 3-3 4.4 5.8 0.55 0.65 13.7 12.5 0.63 0.67 12.4 10.7 1.54 1.16 <2 <2 - Inlet Outlet 3-4 4.4 6.1 0.35 0.17 14.4 13.0 0.36 .19 16.7 14.7 0.75 .89 <2 <2 - Inlet 3-5 4.4 5.6 0.66 0.83 14.6 13.4 0.58 .36 18.3 27.8 1.22 10.14 <2 <2 . Inlet Outlet ro 3-2 3-6 4.3 0.29 13.9 DATA TAttN FOR INLET ONLY 0.37 16.7 2.30 <2 - Inlet Outlet 3-7 4.6 5.9 0.32 0.27 13.9 12.8 0.35 0.28 16.4 14.7 1.50 1.63 <2 <2 - Inlet Outlet 3-8 4.3 4.8 0.30 0.40 14.0 13.6 0.30 0.39 27.6 28.4 0.85 2.29 <2 <2 _ Inlet Outlet 3-9 7.1 8.8 1.23 1.38 11.6 11.0 1.22 1.24 24.7 22.6 1.82 2.31 <2 <2 _ Inlet Outlet 3-10 4.0 5.6 0.30 0.19 13.9 12.4 0.30 0.14 24.5 24.9 1.51 1.04 <2 <2 Inlet Outlet 3-11 4.7 5.8 0.28 0.23 13.6 13.2 0.48 0.51 22.4 21.2 1.88 1.29 <2 <2 _ Inlet Outlet 3-12 4.4 5.6 0.29 0.33 14.0 13.8 0.43 0.56 22.1 22.3 1.75 3.77 <2 <2 _ Inlet Outlet 3-13 3.3 5.2 0.30 0.57 15.6 14.0 0.33 0.96 20.7 18.4 0.90 1.03 <2 <2 _ Inlet Outlet 3-14 3.7 5.3 0.40 1.03 14.8 13.1 0.47 0.74 27.7 29.9 4.21 16.56 <2 <2 - (Continued) �TABLE 2-7. (Continued) Sanpl 1 ng Location Date (1980) o2 (%) Mean o co2 Mean THC (ppm) CO (ppm) (X) a Mean a Mean a Inlet Outlet 1.56 1.87 12.6 10.7 1.45 1.67 22.0 18.7 2.03 2.01 <2 <2 - 3-17 3.7 5.4 0.47 0.32 14.4 12.9 0.62 0.33 21.5 20.0 1.73 1.41 <2 <2 - Inlet Outlet 00 6.3 8.4 Inlet Outlet i-- ro 3-15 3-18 3.8 5.4 0.33 0.30 14.4 13.0 0.46 0.40 23.3 23.7 1.18 9.62 <2 <2 Inlet Outlet 3-19 3.8 5.3 0.58 0.47 14.7 13.2 0.72 0.47 23.6 26.2 1.84 17.55 <2 <2 - Inlet Outlet 3-20 4.1 5.9 0.29 0.25 14.3 12.8 0.41 1.11 20.1 17.4 2.21 1.70 <2 <2 - Inlet Outlet 3-22 3.6 5.4 .34 .29 14.2 12.6 .35 .46 38.3 37.7 25.81 22.61 <2 <2 - Inlet Outlet 3-23 5.9 8.8 1.09 .75 12.7 10.1 1.08 .74 NOT OPERATING <2 <2 _ Inlet 3-24 _ I Inlet Outlet 3-25 Inlet Outlet 3-26 H • .24 H H <2 _ 13.8 13.1 .71 .26 H H M <2 <2 - M .87 4.9 13.7 DATA TAKEN FOR INLET ONLY .73 M N <2 - DATA TAKEN FOR OUTLET ONLY 5.4 .24 13.2 4.4 5.4 .83 .23 �TABLE 2-8. EXCESS AIR READINGS Excess A1r %] Excess Air %2 3-2-80 3-3-80 26.7 22.1 25.5 18.3 3-4-80 25.8 20.1 3-5-80 25.9 18.7 3-6-80 3-7-80 3-8-80 3-9-80 3-10-80 24.9 27.2 24.9 49.4 22.6 18.9 19.3 19.5 34 16 3-11-80 3-12-80 3-13-80 3-14-80 3-15-80 3-17-80 3-18-80 3-19-80 3-20-80 3-22-80 3-23-80 3-24-80 3-25-80 3-26-80 27.9 25.7 18 18 18 17 41 18 20 19 24 26 38 16 18 18 Date o 18.2 20.8 41.7 20.6 21.4 21.4 23.5 19.9 37.8 NA 25.6 29.5 Based on continuous monitoring data from the ESP inlet Control room readings 2-29 183 �TABLE 2-9. AIR PREHEATER CONTINUOUS MONITORING DATA Boiler Ex1t/Preheater Inlet Time %o2 % co2 CO ppm THC ppm 1430 4.237 13.926 28 ESP Inlet/Preheater Outlet 0.42 % rn % LU2 CO ppm THC ppm 4.593 13.784 29 0.1 4.975 13.542 28 0.22 4.544 13.668 29 0.20 4.901 13.520 27 0.19 5.207 12.43 26 0.21 4.879 13,538 26 0.15 4.153 14.246 28 0.18 5.141 13.574 26 0.18 4.359 13.902 28 0.04 4.959 13.564 27 0.25 4.397 13.946 28 0.11 4.401 13.558 36 0.18 27.58 0.304 4.71 13.61 28. 1 0.168 0.114 0.34 0.43 2. 7 0.059 1445 4.094 1500 14.222 27 0.49 1515 3.741 1530 14.414 28 0.45 1545 4.637 1600 13.678 28 0.37 1615 4.083 1630 14.304 28 0.41 1645 4.089 1700 13.972 26 0.22 1715 1730 v 4.198 14.154 27 0.18 1745 1800 4.192 13.740 26 0.23 1815 1830 4.295 13.976 28 0.19 1845 1900 3.937 14.154 29 0.22 1915 1930 4.742 13.492 28 0.26 1945 2000 4.632 13.566 28 0.21 2015 Mean 4.24 13.97 0.30 0.30 0.9 %o2 2-30 184 �Figure 2-1. Oxygen 1n the gas before and after the air preheater 2-31 185 �Air preheater leakage is defined as the ratio of the difference between the amount of flue gas out of the preheater and the amount of flue gas into the preheater to the amount of flue gas into the preheater. In order to estimate this leakage average values for oxygen for the inlet and outlet from the monitored data were used. Based on an average oxygen reading of 4.24 percent at the preheater inlet and 4.71 percent at the outlet an air preheater leakage of 2.9 percent was calculated. It must however be noted that during this period the boiler load averaged approximately 88% and the RDF heat input to the boiler was approximately 20 percent. Air preheater leakage will vary with the steam load and type of fuel fired. 2-32 186 �3.0 SYSTEM DESCRIPTION The coal-fired utility boiler tested was the No. 7 unit at the Ames Municipal power plant. The power plant is owned and operated by the city of Ames. Three boiler units, 5, 6, and 7, at the power plant have been modified to burn solid waste as a supplemental fuel with coal. Boilers 5 and 6 are Stoker-fired boilers and boiler No. 7 is a pulverized coal suspension fired boiler. Under normal operating conditions only unit No. 7 is used. Units Nos. 5 and 6 are operated only under peak demand conditions or when unit No. 7 is down. The power plant is located within the city limits of Ames, Iowa. Ames is approximately 54 Km (34 miles) north of Des Moines. The Ames Municipal power plant layout is shown in Figure 3-1. 3.1 Boiler Description Boiler No. 7 was designed to burn coal or natural gas as the primary fuel. It is a tangentially fired, pulverized coval, balanced draft, Combustion Engineering unit, rated at 175000 kg/hr (385,000 Ib/hr) of steam. The generator is rated at 35,000 KW, gross. Unit No. 7 has been operating since June 1968. However, modification to burn refuse derived fuel (RDF) was made in 1975. Boiler No. 7 specification data is provided in Table 3-1 and a flow diagram of unit No. 7 is given in Figure 3-2. As shown in Figure 3-2, coal from the plant stockpile is fed to two Raymond Bowl Mill pulverizers. Air preheated to about 340°C (650°F) by the combustion gases is supplied to the pulverizers to dry the coal, and to convey the pulverized coal to the burners. Pulverizer air preheat is necessary to prevent pulverizer to burner blockage which can be caused by wet fuel. Design specifications of the Raymond Bowl Mill pulverizer are provided in Table 3-2. Pulverized coal entrained in 15 to 20 percent of the total combustion air is conveyed to the individual burner nozzles which direct the coal and primary air into the combustion chamber. Combustion air is supplied to the boiler unit by a Westinghouse forced draft fan. The combustion air drawn 3-1 187 �1 BAND 5i!FT 1. CUD 1 HOUSE I STREET IS METERING STATION Q COOLING CZ3 FUEL Oil STOXACE POWER PLANT NO. 2 TOWER CLEAR WELL ASH COOLING 'SILO O I TOWER r ELECTROSTATIC 1'RKCIPITATOR UNIT NO. 7 ADDITION jn] n LJ; -I ID co co cEj UATF.R PLANT I nro COVERED ENTRY I TRANSFORMER STACK DWELL NO. 3 CO C O A L S T 0 R A C I Figure 3-1. Layout of plant site A R E A �TABLE 3-1. BOILER DESIGN DATA Description Slzt Dtslgn pressure, psl 108S Total effective heating surface sq ft Boiler 16550 Furnace EPRs 6200 Superheater - Convection zone 5200 Radiant zont 1800 Economizer None Regenerative A1r Heater 67200 A1r Preheating Coll 5070 Furnace Volume, cubic feet 27300 Furnace width and depth by 19'-ir C to C of tubes, ft Furnace design pressure, in H^o positive 8" KG Total weight complete. Ib 2,340,000 Water required to fill boiler and water walls to operating level, gal Appro*, 17,900 U.S Gallons Inside diameter and thickness of steel drum 66" DIA - 4 | " x 2 | • | | Overall length of steam drum Appro*. 27' - 0* Drum head thickness, In lifting weight of drum safety valves 2 1/4" 66" 0 Drum • 85000 LBS Manufacturers, type, number and sizeof drum safety valves Consolidated Two (2) 3" I1757A Manufacturer, type, number and stze of blowdown valves Two C21 sets 2- Yarwey 6968-81 Tubes 1n furnace Size and thickness Water well tube spring, In C to C Furnace exit first row tube spring. In C to C 2 1/2" 0,D, x .180 3" all wells 9* (finishing superheater} NO SA 26 9" Are tubes staggered? Material Number Tube spring In C to C Tubes 1n Boiler Size and thickness Material Tube spring C to C (1n) Number - IN LINE - 192 Assemblies (Finishing superheater) 2 1/2- O.D. x ,12 SA -192 3 3/4" Transverse 1472 Water walls - 10 to 1 Circulation ratio, minimum 3-3 189 �BOILER FEED PUMP SPRAY WATER DESUPERHEATER FEEDWATER FIRST STAGE PRESSURE INTEGRATOR STEAM JET AIR EJECTOR COAL TEMPERATURE FEED WATER IN BLEED STEAM' <A> I | FEED WATER HEATER FEED WATER HEATER UNTREATED -WELL WATER a COMBUSTION ENGINEERING PULVERIZER STEAM GENERATOR REFUSE DERIVED FUEL AIR HEATER 'LEAKAGE ATI.AS BIN T TEMPERATURE FLUE GAS IN NDUC-D RAFT AN VOLUMETRIC FLOW DENSITY COOLING TOWER SLOWDOWN AMBIENT AIR OVERGRATE (RDF ONLY) UNIT NO 7 ELECTROSTATIC PRECIPITATOR TEMPERATURE AIR IN FORCED DRAFT FAM UNDERCRATE AIR (RDF ONLY) SEAL _ WATER TEMPERATURE AIR OUT FLY ASH PRIMARY AIR TO PULVERIZER BOTTOM ASH COMBUSTION AIR Figure 3-2. Flow diagram for unit #7 at Ames Municipal power plant �TABLE 3-2. DESIGN SPECIFICATION FOR RAYMOND BOWL PULVERIZERS DESCRIPTION SIZE Pulverizers Manufacturer's Model No. C. E. Raymond No. 613 No. of pulverizers Two (2) Type and size Bowl Mill Weight including driver Approx. 98500 LBS each journal assembly Weight and dimensions of largest piece requiring removal for maintenance 3 x 4 x 4 ft 3900 LBS. Minimum stable firing rate, Ib per hr each of specified coal 8000 LBS/HR Maximum firing rate, Ib per hr of specified coal each 32000 LBS/HR @ 60 GR 17.1235 M Maximum turndown ratio Pul. - Burner Combination 4 to 1 Maximum horsepower input required 265 each Shaft Incl. Exhauster Primary air temperature, F. For the specified coal 651 Max. allowable 750 Maximum boiler load with one pulverizer in operation with specified coal, no gas firing, Ib per hr 250,000 3-5 191 �by the forced draft fan is obtained from the 9th floor of the power plant building (refer to Figure 3-3). Design specifications for the forced draft fan are provided in Table 3-3. The burners are designed to admit controlled quantities of additional air through separate air ports surrounding or built into the fuel nozzle. In the combustion chamber, the combustible matter reacts with oxygen of the air to release thermal energy at temperatures exceeding 1100°C (2000°F). The walls of the combustion chamber are lined with water-filled tubes which absorb thermal energy and generate steam. The water tubes are filled with liquid or vapor, depending on pressure and temperature conditions. Heat transfer in the combustion chamber cools the combustion gases. The cooler combustion gases flow from the combustion chamber to the superheater where further heat transfer and gas cooling occurs. The superheater is a combination Radiant-Convection type with 13 tube rows and 26 steam passes on the primary side and 26 tube rows and 52 steam passes on the secondary side. The maximum design temperatures in the superheater are: steam side - 350°C (primary), 485°C (secondary); gas side - 1150°C (primary), 1050°C (secondary); and outside metal surface - 470°C (primary), 545°C (secondary). Steam superheat is necessary for thermodynamic efficiency and also to prevent steam condensation which would damage the blades of the steam turbine. Combustion gases from the superheater normally flow to the economizer section where heat is transferred to the boiler feed water. However, the No. 7 unit has no economizer and flue gases from the superheater flow to the air preheater,, then to a cold-side electrostatic precipitator via an induced draft fan (refer to Table 3-3) out through the stack. The regenerative air heater has an effective heat exchange surface area of 67200 sq ft. Combustion gases enter the air heater at texperatures of 370° to 400°C (700 to 750°F) and exit at temperatures of 135° to 150°C (280 to 300°F). Air temperature entering the air heater ranges from 35° to 50°C (100 to 120°F) and exit temperatures range from 315° to 335aC (600 to 640°F). Performance characteristics for unit No. 7 provided by the manufacturer are given in Table 3-4. 3-6 192 �GAS OUTLET OJ ^ Figure 3-3. Schematic of Ames Municipal power plant boiler No. 7. �TABLE 3-3. FAN DESIGN PERFORMANCE Forced Draft Fan Manufacturers name Model No. Westinghouse #4054 Blade type Air foil Operating speed, rpm Air inlet temperature, °F Air flow (100% load), Ib/hr Air flow (100% load), ft3/min Fan static pressure, psi Static efficiency (100% load), % 1180 80° 422,696 99,934 0.28 54.6 167.1 Power required, Kw Induced Draft Fan Manufacturers name Model No. Blade type Operating speed, rpm Air inlet temperature, °F Westinghouse #4073 Air fovil 885 279 482,653 153,900 0.26 52.3 249.9 Air flow (100% load), Ib/hr 3 Air flow (100% load), ft /min Fan static pressure, psi Static efficiency (100% load), % Power to fan shaft, Kw 3-8 194 �TABLE 3-4. PREDICTED PERFORMANCE CHARACTERISTICS OF UNIT #7 AT AMES MUNICIPAL POWER PLANT. FUEL COAL Evaporation Feedwater Temperature Superheater Outlet Temperature Superheater Outlet Pressure Superheater Pressure Drop Gas Drop, Furnace to Econ. Outlet Ib/hr F Gas Drop, Econ. Outlet to A.H. Outlet "wg F F F F F "wg F % Gas Temp. Entering Air Heater Gas Temp. Leaving Air Heater, Uncorr. Gas Temp, Leaving Air Heater, Corr. I-1 t»> 10 I Ul to Air Temp. Entering Air Heater Air Temp. Leaving Air Heater Air Press, at F.D. Fan Ambient Air Temperature Excess Air Leaving Economizer F psig psi "wg Ib/hr % Fuel Fired - Coal 0 9506 BTU/J Efficiency 216,000 375 905 900 30 0:85 2.00 705 281 265 119 598 5.10 80 22 28,600 87.99 COAL 360,000 428 905 900 75 1.85 4.35 732 296 279 101 633 7.75 80 22 45,600 87.28 COAL 385,000 433 905 900 85 2.15 4.90 743 297 280 99 635 8.70 80 22 48,500 87.21 Superheat steam temperature control range is from 216,000 to 385,000 Ib/hr. The fuel specifications on which the above are based are as follows: F.C. V.M. Ash Moist. 37.10 32.27 13.51 17.12 100.00% HHV (as fired) 9506 BTU/# �Unit No. 7 generally burns a mixture of Iowa coal, Colorado coal, and refuse derived fuel (RDF). The ratio of the two types of coal in the mixture varies. However, during the test program a 55 to 45 percent ratio of Iowa and Colorado coal was maintained in the pulverized coal mixture. Approximately 20 percent of the total fuel fired is RDF and 80 percent pulverized coal. Coal is stored in the coal yard in two separate piles. Front-end loaders are used to move the coal to the transport conveyor feeding the storage bunker. Coal is alternately moved to the conveyor and is overlayed in the bunker prior to the coal dropping into the pulverizer. This mixing of coal is done on a weight basis and has proven satisfactory to the plant in maintaining the proper blend. RDF is produced at a separate Ames city facility located approximately two blocks away. All of the RDF produced is pneumatically conveyed to a storage bin (Atlas bin) 25 m (85 ft) in diameter with a holding capacity of 454 Mg (500 tons). The RDF is fed from the Atlas bin at the required rate (8.5 tons/hr maximum) and pneumatically conveyed to the RDF burners. There are two RDF burners located approximately 61 cm (24 inches) below the coal burners at opposite corners of the firebox. The location of the RDF burners is shown in Figure 3-4. The by-products of combustion are stack gases and ash. With pulverizedcoal firing, all of the burning is accomplished in suspension with the result that about 80 percent of the ash remains in the flue gases. Due to the utilization of REF to supplement coal as fuel, modifications were made to the boiler. Grates were installed in April 1978 to assist in the combustion of RDF. Prior to the installation of the grates, RDF burning in suspension was not very effective, and substantial portions of the RDF dropped unburnt into the bottom ash hopper. Deposited ash and slag in the boiler furnace bottom are removed at least 3 times per day. An average of 758,000 liters/day (200,000 gallons/day) of sluice water (raw well water) is used to remove the solid waste from the furnace bottom. This waste is then drained to a holding pond where the ash is dredged out. The water from the holding pond percolates through the soil eventually into the nearby Skunk river. Any overflow from the holding pond 3-10 196 �BOILER NO. 5 BOILER NO. 6 VO CO . Section CC From Atlas Bin South Figure 3-4. Solid waste recovery system �is also absorbed by the river. Also deposited in the holding pond is the electrostatic precipitator (ESP) fly ash. The fly ash from the ESP hoppers is pneumatically conveyed (3 times per day) to the bottom ash hopper drain system which transports it to the holding pond. The dredged ash is stored on site in piles. Make up water for the boiler is obtained from the city water supply. Boiler feedwater is processed by water softeners and deaerators and treated with caustic soda, phosphates and hydrazlne to prevent scaling and corrosion. Tannin is also added to maintain particles in suspension. Normal operation of the boiler is 24 hours per day, 7 days per week. The boiler is scheduled to be offline once per year for 10 to 14 days for various types of maintenance. 3.2 Electrostatic Precipitator Flue gases from the air heater are treated in an electrostatic precipitator (ESP) for the removal of particulate matter. The ESP in unit No. 7 is an American Standard Model 371. It is a wire/plate type with rappers and is designed to handle 4900 m /min (175000 cfm) of gas at an average inlet dust loading of approximately 9.27 gm/m (4 gr/scf). The ESP has 4 cell units with 2 fields and 8 insulator compartments. Performance characteristics for the ESP are given in Table 3-5, The collection system of the ESP has an effective surface area of 2030 m (21840 sq ft) with 28 gas passages having a space of 23 cm (9 inches) each. The collecting surface area rappers are of the electric vibrator type 2 and the maximum collecting surface area rapped at one instant is 113 m (1215 sq ft). Total hopper capacity is 48 m (1700 cubic feet) with overall dimensions of 5.2 m x 6.8 m x 18.1 m (17' x 22.5' x 59.5'). 2 The electrical system of the ESP requires a maximum operating voltage of 45 KV. Power requirement at maximum demand is 83 KVA and the total connected load is 61 KW. There are 8 electric vibrator type high voltage rappers and two rectifiers. The two rectifiers are rated at 45 KV each. The primary voltage is approximately 260 volts at the inlet field and 200 at the outlet field. The primary current is approximately 52.0 amps at the inlet field and 34 amps at the outlet field. The secondary voltage and 3-12 198 �currents average 34.0 KV, 35 ma and 29.0 KV, 80 ma at the Inlet and outlet fields respectively. The spark rate averages around 120 per minute at the inlet field and 145 per minute at the outlet field. TABLE 3-5. PERFORMANCE CHARACTERISTICS OF THE AMERICAN STANDARD ESP Performance at 385,000 Ib/hr load, coal fuel Gas to ESP cfm Gas to ESP, Ib/hr Gas Temp °F 167,000 510,000 300 Inlet dust loading, gr/cf Outlet dust loading, gr/cf Efficiency, % Gas velocity, fpm Pressure drop, in, H20 Time of gas contact, sec. 3-13 199 3.7 0.074 98 266 0.5 2.94 �4. SAMPLING LOCATIONS All sampling locations are identified in Table 4-1 Figure 4-2 is a cross sectional schematic depicting the tions at the stack. Figure 4-3 is a horizontal view of ing port locations, and Figure 4-4 is a cross sectional let depicting the traverse point locations. and Figure 4-1. traverse point locathe ESP inlet showview of the ESP in- The continuous monitoring probe was located on the North side of the ESP inlet duct prior to the gas sampling ports and at a depth of approximately 4 feet. At the stack,the monitoring probe was alternated between ports 2 and 3 and at a depth of 4 feet. These two ports were also used for the gas sampling trains. TABLE 4-1. SAMPLING LOCATIONS Solid Sample Locations 1 - Blended Coal 2 - Refuse Derived Fuel 3 - Bottom Ash 4 - Fly Ash Gaseous Sampling Locations 5 - ESP Inlet 6 - Stack 10 - Hi Volume Ambient Air Sampler Liquid Sample Locations 7 - Untreated Well Water 8 - Seal Uater 9 - Cooling Tower Water 4-1 200 �BOILER FEED PUMP SPRAY WATER DESUPERHEATER FBIiUWATKK FIRST STAGE PRESSURE 1LNTEGRATOR STEAM JET AIR EJECTOR COAL TEMPERATURE [FEED WATER IN GRAVIMETRIC SCALE BLEED STEAM- FEED WATER HEATER FEED WATER HEATER O COMBUSTION ENGINEERING STEAM GENERATOR .£> I i- ro TEMPERATURE FLUE GAS IN INDUCED DRAFT FAN AIR HEATER LEAKAGE AT1JVS BIN REFUSE DERIVED FUEL STACK (6 SAMPLI > UNTREATED -WELL WATER PULVERIZER N> O1 __J VOLUMETRIC FLOW DENSITY COOLING TOWER BIX)WDO«JN AMBIENT AIR OVERGRATE (RDF ONLY) Unit NO. 7 ELECTROSTATIC PRECIPITATOR TEMPERATURE AIR IN FLY ASH FORCED DRAFT FAM UNDERGRATE AIR ( (RDF ONLY) SEAL WATER TEMPERATURE AIR OUT PRIMARY AIR TO PULVERIZER BOTTOM ASH COMBUSTION AIR HI VOLUME SAMPLER Source: Compliance test report data prepared by Iowa State University Engineering Research Institute personnel under the direction of Dr. J. L. Hall, et al. from tests conducted during Sept. 1978. Figure 4-1. Unit 7 flow diagran and measurement locations. �SAMPLING PLATFORM T * 't' • 4.0 ft 1 i f i t ' " I ,, A in. PORT •CAPPED WHEN NOT SAMPLING '',<,>!,>' ,'>; r ' , >, "> |66 —.0 CONCRETE WALL NOT TO SCALE SAMPLING POINTS TRAVERSE DISTANCE FROM POINT OUTSIDE EDGE OF STACK NUMBER CM IN POINT DISTANCE FROM OUTSIDE EDGE OF STACK CM IN 1 38.2 97.03 5 59.4 150.88 2 42.8 108.71 6 66.4 168.66 3 47.8 121.41 7 75. 190.75 4 53.2 135.13 8 87.8 223.01 Figure 4-2. Cross Section of stack showing traverse point locations, 202 4-3 �Figure 4-3. Inl«t Duct - Showing Port Locations 4-4 203 �CONTINUOUS MONITORING PROBES Traverse Point Number Traverse Point Location From Outside of Nipple Centimeters Inches 1 22 53.9 2 34 83.3 46 112.7 58 142.1 Figure 4-4. Inlet Traverse Point Locations 4-5 204 �5,0 SAMPLING This section includes information on the sampling program conducted at the Ames facility. Any changes or pertinent comments are included in this section. 5.1 Gas Sampling The flue gas sampling at the Ames facility was performed at the electrostatic precipitator inlet and at the stack. Sampling for organics was to be performed for fourteen consecutive days with an additional three days sampling for particulate cadmium. However, due to extreme weather conditions the program was modified to collect nine inlet and outlet gas samples. Sampling for organics was accomplished concurrently at the inlet and outlet utilizing two modified method 5 trains (Figures 5-1 and 5-2) at both sampling locations. Inorganic cadmium was only sampled at the stack and utilized one standard Method 5 train, Figure 5-3. The sampling crew collected a ten m (10 + 1 m ) sample by extracting the flue gas at a rate approximating the flue gas velocity. The particulate matter was collected in a cyclone and on the filter media. The gas stream was passed through an XAD-2 resin trap to absorb the organic constituents, and through an impinger system to condense any moisture present in the gas. Parameters such as temperatures, pressures, and gas volumes were monitored throughout the sampling period. The sample fractions were recovered from the sampling trains and turned over to an MRI representative. The outlet (stack) sampling position was sampled with no change to the sampling plan while the ESP inlet sampling was modified. • ESP Inlet During the initial tests, it was found that the outermost ports exhibited little or no flow. At one point of the traverse, the velocity head (AP) was negative while the next point indicated positive AP, thereby cancelling each other. It was therefore recommended that these two outer ports be dropped from the test. The recommendation was accepted and implemented as part of the test program. 5-1 205 �FILTER HOUSING HEATED LINE THERMDncTER CYCLONE FLASK t-o O o> cn i ro OVEN BOX STAND BY-PASS VAL\€ ORIFICE THERMOMETERS VACULM GAUGE R9 NAIN VALVE D.RY TtST Figure 5-1. \. AIR TIGHT PU1P ESP inlet sampling train VACUUM LINE �xX"'FILTER HOUSING THERH3T€TER CYCLONE FLASK OVEN BOX STAND BY-PASS VALVE ORIFICE THERMDMETERS VACUUM GAUGE \ DRY TEST • fHTER AIR TIGHT PIMP Figure 5-2. Stack sampling train 5-3 207 VACULM LINE �12 Figure 5-3. EPA Method 5 particulate sampling train 1) 2) 3) 4) 5) 6) 7) 8) 9) 10) 11) 12) Calibrated nozzle Glass lined probe Flexible teflon sample line Cyclone Filter holder " Heated box Ice bath Impinger (water) Impinger (water) Impinger (empty) Impinger (silica gel) Thermometer 5-4 208 13) 14) 15) 16) 17) 18) 19) 20) 21) 22) 23) 24) Check value Vacuum line Vacuum gauge Main value Air tight pump Bypass value . Dry test meter Orifice Pitot manometer Potentiometer Orifice manometer S type pi tot tube �5.2 Solid Sampling During each test day, four solid streams: coal, precipitator ash, bottom ash, and refuse derived fuel (RDF) were sampled six times per day following a schedule set up by Research Triangle Institute (RTI). The sampling was coordinated between RTI, the sampling crew and power plant personnel. The schedule provided the basis for collection of unbiased samples by obtaining a random selection from the multiple sources available for sampling. This approach was taken to avoid any cyclic biases which might have been present in the daily operation of the power plant. The samples and their sampling frequencies were: • The coal samples were taken from the feed line leading from the storage bunkers into the gravimetric feeders supplying the coal pulverizers. A metal scoop was used to remove the sample from the feed line and transfer it to the sample containers. • The precipitator ash was removed and collected from the bottom of the precipitator hoppers. A metal scoop was used to remove the sample from the access pipe and transfer it to the sample container. The hoppers were pneumatically evacuated after each sample was taken. A visual inspection was made to insure complete evacuation of ash from the hoppers. • The bottom ash samples were collected from the base of the furnace. These samples were collected wet with a high solids content from the furnace floor prior to sluicing out the ash by plant personnel. The ash doors were open during the washing procedure and the ash sample was scooped up in a teflon line pan and transferred to the sample container with teflon lined forceps before the furnace floor was washed with water to remove the ash. To provide representative samples of ash, as distributed over the entire rectangular base of the furnace, the area of the furnace floor was divided into an equal-area grid system. The samples were scooped from a specific grid area as provided by Research Triangle Institute each time a sample was taken. • The RDF samples were taken from the feeders in the Atlas bin prior to being pneumatically conveyed to the boiler furnace for firing. The material was placed into sample containers from a specific feeder and returned to the recovery area for labeling. Protective clothing was worn within the feeder area and plant personnel were notified when entering and leaving the area. 5.3 Liquid Sampling Three liquid streams were sampled during the course of the test program: cooling tower blowdown, well water, and bottom ash seal water (overflow water). Liquid streams which did not have continuous flows, were 5-5 209 �allowed to purge for three minutes prior to obtaining samples. Sample containers were rinsed three times with sample liquid prior to being filled with that liquid. The streams sampled and frequency of sampling were as follows: • Seal water was sampled twice per shift, for a total of six samples per 24 hour period. • Cooling tower blowdown was sampled once per day. • Three well water samples were collected over the testing period. Appendix C contains the time frequency schedule utilized by members of the solid and liquid sampling team. 5.4 Hi Volume Sampler To monitor the ambient air background, a high volume ambient air sampler (Figure 5-4) was used. It was placed on the roof of the Ames facility to obtain a representative background utilizing outside ambient air rather than sampling air inside the building that could have been contaminated or influenced by the combustion process. 5.5 Quality Assurance A quality assurance sample was also taken of the final test day. To collect the quality assurance sample, two sampling trains were placed at the same point in the same port at the inlet of the ESP. No traversing was performed. Both trains were run at the same isokinetic rate for the same duration as a normal test day. Also during the Q/A day, solids and liquids were collected as in a normal test day. 5.6 Sampling Train Background To obtain the train background (blank) an entire sampling train, including resin trap filter and impinger solutions was set up at the ESP inlet. The train was taken to normal operating temperatures and allowed to remain at these temperatures for one (1) hour. All train components were recovered as a normal run and all sample blanks were given to an MRI representative. 5-6 210 �HIGH VOLUME AIR SAMPLER FLOW PROBE \MODEL 230 HIGH VOLUME CASCADE IMPACTOR - OPTIONAL MANOMETER OR ROTAMETE: MODEL 310/310A/310B CONSTANT FLOW CONTROLLEF \ FLOW [ADJUSTMENT LINE CORD Figure 5-4. Ambient air sampler 5-7 211 �5.7 Sample Recovery Upon completion of the ESP and stack sampling, the sampling equipment was brought to the laboratory area for recovery. Each sample train was kept in a separate area to prevent sample mixup and cross contamination. The dry powder in the cyclone, probe, and heated flexline was collected in the cyclone catch bottle. After this collection procedure, the individual sample train components were recovered per the following: • Probe was wiped to remove all external particulate matter near probe ends. • Filters were removed from their housings and placed in proper container. • After recovering dry particulate from the nozzle, probe, heated teflon line, cyclone, and flask, these parts were rinsed with distilled water to remove remaining particulate. They were subsequently rinsed with B & J acetone and cyclohexane and put into a separate container. All rinses were retained in an amber glass container. • Sorbent traps were removed from the train, capped with glass plugs, and given to an on-site Midwest Research Institute (MRI) representative. • Condensing coil, if separate from the sorbent trap, and the connecting glassware to the first impinger was rinsed into the condensate catch (first impinger). t First and second impingers were measured, volume recorded and retained in an amber glass storage bottle. The impingers were then rinsed with small amounts of distilled water, acetone and cyclohexane. These rinsings were combined with the condensate catch. Rinse volumes were also recorded . • Third and fourth impingers were measured, volume recorded and solutions discarded. • Silica gel was weighed, weight gain recorded and regenerated for further use. To preserve sample integrity, all glass containers were amber glass, with Teflon-lined lids. 5.8 Problems Encountered During Recovery t If the temperature of the probe, flexline, or oven box was not sufficient (4 250°F) to prevent moisture from condensing, the particulate would cake on the inner walls and become very difficult to remove. 5-8 212 �• Due to the cyclohexane not readily evaporating and adhering to the inner walls, the flex lines and probe liners gave the appearance of being clean when in reality they were still wet and masked any particulate that remained on the walls. Therefore, all components must be thoroughly dry before a visual inspection can be made. If the initial rinses do not remove all the particulate, then brushing with additional water rinses is required to clean the walls. This is then followed with acetone and cyclohexane rinses. 5-9 213 �6,0 CALIBRATION This section describes the calibration procedures used prior to conducting the field test at Ames Municipal Power. tion equipment and how it was set up. 6.1 Figure 6-1 shows the calibra- Method Five Calibration Data 6.1.1 Orifice meter calibration. The orifice meter calibration is performed using a pump and metering system as illustrated in Figure 6-1(a). The dry gas meter with attached critical orifice is run at various orifice flows for a known time. After each run the volume of the dry gas meter, meter inlet/outlet temperatures, time, and orifice setting is recorded. The orifice meter calibration factor is derived by solving the equation. Aura Am? " 0.317 A H Pb (T d + 460) r (Tw L + 460) 6n2 V w ~ ^ J where AH = Average pressure drop across the orifice meter, inches Pb = Barometric pressure, inches Mercury Tj = Temperature of the dry gas meter, °F Tw - Temperature of the wet test meter, °F 0 = Times, minutes Vw s Volume of wet test meter, cubic feet The AH@ yielded is utilized to adjust the sampling train flow rate by regulating the orifice flow. 6.1.2 Dry gas meter calibration. Meter box calibration consists of checking the dry gas meter for accuracy. The dry gas meter with attached critical orifice is connected to a wet test meter (see Figure 6-1 (b) below) and run at various orifice flows for a known time. After each run wet and dry gas meter volumes, temperatures, time, and orifice readings are recorded. Utilizing the equation v _ Vw Pb (Td+460) " Vd (Pb+AH) (TW + 460) 6-1 214 �where V = Volume correction factor Vw a Volume of wet test meter, cubic feet Pb * Barometric pressure, inches Mercury Td s Temperature dry gas meter, °F Vd = Volume of dry gas meter, cubic feet AH a Average pressure drop across the orifice meter, inches H20 T. = Temperature of wet test meter, °F w a volume factor which compares the dry gas meter with the wet test meter is obtained. * 6.1.3 P1tot tube calibration. Pi tot tubes are calibrated on a routine basis utilizing two methods. The type S pi tot tube specifications are illustrated and outlined in the Federal Register, Standards of Performance for New Stationary Sources, [40 CFR Part 60], Reference Method 2 (refer to Figure 6-1(c)). When measurment of pitot openings and alignment verify proper configuration, a coefficient value of 0.84 is assigned to the pitot tube. If the measurements do not meet the requirements as outlined in the Federal Register, a calibration is then performed by comparing the S type pitot tube with a standard pitot tube (known coefficient of 1.0). Under identical conditions, values of AP, for both S type and standard pitot tube are recorded using various velocity flows (14 fps to 60 fps). The pitot tube calibration coefficient is determined utilizing the following equation, Pitot Tube Calibration = (Standard Pitot Tube XrAP reading of std. pitot j 1/2 -, L Factor (CP) Coefficient) AP reading of S type pitot The coefficient assigned to the pitot tube is the average of calculated values over the various velocity ranges. 6-2 215 �6.1.4 Nozzle diameters. The nozzle diameters were calibrated with the use of a vernier caliper if the nozzle showed excessive wear or was considered not fit for use, it was discarded. 6.2 Instrument Calibration Manufacturers recommended calibration procedures were used with the following gases which had an analytical accuracy of +_ 1%: SCOTT CO 812 ppm C02 11.94% 02 4.98% Propane 34.4 ppm in Nitrogen Balance Zero and Calibration adjustment were made prior to the start of the test day. Zero drift checks were made at the end of each test period. Data was recorded every fifteen minutes thus providing two data points per hour for each sampling position. 6-3 216 �r,r* Central Vi*t» \remeftiurt 7. flnf Control Vat** Come Coni'fi Vj vi\ lunptnlun T, I Tt.Tpcniv't T. OfUe* in '•?• '.H WMTtalMdff Figure 6-1(a) Orifice meter calibration XiV-r;.;-!f Pump CXi C* Uc«r Uignchstie Gtuft Figure 6-1(b) Dry gas meter calibration. X* TopYtiw Figure 6-1(c) Equipment used to calibrate pi tot tubes Figure 6-1. Calibration equipment set-up procedures 6-4 217 �7,0 TECHNICAL PROBLEMS AND RECOMMENDATIONS This section describes some of the problems encountered during the Ames test program and recommends a solution to these problems, 7.1 Problems • Construction of weather shelters was not completed on schedule causing a one day delay, • Because of extreme cold weather additional heaters had to be supplied to both the stack and monitoring truck. This resulted rn additional power requirements and caused approximately a half day down time for installation of power switches. • Cpld weather also effected the following: 11 heat lines did not maintain temperature causing moisture to condense and possibly act as a scrubber for hydrocarbons. Therefore, hydrocarbon data are considered only fair. 21 The gas conditioner would freeze restricting sample gas flow to the monitoring equipment. This created data gaps during the test period, 31 Solutions in the sampling trains would freeze causing the test to be shortened or scrubbed. 4). Cyclohexane would freeze at the temperatures encountered at the sampling locations because it has a freezing point higher than water, • Three instruments malfunctioned due to electronics failure or change. These instruments were: 11. Infrared Industries C0/C02 analyzer. The CO section would not maintain calibration and was removed from the system. It was replaced with the Beckman CO analyzer. 2} Beckman 0« analyzer. Detector malfunctioned and was replaced with backup Og analyzer. 3). Beckman CO.Analyzer. Energy source went out of adjustment and could not maintain calibration. No other replacement was_available, as a result, 2 days of CO data were not recorded. 7.2 Recommendations The only significant problems that occurred at the Ames facility were caused by severe weather conditions. In the future, the testing should preferably take place in a warmer environment, during the warmer time of the year or heated constant temperature shelters should be provided. 7-1 218 �MUCCSS OATA «JKS MUIIICIPAI pout* PLAIIT uUlT mfl. 7 •Not based on 24 hr daU Oat* 3-2-80 Tin* W IA I2N 2* 3A 4A SA 6A 7A 25 Srois Net 9A IOA 2t 24 28 23.1 11A 12N IP 29 30 30 4P 2P 3P SP 29.S 27.2 29 ' 29 26. » 26.6 6P 7P 8P 23S 21S 210 208 Siena pressure pslg 8SS •SO 858 Steam temperature F 900 B9S 895 FeedMter flM rate 1000 's Ibs/hr 250 232 lOf IIP 34 33 30 38.19* 2.«* 26.25* 310 310 312 270 2S2.2 36.49 860 4.16 26.1 26.6 27.6 27.6 220 240 2SO 260 26S 270 27S 260 260 260 280 310 ISS 860 8SS 860 860 860 860 860 860 850 860 860 860 860 860 890 89S 89S 910 910 900 890 910 90S 910 910 910 90S 900 900 -900 22S 220 220 205 230 240 250 270 27S 280 270 26S 26S 275 290 320 322 360 360 370 370 370 37S 36S 370 370 28 27. S 27. S 26 27 29 33. S 33 34 34 32 33 33 33. S 36 38. S 38.6 8SS 850 900 860 220 20S 28. S 27. S 9 34 I9S 208 Mean 35 201 222 Feedwater temp F 19.6 Fuel feed rate (coal) 32 1000's Ibs/hr 37831.4 76454.1 Fuel gauge readings 5788.7 gals/hr Fuel oil •Of 9P 32 29.5 27.1 350 Steam (loo rate 1000' s Ibs/hr VO 8A •60 860 •57.7 900 882 899 899.63 8. S3 330 320 289 261.17 37.94 366* 86S 7.38* 37. S 33.6 38.8 Coal Oil 7.07 4 '6 bcess air 1 18 20 22 22 25 21 21 28 22. S 20 21 22 22 24 24 22. S 22 21 23 20 19 24 23 '21 22 2.1 I.D. Fans amps 45 45 45 46 46 45 45 46 45 4S 46 47 47 47 47 47 47 47 47 48 48 48 48 47 46.42 1.1 29 30 30 29 30 29 29 29 30 30 30 30 30 30 30 30 30 30 32 32 32 33 32 31 30.29 psig FO Fans amps 1.12 0.77 Furnace draft pslg 0.4 0.4 0.3 0.15 0.8 0.65 O.M Ambient temp °F 8 8 Ambient pressure inches Hg 29.54 29.52 29.SI Comments 8 1 7 29.87 29.47 7 7 29.46 29.44 S 0.7 0.7 O.S 0.8 O.S 0.7 0.8 0.6 0.6 0.7 63S 300 0.3 Flue MS boiler e»lt Temp *F ESP Inlet 640 320 640 320 640 320 645 320 660 320 660 320 660 320 640 32S 12 18 19 22 23. S 26 29.36 29.31 29 25 9 29.41 29.4 29.39 29.38 29.38 Soot Blog •attorn Ash Removal and FU Ash Removal Start Finish - 2.30A, 6.00A. 9.48*. 2.12P. 6.0SP. 10. ISP 0.7 0.6 O.S 0.7 650 320 .ISP 26 27 26 23 22 19 29.24 29.2 29.19 29.1S 29.14 29. IS 29.13 RDF Density Mo «OF Fired 19 O.SS 0.60 8.20 647* 318. S* 0.98 9.78* 6.69* 1 1 18 It .06 7.S8 29.12 29.11 29.34 0.18 �PROCESS DATA AMES MUNICIPAL POhO P1ANT Mill NO. 7 •Not based M 24 kr data Oate 3-3-80 Tlae MM Gross Met 12N 1A 2A 3A 4A SA 6A 7A IA M IDA ' 14.75 12.15 IS 12.5 15 12.4 34.25 31.65 11A IP 2P 3P 4P 5P 34.5 12.0 IS 12.5 35 12.4 35 12.6 34.5 12.0 34.5 32.0 12N 7P BP » 10P UP Mean 35 32.5 15 12.6 15 32 .« 15 12.6 M 11.5 31 28.6 30.1 12.04* o.«* 100 271 268.8 71.48 6P a 7.11 29 12 1 1 18 18.5 18.5 27 29 Steaa flew rate 1000* s Ibs/hr 240 95 ISO 155 155 155 240 265 120 10 1 315 315 116 10 1 11 1 120 118 310 15 1 115 US 115 Steaa pressure pslg 860 850 ISO ISO 850 ISO 860 850 850 855 855 860 855 850 850 ISO 145 ISO BSD 855 850 855 865 850 852.71 4.66 Steaa teaperaUre °f 195 820 820 900 89S 890 885 900 900 910 900 910 900 900 900 910 910 900 900 900 890 882 880 865 890.1 24.01 FeedMter MOD rate 1000' s Ibs/hr 255 160 240 270 335 130 330 325 320 320 310 320 315 120 320 325 126 325 328 114 278.18 71.65 180 380 180 310 180 380 IBS US 185 380 380 180 180 HO 180 378 180.81 2.14 21. S 32.7 33.0 39 39 38.5 40 36 16.5 34.0 13.0 3S.O 35.0 16.1 36.9 1 34.7 34.5 11.6 12.0 Coal Oil 31.93 31.69 4.6 7.32 14 16 20 16 22.08 1.21 45 45.75 2.15 1.40 108 16S 160 160 Fuel feed rate (coal) 1000' s Ibs/kr Fuel gauge reading RDF 10.5 10.5 18215.9 76M2.1 5716.1 21.6 21.1 21.5 Excess air t 21 33 Feedxater teap °F 39 36 36 1 1 18 SysUa 1 dm 3. 24P m Systea 1 on 1.,47P Systea A started 10.S1A System 1 started11.10P No RDF IB 19 24 22 18 17.5 20 17.5 20 27 15 IS 10 I.D. fans aaps 46 39 43 41 43 43 46 47 48 48 47 47 47 47 47 48 48 46 46 46 46 46 46 1.0. fans pressure pslg 5.5 2.5 3.0 3.6 3.6 3.6 5.0 5.0 6.7 7.0 6.5 7.0 6.5 7.0 7.0 7.0 7.0 6.0 6.0 6.2 6.4 6.3 6.5 6.9 5.67 27 30 30 32 32 31 32 30 10 10 31 32 30 31 30 31 11 10 30 29.91 F.O. fans aaps 31 26 27 27 27 F.O, fans pressure 4 II . 2.1 2.2 2.5 0.7 0.6 0.61 0.55 0.6 Furnace draft psl9 0.6 0.9 0.51 O.S 0.55 0.4 0.7 0.6 0.65 0.3 O.S 0.65 0.6 700 0.59 0.11 700 688* 17. SI* 0.5 0.65 0.7 0.55 0.5 0.7 700 Flue gas teaperature OF 700 710 660 660 680 680 690 24 31 36 37 31 39 41 42 42 27.19* 10.39* 28.85 28.81 28.8 28.8 21.76 28.75 28.75 28.76 28.8** 0.11* Aablent teaperature 17 17 17 1 1 18 1 1 19 19 20 Aabtent pressure inckes Hg 29.09 29.05 29.01 29.00 28.98 28.95 28.91 28.91 28.91 28.86 Coaaents 1.79 1.13 nt? wWP- tatl Start - 1 WYlOP Flnlsk - 2.2SA. 6.0SA, 10.0OA. 2.4SP. 6.05P. 10.40P * Start - 12.5M. 10*05A. 9.SSP RDF Density - 5 Ibs/cu ft �PMCESS MTA AMES MMICIPAl POMM HJUH UN IT «0. 7_ •tot ktsed ea f 4 kr dlti Oete 3-4-M 12H TbM 1A 2A M 4A 5A 6A 7A 8A 9A 15.5 1S.S 35.5 27 25 21 23 23 23 23 26 21.2 21.1 21.1 21.2 21.2 24.1 26.7 31 31 Steia flow rite 1000' s Iks/kr 235 190 190 190 190 190 235 ZIZ 125 Steui pressure psij 850 840 •40 •SO •45 855 MS 845 Steia t overture °f MO MS •80 IBS 865 880 MS 900 feedwtter flow rite 1000'i los/kr 250 202 201 201 205 205 238 280 26.6 22.6 23.0 22.0 21.0 20.2 27.5 33.5 M 10 FeedMter Uap °F NJ 11A 12» IP 2P IP Fuel feed rite (coil) 1000 's Iks/kr Fuel gtuge readings fillons/kr fuel all RBF 35.5 11.0 35.0 12.5 35.5 32.9 IS 1 1 35.0 12.5 320 125 120 125 120 860 850 855 845 •55 910 900 90S 900 900 130 305 325 380 Gross Net o 10A 380 34.5 36.0 4P SP . 6P 7P •P 9P 35.0 35.0 12.6 1S.O 12.6 15.0 12.6 35.0 32.5 12 10P IIP Hem 29.7 5.19 4.93 320 280 2M.U S6.S9 •SS ISS 865 150.63 5.95 •90 900 MS 191.46 14.63 340 332 330 285 290.79 52.98 400 400 400 390 380 389.7 7.63 35. 2 34.6 34.3 35.3 35. 1 30.5 Coil 31.03 31. H 2.9 5.37 15.0 12.5 325 325 330 125 325 325 130 125 850 850 845 •SS •SO 850 ISO •55 900 90S 900 90S 900' 895 895 945 140 32S 325 330 330 325 115 330 330 385 390 390 380 390 385 390 395 400 34.0 34.0 34.0 34.0 34.5 34.5 33.0 14.0 32. SS 12. S 11590.7 77221.1 $7(7.9 on On Excess llr S 19 25 22 20 26 22 20 IS 20 18 23 22 19 20 10 18 20 23 19 1.0. fin taps 45 43 43 41 43 43 45 46 47 47 48 47 47 47 47 47 47 47 47 1.0. fins pressure a 4 .9 . 29 28 FO fins pressure psfo, « • 1C Furnice drift pslg 0.5 0.4 27 27 27 31 4* 31 19 20 19 20 20.11 2.35 48 47 46 46.04 1.76 t.•« ij 1 28 28 temper Jture 0.2 0.1 0.8 0.9 0.6 O.S 30 30 10 30 30 30 31 31 31 30 30 30 29 28 28 lotto• Ask ind Fly Ask »anvil i Stirt - 1.30A. 5.30A. 9.30A. 1.30P. 5.30P. 9.30P Flnisk - 2.0SA. 6.10A. 10.00*. 2.10P. 6.OOP. 10.2SP 0.6 0.7 0.65 O.S 0.6 0.6 0.5 0.6 0.6 680 340 700 340 670 340 680 340 680 340 690 140 690 340 695 340 31 30 29.54 11 1 . 11 * 1.41 28 27 27 26 26 26 26 26 25 22 28.84 28.85 28.86 28.86 28.83 28.83 28.11 28.82 28.83 0.6 Soot «««• 18 17 0.72 IS 28.89 21.91 28.94 0.60 12 0.67 0.7 10 9 0.515 0.15 617* 341* 0.7 695 340 28.84 32 O.S 690 350 Aaklent pressure tnckes Hj Coanents 30 31 .3 0 .7ft /• Flue gis teap „ taller °F ESP Inlet °F feblent 30 31 C 3 .£ •> f| 28 19 47 « FO fins laps Of . 31.51 21.25 3S.S 33.0 9.19* 1.16* 24.08 6.81 21.96 ». 91 28.99 28.88- 1 0.06* �PROCESS MTA AJCS MUNICIPAL mat PUNT UNIT NO. 7 . Dite 3-5-80 •Not Used an 24 kr d>u Tl«e 12H M 2A 29 26.8 26.5 24.6 26 23.9 22 20 21. S 22 19.S 22.1 Stean fl<M r«te 1000' t Ibs/hr 260 245 225 185 186 Steui pressure pstg 85S 840 850 840 850 MM Gross Net 3A 4A SA 6A 11* 12N IP 2P 3P 4P SP <P 7P 8P 9P Keen a 35 32.7 35 32.5 36 32. < 35 32.7 36 32.7 34.6 32.0 35 . 32. T 35 32.7 36 32.7 35 32.6 36 32.7 36 32.5 35 32.6 36 32.7 32 29.7 31.9 29.72 4.76 4.44 320 315 320 315 315 320 315 325 325 320 320 320 322 325 320 300 289.58 48.47 850 850 850 850 845 850 845 855 855 850 850 855 850 850 850 830 848.54 6.61 ' 885 885 900 880 895.6 10.97 340 336 330 307 300.42 46.6 8A 30 28 32 29.7 35 32.6 188 280 29S 850 850 845 9A 5teu tenpertture °F ' 890 890 885 870 900 895 900 910 910 905 900 890 900 906 910 905 • 910 895 265 245 250 200 205 200 290 298 330 330 330 340 330 315 325 330 330 325 330 330 Feedwter to* °F ISJ 880 895 FeedMter flan rite 1000' s Ibs/hr O 10P IOA 7A 390 36S UP 3*0 348 345 345 380 380 400 400 395 395 390 395 395 395 395 395 390 390 390 385 390 375 382.8 17.36 Fuel feed rite (ciul) 29. S 28.9 HMO's Ibs/br 38982.6 Fuel 9tuge readings 775*9.7 (9>no«s/kr) fuel oil 5788.6 RDF 22.5 19.1 23.4 19.5 36.1 37.4 41 40. S 40.5 37 37.8 34 35 33 32 33 33.6 33.9 32.6 33.2 33.2 32.0 Coil 6.09 on 32.46 33.53 2.5 Eicess ilr S 20 20 20 30 28 31 20 16 17 It 18 19 19 21 19 18 18 20 19 19 18 18 19 21 20.17 3.92 10 f«*s ops 46 46 45 45 45 44 48 48 48 48 47 48 47 47 47 47 47 47 47 47 48 47 47 46 46.75 1.11 10 fans press pslg S.S 7 6.7 fO f«HS MpS 29 FD fins press pslg 4.0 Furuce draft pslg 0.5 S.20A •10.20A RDF Destined 28 28 28 28 32 31 32 32 31 32 31 31 31 30 30 30 31 31 32 31 31 31 30.46 1.36 0.7 0.8 0.3 0.8 1.0 0.7 0.45 0.6 0.6 0.65 0.65 0.8 0.7 0.4 0.45 0.6 0.7 0.6 0.7 0.5 0.6 0.45 0.6 0.62 0.164 695 345 700 345 700 345 680 345 690 346 690 345 695 350 700 345 700 345 700 345 695* 345.5* 6.67* 1.58* 1 4 6 7 8 10 12 14 15 15 7.63 5.22 1.06 Flue *»» teaperiture toiler exit ESP Inlet tabieat ta*p DF Acbtent press Inches Hg Coflttnts 1.04 30 2 4 4 2 29.00 29.03 29.04 29.07 29.08 29.10 29.11 29.13 2 2 1 lotto. Ash fnd Fl» As h RoM»il Surt - rioA. 5.30*. 9 30*. 1 JOP. S 30P. 9.30P ' Finis* - 2. ISA. 6.10A. 10.00A. 2. OOP. 6. OOP . 9.S6P 1 15 14 13 12 10 9 29.13 29.22 29.24 29.24 29.24 29.24 29.24 29.22 29.23 29.22 29.22 29.22 29.23 29.23 29.23 29.23 29.17 Soot tlo.il SUrt - , 10A, 7P RDF density - 5 Ibs/cu ft. 5 Ibs/cu ft, 5 Ibs/cu ft 0.08 �PHC£SS MIA AMES nmncipAi POME* PUWT mi IT to. 7 on •lot tased 24 kr diti tote 1-6-80 Ttw NU trass Net 1A 12N 2A 1A 4A SA 6A 24.5 28 22 22 21. S 21. S 7A 8A 1 1 9A 1 .S 1 10A 11A 35 35 1 . 1 1 12.6 32. S 12K IP 35 35 Hal* • 11.5 12.6 12.5 21.6 120 120 120 110 282 279.71 S6.73 850 MS 845 850 850 850 650 855 850 810 836 847.13 7.22 900 890 910 905 • 90S 890 895 •85 BBS wo 880 895.33 11 . 1 130 130 330 130 130 325 130 330 140 10 1 312 290 211.7 54.23 390 395 390 390 310 185 385 190 190 390 180 377.46 21.03 1 1 36.5 38 36 16 16.4 35.6 36.5 15.1 34.0 1. 18 15.18* 12.15 1.53* 305 325 320 120 120 840 •SO 840 840 BIO 848 850 858 855 840 855 855 855 aao aao 890 900 •90 891 890 900 920 900 900 900 900 FeedMtw f lew rite 1000's Ibs/hr 271 200 196 198 204 15 1 230 292 120 315 330 335 Feeduiter tea? °F ' UP 32 12.6 310 SteM t taper* ture °F LO cn 35 120 285 Steu pressure psil rO IS 12.5 12.6 215 171 338 18 1 338 16 1 340 390 380 185 15.5 35 10P 320 12.6 182 390 15 If 32.6 22. S 30.6 180 16 35 M> 120 11.6 181 390 7P 12.5 11.7 IBS 35 6P 12.6 20.1 185 390 SP 115 20.2 255 36.5 4P 120 25.7 14.5 12.1 Fuel feed rite (out) 28.8 19406.3 1000's Ibs/hr 77980.7 Fuel iiy|t re*dl*fi tillMS/hr fuel oil Srti.2 MF 3P 11.17 28.88 21.5 11.7 SUU flou r«te 1000's Ibs/hr NJ o 2r 35 12.5 390 34 14 IS IS Ul i Oil S.5S $.30 1.75 S.40A System 8 off 8 .00AM only 1 conveyor 6.00A SysUB 1 on 9 .flOAN both conveyors on Excess itr X 21 36 30 34 34 12 28 15 17 20 21 18 20 16 19 21 18 20 18 11 20 18 19 19 22.21 10 fins ops 45 44 44 43 44 44 44 46 47 47 47 47 47 47 47 47 48 47 48 47 48 48 46 46 46.17 1.55 * IM A •• U.ta>9 10 fins press psl9 S C .B I .V FurMce drift psil 29 28 28 28 29 28 28 30 30 30 32 30 31 31 31 32 31 •J C 0.5 32 32 32 31 11 10.29 1.41 ta I.K 0.4S 0.8 0.9 0.65 0.8 0.8 0.7 tafcieot tMp "f 9 7 6 Aabtent press Inchts Hg 29.22 21.21 29.17 6 a 10 12 29.14 29.14 29.12 29.11 29.09 | 8otUB Ash iM1 FIvAsI• «e*»v<, t Mf Stirt I.Jo*. ! Finish - 2. ISA. 6.30A. I0.12A. 2.05P. 6. ISP . I1.21P 12 0.6 0.6 0.45 0.45 0.45 0.6 0.4 0.7 690 340 700 340 680 340 680 340 690 340 690 340 690 140 690 340 690 140 13 0.5 0.7 680 140 0.7 Flue 9is tecnp °F toiler eiit ESP inlet CoBiMts 32 31 C FO fins mfi 6.30 16 20 22 25 26 26 29 32 12 30 30 28 27 25 24 11.79 1.19 28.18 28.95 28.94 28.93 28.95 28.95 28.97 28.97 28.97 28.97 21.04 0.015 29.08 29.06 29.06 29.03 At 10.10* ESP hoppers duxn for repilrs 28.91 28.93 Soot 810M Stirt - LISA. 10 O?». 7. IIP 0.51 0.61 0.60 0.62 0.60 5.0 Ibs/cu ft . 4.0 Ibs/cu ft. 4 Ibs/cu ft 0.13 688* 340 •OF density - 0.61 6.32* 0 �PROCESS DATA AMES MUNICIPAL POUEt PLANT UNIT NO. 7 •Not Used on 24 hr diu Dite 3-7-80 I2H Tine Sross 20 Net HU 1A 2A 3A 4A 5A 20. S IS 15 13.2 13.3 6A 9A 7A 8A 26 24 30 27.7 36 33.5 36 10A 36 11A UP X 32.6 3$ 32.5 32 29.6 30.5 7.51 28.24 7.21 IP 2P 3P 4P 5P 6P 7P 8P 9P 3S.S 33.6 33.0 36 31.6 36 33.4 36 33.4 35 32.6 35.5 33.1 35 32.$ 35 32. S 35 32.5 36 Hun a IOP 12N 18.2 20 11.2 18.6 21 19.2 Ste> flow rite 1000's Ibs/hr 170 169 170 177 128 128 210 280 325 330 330 326 330 326 325 325 328 325 325 327 325 320 318 280 274.8 74.1 Steu pressure psls 945 845 850 840 840 850 850 855 855 8S5 860 855 BS5 855 855 850 850 850 840 850 850 850 855 850 850.21 5.21 Stein tanperiture "f 878 890 896 900 910 912 905 885 890 875 880 895 900 891.8 15.19 Feedwater flow rite 1000' s Ibs/hr 178 175 175 336 322 288 286.33 76.82 Feeduiter leap °f MO 340 Fuel feed rate (out) 1000' s Ibs/hr Fuel gauge readings 91! Ions/tor fuel oil 19.0 20 3 9801. S 78357.1 5790.1 Excess lir 1 40 ID fins Mps 43 90S 843 885 885 900 33.5 33.5 340 340 390 395 870 895 900 185 145 135 225 280 335 340 340 340 320 315 355 378 400 400 20 25.5 17. 6 18.8 32.5 35.0 42 42.5 17 47 37 50 50 21 16 20 21 19 18 20 20 20 42 43 44 42 42 46 47 49 49 48 48 48 48 48 7 7 7 42.5 41.5 RDF 905 900 900 340 345 340 340 350 338 340 335 345 395 395 395 390 390 395 385 385 382 385 385 375 373.75 26.6 41.5 37 36 35.5 35.5 35 25.3 25.7 31. 6 34.9 33.6 31.2 Coil Oil 31.65 8.23 33.6 4.2 20 16 20 19 19 19 19 19 19 25.25 11.2 48 48 48 48 48 48 48 47 45 46.46 2.41 7.5 7 7 7.2 7.0 7.2 7.1 6.6 6.0 6.06 32 32 32 31 32 32 32 32 31 30 30.67 1.79 0.71 0.64 0.51 0.70 0.53 0.66 0.63 -12. SOP RDF Restirted ID fins press pstg FD fins mips 28 FD fins press pslg 2.0 Furnlce drift pslg 0.55 1.4 28 28 28 27 28 30 31 32 32 32 32 32 32 5 5 5 5 5 0.6 0.8 0.85 0.6 0.6 0.25 0.55 0.6 0.7 0.7 0.6 0.6 0.7 0.7 0.8 0.6 0.65 700 350 705 350 700 340 705 340 69S 340 695 340 695 340 695 340 700 340 700 340 26 28 28 28 28 30 30 30 29 29 28 28 24.58 4.2* 28.97 28.95 28.91 28.92 28.92 28.92 28.92 28.92 28.91 28.88 28.92 28.97 Flue 915 two °F toiler Kit ESP Inlet Ambient te*f °F 21 21 19 19 19 20 20 20 20 21 22 26 Anbient press Inches Hg 29.02 29.02 29.02 2».02 29.03 29.02 29.01 29.00 29.00 28.99 28.99 29.00 28.99 COMMItS kottOB Ash ind Fly Ash tauvil Stirt - I.JOA, 5.30A. 9.30A. 1.16P. 5. SOP. 9. IOC Stirt - 3:20*. ll"2A. 7,.20P 699* 342« ROf density . 4 IbS/cu ft, 4 Ibs/cu ft 0.12 3.94* 4.22* 0.04* �PROCESS MU AMES MUNICIPAL fOHUL PLANT UNIT W. 1 •Nut based « 24 kr dtu D»U 3-8-80 12* Tine 1A 2A 3A 4A $A 6A 20 18.2 23 21.2 1$ 13.1 1$ 13.1 2P 3P 4P $P 6P 7P 8f 9P IIP Mean 30.$ 28.0 29.$ 27.2 28 2S.7 31 26.7 32 29.5 32.$ 30.2 3$ 32.6 3$ 32.6 33 30.* 32 21.7 31 28.6 27.8$ 25.66 6.01 $.79 124 23$ 260 27$ 28$ 280 27$ 250 240 26$ 280 290 31$ 317 303 278 262 239.33 61.67 850 650 850 83$ 8$$ 8$$ 8$$ 850 850 84$ 850 850 850 8$0 860 8$$ •SO 870 851.05 6.08 8W 890 900 900 90$ 910 870 88$ 89$ 900 910 900 89$ 89$ 900 870 88$ 90$ 893 12.93 13$ 134 130 24$ 270 280 290 29$ 290 270 2$$ 280 29$ 300 328 33$ 318 28$ 280 251.4 62.96 310 30$ 30$ 18.2 2*5 170 16$ 16$ 19$ 12$ 12$ 860 850 84$ 850 850 850 89$ 900 882 900 »00 860 FeedHiter flew rate 1000' s Ibs/hr 2?$ ISO 17$ 17$ 203 Feedmter twp °F ro i IP 121 31.$ 29.2 Steia teMpenture F Ln -vl 11* 32.$ 30.1 Steia pressure pstg O 10A 29.$ 31.$ 27.1 29.2 20 18.2 Stem flOH rite 1000's Ibs/hr N> 9A 27 2$ 20 37$ 340 330 32$ 34$ Sross Net 8A 23.$ 21.7 30.$ 28.3 W 7A • 10P o • 1 17 3* 10 fins MPS 4$ 44 10 fins press pslg $.6 30 21 370 370 370 370 370 380 37$ 380 38$ 38$ 38$ 380 380 370 360.2 25.81 33.0 33.$ 31.0 31.$ 31.$ 30.$ 31.$ 31.0 31.6 33.4 33.2 33.$ 31.3 31.0 CM! 32.03* 1.17* 28.17 $.4 -No KOF 4 AM 01 -9 AM ROF an 3.$ FO fins net 370 34.0 on Excess llr 1 360 32.$ Fuel feed rite (coil) 30.5 40212.$ 1000's Ibs/kr 78752.0 Fuel gauge readings (Ullons/nr fuel all $7*1.1 Mtf 0.56 30 33 $0 $0 $0 21 20 20 19 19 20 21.$ 21 19 18 19 19 19 19 19 19 2$. 48 10.9 42 43 44 42 42 42 47 47 47 47 46 46 46 4$ 46 4$ 46 46 47 4$ 4$ 4$ 4$ 1.72 28 28 28 28 28 28 30 30 30 30 30 30 30 29.$ 30 30 30 30 31 30 30 30 29.44 0.97 $ FurMCe drift pslg 30 4 3 3 3 4.$ $ $.0 4.3 4.$ 4.2 3.7 3.0 3. $4 1.03 0.51 0.$ 0.$$ 0.$ 0.62 0.61 O.S3 0.10 662* 327« 10.33* 8.23* 1.07 0.$ 0.3$ 0.32 0.6 0.6$ 0.64 Flue «as imp °F laller exit ESP Ulet 0.6 0.$ 0.6 0.$ 0.3$ 0.6 O.t$ 0.$ 0.6 0.$ MO 320 0.3 660 330 660 330 670 330 670 340 660 320 660 320 660 320 660 320 680 340 JUbient ten* °F 27 26 26 26 24 24 21 21 20 21 24 26 28 29 31 34 34 3$ 3$ 34 33 33 32 32 28.17 4.99 tafcieat press Inches Hg 28.92 28.92 28.92 28.93 28.93 28.94 28.97 28.96 28.98 29.03 29.04 29.06 29.0$ 29.04 29. 06 29.05 29.07 29.0$ 29.07 29.07 29.0$ 29.0$ 29.07 29.0$ 29.01 0.06 fnnMfnlT Kft finlsk SUrt - Ash Md Fly Ask teaov.l 4.30*. B.JO*. 12.30P. 4.30P. 8.30P 12.$$*. S.IOA. 9.00A, LOOP. 5. OOP. 9. SOP SUrt - S.20*.°ll.30A. 8P RDF density per shift 4 Ibs/cu ft. 3 Ibs/cu ft. 4 Ibs/cu ft �PROCESS MTA /WSMMICIPALPMER PLANT UNIT NO. 7 DatE 3-9-80 •Not based on 24 hr data Tlae tU 1A 2A 3A 4A 5A 6A 7A 8A 9A 28.0 25.4 26.5 24.2 26.0 24.0 25.0 23.1 25.0 23.1 15.0 13.1 15.0 13.2 15.0 13.3 15.0 13.2 25.0 23.0 25.0 23.1 26.0 24.6 247 225 220 215 212 170 122 121 130 212 210 225 12M Gross Net Steaa flan rate 1000's Ibs/hr 10A HA UP Mean a IP 2P 3P 4P 5P 6P 7P 8P 9r 26.5 24.3 27.0 24.7 26.5 24.3 25.5 23.4 16.5 14.5 16.0 IS.O 16.0 14.2 16.0 14.2 16.0 14.2 16.0 14.2 16.0 14.2 16.0 14.2 20.9 18.) 5.31 S.12 230 230 225 220 135 130 131 131 131 135 135 135 178 46.7 12.3 12N 10P Steaa pressure pslg 860 885 890 855 870 865 845 850 850 850 845 850 650 850 845 850 845 845 650 850 850 850 854 895 900 880 885 835 880 690 900 895 900 905 860 895 900 900 900. 900 885 890 895 675 885 885 888 15.5 260 240 235 228 22S 205 125 130 130 220 230 235 240 245 235 230 140 140 142 142 142 146 142 144 181 59.3 Feeduater teap °F O 1 OO 850 880 Feednater flow rate 1000's Ibs/hr rO to O* 840 Steaa teaperature °F 375 360 360 353 350 335 300 300 310 360 360 360 355 360 370 360 320 325 320 320 320 320 310 315 338 24.0 fuel feed rate (coal) 1000's Ibs/hr Fuel gauge readings Fuel oil 33. S 29.5 29.2 24.0 27.5 25. 0 19.1 18.3 17.5 31.0 31.5 31.0 30.7 32.0 30.5 30.5 19.5 19.0 19.3 19.3 19.0 19.8 20.0 19.3 24.8 23.7 6.25 NA NA Oil 405 590 S.75 790815 579 240 4.4SA- RDF -NO RDF Excess air S 20 17 20 25 27 40 >50 >50 >50 26 20 22 28 20 22 22 47 47 46 46 46 43 45 45 34 12.6 ID fans aaps 45 44 44 44 44 42 42 42 43 46 46 46 46 46 45 44 42 42 42 42 42 42 42 42 44 1.6 FD fan aaps 30 28 30 28 28 28 28 28 28 30 30 30 30 30 30 30 25 27 27 27 27 27 27 27 28 1.5 FD fan pressure 4.2 Furnace draft pslg 0.50 0.70 0.70 0.40 0.42 0.65 0.63 0.58 0.70 0.60 0.50 0.60 0.60 0.50 0.40 0.70 0.65 0.65 0.61 0.61 0.60 0.67 0.61 0.62 0.59 0.092 600 640 640 640 650 640 640 640 600 600 629* 20.2* 265 310 320 320 310 320 320 320 280 280 29 30 38 40 43 44 45 45 46 46 46 43 42 26.85 28.84 28.83 28.80 28.80 28.79 28.82 26.81 28.82 28.62 28.82 28.82 teller 1.05 flue gat ESP Inlet teap °F Aabtent teap °F 31 31 30 28 27 26 26 Aablent pressure Inches Kg 29.07 29.05 29.04 29.02 29.01 29.00 28.96 28.94 Comments lot tea and Fli> Ash Re•oval 27 28.69 28.88 SOOt BlOMI SUrt 4.30A. 11.SO*. 8.03P ROF density - 4.0 tbs/cu ft 305- 40 21.1* 3) 38 37 7.5 28.81 28.78 28.69 O.D97 �PROCESS MIA AMES MMICtMl POME* PLANT UNIT NO. 7 Date 3-10-4)0 •mil based M 24 ar data Tlae MM I2M Sross 1A lf.0 14.0 135 Net Steaa flow rate 1000- « Ibs/fcr U.O 2A ' 3A 14.0 li.O 14.1 U.O 135 137 4A 15.0 16.0 14.1 134 134 5A 6A 7A 8A 9A 10A IP 2P 3> 4P 16.0 14.1 U.O 14.2 2».0 26.6 33.5 30.* 35.0 32.3 35.0 32.1 35.0 32.3 15.0 12.4 35.0 12.4 35.0 32.3 35.0 32.3 15.0 32.1 li.O 32.1 35.0 32.1 130 130 250 310 320 310 310 310 310 310 310 300 310 11A 12N 5P 6P 8I> 9P 35.0 12.1 35.0 32.4 15.0 32.2 35.0 12.1 35.0 12.4 29.1 a.; 8.77 8.43 305 305 311 11 1 307 270 254 80.2 9.1 7P 10P UP Mean • Steaa pressure psli 850 850 ISO 850 850 850 860 835 860 860 860 860 865 860 860 845 855 855 850 855 862 845 825 853 •93 880 891 888 IBS 880 882 900 898 902 90S 904 870 885 902 900 890 904 890 900 895 895 900 860 892 11.5 Feeduater flow rate 1000' i Ibs/kr 144 14S 14S 134 140 146 140 235 320 320 325 325 330 325 320 320 325 320 320 320 320 325 330 300 266 83.1 Feeduater teap °F rO N> •SO Steaa teaperatura °F 315 315 315 310 308 305 340 380 390 3*0 390 390 390 390 390 390 390 380 380 380 380 380 380 M2 34.9 Fuel feet rate (CM!) 1000' s Ibs/kr Fuel gauoe readings 19.5 20.0 20.0 17.1 14.5 25.7 37.0 38.0 38.0 38.5 36.5 37.0 37.0 36.5 32.0 33.0 33.6 34.1 34.0 33.0 35.8 31.9 9.03 Coal on 28.8 11.2 4.17 Fuel oil 310 19.6 17.0 40* 538 713 541 S7»l§0 ao RDF RDF- M M -Start ROF at 3.I2P Excess air I 44 4* 42 46 44 42 43 16 18 16 16 It 16 16 17 14 16 16 17 17 17 17 17 17 24 12.9 10 fans aaps 42 42 42 42 42 41 41 46 47 47 48 48 47 47 48 46 46 46 46 47 47 47 47 45 45 2.5 t.O 6.0 6.5 6.0 6.0 6.0 6.5 6.5 6.0 6.1 6.2 6.7 7.6 5.9 5.4 1.32 28 28 28 28 27 27 30 30 30 30 30 30 30 30 30 30 30 30 31 31 30 32 30 30 1.3 0.40 0.65 O.S7 0.60 0.65 0.65 0.55 0.60 0.65 0.60 0.60 0.60 0.65 0.60 0.55 0.55 0.61 0.55 0.55 0.65 680 690 690 690 680 680 680 680 690 690 10 fans pressure pslg 3.6 FO fins aaps 28 FO fan pressure psti 2.3 Furnace draft psig 0.60 1.18 0.43 0.58 •0.60 •oiler flue (as teap 340 340 340 340 340 340 340 340 340 36 36 36 38 38 38 38 33 26 23 22 21 21 21 22 22 22 22 22 Aabient pressure Inckes Hg 2S.74 28.72 28.70 28.6) 28.68 28.69 28.69 28.67 28.74 28.79 28.87 28.94 28.97 29.02 28.90 29.02 29.05 29.06 29.13 29.15 29.16 29.17 Cnaaentt aottoa an* Flf Ask Reao»al Start - 12. MA, 4.30A. I.30P. 4.27P. 8.10P FUtsk - 12.50A. 5.00A. 4.1W. 5.42P. lO.JOf Soat How* Surt • 4^6A. 11. lo»- i OOP ROF density • 4.0 Ibs/cu ft 21 20 5.3« 340* 340 35 0.036 685* Aafctent leap °F ESP Inlet taw *F 0.60 0.0* 27 20 19 29.18 29.19 28.91 7.5 0.195 �PROCESS DATA AMES NMICIPAL POME»PUU(T UNIT NO. 7 ant 3-ii-ao •Not based on 24 hr data lime 12H 1A 2A 3A 4A Gross Net 30.0 27.5 22.0 19.8 21.0 19.0 20.6 18.5 20.5 18.5 Stew flow rtte 1000' s Ibs/hr 260 200 170 171 Stet* pressure pslg 845 855 850 Stew temperature °F 900 870 880 Feedwtter flow rtte 1000' s Ibs/hr 276 230 Feeduater te»p "f 370 360 Fuel feed rtte (cotl) 1000' s Ibs/hr Fuel gauge retdlngs 29.1 21.5 HI o 1 «J 0 Fuel oil ROT 5A 6A 7A 8A 9A 10A 20.5 18.4 20.5 18.5 30.0 27.5 34.0 31.4 35.0 32.2 35.0 32.4 171 170 170 260 305 310 315 320 850 860 840 855 865 850 850 855 885 893 aao aao 900 910 900 910 185 185 185 194 185 272 315 330 325 330 330 330 330 330 360 380 390 390 15.6 16.5 18.0 17.0 25.0 34.5 35.0 36.5 18.5 IP 2P 3P 4P 5P 6P 7P 8P 9P 10P UP 35.0 32.3 35.0 32.4 35.0 32.4 35.0 32.6 35.0 32.5 35.0 32.4 35.0 32.4 35.0 32.4 35.0 32.3 35.0 32.4 31.0 18.4 30.8 28.0 6.10 6.20 320 320 315 315 320 320 320 328 325 330 325 290 277 62.8 855 855 855 855 855 855 855 860 860 860 870 860 860 855 6.24 905 890 885 906 900 900 895 905 900 900 890 880 880 894 11.2 330 330 338 325 330 330 330 330 330 330 330 325 300 277 78.5 390 390 385 390 390 390 390 385 385 385 385 385 380 372 23.6 35.0 34.0 33.0 33.0 32.5 32.8 33.0 33.0 33.0 33.0 30.8 Coal 21.1 30.3 7.08 11A 12N 35.0 35.0 32.3 32.4 35.0 34.0 on 412 375 797 281 579 490 Net* o NA 11.25 NA Excess tlr t 20 26 30 22 25 35 30 20 19 19 17 16 17 18 20 17 18 • 17 17 17 18 17 17 17 20 5.1 ID hns wps 46 44 42 44 44 44 33 46 46 48 48 48 48 48 47 47 46 46 47 47 47 47 47 47 46 3.1 6.0 1.18 28 28 28 28 30 30 30 30 30 30 31 30 30 30 30 31 31 31 31 31 30 30 1.1 0.58 0.60 0.58 0.60 0.56 0.54 0.58 0.024 664* 37.3* 10 ftns pressure pslg 6*0 3.8 4.6 FO ftn taps 30 28 28 Furiuce drtft pslg 0.60 0.55 0.58 0.55 0.60 0.63 660 680 686 680 690 700 340 340 340 340 340 340 340 340 323* 27.1* 24 28 30 32 32 33 33 33 34 33 32 32 32 32 25 7.9 29.11 29.08 29.06 29.05 29.08 29.08 29.08 29.08 27.06 29.06 29.14 0.061 0.60 0.60 0.57 0.58 0.60 0.60 0.55 620 600 600 660 670 700 700 280 ESP Inlet tt»f "f 280 280 280 320 340 340 16 15 15 15 15 17 20 Aibient imp °F 17 17 Agilent pressure Inches Hg 29.19 29.19 29.19 29.20 29.21 29.21 29.20 29.20 29.17 Cownts 0.60 700 0.54 615 0.58 taller flue aas te-pOF 16 Button and Fly Ash Removal Start - 12.30*. 4.30*. 8.29A. 12.30P . 4.30P. 8.23P Finish - 1.10A. 5.30A. 9.15A. 1.39P. 5.15P. 9.5SP 0.60 0.55 29.21 29.18 29.15 29.14 29.19 Soot Blow Start - 4. 30A.~11.AOA. 8.10P. 11 .OOP ROF density - 4 ,0 Ibs/cu ft. 4.0 Ibs/cu ft. 4.0 Ibs/cu ft �PROCESS PATA AMES MUNICIPAL MUCH PLANT UNIT NO. 7 Date 3-12-80 •Not based «« 24 kr data 1A 2A 3A 4A 5A «A 7A 6A 9A 21.0 19.0 21.0 19.0 21.0 19.0 20.5 11.4 21.0 19.0 21.0 18. » 29.0 26.6 32.5 10.0 34.5 31.8 35.0 12.1 16.0 11.1 36.0 1 . 11 Steam flo« rate 1000'i Ibs/kr 165 180 180 170 175 175 250 291 310 325 325 Steam pressure psig 850 850 850 640 850 650 860 860 850 855 Steam temperature °F 880 890 880 880 690 880 900-890 885 910 Feeduater flan rate 1000' s Ibs/kr 190 190 190 190 190 195 270 290 320 FeedMiter temp °F 340 320 320 320 340 340 160 380 Fuel feed rate (coal) 1000's Ibs/kr Fuel gauge readings 19.0 17.2 20.1 19.3 17.5 19.0 10.0 32.8 Tim* HU O ' 12N Cross Net Fuel oil IP 2P 3P 4P SP 6P 7P 8P 9P 15.0 12.1 35.0 32.2 35.5 12.9 35.5 32.9 15.5 32.9 36.0 31.5 16.0 11.4 3S.O 12.4 15.0 12.1 15.0 12.4 15.0 12.4 32.0 19.5 11.2 27.1 6.26 7.99 325 325 325 325 325 325 130 325 125 320 10 1 120 260 255 94.0 655 855 855 855 865 855 855 855 860 660 660 660 870 650 655 5.1 900 910 900 910 900 900 895 900 890 890 870 680 905 890 691 11.0 335 335 135 335 325 330 330 335 335 338 15 1 350 10 1 126 290 279 80.2 380 380 390 390 390 390 390 390 390 390 365 385 185 380 380 360 370 25.2 35.6 38.0 35.0 35.0 15.6 35.0 35.0 34.5 34.5 33.5 34.0 15.2 36.3 11.5 33.4 32.8 Coal Oil 30.5 7.11 31.0 NA 12.01 NA 10A 11* I2N 10P 416 106 (00 7SS 579 760 •OF UP Nean a 7.45A only 1 conveyor 9. 00* botn conveyors on Excess air S 30 30 30 30 29 27 20 19 19 16 19 15 18 22 15 14 16 14 15 15 16 20 14 24 20 10 fans amps 44 41 43 43 42 43 45 45 46 47 47 47 46 48 47 46 46 46 47 47 48 46 47 45 46 1.1 IP fans pressure 4.1 4.8 4.« 3.8 5.3 4.0 5.6 6.4 6.0 6.0 7.0 7.0 7.5 8.0 7.0 7.0 7.0 7.0 6.8 6.8 7.4 7.2 6.5 6.0 6.2 1.20 27 27 27 27 27 29 30 30 30 30 30 30 30 30 30 30 30 31 11 32 11 31 30 26 6.2 0.64 0.64 0.60 0.60 0.54 0.60 0.58 0.59 0.58 0.58 0.55 0.55 0.70 0.60 0.60 0.60 0.60 0.60 0.62 0.70 0.68 0.64 0.61 0.61 0.042 toller flue gas temp °F 620 605 640 675 680 700 700 700 680 680 680 690 700 700 675* H.I- ESP Inlet temp °F 295 300 320 320 324 325 335 335 335 335 340 140 340 340 127- 14.6* FD fan amps 27 FD fan pressure psig 1.6 Furnace draft psig 0.64 1.46 Ambient temp °F 31 30 Ambient pressure Inches Hg 29.03 29.00 28.48 Comments 5.9 30 30 30 30 26.96 28.94 28.94 31 31 26.97 28.96 lottom and Flv Ask « emoval Start - 12.30*. 4.20A. 8.30*. 12.3SP . 4. SOP. 7.0UP flnlsk - I2.55A. 5.03A. MSA. 1.4SP . S.20P. I.20P 31 31 31 30 30 30 1 0 12 31 29 29 26.92 28.89 28.88 28.85 28.84 28.83 28.60 28.79 28.78 26.76 28.62 Soot 8IOM Start - 4.20*. It. 00*. ,7.25P 29 28 27 26 26 1 0 1.6 28.82 28.82 26.82 28.62 28.82 28.66 0.079 RDF density - 4 .5 Ibs/cu ft. 4.0 Ibs/cu ft �PROCESS MIA AMES MUNICIPAL KMCR PLANT UNIT NO. 7 Date 3-13-80 •Not baud on 24 hr data 1A 2A 27.0 24.6 20.0 17.9 20.0 Stea* flax rate 1000' s Ibs/hr 240 165 12N Tine 1*1 Cross Net 3A 4A 5A 6A 7A 8A 9A 20.0 18.0 21.0 18. 0 20.0 18.0 IB. 9 29.0 26.6 32.0 19.5 16.0 35.0 13.4 32.2 15.0 32.4 165 165 162 170 260 295 330 320 IP 2P IP 4P 5P 6P 7P 8P 9P 35.0 32.3 15.0 35.0 32.3 3 2 . 4 15.0 12.5 35.0 32.6 35.0 32.5 15.0 12.4 15.0 32.4 15.0 32.4 15.0 32.4 15.0 32.3 15.0 32.4 13.0 30.4 11.2 28.1 6.11 6.16 320 120 120 120 120 320 320 320 320 320 320 320 320 290 268 82.2 IDA 11A 12N 10P UP Mean o Steaai pressure pstg 850 830 850 850 835 835 865 850 860 855 855 855 855 855 855 855 855 850 860 860 860 850 860 660 851 8.6 Steu temperature °F 885 860 895 895 885 865 895 890 915 895 900 905 900 905 900 905 900 900 900 895 890 890 880 890 891 12.2 Feednater flon rate 1000' s Ibs/hr 250 120 125 180 182 190 263 300 110 330 10 1 330 110 310 330 310 130 310 310 10 1 330 10 1 10 1 100 286 71.0 Feeduater teap °F 180 330 325 325 325 330 365 370 380 380 385 385 IBS 385 385 385 385 385 185 185 185 185 385 180 171 23.4 Fuel feed rate (coal) 1000' s Ibs/hr Fuel gauge readings 26.1 16.7 20.1 19.6 21.0 20.5 30.1 33.4 41.5 40.5 40.0 40.0 40. S 40.5 41.0 15.6 14.8 14.0 16.8 15.4 11.2 11.9 9.81 33.4 NA 2.08 NA Fuel oil 16.5 41.5 15.4 Coal Oil 419 922 804 395 580 050 7.15A only 1 conveyor 7.40A both conveyors 8.3SA- RDf 9.05P Syste* •A" off 9.25P System "A" on -Start RDF at4.0BP Excess air f 20 >50 18 39 18 38 18 17 14 16 17 18 18 18 18 18 16 17 19 18 18 20 17 23 23 9.8 ID fans amps 45 42 44 43 44 44 45 46 48 46 47 47 47 47 47 47 46 46 47 46 46 47 46 46 46 1.5 FD fan aups 29 27 28 27 28 28 29 30 31 10 11 JO 10 11 11 31 11 10 31 10 31 31 11 10 10 1.5 FO fan pressure psig 3.1 0.62 0.61 0.62 0.63 0.61 0.62 0.65 0.60 0.62 0.62 0.62 0.64 0.65 0.64 0.62 0.61 0.65 0.64 0.64 0.68 0.63 0.024 620 620 605 640 660 680 700 700 700 695 700 700 705 710 720 725 720 720 725 675 686* 37.5* 280 280 280 310 320 130 330 335 335 335 335 335 335 335 335 135 335 315 135 335 26 25 25 24 24 25 26 29 30 31 31 31 31 31 11 31 31 29 29 29 28.79 28.78 28.79 28.79 28.79 28.77 28.76 28.76 28.80 28.80 28.86 28.88 28.87 28.91 28.97 29.03 29.07 29.08 29.10 29.11 29.11 28.89 0.127 0.66 0.70 0.60 frailer flue gas teap °f ESP Inlet ump "f Anbient temf "t 26 26 Avbient pressure Inches Kg 28.82 28.81 28.80 Cowents 26 Bottoa and fly Ash Removal SUrt - 12.30A. 4.28A. B.10A , 3. OOP. 4.35P. 8.30P , 10.30P Finish - l.OSA. 5.12A. 9.26A. 3.50P. 5.20P. 9.35P. 10.44P Soot Blown Start - 4.07A RDf density - 4.5 Ibs/cu ft, 4 .0 Ibs/cu ft 0.66 324- 27 28 20.12.6 �PMCtSS DAI* MKS NMIC1ML NUEt PLANT UNIT NO. 7 Date 3-14-80 •Nat •tied on 24 hir dltl 12H Tie» 1A 2A 1A 6A 7A 8A 9A 35.0 12.7 US 165 165 177 300 315 320 840 850 MS MS 860 855 900 900 890 860 895 900 90S 180 180 180 176 185 180 300 370 315 335 335 335 330 335 380 30.7 20.8 18.8 18.2 19.3 19.9 20.3 31.3 35.0 35.0 35. 0 269 165 166 Steu pressure pslg MS MS MS Stem temperature °F 885 MS Feedmter flow rite 1000' s Ibs/hr 275 FeedMter teap °F Fuel feed rite (coil) 1000' t Ibs/hr Fuel 9«H9e railings Fuel ell «DF Excess ilr X 424 007 808 295 590 100 18 12N IP 2P 3P 4P 5* 6P 7P 8P »P 10P IIP Neu a 35.0 32.4 35.0 32.4 35.0 32.2 3S.O 32.3 35.0 12.4 35. 0 31.8 32\4 29.2 34.0 31.4 15.0 32.1 1S.O 32.4 14.0 11.2 32.0 29.4 10.0 27.4 10.5 28.0 6.25 6.01 310 315 115 315 315 115 310 283 300 305 317 305 280 260 270 62.8 860 850 860 ass ass 855 ass 850 850 850 ass 850 850 870 840 852 7.0 905 900 900 900 910 900 900 895 895 880 900 900 900 860 900 894 12.5 330 325 325 325 125 320 320 120 120 290 310 330 345 315 295 280 281 61.3 380 385 385 385 385 385 385 385 3M 380 380 380 390 385 180 180 171 21.8 34.0 36.5 36.0 36.5 34. S 33.0 32.0 31.0 38.0 32.6 35.0 30.S 32.4 Coil Oil 20.0 20.0 18.0 It.O Cross Net HA 10A 21.0 33.0 19.8 30.5 20.0 17.8 Ste*a f low r<te 1000' s Ibs/hr rO CO 5A 20.0 20.0 18.0 17.9 31.0 28.4 MM 4A 30.4 30.7 1.75 NA NA 15.0 35.0 12.1 32.4 6.64 7.35A only 1 conveyor 7.4SA both coiweyors on 43 >50 43 42 39 36 IB 13 15 15 18 16 16 18 18 17 19 18 17 20 16 IS 24 24 11.3 48 47 47 45 45 45 1.5 ID fens ups 45 43 43 43 43 43 43 45 46 46 46 46 46 46 46 46 46 45 45 FD f» ups 30 27 27 27 27 27 27 30 30 30 311 30 30 30 30 30 30 29 30 32 31 30 29 30 29 1.5 FO fin pressure pslg 4.0 2.9 2.0 1.8 FurMce drift pslj 0.59 0.61 0.7) 0.68 0.61 0.60 0.65 0.61 0.60 0.59 0.7S 0.60 0.65 0.60 0.60 0.62 0.60 0.60 0.62 0.70 0.60 0.62 0.044 615 620 600 630 660 680 685 685 690 665 680 680 685 690 680 690 715 700 690 650 660 669* 30.2* 290 290 290 315 330 335 335 335 335 335 135 15 1 335 335 130 335 335 335 315 130 320 326* 16.9* 21 21 21 21 21 26 34 40 42 49 48 50 52 54 53 51 49 46 42 41 40 37 29.13 29.13 29.11 29.11 29.16 29.11 1.01 taller flue «is te-p<>F EiP Inlet leap 21 1.12 Aablent teap °F 23 27 Anblent pressure Incus Mi 29.11 29.11 29.11 29.12 29.12 Convents 29.13 29.13 29.13 29.12 Bottom end fit Ash Neaonil SUrt - I2.27A. 4.28*. I.82A. 12.30P, 4.30P . 8.30P FUlsh - l.OOA. 5.10A. 9.25A. I.52P. S.OOP . 9.5SP 0.60 0.58 29.11 29.10 29.10 29.10 0.«2 29.09 29.09 29.08 29.09 29.10 29.13 SOOt 8 0 I 1 M SUrt - 4.10A, 11.20*. 8.481' RDF density - 4 .5 Ibs/cu ft. 4 .5 Ibs/cu ft 12.6 0.019 �PROCESS DATA AXES MUNICIPAL POWER PLANT UNIT NO. ? Date 3-15-80 •Hot based aa 24 hr data 1A 2A 3A 4A 5A 6A 7A 8A 9A 29.0 2C.6 19.0 17.0 24.5 22.4 24.0 22.0 24.0 21.9 24.0 22.0 24.0 22.0 24.0 21.6 28,0 25.8 30.0 27.2 31.5 28.9 31.0 28,4 Steaa flov rate 1000's Ibs/hr 245 159 212 201 201 205 205 207 240 260 280 Steaa pressure pslg 835 830 835 850 850 875 855 850 850 855 Steaa teaperature °F 890 880 890 880 905 885 885 885 905 900 Feedwter f low rate 1000's Ibs/hr 256 170 220 210 208 215 215 215 245 FeedMter teap °F 370 335 355 3SS 355 155 355 155 Fuel feed rate (coal) 1000's Ibs/hr Fuel gauge readings 29.6 19.0 24.8 30.1 29.4 10.4 Tlae HU 12N Cross Net CO N3 Fuel on 27.3 19.5 IP 2P 3P 11.0 28,4 16.5 14.4 17.0 15.0 16.0 14.0 282 278 135 118 855 858 855 845 905 860 895 895 265 285 291 281 155 365 375 378 11.5 31.5 35.0 34.4 10A 5P 6P 7P 8P 9P 10P UP 16.0 14.0 16.0 14.0 16.0 14.3 16.0 14.2 16.0 14.3 16.0 14.2 16.0 14.2 16.0 14.2 21.7 19.6 135 135 135 135 135 135 U5 115 135 186 850 850 850 845 850 850 850 850 850 850 850 8.6, 900 895 895 885 880 890 890 870 880 880 888 11.1 145 145 145 145 145 145 145 145 140 145 145 194 54.0 375 330 325 325 315 315 120 320 320 320 320 120 330 69.4 11.5 19.5 19.0 19.0 17.0 18.0 18.2 18.1 18.5 19.0 18.8 18.1 24.2 24.0 6.60 UN 11A 4P Coal on 427 756 430 705 811 911 814 720 580 190 581 100 Mean o 5.95 5.68 55.06 37.92 HA HA Midnight readings, 3-15-80 No ROF RDF Encess air I 24 50 30 29 39 38 36 30 24 19 20 20 21 >50 >50 >50 >50 >SO >SO »50 >50 »50 >50 >50 39 12.5 10 fans aaps 45 41 44 43 44 45 44 45 45 46 46 46 46 42 42 41 31 31 41 41 41 41 41 41 42 4.0 10 fans pressure pstj 5.7 28 28 27 28 29 29 29 30 30 30 10 30 27 27 27 27 27 27 27 27 27 27 27 28 1.4 0.80 0.90 0.90 0.81 0.82 0.90 0.78 0.81 0.72 0.73 0.70 0.70 0.68 0.72 0.68 0.68 0.70 0.69 0.70 0.74 0.60 0.60 0.74 0.092 660 600 600 600 600 625* 27.3* FD fan aaps 30 FO fan pressure psl9 4.3 Furnace draft pslg 0.61 Holler flue gas teap OF 0.88 630 640 640 615 645 650 680 670 600 605 610 610 600 595 305 ESP Inlet teap °F Aablent teap °F 40 40 19 Aablent pressure Inches Hg 29.16 29. M 29.1229.11 38 305 305 110 310 120 325 325 325 290 285 285 275 270 275 275 275 275 275 38 38 35 14 40 48 55 60 62 64 64 65 65 64 61 59 56 54 54 51 51 29.08 29.05 29.07 29.44 29.04 29.03 29.00 29.02 28.96 28.92 28.88 28.87 28.89 27.89 28.90 28.90 28.90 28.90 28.87 28.87 28.48 8ottoa and Fly Ash Reao»al Start - l.OOA. 4.28A. 8.30A. 12.39P. 4.37P. 8.30P Finish • I.27A. 5.00*, 9.03*, 1.15P. 5.OOP. 9.0SP Soot BlQMi Start - 3.58*. 10.30*. 8.40P RDF density - 1.5 Ibs/cu ft 295* 20.211.2 0.098 �PROCESS MIA IS MUNICIPAL POME*. flMT UNIT JO.. 7 •Not based on 24 nr data Bate 3-17-80 12M Tie* 1A 2A 3A 4A SA 6A 7A 8A 9A 16.0 14.0 16.0 14.0 16.0 14.0 16.0 13.9 16.0 14.0 28.0 25. 9 32.5 29.8 34.8 32.3 35.0 32.3 3S.O 33.2 130 130 130 130 IX 265 270 310 310 315 10A 11A 4f SP 6P 7f 8P 9f 34.5 33.8 34.5 31.9 34.5 31.9 35.0 32.4 35.0 32.4 35.0 32.3 35.0 32.3 35.0 32.3 30.5 27.» ' 29.5 27.2 7.74 7.S8 310 310 310 310 310 310 310 320 320 260 259 76.1 IP 2P 35.0 33.2 34.5 31.7 34.5 31.6 315 310 12N 10P UP Mean a * NU Gross 28.0 Net Steam flan rate 1000' s Ibs/br 243 160 Steaa pressure pslg 845 840 850 850 •SO 850 •SO 850 835 855 855 855 855 850 850 850 •SO •SO 860 860 850 •SO 850 850 •50 5.3 Steam teeperature °F 890 •80 890 880 870 900 890 885 900 900 900 910 900 880 895 900 900 900 890 900 890 890 880 890 •92 9.4 FeeAuter flon rate 1000' s Ibs/kr 255 188 140 140 141 140 140 265 2S6 320 315 320 320 326 320 320 320 315 320 315 330 330 320 270 268 74.5 Feedueter teap °F N) 25. S 22.0 20.0 365 340 320 320 320 320 320 375 380 380 380 380 380 380 385 385 385 385 385 385 385 385 385 380 367 26.3 Fuel feed rate (coal) 1000' s Ibs/kr Fuel gauge readings Fuel oil 32.4 22.0 18.6 19.4 17.6 18.9 18.9 34.5 39.6 36.5 36.6 37.5 38.0 35.0 34.5 33.5 34.0 33.0 33.4 36.8 35.2 33.5 29.6 on Coal 30.9 31.2 2.92 7.23 HA NA 434 476 818 349 581 370 tIO:10A7 No «OF- MFEicess air X 22 35 >50 1.0. fans aaps 46 1.0. fans pressure F.O. fan aaps 30 27 27 F.O. fan pressure pslg 3.8 3.1 0.42 0.64 0.59 >50 44 44 No Ulf 11:05A 19 >50 46 21 42 48 17 47 18 48 17 20 46 47 -Start WF at 1 :40P 21 17 47 46 18 46 16 46 16 18 16 46 46 20 18 16 24 26 13.3 47 47 46 45 46 1.6 2.1 Furnace draft pslg 43 >SO 4.8 44 43 >50 33.5 46 1.00 27 27 27 30 27 32 30 31 30 31 31 30 30 30 30 30 31 31 31 30 30 0.65 0.55 0.60 0.60 0.69 0.58 0.55 0.60 0.63 0.60 0.55 0.60 0.60 0.60 0.70 600 600 600 645 670 680 785 695 700 695 665 675 675 0.50 280 280 280 320 320 330 330 330 330 330 330 330 335 32 31 31 31 30 29 29 29 29 29 32 36 36 41 41 42 42 42 41 Aablent pressure Inches Ng 29.04 29.04 29.03 29.03 29.05 29.05 29.05 29.06 29.12 29.10 29.14 29.11 29.10 29.10 29.08 29.09 29.08 29.08 29.13 29.16 29.16 0.52 0.70 335 32 0.70 lotto* and Fly Ask la•oval 1:3SP. 10:OOP Soot llOMi 39 0.074 48.9* 319« 0.54 0.59 669* 0.44 685 Aabient teap °F ESP Inlet leap °F Finis* - 6:OOA, 1.6 1.09 toller flue gas teap Coaaents 30 21.3- 34 4.9 36 34 34 29.15 29.14 29.14 29.09 0.043 �PROCESS DATA AMES tUIICIPAl POHE* PIAIIT UH1T HO. 7 •Not b»ed on 24 kr diU Dite 3-18-80 1A 2A 3A 4A SA 6A JA BA 9A IDA I1A 12M IP 2P 3P 4P SP 6P 7P 8P 9P 10P HP 29.0 Z6.6 27.0 24.9 26.5 24.4 25.5 23.4 25.5 23.4 25.5 23.5 27.0 24.8 31.0 28.6 35.5 32.8 36.0 33.4 35.5 33.1 35.0 32.4 35.0 32.5 35.0 32.5 35.0 32.4 35.0 32.5 33.0 30.6 32.5 30.1 32.0 29.4 35.0 32.2 35.0 32.4 35.0 32.4 32.0 29.3 29.0 26.4 31. « 3.84 29.3 3.65 Stew flo« rate 1000* s Ibs/kr 240 230 230 222 220 220 240 275 31S 325 320 320 320 320 31S 315 300 295 295 319 315 310 285 251 283 40.0 Steal pressure pslg 845 835 850 855 840 850 850 850 855 860 855 855 855 850 850 850 850 845 B45 855 850 855 835 855 850 6.3 835 880 870 885 685 90S 910 900 875 900 900 910 900 900 880 BBS BBS 880 895 900 BBS 890 16.2 251 295 324 335 330 338 330 330 330 330 305 310 300 330 325 311 300 260 295 38.1 11.7 Tim Ml Gross Net 12M Nun o SteM teaperiture °F 895 90S 885 FeedMter flow rile 1000' s Ibs/kr 250 245 241 240 235 240 FeedMter teap °F 365 360 360 355 355 355 360 370 380 385 385 385 385 385 385 385 380 380 380 385 385 385 380 370 375 Fuel feed rite (coil) 1 0 ' s Ibs/kr 00 Fuel Muoe reidlngs Fuel olT «OF 30.1 31.1 438297 822 025 581 440 27.0 24. S 28.4 23.9 28.2 32.5 39.5 38.0 36.0 34.5 35.5 35.5 33.5 35.0 33.0 32.0 31.1 32.6 32.7 32.5 31.2 29.3 Coil on 32.0 3.84 31.6 HA 2.50 NA Excess ilr 25 33 23 18 26 25 20 19 18 20 20 17 22 19 23 20 20 19 20 IB 16 IB 20 21 21 3.6 1.0. fins ops 45 45 44 44 44 44 44 45 47 46 46 46 46 47 46 46 46 45 46 46 46 46 47 45 46 0.98 1.0. fins pressure pslg 5.3 F.O. IMS UPS 29 30 29 27 28 28 28 30 32 30 30 30 30 30 30 30 30 29 30 30 30 30 30 29 30 1.0 2.3 2.5 3.0 3.0 5.0 6.0 4.8 4.8 4.8 4.1 0.97 0.65 0.57 0.45 0.61 0.60 0.60 0.70 0.60 0.70 0.60 0.50 0.75 0.53 0.55 0.50 0.40 0.60 0.80 0.65 O.SI 0.59 0.098 625 625 635 650 695 695 695 68S 680 680 695 700 690 690 690 680 680 680 675 676* 24.0* 305 305 310 320 330 330 330 330 330 330 330 335 330 330 330 335 335 330 320 326" 9.5- 34 34 34 34 37 44 51 56 62 61 64 65 66 64 62 59 55 54 50 49 12.8 29.13 29.13 29.12 29.12 29.13 29.10 F.D. fin pressure pslg 3.6 4.4 2.6 Furnice drift pslg 0.6S 0.45 0.69 teller flue gis teap °F ESP Inlet teap °f Aablent teaperiture 33 33 33 Aabtent pressure Inckes Hg 29.14 29.14 29.14 29.14 fnearnts 1:50 P both connectors on 7:15 A only 1 connector 33 ppttoa tek Mid fly tefc jeaovil SUrt - 2:10A. 5:40A. 10:30A. 2:OOP. C:17P. 9:52P Finis. 6:OOA. 11:20*. 2:32P. 7:3SP. 10:1SP 0.60 49 29.09 29.09 29.09 29.08 29.02 29.02 28.99 28.98 29.00 2 . 0 28.96 28.96 28.96 28.95 2 . 6 0.071 90 90 Soot iloxn Stirt - 2:35A. 10:25A, 6:30A RDF density - 3.5 Ibs/cu ft. 4.0 Ibs/cu ft. 3.5 Ibs/ cu ft �PROCESS DATA MKS MMicirAi taut nun UNIT * 0. 7 •Not btud M 24 r deU 1 DtU 3-19-80 I2M Ttae Ml Cross U 2A 3* 4A SA M 2P 3* 4P 5P <P 7P 8P » 31.0 28.3 35.0 32.2 35.0 34.5 32.4 32.0 35.0 32.4 35.0 32.S 35.0 32.0 35.0 32.6 35.0 32.6 35.0 32.6 31.0 28.6 33.0 30.1 36.0 33.1 35.5 32.6 35.5 32.7 32.0 29.2 23.0 20.8 31.0 27.2 t.K 2O8 243 292 314 315 310 310 315 320 320 320 320 280 292 340 320 319 290 190 277 52.1 170 845 ISO 860 860 85S 850 845 855 855 855 855 855 845 845 845 865 860 860 850 853 7.0 8M 885 895 900 895 910 900 885 894 900 900 902 900 860 880 870 875 BBS 880 875 888 12.1 225 220 250 295 322 31S 325 325 325 326 325 328 325 295 305 349 345 325 295 200 287 50.6 355 350 360 395 380 385 385 38S 385 385 385 385 385 385 380 395 390 390 385 350 375 16.5 22.4 30.4 30.4 33.6 34.5 34.0 34.0 33.0 33. 5 39.5 39.0 39.0 31.0 33.5 35.0 33.3 33.9 31.6 19.5 31.1 31.4 4.17 5.74 M M 20 5.9 45 1.3 5.7 0.65 29 1.5 7* M 9A 1 M 11A 27.0 24.1 12N IP 10P UP 21. 0 U.O 2S.S 23.4 Stt» flo* r«U WOO1 s Ibs/br 175 220 215 212 Steal pressure pstg MS 855 850 845 Stetei temperature °F 875 885 8»5 885 Feeduiter flow r<U 1000' • Ibs/hr IBS 232 225 235 FeedMter leap °F 340 3M 360 355 Fuel feed rile (CM|) 1000's Ibs/kr fuel 9*uge reeding* Fuel oil 18.3 23.4 442 234 «2S i » S81 SOO Encess «lr I 40 24 1» 20 24 22 20 16 15 17 IS 18 16 18 19 17 17 22 18 18 12 15 18 32 I.D. fus «ps 43 43 43 44 43 43 44 45 46 46 45 46 46 46 46 46 46 45 46 46 45 46 45 43 I .0. fMis pressure pi 19 4 F.D. fUS UPS 27 Net hO O OJ I (Jl —• 25.0 2S.O 24.0 2S.O 22. « 22.f 21.8 22.8 205 29.S 30.2 24.2 Coal Oil 1-.10P'a 28 28 28 28 28 30 30 . 29 30 30 31 30 32 • 31 32 30 30 30 29 30 29 26 2 8 1. 18 psl« FUTMCC dreft pslg 0.70 O.tO 0.50 0.5* 0.52 ilS taller flue g*s teap 620 0.72 0.67 0.69 0.5S 0.54 0.70 0.80 0.62 0.61 0.64 0.63 0.50 0.68 t20 630 650 680 685 690 675 675 680 690 685 700 695 305 300 300 310 320 335 335 340 335 335 340 340 340 340 ' 48 45 45 45 43 43 43 44 SO 59 62 62 66 68 68 69 68 Aefclent pressure Inches Hg 28. »S 28.95 28.93 28.93 28.93 28.88 28.87 28.88 28.88 28.05 28.83 28.79 28.77 28.76 28.73 28.72 28.71 28.71 28.73 0.50 0.61 0.65 0.30 340 48 0.59 lotto Md Fly Asli «e«ovil SUrt - 1:SOA. S:0SA. l6:JOA. 1:10P. t:30P. 9:25P flalU - 3:2SA. 5:SM. 11:0&A. I-.3SP, 7:54P. 10:00f> SUrt - 3:iU. IDilSA . 6:45 P 0.60 0.101 66«* 0.61 tafclent te«p °F ESP Inlet °F Coaeents o S.Ol •'SUrt •Of .t 4:10P No WF e .• 28 Neui 30.2- 328* 68 15.9* 65 61 58 59 55 56 9.3 28.73 28.73 28.73 28.73 28.73 28.81 0.088 KDf dtensity - 4.0 Ibs/cu ft. 4.0 Ibs/cu ft �PROCESS MIA AMES MUNICIPAL MUt« PLANT UNIT NO. 7 •Not based M 24 hr data Oat* 3-20-80 Tlw NU Cross Nit Stea> HIM rat* 1000's Ibs/hr 12H 22.0 I9.a 190 1A 22.0 19. a 190 2A 22.0 19.6 190 3A 4A SA 6A 21. S 21. S 19.2 19.3 22.0 19.7 24.0 21.8 175 180 188 200 7A IP 2P V 4P Sf> V 7P 8f> 9P 10P UP 35.0 32.5 35.0 32.4 35.0 32. S 35.0 32.6 35.0 32.0 36.0 32.2 3S.O 32.3 35.0 32.3 35.0 32.2 33.5 31.1 29.$ 27.1 30.6 26.1 S.88 7.68 320 11A 320 320 120 315 315 319 319 319 319 300 260 273 59.8 12N M 9A 27.0 24.2 34.5 31.7 35.0 32.4 35.0 32.5 35.0 32.0 35.0 32.5 240 315 315 320 320 10A 0 MM* Staa> pressure psig O 1 —• 00 850 840 850 850 850 850 850 855 855 860 855 855 850 ass ass 850 855 8SO 855 850 850 860 851 6.0 880 900 880 860 880 890 890 895 90S 910 870 880 900 905 910 900 895 895 895 885 885 890 900 891 12.3 200 200 200 195 210 200 210 250 320 325 330 335 330 325 328 325 325 330 325 325 340 330 305 275 222 115.4 Feed»eter tup °F cr> 840 ago Feeduater flow r»te 1000's Ibs/hr (0 CO 840 Uu> teiperaturt °f 350 350 350 350 340 340 360 360 380 385 385 382 382 385 385 385 385 385 385 385 385 385 380 370 372 16.8 20.0 24. S 29.8 Fuel feed rite (coal) 16.9 24.0 24.6 32.4 26.0 1000-s Ibs/hr 444 122 450 244 I Futl eauoe readings 829 315 833 406 1 Mdnlgkt readings . 3-20-80 Fuel oil sai 600 582 090 | IDF 2:3M-No RDF 38.1 38. 0 39.0 37.2 37.0 37.0 36.6 37.0 37.0 39.6 39.6 40.1 41.6 39.0 36.5 Coal 33.6 34.4 NA Oil 20.42 HA Excess air I 35 40 42 40 40 36 25 24 22 22 20 19 23 21 22 21 23 21 21 21 20 26 24 32 27 7.7 1.0. fans anps 44 43 43 43 44 44 44 45 47 47 46 46 47 47 47 47 47 48 48 48 48 48 48 48 46 1.8 1 .0. fans pressure psll 5.0 F.D. fans aups 28 F.D. fans pressure psig 0.54 toller •F V) 0 .w 28 28 27 28 28 29 29 32 31 31 30 30 31 31 31 31 32 32 32 32 32 31 30 29 4.S 0.80 O.M 0.40 flue gas IMP 0.60 615 0.78 620 0.70 625 0.68 630 0.53 695 6.4 1 . 19 J* 0.55 0.60 0.70 0.62 0.68 0.62 0.60 0.55 0.65 0.60 0.50 0.50 0.60 0.62 0.60 0.60 0.093 705 710 670 680 690 700 700 705 710 715 720 680 685 680 680 681* 32.8- 295 ESP Inlet °F 295 300 320 325 325 330 330 330 330 335 335 335 330 330 330 330 330 330 315 324« 12.7« 46 47 44 43 43 42 42 42 44 46 51 52 51 50 45 44 44 42 42 39 44 9.2 28.95 28.93 28.92 28.93 28.97 28.92 0.086 M>«ent teap °F 50 50 46 taktent pressure Inches Hg 20.72 28.72 28.82 28.82 28.83 28.86 28.90 28.90 28.94 28.96 Counts 7.06 No ROF 3.5 Furnace draft psig 11:OOA 11:35* 34.0 46 !»"?• ft"* Ash «« ' « 5S>t HoMn 28.96 28.96 28.97 Start - 3:MA.'10:lSA, 7:10P KOF density - 3.5 Ibs/cu ft 28. 98 28.97 28.99 29.01 29.03 29.03 �MOCESS DATA AlCS HJHIClrAl fOMt» M.AOT UNIT • . 7 0 •hot kased M 24fcrdata Date 3-22-80 1A 2A 1A 4A SA 6A 7A •A 9A 10A 11* 12* If 2P » V SP 6P 7P sp gp 10P UP 22.0 19.9 22.0 19.1 22.0 19.S 22.5 20.4 21.0 20.9 21.0 21.0 21.0 20.8 23.0 20.8 29.0 26.1 32.0 29.7 34.0 31.6 34.0 31.4 34.5 12.0 34.0 11.4 32.5 30.1 12.0 29.6 12.0 29.6 11.0 10.6 13.0 10.1 15.0 12.1 14.5 11.1 14.5 11.7 32.0 29.3 30.0 27.4 29.4 27.1 5.16 4.9S Stew flan rate 1000's Ibt/hr 188 188 188 190 195 200 195 195 255 288 110 320 110 107 285 280 285 290 295 312 110 110 285 265 260 Sl.l Stew pressure pslg 850 850 860 860 850 850 860 850 868 850 850 880 850 850 850 850 850 850 850 050 850 850 850 850 851 7.4 12M Tin. m Gross Net MM* . Stew twperature °F 890 900 890 870 870 870 880 900 90S 900 900 910 890 890 900 905 900 900 890 890 900 880 880 880 891 11.8 FeedMter flOH rate lOOO's Us/nr 200 200 200 210 210 200 205 200 263 293 110 115 320 115 300 295 295 300 102 322 110 325 295 265 270 50.5 Feedwter twp °F 340 340 340 340 340 340 340 340 365 175 380 385 176 380 380 380 380 180 380 185 380 380 180 365 365 18.9 Fuel feed rate (coal) 1 0 ' s Iks/nr 00 Fuel gaimi readings Fuel ill •OF 19.3 453 901 •36 954 582 768 21.2 19.4 20.8 20.3 18.0 25.0 2B.O 32.0 35.5 36.1 16.0 38.5 35.5 37.0 38.0 19.0 18.5 40.2 4. 05 40.1 38.6 31.5 Coal 11.1 8.12 11.1 M 26.67 NA Excess air I 27 27 27 25 27 27 26 25 17 22 21 1.0. fws aaps 42 42 42 42 43 43 43 43 44 45 46 1.0. fans pressure pslg 4.6 F.O. fans aups 27 28 27 27 27 28 27 27 29 30 30 20.2 on 12: UP F.O. fans pressure pslg 3.0 06 .8 0.44 30 15 30 18 30 19 30 18 20 20 20 20 20 19 " 22 1.1 46 46 46 46 46 46 45 45 I.I 30 30 30 31 31 31 30 30 29 1.5 4.1 31 21 18 46 19 0.99 0.59 0.101 659* 30.4- 1.0 Furnace draft pslg • No ROF 0.40 ESr Inlet °F Ambient tenp °F 16 34 Ambient pressure Inches Hg 29.21 29.21 29.21 29.17 34 31 31 Finish 0.70 0.47 0.45 0.65 0.60 0.70 0.68 0.68 0.65 0.50 0.58 610 615 640 660 685 700 680 675 670 675 670 680 300 300 315 320 330 310 130 330 330 125 325 325 33 34 33 35 16 38 40 44 45 46 50 50 50 29.18 29.18 29.15 29.14 29.11 90 29.08 29.05 29.02 29.00 2 . 8 28.97 28.96 2 . 6 28.87 28.87 28.87 28.87 28.87 2 . 4 0.134 88 89 29.18 29.18 lotto* and Fly Ask Kenoval Comments 0.60 300 0.74 0.68 610 0.40 •oiler flue gas leap •F Soot lloun 0.55 0.56 0.65 0.58 0.62 0.65 120* 46 •OF density - 3.5 Iks/cu ft, 4.5 Iks/cu ft 41 41 41 39 19 12.2* 40 5.9 �PROCESS DATA AMES MUNICIPAl POWER PLANT uHIT NO. 7 •mot based on 24 kr data Date 3-23-80 12* 10P IIP a Men IP 2P 3P 4P 5P 6P 7P 17.0 15.4 17.0 15.2 17.0 15.3 17.0 15.4 17.0 15.4 17.0 15.4 20.0 18.3 20.0 1S.O 20.0 18.0 20.0 18.0 20.0 17.9 20.0 18.0 18.1 16.2 1.98 1.80 144 144 144 144 142 144 144 168 168 168 168 168 168 153 16.2 845 850 850 855 850 855 855 855 860 860 860 860 860 860 852 5.7 885 895 890 890 880 890 890 895 eao 890 870 880 880 880 884 10.0 150 150 165 150 151 150 150 150 180 180 180 180 180 180 162 17.8 320 325 320 320 320 320 320 320 325 330 340 330 330 330 340 325 7.1 19.8 19.6 21.0 21.0 21.0 20.0 20.0 20.5 19.5 22.0 22.6 22.9 23.0 22.6 22.2 Coal Oil 20.8 1.71 20.4 M 33.33 M >50 >50 >50 >50 >50 >50 >50 >50 41 40 29 29 26 26 26 28 '42 11.0 43 43 43 42 42 42 43 42 41 41 42 42 42 42 42 42 42 0.7 1A 2A 3A 4A 5A 6A 7A 8A 9A 25.0 22.4 17.0 15.0 17.0 15.0 17.0 15.2 17.0 15.2 17.0 15.2 17.0 15.1 17.0 15.2 17.0 15.2 17.0 15.2 17.0 15.2 17.0 15.4 SUM flax rate 1000' s Ib/kr 210 145 144 144 144 144 145 145 142 142 143 Steam pressure pslg 850 840 850 850 845 850 850 850 845 850 Steam temperature °F 880 880 890 850 880 890 880 880 890 900 Feeduatcr flow rate 1000 's Ibs/kr 220 162 155 155 152 150 150 150 150 150 FeediMter teap °F 340 320 320 320 320 320 320 320 320 Fuel feed rate (coal) 1000' s Ibs/kr Fuel gauge readings Fuel oil RDF 26.2 19.5 457 717 840 602 583 406 19.6 19.5 19.5 19.6 19.0 20.2 19.4 Excess air X 19 >60 >50 >50 >50 >50 >50 >5fl 1.0. fans aaps 44 43 43 43 43 43 43 43 1.0. fans pressure pslg 4.0 4.0 4.0 F.O. fan aaps 29 28 28 27 27 F.O. fan pressure f>sl| 2.0 2.7 2.7 2.7 2.2 Furnace draft pslg 0.54 0.60 0.64 0.58 0.54 TIM NU w • oo g » ftp Gross Net IDA 11A 12N No RDF 0.22 27 28 27 27 27 27 27 28 27 27 27 26 26 27 27 27 27 27 27 27 0.6 0.67 0.60 0.64 0.58 0.51 0.56 0.60 0.40 0.63 0.60 0.58 0.64 0.64 0.62 0.65 0.57 0.60 0.55 0.56 0.59 0.057 600 600 600 600 605 590 600 600 600 595 595 599* 3.9« 280 280 280 280 280 280 280 280 280 280 280 280* 0* 37 3) 40 38 37 1.6 Boiler flue gas teap ESP Inlet °F Ambient teap °F 40 39 41 Ambient pressure inches Mg 28.87 28.96 28.95 28.94 28.93 28.92 28.92 28.99 28.98 28.98 29.01 Comments _•<""• and Fly Ask Removal 39 37 36 36 36 $S't»!9-? 36 36 Start - 2:30A. 11:15*. 7:OOP 36 38 38 40 37 36 36 36 36 36 28.99 28.97 28.97 28.96 28.95 28.96 28.96 29.00 29.00 29.01 29.01 29.01 29.01 28.97 0.036 RDF density - No ROF �PMCESS DATA UK HJMIClfM KMtR PtANT UNIT NO. 7 Date 3-24-80 •Not based on 24 hr data Time 12M 1A 2A 3A 5A 4* 6A •7A 8A 9A 10A 11A 3S.O 32.4 35.0 32.6 35.0 32.4 310 310 305 4P SP if M.S 33.8 3S.O 32.S 3S.O 32.4 3S.O 32.5 3S.O 32.$ 35.0 32.S 15.0 32.S 310 310 310 US 320 320 IP 2P 3P M.5 32.0 35.0 32.6 310 315 12N 7P 10P UP 3S.O 32. S 15.0 32.4 32. S 30.0 29.7 27.4 7.77 7.55 318 318 318 290 264 73. S 4.9 8P 9P Moan a 20.0 18.0 20.0 18.0 18.0 16.0 17.0 1S.O 17.0 1S.2 17.8 IS. 2 17.0 15.2 30.0 27.3 3S.O 32.3 Steam flox rate 1000' s Ibs/hr 16S 165 ISO 148 148 148 148 260 3IS Steam pressure pslg 860 860 860 ato 860 860 860 860 860 855 855 840 850 860 850 860 860 ass 860 860 860 860 860 860 868 Steam temperature °F 880 900 880 880 900 890 880 890 890 9W 904 900 890 890 900 91S 880 890 890 900 860 890 890 aw 891 11.2 FeedtMter flon rat* 1000's Ibs/hr 180 180 160 160 164 15S 155 270 323 320 320 312 315 32S 320 325 320 320 328 328 332 330 328 290 273 72. S Feednater temp °F 340 340 330 330 330 320 320 3 0 3 0 380 380 380 380 385 385 385 385 385 38$ 390 390 385 390 380 367 25.4 Fuel feed rate (coal 1000's Ibs/hr Fuel gauge readings Fuel oil 22.8 22.8 20.2 19.4 20.3 19.0 20.1 33.7 37.5 37.0 37.0 M.5 32.0 33.0 33.0 M.5 33.4 39.5 41.1 42.8 42. S 41.7 40.6 37.0 Oil 32.3 8.26 32.8 NA 20.42 NA Ml Cross Net 460 266 842 955 S84 200 Coal to ROF at 10:27A NO ROF RDF- 4:10P- No ROF Encess air I 28 29 45 45 41 46 45 24 19 20 18 19 17 18 17 14 1 8 19 18 19 19 19 17 19 25 10.8 1.0. fans amps 42 43 43 43 42 42 43 46 47 47 47 46 48 48 48 46 46 46 47 47 47 47 47 43 46 2.2 1.0. fans pressure pstg 6.1 27 F.O. fans amps 27 27 F.O. fan pressure 2.3 3.0 O.SS 0.57 0.27* 27 27 27 27 29 31 30 30 31 30 30 30 30 30 30 31 31 31 31 31 31 29 1.7 0.92 ps1« Furnace draft psig 0.60 0.50 0.60 0.58 0.58 0.50 0.68 670 685 700 685 600 toiler fuel gas temp 59S 595 655 680 0.38 0.62 0.47 0.62 0.50 0.40 O.SS 0.5$ 660 670 680 680 685 0.55 0.50 0.50 O.SS 0.48 0.073 36.1* 322* 0.40 O.S3 660* O.S2 23.1* •f 280 280 280 335 330 330 33S 335 335 335 335 335 33$ 33S Ambient temp °F 36 35 35 36 36 36 36 36 36 36 36 35 35 36 38 38 38 38 37 37 37 36 36 35 36 1.0 Ambient pressure Inches Kg 28.96 28.96 28.96 28.96 28.96 28.96 28.96 28.96 28.99 26.98 29.01 29.02 29.04 29.01 29.06 29.06 29.06 29.08 29.13 29.13 29.13 29.18 29.18 29.18 29.04 0.079 ESP Inlet temp °F tottM andFly Ash Remove 1 Comments Start finis. - Soot 81lMl *OF density - 4.0 Ibs/cu ft >:3SA. 2:06P. �PROCESS DATA *KS HUHICIPM. POMER It All I UNIT NO. 7 Date 3-25-80 •Hot based on 24 hr data 1* 2A 3A 4* 5* 6* 7* 8* 9* 22.0 19. S 18.0 16.2 18.0 16.2 18.0 16.2 18.0 16.2 18.0 16.2 18.0 16.1 28.0 25.8 35.0 32.3 35.0 32.2 180 148 148 150 155 155 155 250 317 12H TIM Ml Gross Net Steaei flow rate 1000' s Ibs/hr 7P 8P 9P 10P IIP 35.0 36.0 32.3 32.5 35.0 32.3 35.0 32.5 35.0 32.S 35.0 32.5 25.5 23.7 312 312 312 311 312 312 313 252 12N IP 2P 3P 4P 35.0 32.5 35.0 35.0 32.5 32.6 35.0 32.6 34.0 31.4 34.5 32.1 35.0 32.3 315 318 315 315 310 308 312 10* 11* 5P 6P Mean 0 29.57.54 27.27.21 262 71.9 Stean pressure pslg 860 850 850 850 850 850 860 840 860 855 855 855 855 855 845 850 850 850 850 850 810 850 853 850 852 4.8 Steaei temperature °F 870 890 880 880 880 880 880 890 900 905 900 900 880 890 900 900 900 900 900 905 882 900 900 880 892 10.7 Feedwater flow rate 1000's Ibs/hr 210 158 160 160 160 325 324 320 280 272 71.4 Feeduater te«p °F 340 320 382 382 382 380 364 27.6 160 165 250 325 320 325 325 325 320 325 324 320 320 320 318 385 380 385 385 383 383 383 383 34.0 34.0 34.0 35.7 48.3 38.7 320 320 320 320 320 360 380 380 380 380 Fuel feed rate (coal) 21.9 21.0 1000's Ibs/hr 464 277 Fuel tauge readings 846 818 Fuel oil 584 690 RDF 21.0 21.4 21.5 21.5 21.5 33.9 34.7 35.3 33.0 33.0 33.0 Excess air S 38 >50 >50 >50 >50 >50 >SO 22 22 19 20 18 IB 19 19 17 16 17 15 IB 17 15 18 18 . 27 I.D. fans aups 43 45 43 44 45 45 45 46 48 47 48 48 48 48 48 48 46 46 46 46 46 46 46 45 46 1.0. fans pressure ps'9 3.8 5.0 F.O. fans taps 28 28 F.D. fan pressure PSl9 3.0 Furnace draft pslg 0.53 •Start RDF at 7:40* do RDF 37.5 39.0 30.0 31.8 7.66 Coal 31.8 Oil 28.33 N* M 10:OOP system ••" OFF 8:00* . 3-26-80 10:22P Systea T ON 4:OSP reduced RDF flow until 14.3 1.6 1.14 28 28 28 28 28 30 31 31 30 30 30 30 30 30 30 30 31 31 32 31 31 29 30 1.3 0.84 0.90 0.52 0.55 0.60 0.49 0.67 0.61 0.55 0.63 0.63 690 685 690 700 690 665 670 680 685 35 32 Aefclent pressure Inches Hg 29.18 29.18 29.18 29.18 31 31 280 310 330 330 330 330 335 335 335 335 335 29 33 34 36 42 44 43 44 45 46 46 29.18 29.18 29.18 29.22 29.21 29.18 29.19 29. IB 29.17 29.15 29.14 29.14 29.12 29.15 29.14 31 29.18 lotto* and Fir*sh Removal Start - 1:OUA . 5:00*. 9:00*. 1:01P, 5:OOP. Finish 9:45*. MSP. 5l43P. 0.50 O.SO 0.40 0.57* 0.108* 335 31 610 280 ESP Inlet teap °F Actlent te*p °F 0.57 695 605 31 0.60 0.57 640 0.43 toiler flue gas teem Co**ents 39.939.5 7:OOP. 9:05P 7:40P. 9: SOP Start - 275SA. "11:35*. 7:OOP RDF 670* 31.6* 323" 46 density - 3.5 Ibs/cu ft. 4.0 Ibs/cu ft 45 2.03' 38 6.3 45 43 41 40 29.15 29.15 29.15 29.15 29.17 0.024 �o PROCESS OATA AMES MUNICIPAL POHER P1ANT 1 1 NO. I *! •Hot based o» 24 br data Date 3-26-80 1A 2A 3A 4A 5A 6A 7A 8A 9A 10A 11A 12N IP 2P 3f 4P 21.5 19.5 21.5 19.5 21.5 19.S 21.$ 19.5 21.5 19.5 21.5 19.5 30.0 17.5 34.5 31.8 34.5 31.S 36.0 33.4 34.5 32.0 35.0 32.5 34.5 32.0 35.0 32.4 35.0 32.5 35.0 32.5 -180 180 1M 180 180 180 178 270 317 316 310 310 310 310 312 310 310 Stew pressure pslg 850 850 850 850 850 850 850 860 860 855 850 850 855 850 855 855 Stew teaperatur* °F 880 860 890 880 890 890 890 900 900 900 910 900 900 880 920 902 Feedxater flox rate 1000- s Ibs/kr 190 190 190 195 190 190 190 270 327 323 328 328 320 330 328 324 322 FeedHiter teap °F 340 340 340 340 340 340 340 340 3BO 385 380 380 380 380 380 385 385 385 385 385 Fuel feed rate (coal) 1000* s Ibs/hr Coal gauge readings Fuel otl (gallons/hr) ROF 19.0 19.0 18.5 468 170 850561 585 370 Reduced ROF flau 21.0 18.7 19.4 19.4 25.2 34.4 35.1 35.0 33.5 33.0 34.0 40.0 34.0 34.5 33.6 33.5 34.2 Eicess air s 34 28 30 27 27 28 27 20 19 18 18 19 18 18 19 19 19 17 20 20 19 20 1.0. fans aaps 44 44 44 44 44 44 42 45 47 47 46 46 46 46 46 48 46 46 46 46 46 46 l.D. fans pressure pslg 3.8 F.D. fans aaps 27 27 27 27 28 27 27 30 31 31 30 30 30 30 30 30 30 30 31 31 30 F.D. fan pressure pslg 2.0 1.9 Furnace draft psig 0.34 0.50 0.40 0.50 0.60 0.70 0.72 0.60 0.49 0.43 0.60 0.45 04 .8 0.55 0.58 0.52 0.49 0.60 0.52 0.65 toller flue gas top 620 630 620 600 600 600 605 665 690 695 700 700 700 665 680 690 690 690 700 700 ESP Inlet teap °F 290 290 290 290 290 290 290 320 330 325 320 325 325 325 330 330 330 325 325 /tab t Mt teap °F 38 36 36 35 35 35 35 34 34 36 40 40 45 44 45 45 45 45 43 Aabient pressure inches Hg 29.21 29.21 29.21 29.20 29.20 29.20 29.23 29.23 29.23 29.23 29.23 29.19 29.17 23.15 29.12 29.11 29.12 29.11 29.12 29.10 12N Tlae M Gross Net Stew flau rat* 1000* s Ibs/kr ro U* 22.0 20.0 tottoaand Coaaents Start Finish - i Reaova1 .10P. 7P 8P 9P 10P IIP 35.0 32.3 35.0 32.4 35.0 32.2 35.0 32.3 35.0 32.3 32.0 29.3 30.$* 6.17* 27.7* ».»* 31t 312 312 315 312 312 290 258 79.1 855 860 860 860 860 860 850 850 864 4.4 - 910 880 890 890 840 880 890 880 890 16.6 327 325 325 330 322 322 305 283 61.6 385 385 385 385 369 20.9 33.5 34.0 34.9 33.4 Coal on 29.6 31.* 1.67 7.16 NA NA 20 20 22 4.8 46 45 45 1.3 30 30 30 29 1.5 0.60 0.44 0.50 0.55 0.53 0.092 665 675 680 670 664 37.1 325 325 325 325 320 315 16.6 43 42 40 39 38 40 4.1 29.14 29.14 29.14 29.14 29.17 006 .4 No ROF 1:30»——- Start RDF at 2:12P 8 0 * resuae noraal RDF fl ow :0 9:5SA. 2.48P. 6P SP Soot Rloun Start - 27fO». 11.-45A. 7:05P RDF density - 3.5 Iks/cu ft. 3.0 Ibs/cu ft Moan • �APPENDIX B TRW FIELD TEST REPORT FOR THE CHICAGO NORTHWEST INCINERATOR. UNIT NO. 2 242 �PILOT TEST PROGRAM CHICAGO NORTHWEST INCINERATOR BOILER NO. 2 P, S. Bakshi, T. L. Sarro, D, R. Moore, W. F. Wright, W. P. Kendrick, B. L. Riley TRW ENVIRONMENTAL ENGINEERING DIVISION TRW, INC. EPA Contract 68-02-2197 EPA Project Officer: Michael Osborne Industrial Environmental Research Laboratory Office of Research and Development U.S. Environmental Protection Agency Research Triangle Park, N.C. 27711 243 �CONTENTS Figures iii Tables Acknowledgment iv v 1, Introduction 2, Summary . , , . , , 2.1 Sampling and Analysis. , , . , 2.2 Process Data , 2.3 Continuous Monitoring Data , , 3, Riant Description .,, 3.1 General Description. , . , , 3.2 Detailed Descriptions, . . , , , . . , , , , , 4, Sampling Locations. , , . , , , , , . , , , , , 5, Sampling, , , , „ , . , , . . , , , , , , , . , . , 5.1 Gas Sampling , . . . , , , , , , , , , , , , . . , , . 5.2 Solid Sampling , , , . , , . , , , , , . , , , , . . . 5.3 Liquid Sampling. , . , , , , , . , , , . , , , , . . . 5.4 Hi Volume Sampler. . , . , . . , , . , , 5.5 Quality Assurance , 5.6 Sampling Train Background, . , , , , , ,.. 5.7 Sample Recovery , ,., 5.8 Observations During Recovery , , , , , . t , , , , . . 6, Calibration , , 6.1 Method Five Calibration Data ,.... 6.2 Instrument Calibration 7, Technical Problems and Recommendations, 7.1 Problems . . . , , , 7.2 Recommendations, , 1-1 2-1 2-1 2-1 2-25 3-1 3-1 3-3 4-1 5-1 5-1 5-1 5-4 5-4 5-4 5-4 5-6 5-7 6-1 6-1 6-4 7-1 7-1 7-1 Appendices A. B. C. D. Continuous Monitoring Data, . , . , , , . . . , , , , . . . Field Data Sheets , Sample Inventory Sheets ,,.,.,,.,,... Process Data ,,.,., n 244 A-l B-l Crl D-l �FIGURES Number Page 3-1 3-2 Layout of plant site Flow diagram of Chicago Northwest Incinerator 3-2 3-4 3-3 Combustion air and flue gas system 3-11 4-1 4-2 4-3 4-4 Flow diagram and measurement locations Outlet sampling position Top view of ESP inlet showing port locations Cross sectional of ESP inlet showing traverse point locations Sampling train EPA Method 5 particulate sampling train Ambient air sampler Calibration equipment set-up procedures 4-2 4-3 4-4 5-1 5-2 5-3 6-1 m 245 4-5 5-2 5-3 5-5 6-3 �TABLES Number 2-1 2-2 2-3 2-4 Daily Sampling Summary Daily Data Summary 24 Hour Process Data for the Chicago Northwest Municipal Incinerator, Unit No. 2 Means of the Means for 24-Hour Process Data, All Test Days, Chicago Northwest Municipal Incinerator 2-5 2-6 2-7 2-8 Test Duration Process Data for the Chicago Northwest Municipal Incinerator, Unit No. 2 Weekly Inventories of Refuse and Residue at the Chicago Northwest Municipal Incinerator (All Boilers) Charges Fed to Each Boiler on a Shift Basis Chicago Northwest Incineration Facility Down Time Expressed as Lost Furnace Hours for the Entire Chicago Northwest Incineration Facility 2-9 2-10 3-1 4-1 page 2-2 2-9 2-13 2-15 2-16 2-18 2-19 2-26 Continuous Monitoring Data Means of Percent Oxygen Taken by Control Room Gauge and 02 Analyzer for Test Duration 2-27 Characteristics of Chicago Northwest Incinerator Sampling Locations 3-3 4-1 iv 246 2-28 �ACKNOWLEDGEMENTS This sampling and field measurement work was performed for the U.S. Environmental Protection Agency (EPA) under Contract No. 68-02-2197. The program was sponsored jointly by the Office of Pesticides and Toxic Substances in cooperation with the Office of Research and Development (ORD) of the EPA. The ORD-sponsored portion of the program was directed by Mr. Michael C. Osborne, Industrial Environmental Research Laboratory, Research Triangle Park, North Carolina. The Office of Pesticides and Toxic Substances sponsored portion of this study was directed by Mr. Martin Hal per, Washington, D.C. Three contractors participated in the overall test program, namely, TRW Inc., Midwest Research Institute (MRI) and Research Triangle Institute (RTI). TRW Inc. was responsible for the field testing; MRI had responsibility for the sampling analysis;and RTI had overall responsibility for the statistical design of the test program. Many individuals contributed to the sampling, testing, data reduction and report preparation for this study. Mr. Birch Matthews had overall responsibility for this program at TRW Inc. He was assisted in his management activities by Dr. Chris Shin and Mr. Don Price. The Field Team Leader was Mr. Dave Moore and the field sampling team members were Mr. J. Berger, Mr. M. Drehsen , Mr. 0. Gordon, Mr. W. Kendrick, Mr. J. McReynolds, Ms B. Riley, Mr. T. Rooney, Mr. D. Savia, Mr. B. Wessel and Mr. W. Wright. The Process Engineers were Mr. P. Bakshi and Mr. T. Sarro. The Chicago Northwest Incinerator personnel who provided significant assistance in completing the study were: Mr. Emil Nigro, the Supervising Engineer of the city of Chicago, Bureau of Sanitation; Mr. Stanley Oenning, the Chief Operations Engineer at the plant; and Mr. Gerry Golubski, Plant Chemist. In addition, there were numerous other plant personnel who provided assistance during the field testing. Their efforts are greatly appreciated and their contribution is hereby acknowledged. v 247 �1.0 INTRODUCTION This document describes the sampling and monitoring activities performed at the Chicago Northwest Incinerator, Boiler No. 2. The sampling and field measurement work was part of an overall pilot scale test program sponsored by the Office of Pesticides and Toxic Substances in cooperation with the Office of Research and Development, of the U.S. Environmental Protection Agency. The ultimate objective of the pilot scale test program is to develop an optimum sampling and analysis protocol to characterize polychlorinated organic compounds which may be emitted in trace quantities through conventional combustion of fossil fuels and refuse. The genesis of the program is an industrial study by Dow Chemical Company and two groups of European investigators reporting emissions of polychlorincted dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and biphenyls (PCB) from stationary conventional combustion sources. The immediate objective of the sampling and field measurements program is the specification of procedures and equipment to obtain sufficient multimedia samples for the subsequent analytical protocol, and to satisfy the program statistical design requirements. In this respect, the TRW Environmental Engineering Division of TRW, Inc., was one of three contractors participating in the overall EPA program and was responsible for the acquisition of samples and measurements in the field. The sampling was oriented toward acquiring multimedia samples for organic compound analysis by Midwest Research Institute (MRI). Compounds of particular interest included: Benzo [a] pyrene Pyrene Fluoranthene Phenanthene Chrysene Indeno [1,2,3-cd] pyrene Benzo [g,h,i] perylene Anthracene In addition, MRI is to make a determination of total organic chlorine emissions from the acquired samples. Potentially, selected samples are to be analyzed for polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls. 248 �Instrumentation for on-line combustion gas stream monitoring was part of the test program. In addition, Incinerator process Information was also gathered. This Information together with the monitoring data were acquired to assist In evaluating and Interpreting chemical analysis results. This report contains all the field data for the Chicago Northwest Incinerator pilot test program conducted in May 1980. Data provided Include the following: t Chlorinated hydrocarbon collection using a modified EPA Method 5 train and Method 5 sampling methodology. • Gas velocities using EPA Method 2, • Continuous monitoring for C02, 02, and CO and THC, • Part1culate collection for inorganic analysis utilizing EPA Method 5. • Process data. The test program followed was described in the Pilot Test Program, Chicago Northwest Incinerator, Boiler No. 2, site test plan. Deviations from this program are documented and explained in their respective sections of this report. 1-2 249 �2.0 SUMMARY 2.1 SAMPLING AND ANALYSIS The field test activity took place from April 30, 1980 to May 23, 1980. All required tests were completed and all recovered samples were sent to Gulf South Research Institute (GSRI) for analysis,. MRI had subcontracted this part of their assignment to GSRI. A summary of tests conducted including any significant commentary is presented in Table 2-1. A summary of the reduced data on a daily basis as calculated from the field data sheets is presented in Table 2-2. Data listed are corrected to standard conditions, i.e., 20°C and a barometric pressure of 29.92 inches mercury. Sampling and calibration procedures are described in Sections 4, 5 and 6. Hourly data is provided in the appendices. Appendix A contains continuous monitoring data; Appendix B contains field data; and Appendix C contains sample inventory sheets supplied by GSRI. 2.2 PROCESS DATA For every day of inlet or outlet testing, a 24 hour record of process data was obtained. This information is provided in the daily process data sheets in Appendix D. Most of this data was obtained from instrumentation in the control room. The parameters considered important to the operation of Boiler No. 2, and for which instrumentation was available include steam flow rate, steam pressure, feedwater flow rate, feedwater temperature, combustion air flow rate, combustion air temperature, % oxygen, I.D. fan pressure, F.D. fan pressure, furnace draft, and furnace temperature. No data were available for steam temperature, excess air, or the power consumption of the fans. A chart recording instrument located in the control room provided continuous instantaneous readings for steam flow rate, feedwater flow rate, and combustion air flow rate. These were read directly from the instrument in 1000's of pounds per hour, 1000's of pounds per hour, and 1000's of cubic feet per hour, respectively. These are given in Appendix D under the heading "chart recorder" for each of the three parameters. 2-1 250 �TABLE 2-1. DAILY SAMPLING SUMMARY Date (1980) 1 Inlet-North Test started at 0835 hours and ran for 350 minutes. Low volume was obtained. Test was discontinued because of unsuccessful leak checks after filter replacement. Test started at 0835 hours and ran for 193 minutes. Low volume was obtained. Battelle trap also appeared to plug up and was therefore changed. However, this did not occur during remaining tests. Filter blockage also occurred probably due to filter oven temperature not being hot enough (250°F). At 1600 hours the plant had to shut down due to boiler leaks. Test quality was fair. Outlet-North i ro Sampling locations Inlet-South 5/4 Test No. Test started at 0825 hours and ran for 404 minutes. No significant problems occurred. Test quality was good. Test started at 0820 hours and ran for 375 minutes. No new leak rate was obtained at filter change. New filter housing was found to be warped which caused the leak problem. Test quality was good. Sample was lost due to the wind blowing the filter out of the filter holder. No problems were encountered. Test quality was good. Outlet-South to Hi Volume Sampler 5/6 Continuous monitors Inlet-North Inlet-South Outlet-North Test comments Test were Test were with both Test Test were started at 1230 hours and ran for 525 minutes. There no significant problems. Test quality was good. started at 1230 hours and ran for 525 minutes. There no significant problems. Test was inadvertently stopped only 21 of the required 24 points traversed. However, gas volume and particulate collections were sufficient. quality was good. started at 1235 hours and ran for 500 minutes. There no significant problems. Test quality was good. �TABLE 2-1. Date (1980) 5/6 Test No. Sampling locations Outlet-South Hi Volume Sampler 5/7 ro ro m i ro co Continuous monitors Inlet-North Inlet-South Outlet-North Outlet-South Hi Volume Sampler 5/8 Continuous monitors Inlet-North Inlet-South Outlet-North Outlet-South (Continued) Test comments Test started at 1230 hours and ran for 500 minutes. Probe was found to be cracked at the end of test. However, based on a moisture calculation of only Z% (vs. 12% in other test), it appears that the probe cracked during the first 280 minutes. The probe was switched and the test continued an additional 200 minutes. Test quality was poor as only air was sampled for 50% of the test. Test started at 1311 hours and was stopped at 2325 hours, Test quality was good. Test quality was good. Test started at 0835 hours and ran for 420 minutes, No problems were encountered. Test quality was good. Test started at 0837 hours and ran for 480 minutes, No problems were encountered. Test quality was good. Test started at 0930 hours and ran for 500 minutes, No problems were encountered. Test quality was good. Test started at 0955 hours and ran for 500 minutes, No problems were encountered. Test quality was good. Test started at 1215 hours and was stopped at 2000 hours. Test quality was good. No problems were encountered. Test quality was good. Test started at 0845 hours and ran for 420 minutes. No problems were encountered. Test quality was good. Test started at 0832 hours and ran for 480 minutes. No problems were encountered. Test quality was good. Test started at 0930 hours and ran for 500 minutes. Low moisture obtained because of cracked probe. Test started at 0925 hours and ran for 500 minutes, No problems were encountered. Test quality was good. �TABLE 2-1. Date (1980) 5/8 Test No. Sampling locations HI Volume Sampler Continuous monitors 5/9 Inlet-North Inlet-South ro ro Ul u> Outlet-North Outlet-South HI Volume Sampler Continuous monitors 5/10 (Continued) Inlet-North Inlet-South Test comments Test started at 1015 hours and was stopped at 1910. Test quality was good. No problems were encountered. Test quality was good. CO readings were suspect, refer to 5/9/80 continuous monitoring data. Test started at 0820 hours and ran for 480 minutes. After 180 minutes the sampling time was increased from 20 to 25 minutes per point to collect sufficient sample volume. Boiler was operating at lower load conditions during this period. Test quality was good. Test started at 0805 hours and ran for 542 minutes. After 267 minutes the sampling time was increased from 20 to 25 minutes per point. (See Inlet-North above). Test quality was good. Test started at 0905 hours and ran for 500 minutes. Test quality was good. Test started at 0920 hours and ran for 500 minutes. Test quality was good. Test started at 0915 hours and was stopped at 1850 hours. Test quality was good. CO was exhibiting drift problems due to exhausted dessicant. Dessicant was therefore replaced. Previous days (5/8/80) data were suspect as CO dropped to lower level after dessicant changeout. Test quality was good. Test started at 0815 hours and ran for 420 minutes. No problems were encountered. Test quality was good. Test started at 0810 hours and ran for 480 minutes. No problems were encountered. Test quality was good. �TABLE 2-1. Date (1980) 5/10 Test No. Sampling location Outlet-North Outlet-South Hi Volume Sampler N> 5/11 Continuous monitors Inlet-North Inlet-South Outlet-North Outlet-South (Continued) Test comments Test started at 0915 hours and ran for 480 minutes. No problems were encountered. However, test was halted one point from completion due to stormy weather. There was little effect on test data. Test quality was good. Test started at 0840 hours and ran for 550 minutes. No problems were encountered. Test quality was good. Test started at 1100 hours and was stopped at 1900 hours. (Problems due to wind were encountered but the sample was not destroyed). Results were fair to good* CO was taken off line due to span and balance problems. Remaining data were good. Test started at 0828 hours and ran for 462 minutes. No problems were encountered. Test quality was good (changed sampling time to 22 minutes per point for inlet trains prior to starting test). Test started at 0934 hours and ran for 528 minutes. No problems were encountered. Test quality was good. Excessive number of filters were used during this test day for both inlet trains. Test started at 0900 hours and ran for 360 minutes. Due to excessive amount of time needed to correct malfunctioning equipment, the north train was utilized for only 20 points instead of the normal 25 points. Total volume sampled for north and south trains was 20 nr. Test quality was good. (Changed sampling time to 18 minutes per point prior to start of test). Test started at 0915 hours and ran for 540 minutes. South train traversed 30 points (see comments for Outlet-North train for 5/11/80). No problems were encountered and test quality was good. �TABLE 2-1. (Continued) Date (1980) 5/11 5/12 Test No. Sampling locations 7 Hi Volume Sampler 8 Continuous monitors Inlet-North Inlet-South Outlet-North Outlet-South ro i Hi Volume Sampler Ul t_n 5/13 9 Continuous monitors Inlet-North Inlet-South Outlet-North Outlet-South Hi Volume Sampler Test conments Test started at 1014 hours and was stopped at 1930 hours. Test quality was good. CO was still off line. Backup unit was ordered but had not arrived. Remaining data quality was good. Test started at 0840 hours and ran for 462 minutes. No problems were encountered. Test quality was good. Test started at 0837 hours and ran for 528 minutes. No problems were encountered. Test quality was good. Test started at 1040 hours and ran for 450 minutes. No problems were encountered. Test quality was good. Test started at 0854 hours and ran for 450 minutes. No problems were encountered. Test quality was good. Test started at 1243 hours and was stopped at 1840 hours. Test quality was good. No CO data was being monitored. Remaining data was good. Test started at 0833 hours and was down at conclusion of test quality was good. Test started at 0815 hours and quality was good. Test started at 0832 hours and quality was good. Test started at 0818 hours and quality was good. Test started at 0912 hours and Test quality was good. ran for 472 minutes. Boiler for grate cleaning. Test ran for 528 minutes. Test ran for 450 minutes. Test ran for 450 minutes. Test was stopped at 1820 hours. �TABLE 2-1. (Continued) Date (1980) Test No. Sampling locations 5/13 9 Continuous monitors CO was still off line, however remaining data was good. 5/15 10 Inlet-North Test started at 0805 hours and ran for 464 minutes. Test quality was good. Test started at 0803 hours and ran for 528 minutes. Test quality was good. Test started at 0840 hours and ran for 450 minutes. Probe was found with a cracked tip. Based on 8.9% moisture vs. 12% moisture for the other tests, it seems only the last 10 pts. were traversed with broken probe. Test quality was fair. Test started at 0820 hours and ran for 450 minutes. Test quality was good. Test started at 1110 hours and was stopped at 1840 hours. Test quality was good. New CO analyzer came on line. Test quality was good. Inlet-South Outlet-North Outlet-South ro i HI Volume Sampler 5/16 11 Continuous monitors Inlet-North Inlet-South Outlet-North Outlet-South Test comments Test started at 0830 hours and ran for 462 minutes. No problems were encountered. Test quality was good. Test started at 0924 hours and ran for 528 minutes. Final leak rate was not obtained, however the data was corrected by subtracting out the last two unknown points (35 cu. ft.). This caused little effect on the final outcome of the test. Test quality was good. Test started at 0808 hours and ran for 450 minutes. No problems were encountered. Test quality was good. Test started at 0828 hours and ran for 450 minutes. No problems were encountered. Test quality was good. �TABLE 2-1. Date (1980) 5/16 5/17 Test No. Sampling locations 11 Hi Volume Sampler 12 Continuous monitors Inlet-North and South Outlet-North and South Blank Hi Volume Sampler ro i CO 1-0 Ul Continuous monitors -J 5/18 13 Outlet-North Hi Volume Sampler Continuous monitors 5/19 14 Outlet-North and South Hi Volume Sampler Continuous monitors (Continued) Test comments Test started at 0306 hours and was stopped at 1910 hours. Test quality was good. THC data reading was high (300 ppm) between 1000 hours and 1030 hours due to temporary shortage of garbage in chute. Test started at 0928 hours and ran for 500 minutes. QA test was performed simultaneously at Inlets on the north and the south. Test quality was good. Test started at 0815 hours and ran for 250 minutes. This was the first day for the cadmium test. Test quality was good. Test started at 0820 hours and ran for one hour at 250°F. Test quality was good. Test started at 1028 hours and was stopped at 1835 hours. Test quality was good. No problems were encountered. Test quality was good. Test started at 0820 hours and ran for 250 minutes. For the cadmium test the outlet was only tested. No problems were encountered. Test quality was good. Test started at 0800 hours and was stopped at 1305 hours. Test quality was good. The outlet was only tested and no THC data was recorded since it was not required for the cadmium test. Test quality was good. Test started at 0810 hours and ran for 250 minutes. No problems were encountered. Test quality was good. Test started at 0800 hours and was stopped at 1300. Test quality was good. No problems were encountered. Test quality was good. �TABLE 2-2. DAILY DATA SUWWRY Gas Composition^' Samplt Volume Dm (1980) Tert No. Sampling Location 1 5-6 2 5-7 3 00 5-8 5-9 4 5 5-10 6 5-11 7 5-12 8 ""« o"'*' ""«< Ou "« ""« Ou <"< °«««< ""« £2 £2 22 22 S3 22 *2S 22 22 O""" 5-4 £2 '•"«< °— '"•« *""•< °"<"' £2 £2 2SL rf 22 £2 "? THC ppm Stock Temperature *F Molecular Weight Moisture 177® 172 156 156 <2 <2 <2 <2 459.47 444.88 432.76 451.27 28.26 26.52 28.33 28.41 11.66 9.S7 11.56 10.87 ACFM DSCFM IMMCH wtlc Raw • % 20.17 21.27 36.40-39.33 50332.218 61074.783 49138.650 53102.715 24952.931 31543.243 25074.591 26754.698 90.82 79.24 94.61 97.96 12.24 12.03 12.47 2.95 20.62 18.42 38.21 40.60 51452.853 52895.304 51588.415 54822.866 25077.734 26217.875 25528.869 29782.359 96.25 98.32 98.85 93.23 28.34 28.36 28.39 28.41 13.43 13.26 12.88 12.75 19.90 21.23 38.70 38.87 49665.946 24406.919 61306.230 '30511360 49556.634 24144.057 52477.069 25634.970 98.17 97.71 100.75 96.29 445.36 460.60 454.20 464.32 28.57 28.50 28.82 28.47 11.27 11.85 8.60 11.60 19.34 19.96 38.39 41.69 48268.522 57305.160 51835.952 56292.592 24418.162 28349.017 26693.503 2773X316 100.22 97.28 96.59 100.04 <2 <2 <2 <2 423.77 460.80 449.64 437.76 28.30 28.20 28.17 28.24 14.14 14.94 15.46 14.89 17.71 V 17.31 32.99 32.48 44193.534 49705.623 44544.600 43856.604 22187.466 23679.562 21337.899 21431.687 99.85 101.90 105.57 107.99 . <2 <2 <2 <2 452.59 457.63 448.92 452.28 28.37 28.34 28.50 28.33 13.62 13.83 11.94 13.40 18.12 17.86 35.43 39.50 45257.690 51267.447 47837.327 53339.650 21770.430 24476.323 2357X100 25751.431 108.82 105.61 98.61 96.51 . <2 <2 <2 <2 463.29 462.48 462.53 447.47 28.19 28.15 28.37 28.30 13.86 14.24 12.91 13.52 19.12 18.51 38.99 38.13 47760.487 53212.640 42103.978 61760.300 22877.439 25400.444 20345.095 30126.657 100.85 100.82 99.20 102.22 <2 <2 <2 <2 456.24 468.33 44X84 452.88 28.40 28.38 28.41 28.42 12.57 12.79 12.21 12.08 17.58 19.11 36.73 39.17 43898.069 54933.801 49586.850 52884.900 21492.745 26479.880 24703.730 26093.924 98.95 94.93 102.67 100.42 CO ppm GMFlow SDCF Nm? 256.837 135.203 317.860 324.144 7.27 3.83 9.00 9.20 11.2 11.2 11.3 11 J 7.4 7.4 7.7 7.7 408.462 379.181 418.430 457.890 11.57 10.74 11.85 12.97 9.6 9.6 10.4 10.4 10.1 10.1 9.5 9.5 159 159 171 171 <2 <2 <2 <2 459.04 445.78 442.00 451.04 28.53 28.56 28.45 29.58 324.361 400.656 403.319 407.071 9.19 11.34 11.42 11.53 9.4 9.4 9.4 9.4 9.8 9.8 9.7 9.7 IBS 185 189 189 <2 <2 <2 <2 445.55 431.46 459.04 457.78 331.522 370.826 427.497 457.496 9.39 10.50 12.11 12.96 9.9 9.9 10.4 10.4 9.6 9.5 8.9 8.9 142 142 169 169 <2 <2 <2 <2 342.697 367.809 371.551 383.750 9.77 10.42 10.52 10.87 7.9 7.9 8.1 8.1 10.5 10.5 10.7 10.7 61 61 59 59 320.564 347.607 367.971 412.061 9.08 9.84 10.42 11.87 8.8 8.8 9.4 9.4 10.3 10.3 9.7 9.7 344.803 378.495 299.617 459.634 9.76 10.72 8.49 13.02 9.8 9.8 9.8 9.8 9.0 9.0 9.5 9.5 316.551 373.034 376.483 391.172 8.96 10.56 10.66 11.06 8.7 8.7 10.4 10.4 9.7. 9.7 9.0 9.0 * r % Velocity ft/sec �TABLE 2-2. (Continued) G n ixMnpoiilion^1 9 Outlet Inlet 5-15 10 Outlet Inlet 5-16 11 ro rwiti«t i i-jfi) Inler*' 5-17 12 5-18 13 5-19 14 Outlet . Moisture •F <2 <2 <2 <2 466.61 468.65 457.16 453.52 28.19 28.19 28.25 28.20 14.57 14.52 14.10 14.54 <2 <2 <2 <2 465.43 458.88 459.56 463.68 28.29 28.27 28.88 28.24 13.60 13.75 8.89 14.22 <2 466.32 467.67 466.72 28.49 28.42 North South North South 306.728 364.161 366.284 388.729 8.74 10.31 10.37 11.01 9.7 9.7 9.1 9.1 9.6 9.6 9.8 9.8 North South North South 338.450 376.856 377.441 396.275 9.59 10.67 10.69 11.22 9.4 9.4 9.7 9.7 Il l 98 98 North South North South 353.833 357.302 404.610 416.675 10.02 10.12 11.46 11.60 11.1 11.1 11.8 11 J 8.6 8.6 7.0 7.9 88 98 M <a North South 324.920 331.750 9.20 9.40 10.3 10.3 10.0 10.0 80 80 <2 <2 218.810 6.20 10.7 9.0 84 <2 . North South Velocity ft/sec Isokinetic Rale ACFM OSCFM 16.42 17.82 36.85 39.39 41015.923 51223.782 49744.800 19294.229 24032.783 23723.700 105.23 107.11 104.01 iaos 17.67 35.47 3&49 45076.682 50795.373 47889.900 51958.800 21919.803 24835.199 24697.316 25113.412 102.87 102.67 102.40 11.15 11.69 ia79 46930.228 -23389.304 2S8Z3.208 101.23 93.06 MM ii'-9 2*27 28.37 13.47 13.70 *7lf 17.25 16.85 n!ilJi?nfi nifwum 474.80 476.00 461.00 28.16 14.38 39.27 Iff8297 43045.650 48387.834 20524.938 23013.917 l?i"? 97.56 102.20 106035.080 51352.600 103.01 \ © 219.36 North South GaaFlow Molecular Weight Nm3 Outlet Inlet THC ppm SOCF Outlet® Inlet "P CO ppm OtOlNM Inlet Stack 02 I 5-13 Sampling Location "- Test No. wjopp Date (19801 Sample Volume 6.20 10.7 9.2 102 © 463,00 28.25 13.91 44.37 119798.300 57360.170 92.45 6.81 12.7 7.2 304 (!) 465.60 28.36 11.66 44.53 120233.700 69137.720 98.36 © 240.61 Test period average High due to excessive instrument drift Analyzer taken off line (see© ) Due to excessive leak rate in the north train. 60% of sample was collected with south train, 40% with the north Results t 10 ppm due to drift Inlet QA Test, Outlet 1st day Cadmium Test Inlet sample not required for Cadmium Test THC data not required for Cadmium Test �These three parameters were also monitored by means of integrating counters. Each numerical reading multipled by 150 yielded the amount of steam in pounds, the amount of feedwater in pounds, or the amount of combustion air in cubic feet. These numbers have been included in the tables in Appendix D in terms of 1000's of pounds or 1000's of cubic feet. The differences of these numbers were also calculated on an hourly basis to determine flow rates from these quantities and are listed under "digital integrator" in Appendix D. Each integrator reading is assumed to have been taken at the end of the hour in question. For instance, the 5 PM reading represents the hour ending at 5 PM, as opposed to the hour beginning at 5 PM. This was necessary in order to maintain consistency, especially in the case of the integrator differences. The difference between the 5 PM integrator reading and the 4 PM integrator reading represents the flow occuring between 4 PM and 5 PM, and therefore is a 5 PM flow measurement, according to this end-of-the-hour convention. Further, the digital counters recycle occasionally. Since the counters have six digits, the largest possible number is 999,999 x 150 * 1000 or 150,000. It must also be noted that even a 5 minute delay in taking a reading introduces a substantial error in the hourly value. Finally, these integrator values were the only readings not routinely taken by plant personnel on a 24 hour basis. As a result, large gaps exist in this data. Averages were taken over these periods whenever possible. The steam flow rate was also recorded on a continuous basis. This was done by an ink pen recorder located outside the control room. The recorder plotted instantaneous steam flow values on graph paper. Hourly values were recorded from these sheets, and are presented in Appendix D under the heading "disc recorder". Although this instrument may have been very accurate, the operators were not always careful at aligning the paper discs. The erratic nature of steam production at the plant was easily observable from these plots. Oscillations of an amplitude of 30,000 Ibs/hr and a frequency of 6-10 cycles per hour seemed typical. A sample plot is provided in Appendix D. 2-11 260 �Steam pressure, combustion air temperature, % oxygen, I.D. fan pressure, F.D. fan pressure, furnace draft, and furnace temperature were all noted from pointer gauges in the control room. The combustion air temperature was actually a measurement of the flue gas leaving the boiler and entering the economizer. The sensor for % oxygen was located on the ESP side of the economizer. It must also be noted that the furnace draft and I.D. fan meters were actually measuring a vacuum. Other information contained in the daily process data tables includes times of soot blowing, fuel input to Boiler No. 2, down time on Boiler No. 2, a daily barometric pressure and miscellaneous comments concerning the boiler operation. According to plant procedure, soot blowing should have always occurred at 3 AM, 11 AM, and 7 PM every day, but deviations from this schedule were often observed. Fuel input is usually expressed as crane loads, or charges of refuse. In only one instance was natural gas burned to start up the boiler. The amount of gas burned is reported in cubic feet, but the actual measurement involved reading a numeric counter and multiplying by 3.5. Down time is expressed as lost burning time, and was available by consulting plant records. The barometric pressure was obtained once a day from nearby Midway airport. Comments listed on the process sheets (refer to Appendix D) were derived from the operator's log book or by discussing plant conditions first-hand with the operators and firemen on duty. 2.2.1 24-Hour Data The means and standard deviations of the parameters included in the daily process sheets were calculated on a 24-hour basis for every day of testing. This information has been presented in Table 2-3. On some days Boiler No. 2 did not operate for the entire 24 hour period. For these days, data was not available on a 24 hour basis, consequently values have been calculated based on available information. Also, since the integrator differences were often averaged over long periods of time, it did not seem appropriate to provide standard deviations in these instances. A qualitative observation from Table 2-3 indicates that the plant operation is very uniform over a time average of one day. According to the daily process sheets, no strong diurnal variations occurred. This is not to say that large variations did not exist. Shorter averaging times (less 2-12 261 �i ;-3. a to* "Bctss »i« rw TH cmmo mimsi micim WI«««TI».I»IT •». z D»t« 5-4-80 5-6-8D 5-J-SU 5-8-80 5-9-80 5 M>-*0 5- 11-80 5-12-89 5-13-80 5-15-80 5-16-80 5-17-80 N«M " DUc Reorder (Ibt/hr) Chart Recorder (ll»/hr) Digital Integrator (tfas/hr) SteMrrttttire (pitg) KMOOO* 108000* 100000* 11389.3 9358.6 M 91000* 102000* 91000* 30891.2 11827.8 M FeedMter le^er*t«r« 1>F) Cn*«tfo« Mr Flo- 3 late Chart Recorder (ft /hr) Digital Integrator (ftVhr) Conbustlofi Atr Tei^erature (*F) Veneni 0>ygen 103000 »JOO» 99000 13078.3 11804.8 R» 102000 106000 103000 1T545.0 8801.8 M HMOOO 104000 WJOOO 10309.1 M9S7.8 M 100000 WOOD 102000 11262.9 14320.8 M 94000 104000 98000 10490.6 I42D5.S Rft 95000* tOtOBO* 100000* 14826.7 13869.7 RM 9COOQ 102000* 97000 97000 98000 47000 97N.9 1255.0 M M3000* 102000 100000 9330.3 94C5.0 M V2000* •HOW 99088 I395O.9 I3S76.9 m 92000 90000 93800 18800.6 19195.7 M t.O 270* 4.9 284 6.8 784 7.6 2H 6.' 7R5 «J8 783 4.4 282* 7.S 6.1 782 7.0 285* 4.9 284 4.7 277 5.3 9486.8 M 104080* 86000* 793S.6 M 103000 99000* 17740.4 Rft 96000 98000 16606.7 M M3000 102000 10908.6 M 101000 102000 12171.4 A* 102000 180000 13«68.4 Rft 102000 97000 13660.4 M 96000* 99000* K224.4 Nt 96000* IOODDD 9785.0 M 93000 95000 98)6.3 UK 99000 W2OOD* 17032.) » 103800 14676 .0 87000 13947 .9 277* 3.0 ?22* 3.2 220 1.0 720 0.6 220 0.8 271 1.4 270 f.l 221 2.1 270* 8.6 221 0.9 220 O.C 221 771 0.9 770 0.76 87000* 75000* 3010.4 M 79000* 74000* S369.7 M 77000 70000 4505.8 M 8 MHO 73000 S070.5 M 77008 70080 7494.8 M 79000 77000 7979.9 R* 17000 71000 4iB5.l « 77000 69000 46B5.C RA 78000* 70000* 4486.0 « 78000* 72000 5348.0 RH 87000 74000 S7S3.4 W 82000 73080 5«93.7 M 80000 72000 43K.9 m BIOOB 79000 9279.8 M 6S8* 126.3 681 642 26. t 662 27.3 67D 615 38.9 653 651* 71.5 660 66C 73.0 «51 25.8 67S 31.2 V*.I* 21.7 ln . tt.B* 5.0 10.5 306.0 1209 39.4 1.5C \ZA 1.6 U.I t.55 (t.O 20.1 \A\ U.I t.JB 11.1 77.4 1.M 66S* 49.7 M.7* 2.M 1168* 108.7 283 983'.B 9367.3 m 5-19-80 o 98000* 97000* m* 284 8868.5 99*9.8 M PteM 283* Fec«Wt«r F!M flat* Chart Recorder (Ita/hr) Digital Integrator (Ibi/hr) 59.4 »3000 W8000 107000 5-M-80 • 11.1 1.35 13.5 3S.4 2.13 MM 8.93 1. 12 •MOO M.I m 1.50 nooo 12.6 * 1.20 MjO »?0 Fwnace Te^wrater* (f) 1178* * Does not raprtimt fall 24-hB«r period NJ ON ro *1.2 1096* RK • Rot JlpproyrUtt 71.0 IH? 72.7 1189 107.8 1164 77.3 1203 186.4 1)60 «8.l 1170 65.S 1112 60.8 1204 78.« 1207 «.6 1081 99.0 2-13 �than an hour) would indicate large swings, and this is reflected in the large standard deviations for steam production in Table 2-3. This was due to the intermittent nature of fuel feed to the boiler. However, these production swings did not depend on time of day or day of week. Consequently, it was possible to calculate means and standard deviations over a large number of test days. This has been done for all of the test days (refer to Table 2-4). An examination of data in Table 2-4 indicates that the standard deviations are smaller than most of the standard deviations in Table 2-3. Although variations may be expected to decrease over longer averaging times, this would not be true if certain days had significantly different modes of operation. The aforementioned therefore indicates that the Chicago Northwest Incineration facility operates in essentially the same mode 24 hours a day, 7 days a week, although instantaneous swings in steam production do occur continuously over short time intervals (less than one hour). 2.2.2 Test Duration Data Means and standard deviations have been calculated on a test duration basis for all of the test days. This information has been provided in Table 2-5. The discussion on diurnal variations pertaining to the 24-hour data also pertains here, although the standard deviations should, in general, be smaller due to the shorter period of time being considered. An examination of the data in Table 2-5 bears this out. None of the data in Table 2-5 appears particularly anomalous. No significant variation in steam production occurred from day to day indicating a rather consistent fuel feed rate during the duration of the tests. Some days exhibited wider variations as reflected by higher standard deviations, particularly on the 19th of May, The variation of feed water flow does not corelate well with the variation in steam production. The operating parameters seemed to fluctuate rather independently, without any pronounced impact on other aspects of plant operation. 2-14 263 �TABLE 2-4. MEANS OF THE MEANS FOR 24-HOUR PROCESS DATA, ALL TEST DAYS, CHICAGO NORTHWEST MUNICIPAL INCINERATOR. Parameter Steam Flow Rate (Ibs/hr) Disc Recorder Chart Recorder Digital Integrator Steam Pressure (psig) Feedwater Flow Rate (Ibs/hr) Chart Recorder Digital Integrator Mean a 99,000 103,000 99,000 282 4,516.8 3,577.0 4.02 99,000 97,000 4,822.7 5,445.5 221 0.7 79,000 72,000 2,016.4 2,593.3 663 21.2 Feedwater Temperature (°F) Combustion Air Flow Rate (ft /hr) Chart Recorder Digital Integrator Combustion Air Temperature (°F) % Oxygen 11.8 1.23 I.D. Fans Pressure (inches H20) 2.6 0.22 F.D. Fans Pressure (inches H20) 14.1 0.38 Furnace Draft (inches H20) 0.23 Furnace Temperature (°F) 1,160 2-15 264 .061 41.5 �UBXE 2.-, . UST DUMIHBI mass D*U rot rat CHICAGO miMCSi mnicirni Date 5-4-80 5-6-80 S-7-M 5-8-80 5-9-80 5-10-80 "*an StewFlw **t* Disc R«cor4er (Ita/hr) Chart *«C«ntor (lb»/hr) Dljltal InteyHOr (Ibt/hr) StM«Pr«wrc (Bilg) F *ctjrt*»«iXV(IH/hO Bt.ltll iHtefritor (m/V) FertMtcr tv-twratw-c (T) CvtwsttM Air Flo. lite Chart Recorfer (rtVhr) Olfltal Integrator (ftVhr) Cnatasttwi Air Te-veratwe (T) Percent 0*rf*« FBTMCC TtJV«ratvrc (*F) • SOME data points tr* mi**l*i 96000 103000 91000 HH46.3 11319.2 W 98000 104000 104000 17676.4 7H6.1 M W7000 1IB8O 108006 286 7.4 286 7.0 288 95000 90000 7SS9.3 M 104000 100000 7146.1 M M8000 183000* 22J 3.6 221 2.1 87000 7MMO 3770.1 M 79000 74000 701 724 K -* 1M9 26.2 '-*' 45.8 »•' T20S Ne«n 17509.6 12878.7 * 110000 11)000 113000 8165.6 3500.0 IN 103000 112000 MKOBO 12202.5 16465.8 M 99000 109008 WWOO 11121.8 12)01.8 M 4.1 284 6.1 290 8.0 288 6.) 284 S.S 285 5.0 8738.6 M 9SOOO H2000 24494.9 M 114000 I MOOT 4I8S.6 M tMOOO WS008 18C09.6 M 107000 KKOOO 1)64 JJ M 103000 H3000 KH43.5 M 220 1.5 220 0 271 1.7 221 14 222 3.1 4743.4 M 77000 690OD 4101.0 M 80000 73000 3503.2 M 77000 67000 3492.1 Hft 79000 70008 8350.6 M 76000 69000 MM.* M 76000 7 1000 5186.5 M 31.4 6TB 33.2 646 29-* 676 28.5 611 27.1 G92 653 18.9 S9.9 »•* 1275 '•" 52.4 "•* 1189 '-u 71.8 220 *•' 1290 9 '•** 67.9 tt -° 12(75 2 n - 100.6 94 1264 21.6 1.64 M.S 97000* tOSOOO 105000 5- 1?-BO • 110000 111000 104000 '-14 63S6.1 9)42.8 « S- 1 1-80 • M.S I19S 11BB6.0 MH22.0 HA 1.83 121.2 ttun S- 11-80 « 96000 10 WOO KXDOO* 284 102000 WOOOO* 220 77000* 68000* 672 11.1 UN Ncln 1)785.7 N319.4 M 95000 94000* 100000 6.8 287 6687.5 IN 98000* 104000 0.* 220 5669.5 IN 77000* 70000 38.8 S- IS 80 • 657 1.42 48.1 11.2 1188 II2'6.) 3*11.1 M 3.5 8292.6 M 0 U74.7 M 23.1 1.32 73.8 HCM 5- 16-80 • 95000 99000 92000 287 93000 9)000 220 88000 72000 647 14.0 1129 10 MB. 8 7153.6 M 3.3 10972. > M 0 H43.4 M 28.7 1.01 64.7 5- 17-80 • NCM 10)000 106000 94000 289 104000 84000222 81000 67000 671 9.8 12)8 Plean 8533.4 879S.2 IW 5-18-80 a HTOOO 106000 104000 Mean 11604.6 33M.6 M 79000 82000 7 NOD 23741.7 3Q7H.J HI 2.9 288 2.4 281 2.5 8266.4 M 108000 117000 5000.0 M 80000 7 WOO 1789S.S M 0.9 221 1.2 222 1.0 SHOO 69000 2500.0 M 4313.S -ft 75.8 l.ZS 62.6 80000 73000 690 D.9 1269 0 M 8.2 37.5 68.1 645 1.64 13.1 T019 W • MH Appropriate hJ Ul 5- 19-80 • 2-16 1.11 134.1 �2.2,3 Meekly Refuse and Residue Inventory All refuse and residue hauling trucks entering and leaving the incinerator plant were carefully weighed. This facilitates the accurate characterization of overall inputs and outputs. However, there is no accurate way of proportioning these materials between specific boilers for a given period of time. Any attempt to determine the fuel burned or ash discharged from Boiler No. 2 can only be an approximation. Chicago Northwest Incinerator maintains inventory sheets listing inputs and outputs from the facility on a weekly basis. Relevant data from these sheets have been reproduced in Table 2-6. The weight of refuse received was measured on scales before and after the refuse trucks released their loads. The volume of refuse received was determined by multiplying the number of truck loads by the volume of each truck (19.5 cubic yards). Density of the refuse was estimated using these two measurements, and is therefore the density of refuse inside the trucks. In order to quantify the amount of refuse burned, the number of loads, or charges, handled by the grab bucket cranes were noted for each boiler. A total number of charges are listed in Table 2-7. The charges delivered to Boiler No. 2 are given in the daily process data sheets on a shift basis. These are provided in Appendix D, To approximate the amount of refuse burned in Boiler No. 2, it is necessary to determine an average weight per charge, since the number of charges fed into this boiler are known (Appendix D). The method for doing this, however, is not entirely obvious. When refuse trucks enter the plant, they discharge their contents into a large storage pit. Although the weight of refuse added to the pit is well characterized for each weekly period, the carry-over of material from week to week cannot be accurately measured. Furthermore, this carry-over is quite variable over the length of time being considered. It is also significant, as the pit is sometimes over half full, corresponding to roughly 5000 cubic yards of refuse. It is necessary to quantify the carry-over in terms of weight, so that the total weight of refuse burned, and hence, the average weight per charge, can be approximated. This can be done by 3 different methods. 2-17 266 �TABLE 2-6. WEEKLY INVENTORIES OF REFUSE AND RESIDUE AT THE CHICAGO NORTHWEST MUNICIPAL INCINERATOR (ALL BOILERS). 4/28/80 to 5/4/80 5/5/80 to 5/11/80 5/12/80 to 5/18/80 5/19/80 to 5/25/80 6,746.65 24,490 551 9,152.34 29,618 618 7,902.34 26,561 595 8,720.21 28,778 606 84 65 61 42 65 61 42 42 5,205 5,710 5,952 4,714 2,771 7,212 28,562 3,240 9,250 36,634 2,812 8,367 33,138 3,700 8,720 34,535 2,511 3,100 2,500 3,086 1,815 2,240 2,904 3,585 Metal fraction (tons) Metal fraction (cubic yards) 949 5,423 750 4,286 1,514 18,651 629 3,594 Total ash (tons) Total ash (cubic yards) 3,460 8,523 3,250 7,372 3,329 10,891 3,533 7,179 70% 80% 67% 79% 52% 65% 60% 60% Refuse Received By weight (tons) By volume (cubic yards) Density (lbs/yd3) Storage Pit Condition At beginning of week (% full) At end of week (% full) Refuse Consumed # charges burned Average weight per charge (Ibs) Total weight (tons) Total volume (cubic yards) Residue Fine ash fraction (tons) Fine ash fraction (cubic yards) Volume Reduction thru incineration Weight Reduction thru incineration 2-18 267 �TABLE 2-7. CHARGES FED TO EACH BOILER ON A SHIFT BASIS CHICAGO NORTHWEST INCINERATION FACILITY Unit No. 1 Unit No. 2 Unit No. 3 88 101 101 27 89 35 -78 75 38 94 101 101 97 33 27 62 20 94 36 101 98 99 100 94 101 90 94 101 94 49 98 100 98 101 100 102 99 97 96 12 -- 101 100 101 89 97 94 99 94 95 45 93 98 95 96 102 96 97 98 93 101 100 Total for week 1398 1823 1984 Date, Shift 4-28, 4-29, 4-30, 5-1, 5-2, 5-3, 5-4, 5-5, 2nd 3rd 1st 2nd 3rd 1st 2nd 3rd 1st 2nd 3rd 1st 2nd 3rd 1st 2nd 3rd 1st 2nd 3rd 1st 2-19 268 Unit No. 4 Total 287 300 302 210 287 219 193 273 264 132 285 299 294 294 235 225 258 215 283 149 201 0 5205 �TABLE 2-7. Date, Shift 5-5, 2nd 3rd 5-6, 1st 2nd 3rd 5-7, 1st 2nd 3rd 5-8, 1st 2nd 3rd 5-9, 1st 2nd 3rd 5-10, 1st 2nd 3rd 5-11, 1st 2nd 3rd 5-12, 1st Total for week Unit No. 1 Unit 106 83 102 104 70 37 14 . 101 (Continued) • • • No. 2 Unit No. 3 -._ 68 112 99 101 86 103 107 111 98 77 102 102 101 101 101 98 52 101 103 102 99 104 84 100 81 101 100 100 98 100 99 101 100 102 101 105 103 83 97 101 101 98 100 100 101 101 100 102 103 101 102 100 1860 1754 2096 Unit No. 4 2-20 269 Total 207 169 205 279 293 234 181 298 259 304 300 301 299 302 298 253 303 308 304 306 307 0 5710 �TABLE 2-7. (Continued) Date, Shift 5-12, 2nd 3rd 5-13, 1st 2nd 3rd 5-14, 1st 2nd 3rd 5-15, 1st 2nd 3rd 5-16, 1st 2nd 3rd 5-17, 1st 2nd 3rd 5-18, 1st 2nd 3rd 5-19, 1st Total for week Unit No. 1 Unit No. 2 Unit No. 3 39 97 102 104 98 100 98 94 99 99 100 100 60 --96 98 99 100 104 103 236 295 302 308 261 100 96 102 200 194 292 106 105 107 104 106 108 106 97 110 107 106 no 85 108 320 318 321 324 220 330 98 118 112 97 114 112 98 108 334 293 340 106 75 -- 108 104 118 109 105 124 -- 105 110 323 284 242 215 1943 2194 108 38 112 no 1815 Unit No. 4 no 2-21 270 0 Total 5952 �TABLE 2-7. (Continued Unit No. 1 Unit No. 2 Unit No. 3 5-19, 2nd 3rd 5-20, 1st 2nd 3rd 5-21, 1st 2nd 3rd 5-22, 1st 2nd 3rd 5-23, 1st 2nd 3rd 5-24, 1st 2nd 3rd 5-25, 1st 2nd 3rd 5-26, 1st „ 103 110 105 104 118 110 100 106 90 80 105 100 114 105 106 100 108 103 104 Total for week 416 Date, Shift 104 120 __ — -68 21 -__ — -__ — — __ — — -— 107 105 2139 107 107 102 98 105 94 101 105 2-22 271 Total 224 313 314 338 218 203 210 246 183 88 82 107 100 104 104 100 92 107 101 104 108 102 100 2159 Unit No. 4 212 200 211 211 202 190 212 195 205 213 209 205 0 4714 �The first method involves using visual measurements of the pit volume taken at the end of each week. This "pit estimate" can then be used in association with the density of the incoming garbage to approximate the weight of refuse in the pit. Then the average weight per charge can be determined by the following equation: Average wt per charge (pit estimate for previous week - pit estimate ~ + refuse delivered) * total number of charges All terms in parenthesis must be expressed as weights. This method however has a drawback in that the density in the pit is probably not the same as the density inside the refuse trucks, since the refuse inside the trucks is compacted and is liable to expand somewhat as the trucks are unloaded. The second method is essentially the same as the first, but a different assumption is made for pit density. It seems likely that the level of compression would have a more pronounced effect upon the refuse density than the actual characteristics of the refuse. Since the compaction inside the pit is always similar, one would also expect the density in the pit to be reasonably constant. In principle, this is the method applied by the plant personnel, but in practice it is not consistently used by them. It has been found from plant operational experience that a density of 505 Ibs/yd is typical of the pit contents. Therefore, this value can be used as an assumed density, and the pit estimates used in the equation as before. The third method circumvents the problem of pit estimation entirely. Assuming that every charge constitutes a full load of the crane grab bucket, the weight of the charge can then be estimated by multiplying the maximum volume of the bucket by an assumed density. The maximum volume of the bucket is five cubic yards. The primary disadvantage of this method is that any inaccuracy in the density is directly reflected in the average weight per charge. In this report the second method was chosen as the most appropriate, and the values for total refuse consumed and average weight per charge were tabulated (refer to Table 2-6 ). A constant, assumed pit density (assumed in method 2) was preferred to a variable "measured" density of method 1. 2-23 272 �Furthermore, a "bad" density assumption will cause smaller errors in the first and second cases than in the third case. The second method can be summarized as follows: Volume of refuse in pit = pit estimate (% of total volume) X total pit volume 100 total pit volume = 9700 yd3 Weight of refuse in pit = volume of refuse in pit X refuse density in pit assumed refuse density = 505 Ib/yd Weight of refuse incinerated per week = (weight of refuse in pit at beginning of week - weight of refuse in pit at end of week + weight of refuse delivered) Average weight per charge = total weight of refuse incinerated total number of charges Volume of refuse weight of refuse incinerated incinerated - assumed refuse density The amount of fine ash and metal fractions produced by the incinerator during the test period are listed in Table 2-6 . It should be noted that these are the amounts leaving the plant during this time period, and are not necessarily the same as the ash being produced during this period. Since no account has been taken of any carry-over from week to week, it can only be assumed the carry-over is similar each week. In order to obtain total ash, the metal and fine ash fractions were summed together. The ash volumes were calculated using the following densities: Density of fine ash fraction = 1620 Ibs/yd Density of metal fraction = 350 Ib/yd3 These values are based on previous analyses done by the plant, and have been assumed to be typical. Since all of the combined ash was subjected to a water quench, these weights incorporate a rather large moisture content. However, no better characterization was available. The volume and weight reductions achieved through incineration have been calculated as an indication of how efficiently the boilers were operating. 2-24 273 �The ash produced by each boiler can be estimated by either of two ways. First, by estimating the number of hours each boiler was down, the total number of operating hours can be found, and an approximate ash production rate per boiler operating hour can be calculated. All necessary information concerning boiler down hours is presented in Table 2-8. Alternatively, by knowing the number of charges fed to the boilers in a weeks time, an approximate ash production rate per charge of refuse can be calculated. A distribution of charges fed to each boiler on a shift basis is presented in Table 2-7. 2.3 CONTINUOUS MONITORING DATA Table 2-9 presents daily averages of 02, C02, CO, total hydrocarbons, and ambient temperature as monitored by continuous data logging instrumentation over test duration periods. Hydrocarbon values were consistently lower than the instrument sensitivity of 2 ppm. Most of the data indicates very little variation except for the CO values. The rapid change between May 8, 1980 and May 9, 1980 was due to instrument drift, which places doubt on the validity of the previous data also. The CO analyzer was taken off line, and a new one replaced on May 15, 1980. The high CO value on May 19, was due to unusally high moisture in the fuel on this day. Moreover, the operators did not compensate for the wet feed by changing boiler condition. They were reluctant to change conditions because a new supply of dry feed was anticir pated. The high moisture content in the fuel probably inhibited combustion and made burning less efficient. This is reflected in higher 02, lower C02, and higher CO concentration as compared to those on normal operating days. In Table 2-10, values of percent oxygen measured in the control room and by TRW continuous monitoring instrumentation are compared. The control room readings were observed to be higher than the 02 analyzer readings on all days except one. This is unusual since the readings should be identical. In any event, the 02 analyzer should either yield identical or higher readings, because the sample was obtained further downstream and any leakage in the duct would tend to increase the 02 level of the gas stream. This discrepancy could be due to offset instrument calibrations. It must be noted that the 02 analyzer indicating lower readings was calibrated (for zero and span) prior to the start of testing and also after the testing concluded for each test day. The control room oxygen analyzer was calibrated once a week. 2-25 274 �TABLE 2-8. DOWN TIME EXPRESSED AS LOST FURNACE HOURS FOR THE ENTIRE CHICAGO NORTHWEST INCINERATION FACILITY Unit Unit No. 2 Unit No. 3 Unit No. 4 Total 16 0 0 1 8 0 15 9 5 0 0 7 0 0 0 6 0 0 0 24 24 24 24 24 24 24 25 32 41 43 24 39 40 ~57~ ^T3~ T- T5S~ 2~4T~ 0 5 13 2 0 5 0 24 12 0 2 0 0 0 0 0 0 0 0 24 24 24 24 48 41 37 28 0 0 24 24 24 24 29 24 25 38 0 168 231 5 0 0 0 6 0 11 0 5 16 0 1 0 0 0 0 0 29 29 40 0 0 24 24 24 24 24 24 24 ~22~ "22" ^r T58~ 2l3~ 10 0 8 18 23 24 24 24 0 0 0 24 24 0 0 0 0 0 24 24 0 0 0 1 0 24 24 24 34 32 42 47 48 49 48 Total for week 131 0 1 168 300 Total 235 73 8 672 988 Date 4-28-80 4-29-80 4-30-80 5-1-80 5-2-80 5-3-80 5-4-80 Total for week 5-5-80 5-6-80 5-7-80 5-8-80 5-9-80 5-10-80 5-11-80 Total for week 5-12-80 5-13-80 5-14-80 5-15-80 5-16-80 5-17-80 5-18-80 Total for week 5-19-80 5-20-80 5-21-80 5-22-80 5-23-80 5-24-80 5-25-80 No. 1 1 8 0 1 Total possible hours • 2688 Hours lost » 36.8% 2-26 275 24 32 24 35 �TABLE 2-9 . Sampling Location oz (») Date (1980) CONTINUOUS MONITORING DATA co2 Mean a Mean CO (pom) (*) a THC (ppm) Mean o Mean a *nb1ent Temperature (°C) Mean o ESP Inlet ESP Outlet 7.4 7.7 1.07 0.82 172 156 32.76 25.38 <2 <2 24.7 2.36 5-6 9.6 10.4 1.43 1.37 10.1 9.5 1.34 1.20 163 171 20.92 25.04 <2 <2 15.5 5.45 5-7 9.4 9.4 1.06 1.78 9.8 9.7 0.96 1.51 185 198 17.28 44.88 <2 <2 11.6 1.10 Inlet Outlet I 1.38 0.90 Inlet Outlet N> 11.2 11.3 Inlet Outlet ro 5-4 5-8 9.9 10.4 1.98 1.81 9.5 8.7 1.B1 1.43 142 169 51.32 90.54 <2 <2 10.0 1.21 Inlet Outlet 5-9 7.9 8.1 1.09 1.62 11.0 10.7 0.96 1.37 78 71 38.76 38.66 <2 <2 14.1 1.98 Inlet Outlet 5-10 8.8 1.36 <2 18.4 3.56 1.74 10.3 9.7 1.38 9.4 Inlet Outlet 5-11 9.8 9.8 1.18 1.58 9.5 9.5 1.06 1.05 <2 <2 16.7 1.77 Inlet Outlet 5-12 9.6 10.4 1.11 1.69 9.7 9.0 0.89 1.42 <2 <2 12.4 0.66 Inlet Outlet 5-13 9.7 9.6 1.67 1.42 9.6 9.8 Inlet Outlet 5-15 10.2 9.6 1.51 1.47 Inlet Outlet 5-16 11.1 11.8 Inlet Outlet 5-17 Inlet Outlet 5-18 Inlet Outlet 5-19 1.54 Instrument Malfunc. tion ., <2 H n N M .38 .14 " " <2 <2 11.6 5.60 9.4 9.7 .38 .18 112 98 36.01 25.70 <2 <2 15.6 2.71 1.39 1.32 8.5 7.9 .18 .16 88 98 61.92 75.58 <2 <2 16.3 1.19 10.3 10.7 0.90 1.36 10.0 9.0 0.75 1.17 80 84 29.61 27.26 <2 <2 12.8 1.23 Kl_«. 12.0 1.34 0.93 not Required 10.7 u_a. HOt Required 13.0 0.96 12.7 1.86 n^+ . n-.*- -. taken for outlet only 0.35 102 9.2 —• 18.71 taken for outlet on 1 y 304 1.69 7.2 184.86 �TABLE 2-10. Testing Date 5-4 5-6 5-7 5-8 5-9 5-10 5-11 5-12 5-13 5-15 5-16 5-17 5-18 5-19 MEANS OF PERCENT OXYGEN TAKEN BY CONTROL ROOM GAUGE AND 0« ANALYZER FOR TEST DURATION Control Room (%) 16.4 10.1 10.3 11.5 9.2 12.0 9.8 10.3 11.1 11.2 14.0 9.8 10.9 13.1 2 Analyzer Difference (ESP inlet) (%) (Control Room Analyzer) 11.2 9.6 9.4 9.9 7.9 8.8 9.8 9.6 9.7 10.2 11.1 10.3 10.7 12.7 2-28 277 5.2 0.5 0.9 1.6 1.3 3.2 0.0 0.7 1.4 1.0 2.9 -0.5 0.2 0.9 �3.0 PLANT DESCRIPTION Chicago Northwest Incinerator is located south of W. Chicago Avenue between the tracks of the Chicago and North-western Railway on the west and Kilbourn Avenue on the east. The principal building of the complex is the Incinerator, a multi-storied structure of reinforced concrete with dimensions of 330 feet by 180 feet and with a maximum height of 79 feet from grade to the main floor. The lowest part of the structure is the floor of the refuse storage pit, approximately 37 feet below grade. To the south of the Incinerator Building and connected to it by the residue conveyors enclosure is the Ash Discharge Building. To the north is the Incinerator Office Building which also houses the maintenance shops. Two stacks each 250 feet in height are located east of the Incinerator Building. The electrostatic precipitators and the induced draft fans are situated between the Incinerator Building and the stacks. The Chicago Northwest Incinerator layout is shown in Figure 3-1. The general characteristics of the Chicago Northwest Incinerator are listed in Table 3-1. 3.1 General Description Refuse is delivered to the dumping pit of the plant by trucks which back into position above the refuse pit. From the refuse storage pit, crane grapple buckets pick up the refuse and dump it directly into the four furnace feed hoppers. The furnace feed hoppers open into feed chutes which feed automatically onto the stoker grates of the four furnaces. The grates operate with a reverse-reciprocating action producing an initial downward movement of the refuse and then an upward movement. This combined movement results in a tumbling action. The motion of the grates, an underfire grate jet action, and overfire air jets above the grates all combine to promote highly effective burn-out and complete oxidation of the furnace gases. The hot furnace gases travel through five boiler passes enroute to the electrostatic precipitator (ESP). Approximately 110,000 pounds of steam is generated by each of the four boilers. In passing through the boiler, the 3-1 278 ' �WEIGF STATION ^STACKS CHICAGO NORTHWEST INCINERATOR ELECTROSTATIC PRECIPITATOR ASH REMOVAE EQUIPMENT INCINERATOR 286 REFUSE STORAGE PIT I IN) 330' TIPPING FLOOR AREA VO SERVICE STATION PARKING AREA Figure 3-1. Layout of plant site �TABLE 3-1. CHARACTERISTICS OF CHICAGO NORTHWEST INCINERATOR Number of incinerator units Number of refuse cranes Number of chimneys Refuse pit capacity Capacity of each crane bucket Average heating value range of refuse Capacity: Refuse Steam Generation Furnace temperature Stack gas temperature Gas cleaning equipment Precipitator efficiency Precipitator outlet grain loading 4 3 2, each 250 feet high 9,700 cubic yards 5 cubic yards 5,000 BTU/lb 1,600 tons/days 440,000 Ibs/hour 1,500° - 2,000°F 450°F 4 electrostatic precipitators 972 0.05 grains/std. cu. ft. gases are reduced in temperature to approximately 450°F. The residue from the grates and the fly ash collected by the ESPs are dumped into the ash discharger. The discharger which is partly filled with water quenches the ashes and via residue conveyors transferred to the ash building. The ashes are then screened. Salvageable metals are sold for reuse. The remaining ashes are taken from the ash building by trucks and used in construction projects or places as sanitary landfill. A line diagram of the Incinerator is presented in Figure 3-2. 3.2 DETAILED DESCRIPTIONS 3.2.1 Refuse Handling Mixed refuse from domestic sources 1s brought to the incinerator plant in collection trucks, each truck has a capacity of 5 tons or 25 cubic yards. The refuse averages 400 pounds per cubic yard. The refuse varies considerably in consistency and moisture content over a period of time and 3-3 280 �r TRUCKED REFUSE FEED MATER AIR COOLED CONDENSERS UPSCALE REFUSE DELIVERY PIT EH i REFUSE FEED HOPPER I BOILER OVERFIRE •> COft€RCIAL STEAM STEAM DRUMS INTAKE FAN i. • BOILER HOPPER FLY ASH (ECONOMIZER] 1 HOPPER 1 AIR hO 00 S T A C K 1 HOPPER i f f ASH DISCHARGE HOPPER STOKER GRATES COMBINED ASH SIFTING GRATES I FORCED DRAFT FAN HEAVY METALS Figure 3-2. Flow diagram of Chicago Northwest Incinerator FINE ASH �this condition is reflected in the changeable calorific (heat) content of the refuse. Trucks are weighed over scale platforms. After weighing these trucks are directed to eleven stalls in front of the refuse storage pit. After depositing their load the trucks leave the building through doors in the south end. Refuse items that are too large to be handled through the charging hopper and feed chute (such as mattresses, upholstered furniture, etc.) are removed. Bulky metal objects from the storage area are removed by trucks. The refuse storage pit has a storage capacity of 9,700 cubic yards or 1,940 tons or sufficient "fuel" to last 29 hours when the four incinerators are operating normally. This necessitates refuse collection on six days of the week. However this is not always possible due to various reasons such as unfavorable weather etc. At such times auxiliary gas firing is utilized to meet steam demand and to keep the furnaces from cooling down. The refuse is removed from the pit by one of three transfer cranes. These cranes are overhead, high speed, two-girder, single trolley, travelling, grab bucket cranes each of 8.5 tons capacity handling mixed refuse from the storage pit to the furnace charging hoppers. An auxiliary hoist of 2.5 tons capacity is provided on each of the end cranes and mounted on crane trolleys. Each crane bucket has a 5 cubic yard capacity and is a fourline, line-type grapple. All crane components are electric motor driven under control of an operator in a cab suspended from the bridge and located so as to permit the operator to see the bottom of the refuse storage pit as well as the charging hoppers. The cranes are capable of performing a maximum of 29 cycles per hour per crane including an allowance of approximately 20 percent for rehandling refuse and other interruptions. The cranes span 44' - 8" center to center of rails and the crane runaway is 286' - 0" in length. Crane operations are manually controlled from within each respective crane cab. Each refuse transfer crane was initially equipped with solidstate computerized weighing systems to record the amount of material charged into the hoppers by each crane and also record into which hopper the material is charged. Due to various problems the use of the solid state systems was abandoned and now the number of times the refuse is charged into the hopper 3-5 282 �is monitored manually by the crane operator. of 5 cubic yards capacity. 3.2.2 Each charge is assumed to be Refuse Burning The plant has four incinerators each having a nominal burning capacity of 400 tons per 24 hour day. Each incinerator has a charging hopper, feed chute, hydraulic powered feeders and stoker (manufactured by Josef Martin, Germany), boiler, economizer and fly ash hoppers. Draft throught the furnace (boiler) is provided by forced draft fans, overfire air fans and induced draft fans. Refuse in the charging hopper of each incinerator flows by gravity from the hopper to three stoker feeders through a feed chute, the lower portion of which is water cooled. Near the bottom of each charging hopper is a hydraulic powered pivoted type gate normally open but closed when the feed chute is empty of refuse. The charging hopper gates are manually controlled through operation of a four-way valve on the charging floor. The stoker feeders at the bottom of the feed chute push the refuse into the stoker by the reciprocating action of their hydraulic powered rams. The stokers of each incinerator are assembled with three runs or sections and have a sloping activated surface consisting of 17 rows of grate steps. The grate sections incline from the hortizontal at an angle of 26°, the lower end being at the rear. The stoker is of the reverse acting, reciprocating grate type. Alternate lateral rows of grate steps have controlled continuous reciprocating action with the moving grate steps pushing in reverse direction to the flow of refuse. This action moves a portion of the burning refuse under the unignited material and thereby effects an agitation and blending of the whole burning mass. Combustion air entering from below the grates cools the grates, helps to agitate the burning refuse and supplies the oxygen which produces a maximum burn-out in the shortest length of grate travel. Although the spacing between the grate bars comprises less than two percent of the total grate area, it is still possible for small siftings or ashes to find their way through the grate. These ashes are handled by the automatic sifting discharge which extends underneath the air plenum chambers serving the stoker. At regular intervals high pressure air is 3-6 283 �directed through the siftings channel, driving the siftings into the ash discharges. In order to obtain maximum burn-out, the depth of the refuse bed is controlled by automatic discharge or clinker rollers located at the end of the grate. As the residue reaches this point it is dumped into the Martin ash discharger where it is immediately quenched in water. The residue, following quenching by means of a hydraulic powered ram is pushed up an inclined slope which permits draining. This produces a residue of less than 15 percent moisture, and permits dry type conveying. In addition to quenching, the ash discharger also serves as a water seal for the furnace. This seal prevents infiltration of air into the furnace which is under negative pressure. Each refuse burning boiler is provided with two gas burners suitable for use with natural gas. They are automatically controlled and have an electric ignition. 3.2.3 Residue Handling The residue leaving each incinerator ash discharger passes through a hydraulically operated bifurcated chute to one or the other of two residue conveyors. These apron type conveyors travel at a rate of 17 feet per minute and have a capacity of 35 tons per hour. Only one conveyor operates at a time and extends horizontally past the four incinerators. It discharges its load onto rotary screens and storage hoppers in the Ash Discharge building. The electric motor driven rotary screens separate material larger than 2 inches in diameter from smaller sized material. Hydraulic power operated diverting chutes are provided to direct the flow of residue away from the rotary screens and into a bypass hopper. Material from the hoppers is removed from the plant by motor trucks. The weight of the residue leaving the plant is measured and recorded at the weighing station. The residue conveyors also receive and transport stoker grate siftings and fly ash accumulations from the boiler hoppers, economizer hoppers, and the electrostatic precipitators. Stoker grate siftings collect in six hoppers under each of three stoker grate sections. The siftings are conveyed 3-7 284 �to the residue conveyors through automatically controlled, pneumatic cylinder actuated ash dampers to ducts connected to the residue discharge (drop) chute. Boiler fly ash is collected in four hoppers and the front two hoppers discharge to the stoker grates through ducts equipped with pneumatic cylinder actuated pendulum dampers. The rear two hoppers discharge to the residue discharge chute through a common connecting pipe equipped with slide gate and an electric motor driven rotary valve. Fly ash from the economizer hoppers passes through a common pipe connected to the discharge end of the conveyor handling fly ash from the electrostatic precipitator. The two fly ash hoppers located under each precipitator discharge ash onto a drag conveyor which transmits the fly ash into the incinerator building onto a conditioning conveyor. This conveyor discharges into the residue discharge chute. Water is mixed with the fly ash in the conditioning conveyor. The fly ash handling system is designed for continuous operation and the various devices are actuated from controls on the stoker panel. The control of residue handling equipment is manual. 3.2.4 Steam Supply Refuse with a calorific value of approximately 5,000 BTU per pound at the rate of 400 tons per day is used to generate 110,000 pounds per hour of steam at 250 psig. Each boiler has the capacity to produce up to 135,000 pounds/hour of steam. The stokers and boiler heating surfaces are designed to receive refuse of up to 6,500 BTU/lb. The allowable design of the stoker grate loading is 65 Ibs/sq.ft. per hour and thus the average stoker heat release is 325,000 BTU per hour/sq.ft. of projected grate area. The boilers are convection, water well, natural circulation types with economizers. Each boiler has 19,776 sq.ft. of heating surface and is designed for a 300 psig working pressure. Steam produced in the boiler accumulates above the water surface in the steam drum and leaves the drum through double row of tubes connected to the saturated steam header outside of and supported on the boiler steam drum. From the saturated steam header the steam flows to the main header and then through branch lines to turbines driving fans and pumps, export lines and 3-8 285 �high pressure condensers. Steam at reduced pressure is also used for heating various systems such as water chiller absorption units, office buildings, low pressure condensers, etc. When the steam produced in the plant is more than that required for operating the steam turbine equipment, heating purposes or export, the excess quantity "spills over" to the high pressure condensers located on the roof of the incinerator building. From the condensers the condensate flows to the deaerating feed water heater, the rate of flow being automatically controlled and modulated to equal the rate of condensation. The requirements for make-up to replace steam condensate lost or wasted are met by using softened water. The water softening unit includes duplex softening units containing synthetic type zeolite resin, a salt storage tank, a brine measuring tank, electric motor driven brine pumps and interconnecting piping. It has a nominal flow rate of 260 gpm and a maximum rate of 480 gpm. From the feedwater heater, water flows by gravity to the inlets of the boiler feed pumps. There are four pumps, each having a nominal capacity of 400 gpm. The pumps are multi-stage, horizontal, centrifugal type. These pumps transmit the water to the boilers. Each boiler has a continuous blowdown system with water drawn from the steam drums. The blowdown pipe lines from the four boilers extend to a single flash tank. Fla>sh steam is returned to the deaerating feedwater heater at 5 psig. From the heat exchanger the blowdown water flows to an underground concrete blowdown tank where the water cools before overflowing to a sewer. 3.2.5 Combustion Air and Flue Gas The incinerator stokers are designed to utilize 67,200 scfm of primary air (introduced under the stoker grates) at 18 inches w.c. and an overfire air (secondary) flow of 16,800 scfm at 15 inches w.c. Overfire air is introduced into the furnace to reduce stratification of gas and thus provide more complete combustion of the gases. The air enters through the front and rear water walls. The underfire air is discharged into several compartments under the stoker grate. The compartments are provided with dampers which are individually adjustable by manual operation of regulating stands 3-9 286 �located on the stoker operating floor. During the burning of refuse a constant air pressure is maintained under the stoker grates by means of automatic pneumatic controls. Combustion air combines with the burning refuse to generate heat and raise the temperature of the flue gas to as high as 2000°F. At rated burning capacity and based on 50 percent excess air (dry) the flue gas flow rate at 550°F is estimated to be 142,300 acfm. The flue gas passes upward through the furnace, through the boiler passes and finally through the economizer to the electrostatic precipitator. As it passes through the boiler it transfers heat to the water. At the inlet to the electrostatic precipitator the temperature is reduced to approximately 500°F because of the above heat exchange. During the passage of the flue gas through the boiler passes and economizer the heavier fly ash particles drop out. Hoppers are provided below the boiler and economizer for the collection of the drop out material. The plate type electrostatic precipitators (ESP) (one for each incinerator) have a series of vertical collector plates between which are suspended the charging electrodes. The ESP's are designed for an inlet grain loading of 1.6 gr/scf (70°F and 29.92 in Hg) and an outlet grain loading of 0.05 gr/scf with a collection efficiency of 97 percent. The gas velocity through the ESP is around 3 ft/sec. From the precipitator the flue gas passes through a breaching continuation to the inlets of the induced draft fans and then through the 250 ft. stacks to the atmosphere. A line diagram of the combustion air and flue gas system is provided in Figure 3-3. 3-10 287 �FRESH AIR BOILER INTAKE A I i FURNACE STORAGE ro go 00 to i —i FURNACE ROOM "pTf A I I FORCED DRAFT FANS OVERFIRE AIR FAN STOKER Figure 3*-3. Combustion air and flue gas system �4.0 SAMPLING LOCATIONS All sampling locations are identified in Table 4-1 and Figure 4-1. Figure 4-2 is a schematic depicting the traverse point locations at the stack. Figure 4-3 is a top view of the ESP inlet showing port locations, and Figure 4-4 is a cross sectional view of the ESP inlet depicting the traverse point locations. The continuous monitoring probe was located on the South side of the ESP inlet duct utilizing one of the gas sampling ports and at a depth of approximately 4 feet. At the outlet, the monitoring probe was alternated between ports 2 and 3 and at a depth of 4 feet. These two ports were also used for the gas sampling trains. TABLE 4-1. SAMPLING LOCATIONS Solid Sample Locations 1 - Refuse derived fuel 2 - Fly ash 3 - Combined ash Gaseous Sampling Locations 4 - Hi volume ambient air sampler 5 - ESP inlet 6 - ESP outlet Liquid Sample Locations 7 - City tap water 4-1 289 �TRUCKED REFUSE BOILER FEED WATER AIR COOLED CONDENSERS REFUSE DELIVERY PIT LECTROSTATld PRECIPITATOR BOILER OVERFIRE AIR ASH STOKER GRATES DISCHARGE HOPPER COMBINED ASH SIFTING GRATES FORCED DRAFT FAN HEAVY METALS Figure 4-1. Flow diagram and measurement locations �OUTLET - FRONT V I E W (CONTINUOUS M O N I T O R I N G PORTS) • • • • • (PARTICULATE SAMPLING PORTS) OUTLET - TOP V I E W 60" u. 1 1=1 2 K- U 3 U 4 •H •108" SAMPLING POINTS - Traverse Point OUTLET Distance from Outside Edge of Nipple No. In. Cm. 1 11.5 29.21 2 17.5 44.45 3 23.5 59.69 4 29.5 74.93 5 35.5 90.17 6 41.5 105.41 7 47.5 120.65 7 53.5 135.89 9 59.5 151.13 10 65.5 166.37 Figure 4-2. Outlet sampling position 4-3 291 �Figure 4-3. Top view of ESP inlet showing port locations �71" 60" EL 60" DUSTCAKE SAMPLING POINTS - INLET Traverse Point No. Distance from Outside Edge Nipple No. In. Cm. 1 11.5 2 15.375 29.21 39.05 3 19.625 49.35 4 23.875 28.125 32.375 36.625 40.875 45.125 49.375 60.64 71.44 82.23 93.03 103.32 114.62 53.625 57.375 136,21 145.73 5 6 7 8 9 10 11 12 Figure 4-4. 125.41 Cross sectional of ESP inlet showing traverse point locations. 293 4-5 �5.0 SAMPLING This section provides information on the sampling program conducted at the Chicago Northwest Incinerator (CNI). 5.1 GAS SAMPLING The original test plan called for sampling to be performed on Boiler No. 1. However, upon arriving at the test site, this unit had been taken off line for repairs. As all four (4) units at the Chicago Northwest facility are identical, the sampling effort was switched from unit 1 to unit 2. The flue gas sampling was performed at the electrostatic precipitator (ESP) inlet and at the duct leading from the precipitator to the stack. The stack was common to two boiler units and for this reason, no testing was performed at the stack level. Sampling for organics was to be performed for fourteen consecutive days with three additional days for sampling of inorganic cadmium. Due to boiler down time and equipment malfunction, only eleven organic samples were taken. Sampling for organics was accomplished concurrently at the inlet and outlet utilizing two modified Method 5 trains (refer to Figure 5-1) at both sampling locations. Inorganic cadmium was only sampled at the stack and utilized one standard Method 5 train, Figure 5-2. The sampling crew collected a ten m 3 (10 +_ 1 m 3) sample by extracting the flue gas at a rate approximating the flue gas velocity. The particulate matter was collected in a cyclone and on the filter media. The gas stream was passed through an XAD-2 resin trap to absorb the organic constituents and through an impinger system to condense any moisture present in the gas. Parameters such as temperatures, pressures, and gas volumes were monitored throughout the sampling period. The sample fractions were recovered from the sampling trains and turned over to an MRI representative. 5.2 SOLID SAMPLING During each test day, 3 solid streams: precipitator ash, combined ash, and refuse derived fuel (RDF) were sampled six times per day following a schedule set up by Research Triangle Institute (RTI). The sampling was coordinated between RTI, the sampling crew and plant personnel. The 5-1 294 �XX X FILTER HOUSING THERMOf-ETER DRY TEST • fKTER AIR TIGHT PUMP Figure 5-1. Sampling train 5-2 295 �figure 5-2. EPA Method 5 particulate sampling train 1) 2) 3) 4) 5) 6) 7) 8) 9) 10) 11) 12) Calibrated nozzle Glass lined probe Flexible teflon sample line Cyclone Filter holder Heated box Ice bath Impinger (water) Impinger (water) Impinger (empty) Impinger (silica gel) Thermometer 5-3 296 13) 14) 15) 16) 17) 18) 19) 20) 21) 22) 23) 24) Check value Vacuum line Vacuum gauge Main value Air tight pump Bypass value . Dry test meter Orifice Pitot manometer Potentiometer Orifice manometer S type pi tot tube �schedule provided the basis for collection of unbiased samples by obtaining a random selection from the multiple sources available for sampling. This approach was taken to avoid any cyclic biases which might have been present in the daily operation of the power plant. The CNI sampling plan did not call out specific sampling protocol for the RDF. At a meeting prior to the start of testing, it was decided that the RDF would be sampled 6 times during the course of the day. The sample was taken directly from the charge hopper, utilizing a post-hole digger and alternating grab spots across the hopper. At the conclusion of RDF sampling, one days collection (6 samples) was shredded, mixed and stored in an amber glass jar. MRI had purchased a large leaf mulcher to do the shredding. TRW performed the shredding of the sample provided by GSRI 5.3 LIQUID SAMPLING Only one liquid stream (city water) was sampled at the incinerator facility. The sampling was performed by GSRI. The sampling protocol and frequency of sampling will be supplied by GSRI in their report. 5.4 HI VOLUME SAMPLER To monitor the ambient air background, a high volume ambient air sampler (Figure 5-3) was used. It was placed on the roof of the Chicago Northwest Incinerator facility to obtain a representative background utilizing outside ambient air rather than sampling air inside the building that could have been contaminated or influenced by the combustion process. 5.5 QUALITY ASSURANCE A quality assurance sample was also taken of the final test day. To collect the quality assurance sample, two sampling trains were placed at the same point in the same port at the inlet of the ESP. No traversing was performed. Both trains were run at the same isokinetic rate for the same duration as a normal test day. Also during the Q/A day, solids and liquids were collected as in a normal test day. 5.6 SAMPLING TRAIN BACKGROUND To obtain the train background (blank) an entire sampling train, including resin trap filter and impinger solutions was set up at the ESP inlet. The train was taken to normal operating temperatures and allowed to 5-4 297 �HIGH VOLUME AIR SAMPLER FLOW PROBE \MODEL 230 HIGH VOLUME CASCADE IMPACTOR - OPTIONAL MANOMETER OR ROTAMETE: MODEL 310/310A/310B CONSTANT FLOW CONTROLLEF FLOW iJUSTMENT LINE CORD Figure 5-3. Ambient air sampler. 5-5 298 �remain at these temperatures for one (1) hour. All train components were recovered as a normal run and all sample blanks were given to an MRI representative, 5J SAMPLE RECOVERY Upon completion of testing, the sampling equipment was brought to the cleaned laboratory area for recovery. Each sampling train was kept in a separate area to prevent sample mixup and cross contamination. The individual sample train components were recovered per the following: • Dry particulate in cyclone r cyclone flasks were transferred to cyclone catch bottle. t Probe was wiped to remove all external particulate matter near probe ends, • Filters were removed from their housings and placed in proper container, • After recovering dry particulate from the nozzle, probe, cyclone, and flask, these parts were rinsed with distilled water to remove remaining particulate, They were subsequently rinsed with B & 0 acetone and cyclohexane and put into a separate container. All rinses were retained in an amber glass container, t Sorbent traps were removed from the trainl capped with glass plugs, and given to an on-site Midwest Research Institute (MRI; representative, • Condensing coil \ if separate from the sorbent trap, and the connecting glassware to the first impinger was rinsed into the condensate catch (ftrst impinger). • First and second impingers were measured, volume recorded and retained in an amber glass storage bottle. The impingers were then rinsed with small amounts of distilled water, acetone and cyclohexane. These rinsings were combined with the condensate catch. Rinse volumes were also recorded. • Third and fourth impingers were measured, volume recorded and solutions discarded. • Silica gel was weighed, weight gain recorded and regenerated for further use. To maintain sample integrity, all glass containers were amber glass, with Teflon-lined lids. 5-6 299 �5.8 OBSERVATIONS DURING RECOVERY 0 The first day setup of impingers did not include ^Og, as the shipment had not been delivered from the manufacturer. • Many filters that were supplied for the particulate catch, had the identification number stamped in blue ink on the top; or, particle gathering side. • Some Battelle Traps were packed with too much glass wool. (As a result, flow rate was somewhat restricted.) The probe and oven box did not remain hot enough to keep the cyclone and flask dry. For the first few days of testing, the cyclone had moisture on the inside walls, so no dry particulate could be collected. • On 5/10/80, the wind blew the Hi Volume Air sampler cabinet over. The cabinet had to be moved to a less exposed area nearer the building. • On 5/5/80, 5/8/80, and 5/9/80 yellow residue was noted in the teflon line connecting the back of the filter housing to the front of the Battelle cooling coil. When the teflon line was rinsed with acetone, the rinse turned to reddish-brown. • When the filters were not kept completely dry throughout the particulate test period, the filter paper would stick to the rubber gasket and was very difficult to completely remove. t A reddish color remained on the inlet filter backing plates on 5/8/80 and 5/15/80. The color washed off with water, and the rinse was discarded. § The inlet glass transition tubes connecting the probe to the cyclone, had to be wrapped in an attempt to keep moisture and particulate from dropping out and depositing on the walls. • All parts were inspected for cleanliness after the water and acetone rinses, but before the cyclohexane rinse. Cyclohexane does not rapidly evaporate and gives any part rinsed with it the appearance of being clean. In reality the parts were still wet and masked any particulate that remained on the walls. 5-7 300 �6.0 CALIBRATION This section describes the calibration procedures used prior to conducting the field test at Chicago Northwest Incinerator facility. Figure 6-1 shows the calibration equipment and how it was set up. 6.1 METHOD FIVE CALIBRATION DATA 6.1.1 Orifice Meter Calibration The orifice meter calibration is performed using a pump and metering system as illustrated in Figure 6-1 (a). The dry gas meter with attached critical orifice is run at various orifice flows for a known time. After each run the volume of the dry gas meter, meter inlet/outlet temperatures, time, and orifice setting is recorded. The orifice meter calibration factor is derived by solving the equation. AHia - 0.317 A H - Pb (Td + 460) AH@ + 460) e n 2 —TO- ] r (Tw C where AH = Average pressure drop across the orifice meter, inches H20 Pb Td Tw e Vw = = = = = Barometric pressure, inches Mercury Temperature of the dry gas meter, °F Temperature of the wet -test meter, °F Times, minutes Volume of wet test meter, cubic feet The AH@ yielded is utilized to adjust the sampling train flow rate by regulating the orifice flow. 6.1.2 Dry Gas Meter Calibration Meter box calibration consists of checking the dry gas meter for accuracy. The dry gas meter with attached critical orifice is connected to a wet test meter (see Figure 6-1 (b) below) and run at various orifice flows for a known time. After each run wet and dry gas meter volumes, temperatures, time, and orifice readings are recorded. Utilizing the equation: 301 �v . Vw Pb (Td +460) Vd (Pb + AH)(t + 460) TT.6 w where V = Volume correction factor Vw = Volume of wet test meter, cubic feet Pb = Barometric pressure, inches mercury Td = Temperature dry gas meter, °F Vd = Volume of dry gas meter, cubic feet AH = Average pressure drop across the orifice meter, inches H20 TW = Temperature of wet test meter, °F a volume factor which compares the dry gas meter with the wet test meter is obtained. 6.1.3 Pi tot Tube Calibration Pitot tubes are calibrated on a routine basis utilizing two methods. The type S pitot tube specifications are illustrated and outlined in the Federal Register, Standards of Performance for New Stationary Sources, [40 CFR Part 60], Reference Method 2 (refer to Figure 6-1(c)). When measurement of pitot openings and alignment verify proper configuration, a coefficient value of 0.84 is assigned to the pitot tube. If the measurements do not meet the requirements as outlined in the Federal Register, a calibration is then performed by comparing the S type pitot tube with a standard pitot tube (known coefficient of 1.0). Under identical conditions, values of AP, for both S type and standard pitot tube are recorded using various velocity flows (14 fps to 60 fps). The pitot tube calibration coefficient is determined utilizing the following equation, Pitot Tube Calibration = (Standard Pitot Tube X rAP reading of std. pitot J -il/2 L Factor (CP) Coefficient) AP reading of S type pi tot The coefficient assigned to the pitot tube is the average of calculated values over the various velocity ranges. 6-2 302 �tttgnchstic Gtupe Figure 6-1(a) Orifice meter calibration Figure 6-1(b) Dry gas meter calibratipn fcunf Wftcrc 7m or filer Ti/t* Wou/tf £f WAen Too View Figure 6-1(c) Equipment used to calibrate pi tot tubes Figure 6-1. Calibration equipment set-up procedures 6-3 303 �6.1.4 Nozzle Diameters The nozzle diameters were calibrated with the use of a vernier caliper. If the nozzle showed excessive wear or was considered not fit for use, it was discarded. 6.2 INSTRUMENT CALIBRATION The manufacturer's recommended calibration procedures were used with the following gases: Zero gas: Nitrogen, high purity dry grade (99.997%) Union Carbide Co., Linde Division Calibration gas: Carbon monoxide 798.5 +_ 0.8 ppm Carbon dioxide 11.93 ±0.01% Propane 39.6 + 0.04 ppm Oxygen 5.03 ± 0.005% Nitrogen Balance (all gases contained in one cylinder) Scott Environmental Technology Inc. Specialty Gas Division Zero and Calibration adjustment were made prior to the start of the test day. Zero drift checks were made at the end of each test period. Data was recorded every fifteen minutes thus providing two data points per hour for each sampling position, or four data points per hour for a single sampling position 6.4 304 �7.0 TECHNICAL PROBLEMS AND RECOMMENDATIONS This section describes some of the problems encountered during the Chicago Northwest Incinerator test program and recommends a solution to these problems. 7.1 PROBLEMS • Electrical outlets were not installed on schedule (lost time 1 day). • One of the tubes in Boiler No. 2 developed a leak. The boiler had to be shutdown for repairs. This caused a delay of one day. • The boiler grates malfunctioned and required cleaning. This resulted in down time of one day. • Sampling equipment malfunctions caused further delays. This was due to: 1) Difficulty in containing leaks during equipment operation. 2) Failure of oven box heaters. 3) Drift problems of the Beckman 865 CO analyzer. The analyzer had to be taken off line and subsequent inspection by manufacturer indicated that the stationary shutters were knocked out of alignment. This resulted in the loss of 4 days of CO data before a replacement was obtained. 7.2 RECOMMENDATIONS Most of the above problems frequently occur in the field and should be considered normal during the course of a major field effort. The instrument problem may have been caused during shipment. Perhaps, stronger shipping containers should be used in the future. 7-1 305 �REPORT DOCUMENTATION PAGE 4. T,tie and subntie . '•- Rtno-n NO. | 3. ''L-r.iptent's Arc;e*3'un No 2. i 560/5-83-004 i •' ' : Comprehensive Assessment of Specific Compounds Present in Combustion Processes. Vol. 1.-Pilot study of Combustion Emissions Variability. 7 Au-hcriM Clarence" Ha lie and JoTfn Stanley (MRI) Carter Nulton (SWRI) William Yauger, Jr. (GSRI) 0. Performing O-,;.iniz,ition Name and Acdress 5, Report Date June 19_83__ 6. ! a. Performing OrRanizanori Rept. No I I 10. Proiect/TaskAVork Unit No. ! - Midwest Research Institute 425 Volker Blvd. Kansas City, MO 64110 Task 3 ; 11. Conlract(C) or C r a r . t ( G ) No. i'c> - . 68-01-5915 ! (G) 1C*. Spon c ,orrii? Or^ani* .itii'n Namf and Address 13. Type of Report & Period C o w e r e d Field Studies Branch, EED.TS-798 US EPA 401 M St. SW Final _ . 1 i _ _ _ 14. Washington, DC 20460 IS. Supolcrrent.iry N c t e s F.W. Kutz, Project Officer D.P. Redford, Task Manager is. Abstract (urn,:-200 words) xhis pilot study was conducted as a prelude to a nation wide survey of organic emissions from major stationary combustion sources. The primary objectives of the pilot study were to obtain data on the variability of organic emissions from two such sources and to evaluate the sampling and analysis methods. These data are used to construct the survey design for the nationwide survey. The compounds of interest are polynuclear aromatic hydrocarbons (PAHs) and chlorinated aromatic compounds, including polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated di-benzofurans (PCDFs). Of particular interest is 2,3,7,8tetrachlorodibenzo-p-dioxin (TCDD). In addition total cadmium was also determined in special samples from both plants to meet special Environmental Protection Agency (EPA) needs. A summary of the results of this study is contained in Section 2 of this report. Section 3 presents recommendations for future work. Brief descriptions of the two combustion sources are contained in Section 4. The sampling and analysis methods are described in Sections 5 and 6. Sections 7 and 8 present the field test data and analytical results. The analytical quality assurance results are summarized in Section 9. Section 10 presents the emissions results and Section 11 is a statistical summary of the emissions results. 17. Document Analysis a. Descriptors Combustion, Emissions, Sampling and Analysis b. Identifiers/Open-Ended Terms PAH,PCDD,PCDF,POM c. C O S A T I f i e l d / G r o u p 18. A v a i l a b i l i t y Statement 19. Security Class (This Report) Unclassified Release to public (Sr-v A N S I - / 3 9 13) 20. Security Cln$,s(T,his, PaRe) Unc See Instructions on Reverse 1 21. No. of Pages i 305 22. Price OPTIONAL FORM 2 7 2 ( 4 - 7 7 r m m e r l y NTIS-3S) r>v-~^rlrnent of Commerce � Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 192 Folder The folder containing the original item. 5421 Series The series number of the original item. Series VIII Subseries I Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Haile, Clarence L John S. Stanley Robert M. Lucas Denise K. Melroy Carter P. Nulton William L. Yauger, Jr. Date A point or period of time associated with an event in the lifecycle of the resource 1983-06-01 Title A name given to the resource Comprehensive Assessment of the Specific Compounds Present in Combustion Processes, Volume I: Pilot Study of Combustion Emissions Variability ao_seriesVIII https://www.nal.usda.gov/exhibits/speccoll/files/original/bb1834344c7745c2c615041f9240d6ac.pdf d469d5bfab7762ff9f1098f3a59b65f4 PDF Text Text Item D Number 05384 Author Erickson, Mitchell D. CorDOratB Author D MotSBannad Midwest Research Institute RflpOrt/ArtlClB TltlO Methods of Analysis for By-Product PCBs - Literature Review and Preliminary Recommendations Journal/Book Title Year 1982 Month/Day October^ D Color Number of Imagos 137 Doscrlnton NotBS Task 51 M • Interim Report No. 1, EPA Contract No. 68-01 -5915, MRI Project No. 4901 -A(51) Friday, March 08, 2002 Page 5384 of 5427 �United States Environmental Protection Agency Office of Toxic Substances Washington DC 20460 EPA-560/5-82-005 October, 1982 Toxic Substances oEPA Methods of Analysis for By-Product RGBs Literature Review and Preliminary Recommendations 100.0 i C12H6Cl4 11 14 100.0 C12D6Cl4 1 1 iL. 100.0 13c12H6Cl4 1 280 285 290 295 300 I 305 Gallons 310 315 320 325 �DISCLAIMER This document has been reviewed and approved for publication by the Office of Toxic Substances, Office of Pesticides and Toxic Substances, U.S. Environmental Protection Agency. Approval does not signify that the contents necessarily reflect the views and policies of the Environmental Protection Agency, nor does the mention of trade names or commercial products constitute endorsement or recommendation for use. �METHODS OF ANALYSIS FOR BY-PRODUCT PCBs--LITERATURE REVIEW AND PRELIMINARY RECOMMENDATIONS By Mitchell D. Erickson and John S, Stanley Midwest Research Institute 425 Volker Boulevard Kansas City, MO 64110 TASK 51 INTERIM REPORT NO. 1 EPA Contract No. 68-01-5915 MRI Project No, 4901-A(51) October 12, 1982 For U.S. Environmental Protection Agency Office of Toxic Substances Field Studies Branch TS-798 Washington, DC 20460 Attn: Dr. Frederick W. Kutz, Project Officer Mr. Dayid P. Redford, Task Manager �PREFACE This report presents the results of a literature review and preliminary methods recommendations accomplished on MRI Project No. 4901-A, Task 51, "PCB Analytical Methodology Task," for the Environmental Protection Agency (EPA Prime Contract No. 68-01-5915). The review was performed and the document prepared by Drs. Mitchell D. Erickson and John S. Stanley, with assistance from Elliot Hirsch, Scott Meeks, Betty Jones, Kay Turman, Kathy Funk, Lanora Moore, Cindy Melenson, Carol Shaw, and Gloria Sultanik. MRI would like to thank the people listed in Appendix A for their cooperation, We are especially indebted to Phillip W. Albro, Thomas A- Bellar, Michael D. Crouch and associates, Ralph C. Dougherty, Larry F. Hanneman, Edo D. Pellizzari, James D. Petty, and David L. Stalling, J. Lawrence Robinson, and the CMA PCB Analytical Task Group through Robert J. Fensterheim who provided valuable written peer review comments on the draft document. In addition, the helpful comments of John Smith, DDE, OTS, EPA; Dave Redford and Ann Carey, FSB, OTS, EPA; and the members of the PCB Analytical Task Force of CMA are especially appreciated. MIDWEST RESEARCH INSTITUTE John Going, Head Environmental Analysis Section Approved: James L. Spigarelli, Director Analytical Chemistry Department iii �CONTENTS Preface Figures Tables . , List of Terms, Abbreviations, and Symbols 1. 2. 3. 4. 5. Summary . . , Introduction , Literature Review Sources of Information. , Review Procedure Review Articles on PCBs Standard Methods Sampling Extraction Cleanup Determination Data Reduction • Confirmation. Screening Techniques Quality Assurance By-Product Analyses Applicable Techniques Extraction. . . < , Cleanup . . . . . . . Determination Data Reduction Limit of Quantitation Data Reporting Confirmation Techniques Screening/Equivalent Methods Possible Analytical Schemes Issues to be Addressed Quality Assurance , iii vi . vii viii , . . . . , • • • • . .... 1 3 5 5 6 6 7 10 11 15 20 45 55 56 57 59 62 62 64 64 66 70 70 71 71 73 73 74 Appendices A. Personal Contacts B. Bibliography 76 81 v �FIGURES Number 1 Page Comparison of packed column gas-liquid chromatography and and capillary column gas-liquid chromatography with Aroclor standards 24 Comparison of packed column gas-liquid chromatography and capillary column gas-liquid chromatography with a milk extract 25 3 Comparison of PCB resolution on different columns 27 4 Electron capture detection of Aroclors 1242, 1260, and 5460 (400 pg each) chromatographed on an Apiezon L (WCOT) silanized Pyrex glass capillary, 0.20 mm i.d. x 50 m in length 29 Electron capture detection of PCB in an extract of yellow perch 29 Scanning capillary column gas-liquid chromatography/mass spectrometry analysis of a mixed Aroclor standard used to establish retention windows for the CGC/MS-SIM analysis of PCBs 30 Detection limits/dynamic range for several instrumental methods 32 Packed column gas-liquid chromatography/electron capture detector chromatograms illustrating potential interferences between pesticides and PCBs 36 Total ion current profiles for negative chemical ionization data (upper) and electron impact data (lower) obtained on a Finnigan 4000 glass capillary GC/MS system for Ashtabula River fish sample 43 Partial high resolution mass spectrum obtained from 2.5 x 10 10 g TCDD plus matrix from 10 g human milk, illustrating potential interferences in low resolution MS 44 2 5 6 7 8 9 10 vi �TABLES |if umber Page 1 Standard Methods of Analysis for PCBs 8 2 Reported Limits of Detection for PCBs 33 3 Relative Molar Responses of Electron Capture and Flame lonization Detectors to Some Chlorobiphenyls 37 Comparison of Relative Response Factors Between (GC)2-ECD, GC-EIMS (Molecular Ion) and (GC)2-NICIMS (m/z 35) for Homologous Series of PCBs ~ 38 Summary of Laboratory Techniques Used for the CMA Round-Robin Study 46 Summary of Laboratory Techniques Used for the CMA Round-Robin Study , 47 4 5 6 vii �LIST OF TERMS, ABBREVIATIONS, AND SYMBOLS Accuracy Closeness of analytical result to "true" value, Aroclor Trade name (Monsanto) for a series of commercial PCB mixtures marketed in the United States, Askarel Nonflammable synthetic chlorinated hydrocarbon insulating liquids used in capacitors, transformers, etc,; often containing PCBs. Byproduct PCBs PCBs generated as by-products or impurities in synthesis of other products (as opposed to commercial PCBs). CGC Capillary column gas-liquid chromatography (includes WCOT, SCOT, fused silica, glass, and metal). CI Chemical ionization (mass spectrometry), CIMS Positive chemical ionization mass spectrometry, Congener One of 209 PCBs, not necessarily the same homolog. Cutoff Lowest PCB concentration of regulatory concernf DDE l,l-Dichloro-2,2-bis(|>-chlorophenyl)ethylene. DDT 1,1,l-Trichloro-2,2-bis(g-chlorophenyl)ethane. BCD Electron capture detector. El Electron impact ionization (mass spectrometry). EIMS Electron impact mass spectrometry. Equivalent method Any method, certified against the primary method, which can be used for routine analysis of samples. Also, termed screening method. External standard Standards for calculation not added to the sample extract. FFAP Free fatty acid phase. viii �FID Flame ionization detector. FTIR Fourier transform infrared spectrometry. GC Gas-liquid chromatography (column type unspecified). GC/MS Gas-liquid chromatography/mass spectrometry (ionization mode unspecified) . GPC Gel permeation chromatography. HECD Hall electrolytic conductivity detector (other similar detectors such as the Coulson are included) . HEETP Height equivalent to an effective theoretical plate. Homolog One of the 10 degrees of chlorination of PCBs through C12Clio). HPLC High performance liquid chromatography. High resolution electron impact mass spectrometry. Internal standard Standards used expressly for quantitation added to sample extract immediately prior to the analytical determination. IR Infrared spectrometry. Isoraer One of up to 46 PCBs possessing the same degree of chlorination (3,4- and 4,4' -dichlorobiphenyl are different- isomers). KOH Potassium hydroxide. LMS Limited mass scanning (mass spectrometry). LOD Lower limit of detection (also MDL) . Lowest concentration which an analyte can be identified as present in the sample at a stated statistical confidence level. LOQ Lower limit of quantitation. Lowest concentration to which a value can be assigned at a stated statistical confidence level . MDL Method detection limit. Mean Arithmetic mean. MS/MS Mass spectrometry /mass spectrometry. m/z Mass-to-charge ratio. ix �NAA Neutron activation analysis. NCI Negative chemical ionization (mass spectrometry), NCIMS Negative chemical ionization mass spectrometry, NMR Nuclear magentic resonance spectrometry. PBB Polybrominated biphenyl. PCB Polychlorinated biphenyl (including monochlorobiphenyl, but excluding biphenyl). PCN Polychlorinated napthalene. PCT Polychlorinated terphenyl. PGC Packed column gas-liquid chromatography. Parts per billion (109). ppm Parts per million (10~6). Precision Reproducibility of an analysis, measured by SD of replicates. QA Quality assurance. An organization's program for assuring the integrity of data it produces or uses, QC Quality control. The specific activities and procedures designed and implemented to measure and control the quality of data being produced. Remand Rule Rulemaking for new PCB regulations for inclusion in 40 CFR, Part 761 in response to orders from the U.S. Court of Appeals from the District of Columbia on, October 30, 1980 and April 13, 1981. RI Retention index. RIA Radioimmunoassay or radio isotope dilution assay. RJC Reconstructed ion chromatogram. RMR Relative molar response. RSD Percent relative standard deviation (SD/mean x 100), SCOT Support coated open tubular (CGC column). x �SD Standard deviation. Sensitivity The slope of instrument response with respect to the amount of analyte. Also used colloquially in reference to lowest detectable amount of analyte. SIM Selected ion monitoring (also mid or mass fragmentography). Surrpgate Standard compounds added to the sample prior to any analytical manipulations for the express purpose of measuring recovery through extraction, cleanup, etc. TCP Thermal conductivity detector. TCDD Tetrachlorodibenzo-jj-dioxin. TIC Total ion current chromatogram. TLC Thin-layer chromatography. WCQT Wall coated open tubular (CGC column). xi �SECTION 1 SUMMARY The published literature on PCB analysis is critically reviewed. Several hundred references are cited in a bibliography. The review is subdivided into extraction, cleanup, determination, data reduction, confirmation, screening, quality assurance, and by-product analysis sections. The determination section includes TLC, HPLC, GC (PGC and CGC), GC detectors (BCD, FID, HECD, EIMS, and other MS) and nonchromatographic analytical methods (NMR, IR, electrochemistry, NAA, and RIA). Based on the review of the literature, personal communications with researchers in the field, and the authors' judgment, techniques applicable to analysis of commercial products, air, and water for by-product PCBs under the Remand Rule are discussed. Each individual analytical component (extraction, cleanup, determination, etc.) is separately discussed. The final section of this report presents the recommended overall primary analytical scheme: 1. Homogenize sample and subsample if necessary. 2. Incorporate surrogate compounds (e.g., four 13 C PCB congeners). 3. Dilute, extract, or clean up as required. 4. Concentrate or dilute to a known volume. 5. Analyze a known aliquot by GC/EIMS. 6. Identify PCBs by relative retention time and mass spectral characteristics. 7. Integrate the PCBs by homolog and calculate amounts of each homolog by normalizing the responses to responses for the surrogate compounds, using one or more homolog response factors. 8. Sum all 10 homolog concentrations to obtain a total PCB value. 9. Report on standard reporting form. 10. Follow specified routine QC (blanks, controls, duplicates, standard condition, instrument performance criteria, etc.). 11. Maintain appropriate records. �Several details in this scheme are subject to revision, as discussed in the report. Several unresolved issues are discussed, including the permissi^ ble flexibility in the method, the use of equivalent methods, and quality assurance. �SECTION 2 INTRODUCTION PCBs have been manufactured as commercial products since 1929 and marketed under trade names such as Aroclor (United States), Chlophen (Germany), and Kanechlor (Japan). These were all complex mixtures of many congeners and several homologs. They were used as dielectric fluids in capacitors and transformers, hydraulic fluids, fire retardants, plasticizers, and many other applications. Their manufacture and use have been frequently reviewed (Hutzinger et al., 1974; and many other reviews listed in "Review Articles on PCBs" section below). Beginning in 1966 (Jensen, 1972; anonymous, 1966), PCBs were found in environmental samples as interferents with chlorinated pesticides (e.g., DDT) analysis with increasing frequency. As the magnitude of the problem grew, the emphasis on PCBs gradually shifted from interferents to analytes. Concomitantly, their toxicology was being studied. While their toxicity varies among isomers and species, PCBs have been sufficiently implicated in animal and human toxicity to warrant their ban in the United States (Toxic Substances Control Act (TSCA), Public Law 94-469, October 11, 1976). The public outcry prior to TSCA and enforcement of the law thereafter have prompted increased scientific interest in all aspects of PCBs. Central to the environmental studies of PCBs is their analysis. Most of the early methods were direct adaptations of chlorinated pesticide procedures. As interest grew, analytical techniques improved and methods of analysis became increasingly sophisticated. However, PCB analysis is plagued by the fact that PCBs are not one specific compound like most pesticides, but in fact are a class of 209 congeners. Until very recently, all of the PCB analyses were directed toward commercial (e.g., Aroclor) products or their derivatives (metabolites, weathered samples, etc.). The complexity of the raw data (chromatograms) and lack of other standards have led scientists to report PCB findings in terms of Aroclor (or other products) calibration standards. This procedure is at best approximate when the sample resembles the standard and becomes hopeless if the sample does not "match" standards. The problem of PCB analysis has recently become more complex due to concern over incineration products and by-product PCBs, where the PCB mixture in no way resembles an Aroclor pattern. Incinerator products are of concern since U.S enforcement efforts have recently concentrated on destruction of existing PCB products rather than on landfill disposal. The concern over by-product PCBs may be traced to the opinion of U.S. courts that PCBs generated as impurities in other products are subject to the TSCA ban on PCB manufacture. �This document presents a review of analytical techniques used for the analysis of PCB and discusses which of these may be applicable to determination of by-product PCBs. A general analytical scheme is proposed with several options in areas where there is no clear best available technology. �SECTION 3 LITERATURE REVIEW This section is a critical review of the published literature on analytical techniques for PCBs. Where possible, comments have been made regarding the quality of the work and the utility of the technique. However, discussion of the relevance of techniques toward the PCB Remand Rule has been left to Sections 4 and 5. SOURCES OF INFORMATION Computerized and manual searches and relevant references in recent articles were used. Many documents were obtained from the personal files of MRI employees. Recent issues of several key journals (Analytical Chemistry, Journal of Chromatography. Journal of the Association of Analytical Chemists, Environmental Science and Technology, etc.) were searched manually to pick up any recent references not yet in the computer data bases. In addition, several known PCB researchers (Appendix A) were called to discuss approaches to the Remand Rule. In these discussions, they were asked to send copies or give references to any recent publications or preprints. The computer searches were done using DIALOG. Chemical Abstracts (CA) files were searched back to 1972, printing all references containing "PCB" and synonyms and keywords beginning with the following letters: "anal," "chromatogr," "mass spectr" and synonyms. A similar search was performed on the National Technical Information Service data base (now including Smithsonian Science Information Exchange). These searches printed out 349 citations, of which 188 were judged sufficiently relevant to obtain at least the CA abstract. In addition to nonanalytical articles, articles where PCBs were mentioned but were clearly not the major focus of the article, and articles which clearly contained only analytical results and not methods, the majority of citations not obtained were in obscure foreign language journals and apparently were similar to other available references. Once the primary search data had been digested, it became apparent that several authors were of primary interest and all of their recent (1980 and 1981) publications were retrieved by a CA search on their name. These authors were P. W. Albro, T. F. Bidleman, U. A. Th. Brinkman, 0. Hutzinger, R. G. Kaley, S. Safe, D. L. Stalling. Most of the new citations retrieved by this search were irrelevant (metabolism studies, synthesis, etc.) to this report. An additional manual cross-check was made with the document "Polychlorinated Biphenyls, Polybrominated Biphenyls, and Their Contaminants: A Literature Compilation 1965-1977" (Winslow and Gerstner, 1978). This document contains 1,880 PCB citations, although not all pertain to analytical methods. �References contained in review articles and primary literature were also checked to assure that no important articles were missed by the computer search. Several articles were added to the files by these searches. REVIEW PROCEDURE All articles cited in the bibliography (Appendix B) were surveyed for relevant analytical details. The salient features of each article were noted and any key subject areas were listed. Each citation was cross filed in any of 33 applicable key subject areas (PGC, CGC, EIMS, Review, etc.). REVIEW ARTICLES ON PCBs Any class of chemical compounds as often studied and as subject to regulatory pressure as PCBs has been the subject of review articles. A total of 27 books and articles were characterized as PCB reviews. The PCB review most often cited is probably the book The Chemistry of PCBs by Hutzinger et al., (1974). This book characterizes commercial PCBs; synthesis routes; chemical and photochemical reactions; metabolism; mass spectrometry; NMR, UV, and IR spectral properties; determination methods, and recent developments. Although dated, this review covers the general subject and the analysis of PCBs (in 1974) comprehensively. Reynolds (1969) reviewed the problems of PCB interference with the analysis of pesticide residues and later expanded on this in Residue Reviews (Reynolds, 1971). Risebrough (1971) reviewed analytical techniques for PCBs in environmental samples. Fishbein's (1972) review of the chromatographic and biological aspects of polychlorinated biphenyls discussed column chromatography, TLC, GC, and GC/EIMS in some detail, DeVos (1972) reviewed the methods for pesticides and PCBs in. wildlife samples used by various laboratories in the Netherlands. Lincer (1973) reviewed PCBs, again as interferents with pesticide residue analysis. - Safe (1976) reviewed the analytical problems and methods for PCBs as part of a national conference on PCBs (Ayer, 1976) which covered all aspects of the PCB issue (biology, metabolism, destruction, regulatory, etc.). Sherma (1975) reviewed GC of PCBs, including extraction, cleanup, GC systems, identification, confirmation, and quantitation. Chau and Sampson (1975), in an attempt to standardize quantitation, surveyed and reviewed the various methods for PGC/ECD quantitation. Lao et al. (1976) reviewed the application of GC/MS to PCB analysis. Extraction, chromatographic separation (cleanup), GC/ECD, and computer-aided data interpretation were discussed by Krull (1977). Brinkman et al. (1978) discussed various literature procedures for discrimination between PCBs and polychlorinated naphthalenes (PCN). Lawrence and Turton (1978) included PCBs in a tabulation of HPLC data for 166 pesticides. Environmental Health Perspectives devoted an entire issue (Rail, 1978) to PCBs. Pomerantz et al. (1978) reviewed the chemistry of PCBs; Matthews et al. (1979) reviewed metabolism and toxicity; Cordle et al. (1978) reviewed human exposure; Kimbrough reviewed animal toxicology; and the DHEW Subcommittee �of Health Effects of PCBs and PBBs (1978a, 1978b) provided general recommendations and general summary and conclusions which included discussions of the analytical aspects of PCBs. Stalling et al. (1979) reviewed PCS analysis with particular emphasis on their own work of automating the extraction and cleanup processes. The sampling and analysis of PCBs in air have been reviewed by Lao et al. (1976), Margeson (1977), and Fuller et al. (1976). The analytical aspects of PCBs have also been reviewed by Sherma (1981), Nose (1976), and Tanabe (1973). Finlay et al. (1976) reviewed PCB levels in the environment but did not discuss analysis. Other reviews not discussing analysis include Resource Planning Commission (1982), Fishbein (1979), and Kimbrough (1980). None of the review articles discussed above is current (the most recent was 1979), nor do they discuss the problems of determination of incidentally generated PCBs. In response to the PCB Remand Rule, the Chemical Manufacturers Association (1981) critically reviewed the PCB analytical techniques potentially applicable to the rule and recommended that GC/EIMS be the method of choice for analysis under this rule. STANDARD METHODS Table 1 lists the standard analytical methods available for PCBs. It should be noted that not all of the methods listed are sanctioned at this point. Many have interim status and some have been proposed but never endorsed by an organization. The standard methods provide analytical approaches for the measurement of PCBs in a variety of materials including water, wastewaters, soils, sediments, sludges, air, combustion and incinerator emissions, capacitor askarels, transformer'fluids, waste oils, mixtures of chlorinated benzenes, pigments, food, milk, and adipose tissues. Table 1 summarizes each of the standard methods. Extraction and cleanup procedures are presented in terms of the materials and reagents required for analysis. Less than half of the methods comment on the criteria required to make qualitative determinations for the presence of PCBs in sample extracts. The method of quantitation for each of the analysis schemes is presented along with the limit of detection (LOD), if specified. Additional analytical procedures to confirm the levels or presence of PCBs are also indicated. More than half of the standard methods mention quality assurance in some respect. The quality assurance steps include analysis of blanks, replicates, control samples, spiked additions, and accuracy, precision, and instrumental performance criteria. All of the are directed to DCMA (1981) and product PCBs in methods, except those provided by DCMA (1981) and Dow (1981) the analysis of PCBs as Aroclors or similar mixtures. The Dow (1981) methods were developed for the analysis of bycommercial products. �TABLE 1. Method Matrix ANSI Air (toluene impinger) ANSI Extraction Cleanup STANDARD METHODS OF ANALYSIS FOR PCBs Determination method Quant . method Qual. LOD Confirmation QA Reference - (H2S04) PGC/ECD (Saponif ication) (Alumina) No Single peak 2 ppb None Yes ANSI, 1974 Water Hexane (H2S04) PGC/ECD (Saponif ication) Alumina No Single peak or summed peaks 2 ppm None Yes ANSI, 1974 ANSI Sediment soil CH3CN/ hexane H2S04 Saponify/ alumina PGC/ECD No Single peak or summed peaks 2 ppm None Yes ANSI, 1974 AOAC ( 9 2) Food CH3CN/Pet. ether Florisil MgO/ PGC/ECD Celite saponif ication . So Total area or Ind. peaks NSa TLC paper chrom. No AOAC, 1980a AOAC, 1980b Paper and paperboard saponification Capacitor Askarels DIb None SCOT CGC/FID No Total area 2.8 x 10~8 mol/1 None No ASTM, 1980a PGC/ECD No Total area NS None Yes ASTM, 1980b PGC/ECD No 10 isomers ~ 1 ppm/homolog PGC/MS Yes DCMA, 1981 D3303-74 D3304-74 DCMA Air DI Water Soil, sediment Hexane H20/CH3CN 3 pigment types A. Hexane/ H2S04 B. CH2C12 Florisil 00 ( 2 0) HS 4 (Saponif ication) (alumina) None Devenish Water Hexane Alumina PGC/ECD No NS 106 ng/£ None No Devenish and Harling-Bowen 1980 DOW Chlorinated benzenes DI None PGC/EIMS Yes Total peak height/ homolog NS None Yes Dow, 1981 EPA Sludge (Halocarbon) Hexane/ CH2C12/ acetone (83/15/2) GPC S removed PGC/ECD Yes Peak area or peak height NS GC/MS Yes Rodriguez et al. , I960 EPA ( P P) Sludge CH2C12 (base/ neutral and acid fractions) GPC PGC/EIMS Yes NS NS None Yes EPA, 1979e EPA ( 0 h 34) Water Hexane/ CH2C12 (85/15) Florisil/ silica gel (CH3CN) (S removal) PGC/ECD or HECD Yes Summed areas or or WebbMcCall NS None Yes EPA, 1978 EPA (B100) Sludge CH2C12 ( fractions) 3 GPC Silica gel CGC/EIMS or PGC/EIMS Yes NS NS None Yes Ballinger, 19 (continued) �TABUS 1 (continued) Qnant. method Ttetenniflation method Qua I . CH3CH Florisil Silica acid PGC/ECD Yes Ind. peaks 50 ppb Perchlorination Yes Watts, 1980 Sherroa, 1981 Pet. ether/ CH3CN Saponif ication Florisil TLC No Semiquant. 10 ppm None No Watts, 1980 Dl ( 2 0) HS 4 (Florisil) (Alumina) (Silica gel) (GPC), (CH3CH) PGC/HECD or /ECD or /E1MS (CGC) No Total area or WebbMcCall 1 mg/kg None Yes EPA, 1981 Bellar and Ltchtenberg, 1981 Natural gas Hexane sampled with Florisil H2S04 PGC/ECD No Harris and Mitchell, 1981 608 Water CH2C12 (Florisil) (S removal) PGC/ECD No Area 0.04-0.15 JJg/£ None Yes EPA, 1979a 625 Water CH2C12 None PGC/EIMS (CGC) • Yes Area NS None Yes EPA, 1979b 10 ng GC/MS Method Matrix Extraction EPA (HERL) Milk Acetone/ hexane EPA (HERL) Adipose EPA ( i ) ol Transformer fluids or waste oils EPA (gas) Hexane Cleanup Total area 0.1-2 (Jg/m3 peak height or Webb-McCall (Perchlorination) 2S04 emissions and ambient air collected on Florisil LOD Confirmation N °ne QA Reference '-lHa i ic -_,! ana Baladi, 1977 nation PGC/ECD EPA Combustion sources collected on Florisil Pentane or CH2C12 (Florisil/ silica gel) PGC/HS Yes Area/ homolog 0.1 ng/inj None No Levins et a 1 . , 1979 NIOSH (air) (P&CAM 2 4 4) Air collected on Florisil Hexane None PGC/ECD No Peak height 0.01 mg/m3 or area from standard curve or Webb-McCall None No NIOSH, 1977a HIOSH (air) (P&CAM 253) Air collected on Florisil Hexane Hone PGC/ECD Perchlorination No Peak height 0.01 mg/m3 or area from standard curve Perchlorination Japan Food Several Silica gel Saponif ication (Florisil) PGC/ECD Yes Summed NS areas perchlorination None No Tanabe, 1976 PAM Food CH3CN/Pet. ether Silicic acid (Saponif ication) (Oxidation) (Florisil) PGC/ECD (PGC/HECD) (HP-TLC) (RP TLC) Ho Area TLC No FDA, 1977 a No specific details. b Direct injection. c Techniques in parentheses are described as optional in the protocol. NS Ho NIOSH, 1977b �The ANSI methods are based on techniques that were used by the Monsanto Industrial Chemical Company for the isolation and determination of PCps in water, soil, sediment, and biological materials. Packed column gas chromatog17 raphy with electron capture defection (POC/JSCD) is the designated method for quantitation pf PCBs as Aroclops in, the ANSI methods, Mass spectrometry, however, is recommended for eaph of the designated analysis schemes if confirma-» tion is required. The cleanup techniques are required only if interferences are noted for the PGC/ECD determination. The quality assurance procedures in the ANSI methods emphasize t;he number of theoretical plates and tailing factor for the packed gas chromatography column, The ASTM, AOAC, and EPA methods are generally designed for a particular matrix. The level of quality assurance procedures varies from method to method. The recent methods provide quality assurance programs of greater de"tail and require reasonable effort to maintain the accuracy and precision of the overall determination. The EPA method for analysis of PC$s in transformer °ils, and crude oils provide^ the most generalized approach, with respect to sample preparation, cleanup procedures, and^ instrumental analysis. Several cleanup procedures are provided as optional approaches in this protocol, and instrumental analy* sis by halogen specific, electron capture, pr mass spectrometry detectors are allowed, provided appropriate limits of detection can be achieved. A strong quality assurance program including control samples, daily quality control check samples, blanks, standard additions, accuracy and precision records, and instrumental and chromatographic performance criteria is required to support all data generated by the method. The Dow (1981) and DCMA (1981) procedures also require strong quality assurance programs for analysis of by-product PCBs. first $tep in any successful analysis is the collection of ta,tive samples, The selection of sampling sites, frequency of sampling, number of samples, measurement of physical a,n.d chemical parameters of the sample, and the ovejraU statistical design of sampling methods have been provided in extensive detail (Moser and Huibregtse, 1976; EPA, J976). The sampling design in roost cases is directly related to the objectives pf a specific research program as a regulatory action. The methods that are of interest in the context of this report are the procedures practiced for obtaining representative specimen of air, water, and solids f Aqueous and solid media are generally collected as grab samples, although aqueous samples have been preconqentrated on solid adsorbents prior to extraction. Water The solid adsorbents used for aqueous preconcentration methods include macroreticular resins (Cobum et al,, 1977; Seiber, 1974; Musty and Nickless, 1974; Webb, 1975; Picer and Picer, 1980), polyurethane foam and Chromosorb W 10 �coated with a mixture of undecane and Carbowax 4000 monostearate (Gesser et al,, 1971; Lawrence and Tosine, 1976; Bellar and Lichtenberg, 1975; Ahling and Jensen, 1970; Osterrpht, 1974; Musty and Nickless, 1976), as well as Tenax (Leoni et al,, 1976). Preconcentrating organic analytes from aqueous media allows the analyst to work with large volumes of water and thus lowers the method detection limit for the compounds of interest. The sorbent preconcentration method also can be used as a continuous on-site sampling procedure. Air Sampling The PCBs in ambient air and flue gas emissions have been collected on sqlid adsorbents including polyurethane foam plugs, Tenax, XAD-resins, Florisil, Chromosorb, and Poropak and combinations of these materials (Bidleman and Olney, J974; Bidleman et al., 1980; Bidleman, 1981; Bidleman et al., 1981; Billings and Bidleman, 1980, 1982; Burdick and Bidleman, 1981; Simon and Bidleman, 1978, 1979; Lewis et al., 1977a, 1977b; Lewis and MacLeod, 1982; Lewis and Jackson, 1982; Williams et al., 1980; Haile and Baladi, 1977; Giam et al., 1975; Haile et al., 1982; Stanley et al., }982; Harris and Mitchell, 1981). The solid adsorbents are effective for sampling PCBs in air although some problems have been encountered with breakthrough of the lower molecular weight PCBs at high flow rates for extended sampling periods. Doskey and Andren (1979) evaluated polyurethane foam coated with DC 200, Florisil, and Amberlite XAD-2 resin for their ability to sample airborne PCBs. The collection efficiency of the adsorbents was studied using carbon-14 labeled 2,5,2',5'-tetrachlorobiphenyl. The XAD-2 resin was found to have an excellent collection efficiency for the tetrachlorobiphenyl at a flow rate of 1 liter/min. Their sampling system yielded 96.5% collection efficiencies for the tetrachlorobiphenyl and 83.0% for Aroclor 1221. Further investigations demonstrated low retention efficiencies for monochlorobiphenyl (72%) and dichlorobiphenyl (86%), thus demonstrating that the sampling system was not equally effective for all PCB congeners. The analytical recoveries for tetrachlorobiphenyl, Aroclor 1242, and Aroclor 1221 were 85.5%, 80.1%, and 64.9%, respectively. Hanneman (personal communication, 1982) reported that PCBs were not retained at acceptable levels on common solid adsorbents when the flue gas temperature was greater than 150°C or in cases where the air contained an aerosol of a nonpolar material in which PCBs are very soluble, Hanneman reported successful collection of PCBs in these instances using polyurethane foam plugs coated with liquid polydimethylsilocane. Several plugs of the coated polyurethane were placed in a water-cooled jacket to sample the air at elevated temperatures, A PCB isomer was added to the surface of the foam plugs as a surrogate prior to sampling. A second PCB isomer was added to the foam plugs after sampling to monitor surrogate recovery and collection efficiency. EXTRACTION Reliable PCB analysis begins with the quantitative extraction of the analytes from the sample matrix. The extraction method is dependent on the sample type and the complexity of the matrix encountered. In general, the extraction methods require the use of solvents such as petroleum ether, hexane, methylene chloride, acetone, and acetonitrile. Digestion of the sample matrix with sulfuric acid or saponification with alcoholic potassium hydroxide is necessary 11 �in some instances to effectively extract incorporated PCBs. Dilution with suitable organic solvents prior to gas chromatography and even direct injection of some PCB-contaminated samples have provided suitable quantitative analysis. PCBs in air and flue gas emissions are typically collected on solid adsorbents and removed by extracting with a suitable solvent. Standard Methods A number of standard extraction methods for specific sample types are listed in Table 1. The standard methods include extraction techniques for transformer and capacitor oils, food, soils, sediments, dyes, milk, adipose tissue, sludge, wastewater, natural waters, emissions from combustion sources, and ambient air. Review Articles Extraction methods have been reviewed previously (Hutzinger et al., 1974; Sherma, 1975; Krull, 1977). Factors and problems that should be considered for a given extraction procedure (Albro, 1979) include the following: (a) each extraction method must be validated for each different matrix; (b) the nature of the sample matrix influences the effectiveness of a given extraction procedure through various matrix properties. These properties include the solubility of the matrix in solvent, the ease of homogenizing the sample for subsampling, the water content of the sample which greatly affects the extraction efficiency of the solvent, and the lipid content of tissue samples that governs the volume of solvent required for quantitative extraction; and (c) the incorporation of the analyte in a sample matrix and the most effective means of adding spikes to the sample for method evaluation and quality assurance measurements. Primary Literature A large number of extraction techniques provide quantitative recovery of PCBs from widely different matrices. The application of the various extraction procedures to specific sample types is discussed below. Air-- Simple and straightforward extraction procedures are used for extraction of adsorbents from air sampling. Ambient air and flue gas emissions have been collected on adsorbents including polyurethane filter plugs (Bidleman and Olney, 1974; Bidleman et al., 1980; Bidleman, 1981; Bidleman et al., 1981; Billings and Bidleman, 1980, 1982; Simon and Bidleman, 1977a, 1977b, 1977c; Lewis and MacLeod, 1982; Lewis and Jackson, 1982), Florisil (Harris and Mitchell, 1981; Williams et al., 1980; Haile and Baladi, 1977; Giam et al,, 1975), and Amberlite XAD-2 resin (Haile and Lopez-Avila, 1981; Stanley et al., 1982). PCBs were quantitatively recovered from these adsorbent materials via extraction with hexane, petroleum ether or benzene in a Soxhlet apparatus or as small chromatographic columns. Water and Wastewater-PCBs in aqueous samples, including natural waters, potable supplies, sewage effluents and industrial wastewaters, have been extracted by a number of 12 �procedures. Liquid-liquid extraction with hexane, cyclohexane or methylene chloride provide quantitative isolation of PCBs from aqueous samples (Brownrigg et al., 1974; Devinish and Harling-Bowen, 1980; EPA, 1979a, 1979b; Haque et al., 1974; Adams et al., 1979; Bellar and Lichtenberg, 1975; Caragay and Levins, 1979). In principle it is possible to extract all PCBs present in any water sample without large scale solvent extraction (Krull, 1977). Lower levels of detection of PCBs in aqueous samples have been achieved through the application of solid adsorbents for large volumes that cannot be effectively handled by classical liquid-liquid extraction procedures. The adsorbents are extracted with hexane, petroleum ether, and diethylether to recover the PCBs. Macroreticular resins (XAD-2, -4, -7, and -8) have been evaluated in a number of Studies (Coburn et al., 1977; Seiber, 1974; Musty and Nickless, 1974; and Webb, 1975; Picer and Picer, 1980). Polyurethane foams and Chromosorb W coated with a mixture of undecane and Carbowax 4000 monosterate as a reversed liquid-liquid partition method have also demonstrated successful isolation of PCBs from aqueous matrices (Gesser et al., 1971; Lawrence and Tosine, 1976; Bellar and Lichtenberg, 1975; Ahling and Jensen, 1970; Osterroht, 1974; Musty and Nickless, 1976). Two studies (Bellar and Lichtenberg, 1975; Webb, 1975) compared various extraction methods including batch liquid-liquid extraction, vortex stirring with an organic solvent, and adsorbent concentration on polyurethane and amberlite macroreticular resins. Extraction efficiencies of PCBs were greatest with liquid-liquid extraction. Continuous liquid-liquid extractors (Leoni, 1971; Ahnoff and Josefsson, 1973, 1974; Ahnoff et al., 1979) and steam distillation of aqueous samples with simultaneous liquid-liquid extractions of the distillate into pentane (Godefroot, 1982) have been studied as alternate means to lower detection limits for specific organic compounds including PCBs present in water. Wastewaters from some industrial processes have posed some interesting problems in measurement of total PCBs released. In particular, the cellulose fibers collected from paper mill effluents required hydrolysis with alcoholic potassium hydroxide and extraction with hexane or methylene chloride as well as extraction of the aqueous phase to effectively quantitate total PCBs (Delfino and Easty, 1979; Easty and Wabers, 1978). Dissolution of the residual fibers in paper mill effluents with 72% H2S04 followed by dilution with water and extraction with hexane was demonstrated to promote quantitative isolation of PCBs. Colenutt and Thorburn (1980) have discussed the application of gas stripping or purge and trap techniques for the analysis of PCBs in water. Spiked PCBs were removed from water samples by purging with nitrogen at ambient temperature. The PCBs were concentrated on activated charcoal and desorbed with a minimum volume (50 (Jl-1.0 ml) of organic solvent. Recoveries of greater than 90% were reported for Aroclors 1221, 1248, and 1254. The efficiency of this extraction technique is dependent on the gas flow rate, the time of stripping, adsorbent particle size, and the desorbing solvent. 13 �Soils, Sediments, and Sludges-Soxhlet extraction of soils and sediments with hexane-acetone, petroleum ether-acetone, or hexane has been a common method of isolating the PCBs (Bellar and Lichtenberg, 1975; Eder, 1976a; Goerlitz and Law, 1974; Jensen et al., 1977; Macleod, 1979; Seidl and Ballschsmiter, 1976; Adams et al., 1979; Hutzinger et al., 1974). Other methods that have been used for soils, sediments, and sewage sludges have included silica sonication (Chau and Babjak, 1979), blending with suitable solvent such as methylene chloride with centrifugation for separation of the phases (Rodriguez et al., 1980), and a column technique that required mixing sediment with Florisil and eluting with 10% water in acetonitrile. Ethanolic potassium hydroxide reflux prior to extraction of the sediment has been reported in at least one instance (Wakimoto et al., 1971). Soxhlet extraction, solvent shakeout, solvent blending, two column elution methods, and high frequency dispersion (Tissumizer) extraction techniques were compared for the same bottom sediment (Bellar and Lichtenberg, 1975). The results indicated that the highest recovery of PCBs was achieved by Soxhlet extraction of dried samples. The authors concluded that this should be the technique of choice for bottom sediments and sludges. Bellar et al. (1980) extended this study using Soxhlet extraction, Bonification, and steam distillation for the recovery of PCBs from environmentally contaminated lake and river bottom materials. The high frequency dispersion extraction technique was not used in this study because of excessive and rapid wearing of parts of the device and excessive breakage of glassware. Bottom sediments were spiked with Aroclor 1254 and extracted by the three techniques. The mean recovery of PCBs for spiked samples was 81-109% for the different methods, indicating that any of the three might be used for quantitative extraction. However, the Soxhlet extraction method yielded higher levels of PCBs from environmentally contaminated sediments than either steam distillation or Bonification. The results of this study are not conclusive since only one solid sample matrix was considered. Seidl and Ballschmiter (1976a) studied the recovery rates of PCBs from soil using Soxhlet extraction with hexane, acetone/acetonitrile, or ultrasonic extraction with acetone. Carbon-14 labeled Clophen A-30 was added to the soil to simplify the extraction studies. The authors concluded that Soxhlet extraction with acetone/acetonitrile yielded the best recoveries (greater than 95%) and Soxhlet extraction with hexane or ultrasonic extraction with acetone was not suitable for good recoveries of PCBs from soil. Biological Matrices-Considerable emphasis has been placed on the analysis of biological materials for the presence of PCBs. Tissues are generally homogenized and ground with sodium sulfate, sand, or Florisil and are either Soxhlet extracted (Bagley et al., 1970; Curley et al., 1971; deVos, 1972; Hattula, 1974; Holden, 1971; Kuehl et al., 1980; Stalling et al., 1972) or packed into a chromatographic column and the PCBs are eluted with an appropriate solvent (Bowes and Lewis, 1974; Call et al., 1974; Donkin et al., 1977; Erney, 1974b; Ernst, 1974; Hattula, 1974; Stalling, 1971; Wardall, 1977; Hutzinger et al., 1974; Stalling et al., 1972; Sawyer, 1973; Armour and Burke, 1970). Recently, microcontinuous 14 �liquid-liquid extraction combined with steam distillation has been shown to be an effective extraction procedure for tissues (Kuehl et al., 1980). Other tissue extraction techniques have included blending with chloroform and methanol mixtures followed by centrifugation (Sherma, 1975) and saponification of fat and animal tissue with methanolic potassium hydroxide followed by liquid-liquid extraction with hexane (Adams et al., 1979). PCBs in serum and blood samples have been extracted by dilution with methanol followed by liquidliquid extraction with either hexane or diethylether. Miscellaneous-The other materials that have been analyzed for PCB content include transformer oil, silicone fluids, chlorinated benzenes, paper, packaging materials, and pigments. Generally, transformer oils, silicone fluids, and chlorinated benzenes are simply diluted with solvent prior to cleanup or direct analysis (Adams et al., 1979; ASTM, 1980a; EPA, 1981; Bellar and Lichtenberg, 1981; Klimisch and Ingebrigtson, 1980; Dow, 1980). The paper and packaging materials have required homogenization by grinding before Soxhlet extraction with hexane or acetone (Kurastune and Masuda, 1972; Giacin and Gilbert, 1973; Serum et al., 1973) or hydrolysis with refluxing alcoholic potassium hydroxide and final extraction with petroleum ether (Burke et al., 1976; Easty, 1973; Shahied et al., 1973). In a method published by the DCMA (1980), extraction of phthalocyanine blue pigment required dissolution with sulfuric acid prior to hexane extraction to isolate incorporated PCBs. The PCBs in other pigments, such as phthalocyanine green and diarylide yellow are quantitatively extracted by high speed homogenization with methylene chloride (DCMA, 1980). Only the extraction methods described for the colored pigments (DCMA, 1980) were developed for PCBs as nonAroclor chlorinated compounds. All other methods were used in studies that considered the environmental impacts of the commercially distributed PCBs as Aroclors. CLEANUP In addition to PCBs, a large number of chlorinated compounds, lipid materials, and sulfur are extracted from aqueous, oil, tissue, sludge, and sediment samples by the methods described above. Hence, it is necessary in many cases to provide an additional sample preparation step or cleanup to remove the coextractants that may act as interferences. Cleanup techniques vary considerably according to the particular sample matrix and needs for final instrumenta1 analys i s. Review Articles Sample extract cleanup procedures for PCB analyses have been partially reviewed previously (Holden, 1971; Fishbein, 1972; deVos, 1972; Hutzinger et al., 1974; Krull, 1977; Albro, 1979). 15 �Standard Methods Table 1 listed the cleanup procedures that are typically used with a number of standard methods for these materials. These cleanup procedures include liquid-liquid partition of the sample extract, saponification with alcoholic potassium hydroxide, addition of concentrated sulfuric acid, gel permeation chromatography, and oxidation of interferences in the sample matrix. Primary Literature Adsorption Chromatography Cleanup-Perusal of the literature indicates that adsorption column chromatography is the most often practiced method of sample extract cleanup prior to instrumental analyses. The extent of sample cleanup required is dependent, in many cases, on the specificity of the detector used for identification and quantitation. Electron capture and halogen specific detectors (i.e., Hall electrolytic conductivity detector) require clean extracts since so many other compounds can interfere. Chromatographic column cleanup procedures have been used extensively with adsorbents such as Florisil, silica gel, and alumina. Cleanup procedures may require the use of only one column, combinations of adsorbent materials, use of an adsorbent following liquid-liquid partition, or cleanup after matrix destruction by sulfuric acid or saponification. Proper activation of adsorbed materials and the characterization of the degree of activation is essential for effective and reproducible cleanup of sample extracts by a particular chromatography procedure (Edwards, 1974; Zitko, 1972). Reproducibility of a column method requires avoidance of overloading the column, accidental deactivation of the adsorbent during cleanup, and use of pure solvents (Edwards, 1974). Optimum cleanup and separation of PCBs from interferences require fully activated adsorbents, and large eluent volumes (Edwards, 1974; Albro and Parker, 1980). The alternative to large, eluent volumes is to use only a fraction of the extract with microcolumn adsorbent procedures. A notable example is the Sep Pak marketed by Waters Associates. Several investigators have reported the application of Sep Pak for PCB cleanup as discussed below. The most commonly used adsorbents are Florisil and silica gel at various levels of activation. Florisil has been used to remove gross interferences from sample extracts from air, water, wastewater, tissues, and dairy products as well as paper, paperboard, and paper mill effluent (AOAC Methods, 1980; Adams et al., 1979; Delfino and Easty, 1979; Easty, 1973; EPA, 1979a; EPA, 1979b; EPA, 1978; EPA, 1980; Kamops et al., 1979; Kuehl et al., 1980; Modi et al., 1976; Price and Welch, 1972; Reynolds, 1971; Reynolds, 1969; Robbins and Willhite, 1979; Rodriguez et al., 1980; Stijve et al., 1974; Swift and Settle, 1976; Tessari and Savage, 1980; Yakushiji et al., 1978; Bagley et al., 1970; Bagley and Cromartie, 1973; Bellar and Lichtenberg, 1976; Chau and Babjak, 1979). Florisil has also been used to provide additional separation of sample extracts following initial cleanup of matrices by low temperature precipitation, acetonitrile partitioning, oxidation, sulfuric acid digestion, alumina chromatography, or gel permeation chromatography (Eden, 1976; Ernst et al., 1974; Kohli et al., 1979; Mes et al., 1977a, Mes et al., 1977b; Mulhern et al., 1972; Stanovick et al., 1973; Swift and Settle, 1976; Tessari and Savage, 16 �1980; Trotter, 1974; Uk et al., 1972; Bagley et al., 1970; Bagley and Cromartie, 1973; Copeland and Gohmann, 1982), Seidl and Ballschmiter (1976b) investigated the recovery and efficiency of cleanup methods for the isolation of PCBs from vegetable oils. Column chromatography on Florisil, matrix destruction via saponification and sulfuric acid treatment, and liquid-liquid partition with hexane/acetonitrile or hexane/ dimethylformamide were compared as cleanup techniques. The Florisil chromatographic column with hexane/methylene chloride (80:20) as the eluent and liquidliquid partition with hexane/dimethylformamide were shown to be the methods of choice with recoveries of greater than 90%. Silica gel or silicic acid has also been used for a large number of sample matrices including water, sediments, sludges, foodstuffs, tissues, and transformer fluids (Armour and Burke, 1970; Devinish, Harling-Bowen, 1980; Erickson and Pellizzari, 1977, 1979; Ernst, 1974; Giacin and Gilbert, 1973; MacLeod, 1979; Masumoto, 1972; Mes et al., 1976; Mes and Campbell, 1977; Nose, 1973; Ogata et al., 1980; Picer and Abel, 1978; Price and Welch, 1972; Sawyer, 1973; Stalling, 1971; Steichen et al., 1981, 1982; Balya and Farrah, 1980; Beezhold, 1973; Bellar and Lichtenberg, 1975; Coburn et al., 1977). Many applications have utilized the excellent separation properties of silica gel to remove other halogenated interferences from PCB fractions. The separation of a number of halogenated pesticides has been accomplished by using silica gel after preliminary cleanup of gross interferences and controlling the degree of activation and size of the column or by slightly modifying the adsorbent with silver nitrate or an oxidizing agent (Erney, 1974a; Erney, 1974b; EPA, 1978; Herzel, 1971; Huckins et al,, 1976; Kreiss et al., 1981; Kveseth and Brevick, 1979; Leoni, 1971; Mitzutani and Matsumoto, 1973; Musial et al., 1974; Needham et al., 1980; Public Health Services, CDC, Atlanta, 1980; Serum, 1973; Snyder and Reinert, 1971; Stratton, 1977, Swift and Settle, 1976; Trevesani, 1980; Underwood, 1979; United Kingdom, Department of Environment, 1979; Wakimoto et al., 1975; Bidleman et al., 1978). Cleanup and separation of interferences from PCBs has been accomplished with Sep Pak miniature silica gel cartridges for transformer (Gordon et al., 1982; Steichen et al., 1981), mineral, phosphate ester, glycol base, and sulfonated mineral oils (Balya and Farrah, 1980). Alumina has been used as an adsorbent in more recent applications for cleanup of matrices from oils, fats, and tissues (Donkin et al., 1977; Hattula, 1974; Kohli et al., 1979; Kveseth and Brevick, 1979; Ofsta'd et al., 1978; Teichman et al., 1978; Wardall, 1977; Zitko, 1976) and other biological materials such as blood and human milk (Musial et al., 1972; Siyali, 1973; Tuinstra and Traag, 1979a, 1979b; Welborn et al., 1974) and from oil, water, sediments, and vegetable materials (Goerlitz and Law, 1974; Lewis et al., 1977; Tuinstra et al., 1981; United Kingdom, Department of Environment, 1979). Dispersion of activated carbon on polyurethane foam, termed carbon foam chrpmatography, and use of activated charcoal have also proven to be effective means of isolating PCBs from complex matrices such as tissues and sediments (Chau and Babjak, 1979; Jensen and Sundstrom, 1974; Stalling et al., 1979a; Stalling et al., 1979b; Stalling et al., 1978; Stalling et al., 1975; Tiechman et al., 1978). 17 �Gel Permeation Chromatography-Gel permeation chromatography (GPC) has arisen as a popular cleanup procedure for complex matrices, especially samples containing macromolecular interferents such as biological materials containing high levels of lipid materials. The GPC method has been fully automated for large numbers of sample extracts. However, it is necessary to fully validate the GPC method for each different sample matrix as with other cleanup procedures. Gel permeation chromatography has been successfully used as a cleanup for matrices of high molecular weight content and has provided a cost effective approach towards automation of large numbers of samples (Albro, 1979; Caragay and Levins, 1979; Griffitt and Craun, 1974; Haile and Lopez-Avila, 1981; Hopper and Hughes, 1976; Kohli et al., 1979; Kuehl et al., 1980a, 1980b; Rodriguez et al., 1980; Stalling, 1971, 1976; Stalling et al., 1972, 1979; Tessari, 1980). Gel permeation chromatography of tissue and vegetable material extracts followed by carbon-foam chromatography provides a cleanup that is exceptionally selective for planar aromatic hydrocarbons and the chlorinated analogs such as PCBs (Dougherty et al., 1980). Lipidex was shown to separate PCBs and other semivolatile halocarbons from water, fat, butter, and milk (Egestad et al., 1982). Elution conditions could be adjusted to separate the halocarbons from steroids and fatty acids. The authors noted that a combination of partition, molecule sieving, and aromatic adsorption was involved in the separation. High Performance Liquid Chromatography and Thin Layer Chromatography— High performance liquid chromatography (Aitzetmiiller, 1975; Dolphin and Willmott, 1978; Rohleder, 1976) and thin-layer chromatography (Fishbein, 1971; Hattula, 1974; Koeniger, 1975) have also received limited attention as chromatographic cleanup methods. Recently, an HPLC cleanup method for determination of PCBs in oils and waste oils has been devised (Chesler et al., 1982). Acid Cleanup— Sulfuric acid is added as the first step of many cleanup procedures to remove gross interferences, although a number of studies found sulfuric acid cleanup alone sufficient for PCB analysis (Ahling and Jensen, 1970; Becker and Schulte, 1976; Haile and Baladi, 1977; Hattula, 1974; Mattson and Nygren, 1976; Murphy, 1972; Veierov and Aharonson, 1980; Harris and Mitchell, 1981). Losses of the mono- to trichlorobiphenyls were reported in two studies (DCMA, 1981; Lincer, 1973) which used a heated sulfuric acid cleanup. No losses were observed at room temperature (Haile and Baladi, 1977). The chemical destruction cleanup methods are extremely useful but care must be taken to ensure valid recoveries of the particular PCB isomers of interest. For example, mono-, di-, and trichlorobiphenyl isomers were not quantitatively removed from pigment matrices that were treated with concentrated sulfuric acid (DCMA, 1981; Lincer, 1973). Low recoveries were presumed to be due to sulfonation of the biphenyl ring (Lincer, 1973). Liquid-liquid Partitioning— Liquid-liquid partition is also used to remove large amounts of interferences from water, wastewater, milk, food products, packaging materials, silicone fluids, oil, and tissue extracts before final cleanup by a chromatography technique (EPA, 1978; Gordon et al., 1982; Leoni et al., 1973; Mulhern 18 �et al., 1972; Siyali, 1973; Swift and Settle, 1976; Tessari, 1977; Tessari and Savage, 1980; Klimisch and Ingebrigtson, 1980; Welborn et al., 1974). Large amounts of an interference in a sample extract, such as the lipid content of a tissue extract, has a pronounced effect on the efficiency of liquidliquid partition cleanups (Albro, 1979). Validation of a cleanup procedure using spiked blanks provides much better recovery values than can be achieved for an actual sample. Therefore, it is necessary to spike actual sample extracts to fully characterize the limitations of this type of cleanup step. Seidl and Ballschmiter (1976b) have demonstrated PCB recoveries of greater than 90% for cleanup of vegetable oil extracts by liquid-liquid partition with hexane and dimethylformamide. Saponification— Saponification of the sample matrix has been discussed as a method for extracting PCBs from certain materials. Saponification may also be considered a cleanup procedure (Lincer, 1973; Tatsukawa and Wakimoto, 1972; Trotter, 1974). Saponification of sample matrices with ethanolic potassium hydroxide has been accomplished without chemical change to the PCBs present (Young and Burke, 1972). Miscellaneous— Other cleanup procedures that have been shown to be effective but have limited use are low temperature precipitation of lipids from tissues and human milk samples prior to solvent extraction or liquid-liquid partitioning (Mes et al., 1977a, 1977b; Mes and Campbell, 1976). Oxidation of interfering chloronaphthalenes and chlorinated pesticides such as DDT and DDE with chromium trioxide or chromic acid has been shown to be effective when used in conjunction with a final chromatographic cleanup (Holmes and Waller, 1972; Mulhern et al., 1972; Underwood et al., 1979). However, Szelewski et al. (1979) have questioned the reliability of the chromium trioxide oxidation of interferences in sample extracts. Fish extracts, spiked with Aroclor 1016, 1221, and 1254, were treated with the chromium trioxide oxidation technique. Recoveries of Aroclor 1016 from this oxidation step ranged from 30 to 90% for eight replicates, while Aroclor 1254 recoveries ranged from 40 to 80% for eight replicates. Aroclor 1221 was reported to have 0% recovery from this oxidation step for six replicate samples. Szelewski et al. (1979) theorized that PCBs in the extracts were lost by oxidation, by volatilization due to the highly exothermic nature of the oxidative process, or a combination of the two. Steam distillation of water, sediments, and tissues provides relatively clean extracts that require little or no additional cleanup (Veith and Kiwus, 1977; Dougherty et al., 1980). Interference from elemental sulfur is a serious problem, especially for electron capture detector methods of analysis. The sulfur interference in water, wastewater, sewage sludges and sediments can be effectively removed by precipitation of sulfur with mercury (Bellar and Lichtenberg, 1976; Goerlitz and Law, 1974; Rodriguez et al., 1980) or by converting sulfur to thiosulfate by addition of tetrabutylammonium sulfate (Jensen et al., 1977). Recovery Measurement Regardless of the cleanup procedure required for PCB analysis from a particular sample, it is of utmost importance to document recovery of PCBs from the method. Routine quality assurance governs that the recovery be determined 19 �for each different sample matrix encountered. Also, recovery of the PCBs should be determined each time a given parameter of an established cleanup procedure is changed. For example, different batches of an adsorbent may differ greatly with respect to activation. Cleanup steps should be monitored with spiked samples to support overall quality of the data. In some instances, a visible marker such as azulene can be used as a real time monitor to determine the performance of column chromatography methods (Nowicki, 1981). DETERMINATION Thin-Layer Chromatography In addition to its use as a cleanup technique, thin-layer chromatography (TLC) has been used extensively as a determination technique. TLC was used early (latter 1960s, early 1970s) because HPLC was not readily available and the GC techniques were not well-developed. Most of the early TLC reports were normal phase (silica gel) and included elaborate cleanup steps to remove interferents (e.g., oxidation of DDE to a benzophenone derivative). In the mid-1970s when packed column gas-liquid chromatography/electron capture detection (PGC/ECD) became the method of choice, emphasis on TLC methods dwindled. Several articles have been published which take advantage of modern TLC techniques: high performance TLC, two-dimensional TLC, reverse phase TLC, and new detection methods. TLC has been shown to be an effective technique for determination of (Aroclor) PCBs in a wide variety of matrices. The advantages included its ease of use and the simplicity of the apparatus. The disadvantages include lack of resolution, moderate sensitivity, and specificity. Review Articles-TLC analysis of PCBs was reviewed by Fishbein (1972). Standard Methods— TLC is included as an alternate technique for "semiquantitation" analysis of PCBs in human adipose tissue in EPA manuals (Watts, 1980; Sherma, 1981). It is also included in the Association of Official Analytical Chemists methods for confirmation of identity (AOAC, 1980). TLC is mentioned by the Food and Drug Administration (1977) as a technique which they feel may also be useful in dealing with particular resin combinations . Primary Literature— Since the publication of a TLC method for PCBs by Mulhern (1968) and Mulhern et al. (1971), several researchers have used a similar method for analysis of PCBs in food (Stijve and Cardinale, 1974), animal feeds (Westoo and Noren, 1970), food packaging (Zimmerli et al.), bald eagles (Bagley et al., 1973), Aroclor mixtures (Willis and Addison, 1972), animal tissue (Collins et al., 1972; Koeniger et al., 1975; Bush and Lo, 1973; Hattula, 1974; Mes et al., 1977), human adipose tissue (Price and Welch, 1972; Lucas et al., 1980), and human milk (Savage et al., 1973a, 1973b; Mes and Davies, 1979). 20 �Many of these researchers employed TLC in conjunction with other techniques such as GC/ECD. Often, TLC was used as a confirmation technique. Several publications have reported developments claimed to improve the technique. Circular TLC reportedly improves sensitivity by an order of magnitude with a PCB limit of detection of about 0.05 M8 (Koch, 1979). Fused glass TLC has been reported as yielding longer plate life (Okamura et al., 1973). Reverse phase TLC has been reported to yield better separation of PCBs from interferences (deVos and Peet, 1971; deVos, 1972; Stalling and Huckins, 1973; Brinkman et al., 1976a). An impregnated silica gel plate has been reported (Bergman et al., 1976) which improves selectivity apparently on the basis of ion-pairing. The use of surfactant micellar solutions as the mobile phase is certainly novel and reportedly has potential for separation of chlorinated aromatics, including decachlorobiphenyl (Armstrong and Terrill, 1979). Improvements in detection have included an AgNOs spray followed by UV irradiation (deVos and Peet, 1971; deVos, 1972; Kawabata, 1974) and fluorescence (Kan et al., 1973; Ueta et al., 1979). A two-dimensional TLC method was developed which barely separated the DDT analogs from PCBs (Fehringer and Westfall, 1971). This last reference points to one of the major problems with TLC determination of PCBs. Many common interferences (e.g., DDE in biological tissues) have similar elution characteristics and are not easily resolved. One common technique for removal of DDE prior to TLC is oxidation of the DDE to dichlorobenzophenone with chromium trioxide or other oxidant (Biros et al., 1972; Sherma, 1981; Watts, 1980; Collins et al., 1972). Two studies (Bush et al., 1971; Collins et al., 1972) compared TLC and GC/ECD. In both studies the PCB values obtained were generally comparable, although in the study by Bush et al., the TLC results were generally lower than GC/ECD. Lucas et al. (1980) reported a statistical analysis of semiquantitative determinations of PCBs in human adipose tissue generated by the EPA's National Human Monitoring Program during FY 1972 to 1976. Results were reported only as ranges (not determined, < 1, 1 to 3, and > 3 ppm) for 5,259 samples. The EPA TLC technique (Watts, 1980; Sherma, 1981) was used in this study through November 1974 and a GC/ECD technique involving a single PCB peak quantitation was used thereafter. A total of 3,802 TLC results and 1,457 PGC/ECD results were compared and not found significantly different, High Performance Liquid Chromatography High performance liquid chromatography (HPLC), with ultraviolet and other detectors, has been reported in the characterization of commercial PCBs as a cleanup technique and as an analytical technique. Despite its general applicability in analytical chemistry, HPLC has not been as popular as gas chromatography (GC) for PCB analysis. The major reason is that GC detectors, especially those selective toward halogens, exhibit much lower limits of detection. Since HPLC is basically an instrumental version of the column chromatographic cleanup techniques, described above, it is applicable both as a cleanup 21 �and a determination technique. Some researchers have exploited this and combined cleanup and determination into one step with HPLC (Hanai and Walton, 1977; Van Vliet et al., 1979). Review Articles— Krull (1977) mentioned HPLC in a review of PCB analysis. Lawrence and Tuiton (1978) reviewed the HPLC data on pesticides, including PCBs in their tabulation. Standard Methods-No standard methods utilize HPLC. Primary Literature— Several authors (Brinkman et al., 1976a, 1976b; Veith and Austin, 1976; Albro and Parker, 1979; Brinkman and deVries, 1979) have used HPLC in characterization of commercial PCB products or establishing the chemical behavior of PCBs. HPLC has been used as a cleanup technique prior to gas chromatographic determination (Aitzenmiiller, 1975; Dark and Grossman, 1973; Rohleder et al., 1976; Krupcik et al., 1977; Dolphin and Willmott, 1978). More recently it has been used on a preparative scale to clean up waste and transformer oils prior to CGC/ECD determination (Anonymous, 1982; Chesler et al., 1981). In the course of these investigations, the researchers noted that the CGC/ECD limit of detection was about 100 times lower than the HPLC/UV limit of detection. As HPLC became increasingly popular in the early 1970s, Eisenbeiss and Sieper (1973) performed preliminary investigations of the use of HPLC for pesticide (and PCB) analysis. They concluded that HPLC can be regarded as an alternative or supplementary method to conventional methods such as gas chromatography. Hanai and Walton (1977) developed an HPLC/UV method for determining PCBs in water. No LOD was determined, but good recoveries were obtained for 250-|Jg/ liter Aroclor 1232 spiked into distilled water. The water was pumped directly through the HPLC system and the PCBs subsequently eluted by gradient elution. A similar application (Van Vliet et al., 1979) used an HPLC precolumn to concentrate PCBs from water and then elute them onto the analytical column for separation and determination. Belliardo et al. (1979) developed an HPLC/UV procedure for PCBs in oil and compared it with a PGC/ECD method. The HPLC method was judged suitable to approximate, but not quantitate, the PCB content. Seidl and Ballschmiter (1979) used HPLC/UV to detect biphenyl after dehydrochlorination of PCBs. Electron capture detection of HPLC effluents has been described (Willmott and Dolphin, 1974) for the analysis of PCBs. The LOD of HPLC/ECD is reported to be about 10 times higher than for GC/ECD (Brinkman et al., 1978). Stalling et al. (1980) gave a preliminary description of an HPLC/MS (presumably the chemical ionization MS mode) system for rapid screening for PCBs. 22 �Gas Chromatography Gas chromatography (GC), in combination with various detectors, has been by far the most popular and useful analytical procedure for PCBs. In recent years, capillary column GC (CGC) has been used increasingly, although most investigators still use packed column GC (PGC). The popularity of GC lies in its resolution and speed (most PGC analyses take less than 30 min) and the sensitivity (ECD), selectivity (BCD, HECD), and specificity (electron impact mass spectrometry) pf the available detectors. Separation-Packed column GC (PGC)—Over 215 references were abstracted which used PGC as the analytical separation technique. The vast majority of these used PGC in a routine manner with a common liquid phase. The quality of the chromatography (resolution and tailing) was generally adequate for low resolution separation of Aroclor-derived samples into a "fingerprint" for identification or quantitation. Since the Aroclor mixtures are too complex for resolution, little or no emphasis was placed on improving resolution by PGC. The most common PGC detector has been ECD. ECD has historically required isothermal GC operation (not so with modern instruments). Figures 1 and 2 present some PGC/ECD chromatograms (Mullin and Filkins, 1981). Review articles—By 1971 sufficient work in PCB analysis by PGC had been completed to merit a review (Reynolds, 1971). This was followed by several other reviews (Fishbein, 1972; Hutzinger et al., 1974; Fuller et al., 1976; Krull, 1977; Margeson, 1977; and CMA, 1981). One review by Sherma (1975) was devoted to PGC analysis of PCBs and related chlorinated aromatic pollutants. Standard methods—PGC is the recommended analytical separation method in all but one of the 11 standard methods listed in Table 1. Primary literature--Since over 215 citations on the use of PGC in the analysis for PCBs have been abstracted, a complete discussion of the pri-1 mary literature would be a formidable task. Most of these citations used PGC in a routine manner and included little or no discussion as to why a liquid phase or GC condition was chosen (if they were even mentioned). Several articles are worth noting. Albro et al. (1977) evaluated 13 packed columns ranging in polarity from Apiezon L to OV-225. The number of observed theoretical plates ranged from 491 to 3,833. None of the columns could successfully resolve all PCBs, In the best case, it was calculated that of the 21,945 theoretically possible pairs of PCB congeners, 465 would be indistinguishable using the best column tested. The researchers discussed the use of multiple columns for resolving indistinguishable pairs and concluded that five columns were necessary to resolve all isomers. Thus, using this scheme, each sample would have to be analyzed once on each of five PGC columns to resolve all congeners. 23 �UJ CO O a. CO 01 O O LU K J 34 LU O /A/.; TIME, min UJ CO z O H (Hi) - 4 5 rrn/sor Q. CO UJ QC o UJ H LU a 120 60 TIME, min INJ Figure 1. Comparison of packed column gas-liquid chromatography (top) and capillary column gas-liquid chromatography (bottom) with Aroclor 1242 and 1260 standards (Mullin and Filkins, 1981). 24 �LLJ CO 1 CO LU tr tr g ui UJ Q I 34 TIME, min INJ i1 I 1,(H,, - 45 , 1/Sl'l1 T -- 5 LU •-T z o a. CO LU cc cc . 1 .. ,,h , yj JJ o a • LU o !, 1 i i 100 70 30 "17 INJ TIME, min Figure 2. Comparison of packed column gas-liquid chromatography (top) and capillary column gas-liquid chromatography (bottom) with a milk extract (Mullin and Filkins, 1981). 25 �Albro and Parker (1979) applied this technique to the identification of the components in Aroclor 1016 and 1242. The identity of 44 congeners was reported. A report by Jensen and Sundstrom (1974) presents what may be the highest resolution PGC chromatogram of PCBs. Even though it was operated isothermally, this 5.2-m Apiezon L column resolved 59 peaks in a Chlophen mixture. Capillary column gas chromatography--CGC has not been nearly so popular as PGC, although 42 citations have been abstracted. In recent years the quality of the CGC separations reported have been truly impressive. Despite these advances, no CGC method reported or predicted will separate all 209 PCB congeners. As an example of the overlap problem, Pellizzari (1982a) reported CGC/ECD and CGC/NCIMS identification of PCB congeners in an Aroclor 1016/1254/ 1260 mixture. Of the 103 peaks listed, 73 were identified, but only 43 corresponded to a single congener. The others were possibly two (19 peaks), three (9 peaks), four (1 peak), or even six (1 peak) co-eluting congeners. In addition to the problem of congener separation, interferences may coelute. EIMS can readily discriminate against non-PCBs; however, co-eluting major components may affect the mass spectral response of PCBs. Review articles—CGC was briefly cited (five references) in one review (Sherma, 1975). An Aroclor CGC/ECD chromatogram was included in a CGC monograph (Jennings, 1978) as an application of CGC. Standard methods-1-One of the 11 standard methods in Table 1 recommends CGC, specifically a support coated open tubular (SCOT) column coated with FFAP (free fatty acid phase) for analysis of PCBs in capacitor Askarels. EPA Method 625 (EPA, 1979b) recommends PGC or if desired, capillary or SCOT columns may be used. Capillary gas chromatography is also allowed, if desired, for the analysis of PCBs in transformer fluids or waste oils (EPA, 1981). Primary literature—CGC was utilized in 43 articles abstracted for this review. The level of detail and column specifications span a wide range. Sissons, and Welti (1971) published an early article which characterized many of the PCB isomers in Aroclor 1254. Using an Apiezon L packed column, 23 peaks were resolved, while the same phase on a SCOT column (24,000 to 27,000 plates) separated 65 peaks. The next year, Webb and McCall (1972) performed similar experiments using an SE-30 SCOT column. Although the resolution was poor by today's standards, Biros et al. (1970) used CGC/EIMS to determine PCBs in human adipose even earlier. Krupcik et al. (1971) evaluated metal WCOT columns coated with Apiezon L or OV-101 and found them unsuitable. However, OV-101 on a glass WCOT column gave good results. An example of the separations obtained by CGC using liquid phases of different polarity is shown in Figure 3 (Krupcik et al., 1977). The quality of the chromatography is less than optimal because the GC was operated isothermally. Krupcik et al. (1982) have also reported on the optimization of experimental conditions for the analysis of complex mixtures by capillary gas chromatography. The optimization procedure for complex materials was demonstrated with Aroclor 1242. Forty PCBs were separated 26 �Separation of a PCS mixture by OLC on a glas$ capillary column coated with OV-101 at 200 °C (column E)f ULJ Separation of PCB mixture by GLC on a glass capillary column coated with Carbowax 20M at 200 °C (column FJ. Figure 3. Comparison pf PCB resolution on different columns (Krupcik et al., 1977). �at 170°C using a 40.0 m Carbowax 20M glass capillary column connected to a 75.6 m Apiezon L glass capillary column. Using a 50-m Dexsil 410 glass capillary Albro et al. (1981) have achieved 175,000 effective theoretical plates for 2,3,5,2',3',5'-hexachlorobiphenyl. Resolution of Aroclor 1260, which required an isothermal chromatogram of 5 h, generated 110 peaks, of which only 4 were unidentified. Even at this resolution, the Dexsil 410 did not resolve all congener pairs. Less efficient columns coated with Silar 5 C, Apiezon L, and OV-25 were used to provide different separations which resolved the congener pairs not previously resolved. Although no column performance parameters were given, Mullin and co-workers have achieved impressive resolution by temperature-programmed CGC/ BCD on C-87 columns (Mullin and Filkins, 1981; Mullin et al., 1981) and SE-54 columns (Safe et al., 1982). Pellizzari et al. (1981) have compared a number of capillaries (capillary material, pretreatment, and liquid phase). Apiezon L was judged to be the best of the liquid phases tested (SE-54, C-87, SP-2100, and Apiezon L), for PCB analysis, based on resolution, separation number, and HEETP. Two examples of this column's performance are shown in Figures 4 and 5. This conclusion supports that of several other investigators who have used and recommend Apiezon L (Sissons and Welti, 1971; Albro et al., 1977; Stalling et al., 1978; Albro et al., 1981; Jensen and Sundstrom, 1974; Nakamuna and Kashimato, 1977; United Kingdom Department of the Environment, 1979) or similar hydrocarbon phases for PCB analysis (Mullin and Filkins, 1981). Tuinstra and coworkers (Tuinstra and Traag, 1979a, 1979b; Tuinstra et al., 1980; Tuinstra et al., 1981) have explored the automation of CGC/ECD analysis with autoinjection onto a splitless injector. This approach, although not thoroughly presented in Tuinstra (no mention of sample throughput or automation of data recording and reduction is mentioned), should be pursued by laboratories facing large sample loads. Recently, bonded liquid phases have been made available on capillary GC columns. These exhibit low bleed and background and have long lifetimes. Figure 6 presents a CGC/EIMS chromatogram of a PCB standard on a DB-5 column. It is interesting to note that J&W Scientific, Analabs, and Supelco present CGC/ECD chromatograms of Aroclor mixture in their catalogs. This indicates that CGC is commercially available and that the capillary manufacturers consider their PCB separations good enough to advertise. Comparison of PGC and CGC—The relative merits of PGC and CGC are well-known and apply to the separation of PCBs. CGC provides better resolution, retention time precision, and higher qualitative reliability. PGC yields a simple chromatogram (less data reduction), permits higher sample loading (and therefore possibly lower LOQs), and is generally considered easier to use. Historically, PGC quantitation has been more precise, although it has not been established how much of the imprecision attributed to CGC has been due to poor technique on the part of the analyst. 28 �Figure 4. Electron capture detection of Aroclors 1242, 1260, and 5460 (400 pg each) chromatographed on an Aoiezon L (WCOT) silanized Pyrex glass capillary, 0.20 mm i.d. x 50 m in length. The carrier was 53 cm/s; capillary was temperature-programmed from 150 to 390°C at l°C/min (Pellizzari et al., 1981). Figure 5.. Electron capture detection of PCB in an extract of yellow perchSee Figure 4 for chromatographic conditions (Pellizzari et al., 1981). 29 �Sample: Combine^ Aroclor 1248,1254,1260 250ng/^r&DCB l^bngX/il, 1/il Injection 10 800 20:00 1000 25:00 1200 30:00 1600 40:00 1400 35:00 1800 45:00 2000 50:00 2200 SC;AN 55;QQ TIME Figure 6. Scanning capillary column gas-liquid chromatography/mflsis spectrometry analysis of a mixed Aroclor standard used to establish retention windows for the CGC/MS-selected ion monitoring analysis of PCBs. Instrumental parameters: column, 15-m, fused silica, DB-5; column temperature, 80°C for 2 min, 8°C/min to 300°C; helium carrier at 2,5 psl; J&W on column injector. (J. S. Stanley and C. L. Haile, Midwest Research Institute, personal communication, 1982). 30 �Figures 1 and 2 (Mullin and Filkins, 1981) present graphic comparisons of PGC and CGC results for PCBs. Similar results have been presented by Onsuka and Comba (1978). Detectors-GC detectors are classified as either universal or selective. The BCD and HECD are highly selective toward halogenated compounds. This selectivity, coupled with its extreme sensitivity, has made BCD very popular for analysis of trace levels (residues) of pesticides and PCBs and has, in fact, had a significant role in regulatory actions on these classes of compounds. FID is the most common GC detector and is a universal detector, giving similar responses for most organic compounds. Thus, FID would be unsuitable for detection of PCBs in a complex matrix. Mass spectrometry and Fourier transform infrared spectrometry (FTIR) are in essence both universal and selective GC detectors. By focusing on a spectral property characteristic of a compound or class of compounds, these detectors can be quite specific. However, by using the full spectral range, nearly any compound eluting from the GC will be detected. Due to the much higher information content of mass and infrared spectra, identifications by GC/MS or GC/FTIR are generally made with greater certainty than by other detectors . The analysis of PCBs generally requires selectivity and sensitivity. Usually, even after cleanup, PCBs are a minor component of the sample, mixed in with other halocarbons (e.g., DDE), hydrocarbons, lipids, etc. Thus, the detector must selectively detect PCBs in the presence of other compounds present at orders of magnitude higher concentration. Furthermore, the levels typically observed in food, biota, tissue, soil, and other matrices of interest are in the parts per billion range. These levels strain the capabilities of even the most sensitive detection device such as BCD, resulting in a large number of "not detected" values in many reports. The choice of detector often depends upon the level of analytes. LOW concentrations demand a detector capable of detecting low amounts (high sensitivity) . Figure 7 presents the typical range and detection limits for most of the GC detectors used in analysis for PCBs. The detection limit of the HECD is 10 lx g with a linear range up to about 10 2 g, as measured for lindane (Anderson and Hall, 1980). As can be seen, BCD exhibits the lowest limit of detection (LOD). The reported LOD for PCBs in a variety of matrices are listed in Table 2. Comparison of the reported LODs is difficult because no standard definition of LOD was used. Glaser et al. (1981) followed a rigorous definition and experimentally determined the LOD with a fair degree of confidence, while other investigators clearly guessed at the LOD based on this work. The issue is further clouded by inconsistency in discussing the LOD with respect to the instrumental determination versus the entire procedure. Some LODs are reported for standard solutions, while others take into account the interferences in the matrix which often raise the LOD considerably. 31 �Detection Mode Selectivity Grans NT13 10 "12 ID'11 10"10 HT9 KT* Ifl"7 10"* 18"s 10"* NT3 10"2 1 Thermal Energy Analyzer Photoionization EleclionXiptuie Mass Spectrometry Election Impact Multiple Ion Del. Neg. Chemical Ion. Fluorescence Rame lonization Thermal Conductivity FT/IR t)V Figure 7. Detection limits/dynamic range for several instrumental methods (Pellizzari, 1981) �TABLE 2. REPORTED LIMITS OF DETECTION FOR PCBs Converted LODa (Mg/g or ppm) Instrument Reported LOD GC/ECD 0.065 yg/£ 0.5 ppb 6.5 ppb 50 ppb 1-0.1 ppb/isomer 0.5 ppm 1 ppm 0.5 ppm 0.6 Mg/£ 1 ng/m3 0.1 ng/m3 0.000065 0.0005 0.0065 0.05 0.001-0.0001 3 MgM 1 ppm 0.003 1 ppm 0.5 1.0 0.5 O.g006 NA, NA Substance Matrix Aroclor 1242 Aroclors Aroclors Aroclors Isomers Aroclors Total PCB Total PCB Perchlorinated Perchlorinated Theoretical per isomer Aroclor 1260 10 homologs Dist. water River water Pure solution Milk Vegetable Transformer fluid Reference Air Air Glaser et al., 1981 Kuehl et al., 1980 Teichman et al., 1978 Tessari and Savage, 1980 Tuinstra et al., 1981 Kirshen, 1981 Chesler et al., 1981 Balya and Farrah, 1980 Stratton et al., 1979 Stratton et al., 1978 Lewis et al., 1977 Blood serum Pigments Kreiss et al., 1981 DCMA, 1980 Oil Oils Ground water GC/HECD 1 mg/kg 1.0 Aroclors Oil EPA, 1981 GC/EIMS 30 | g £ j/ 36 |ag/£ 0.01-0.2 pg/£ 0.030 0.036 0.01-0.2 Aroclor 1221 Aroclor 1254 Single isomer 5 ppm 5 Single isomer Dist. water Dist. water Industiral sample extract Chlorinated hydro carbons Glaser et al., 1981 Glaser et al., 1981 Tindall and Winninger, 1980 Collard and Irwin, 1982 HREIMS 10 ppb 0.01 Aroclors Biological extracts Safe et al. , 1975 GC/NCIMS None (continued) �2 ^continued) Converted Instrument Reported IOD Dir. Probe NCIMS •*• 1 ppb tLC 0.5 ppm < 0 0 ppm .4 0.1 pg 0.05 jig 0.2 jjg 1 }ig a -o 0.031 Substance NSC Reference Matrix 0.5 < 0.04 Aroclor Aroclor Aroclor Aroclor Aroclor Aroclor Biological Dougherty et al . , extracts 1980 Adipose Milk Animal tissue NS Animal tissue NS Bush and Lo, 1973 Savage, 1973 deVos and Peet, 1971 Koch, 1979 Mulhern et al. , 1971 Ismail and Bonnerj 1974 Converted to common units of micrograms per gram (parts per million) assuming 1 ml = 1 g density. b NA = not applicable. c (pg/g or ppffl) NS = not specified. �Reviews Articles-Every review article abstracted covered the subject of BCD detection of GC effluents (Riseborough, 1971; Reynolds, 1971; Fishbein, 1972; Linear, 1973; Hutzinger et al, 1974; Sherma, 1975; Fuller et al., 1976; Margeson, 1977; Krull, 1977; Safe, 1976). Fishbein (1972), Sherma (1975), and Hutzinger et al. (1974) all reviewed the use of electrolytic conductivity detectors for PCB determina*tion. Safe (1975) and Hutzinger et al. (1974) discussed the use of flame ionization detection (FID), mostly with respect to calibration of ECD or establishing BCD response factors. Hutzinger et al. (1974) did mention that for the mono- and dichlorobiphenyls FID and ECD sensitivities are comparable. Standard Methods— As noted in Table 1, most of the standard methods specify ECD as either the detector or one of the options. FID is the detector prescribed in the American Society for Testing and Materials (1980a) procedure for determining PCBs in capacitor Askarels. In this case, the matrix is well-characterized and generally contains no other compounds in the PCB retention window. HECD is permitted as an alternate detector in three procedures (EPA, 1978; EPA, 1981; FDA, 1977). Electron capture detection—Based on literature citations and number of samples processed, the electron capture detector (ECD) has been the most common detector for GC analysis of PCBs. ECD is extremely sensitive for PCBs. It does, however, detect many nonPCB compounds (halogenated pesticides, PCNs, chloroaromatics, phthalate and adipate esters, and other compounds) which may be differentiated from PCBs only on the basis of retention time. Figure 8 illustrates the potential interferences from chlorinated pesticides. A major disadvantage of ECD is the range of response factors (Tables 3 and 4) which different PCB congeners exhibit. This seriously inhibits reliable quantitation. The opposite trends in the two tables presumably result from differences in the equations used (i.e., whether the PCB response is in the denominator or numerator). The earlier PGC/ECD work (Table 3) has a range of about 1,400, while the later CGC/ECD work (Table 4) has a range of only about 120. This may be a function of the differences in detector design and GC column throughput. In addition, the CGC is temperature-programmed, while PGC data were presumably obtained isothermally. Despite these differences, both tables clearly illustrate that, even within a homolog, the % RSD is very large and would result in poor accuracy if quantitation involves extrapolation from one isomer to another. A recent report of the ECD relative response factors for all 12 octachlorobiphenyls showed a range from 0.007 to 2.644 with a RSD of 35% (Mullin et al., 1981). This also illustrates the problem of PCB quantitation by ECD. This subject is treated in more detail in the Quantitation section. Over 175 references were abstracted in which ECD was used as a GC detector. Any novel aspects of the articles dealt with qualitative or quantitative aspects of ECD and will be treated in the appropriate subsections below. 35 �1248 4%SE-30/6%OV-210 Chromatograms of three AROCLORS on column of \& SE-30 / 6$ OV-53.0. Column temp. 200°C., carrier flow 60 ml/min., % detector, electron, attenuation on an E-2 10 x 16; dotted line a rdxture of chlorinated pesticides, identity and injection concentration given below: 1. 2. 3. U, 5. 6. 1.5 ng Diazinon Heptechlor -- 0.03 Aldrin .Ol}5 Kept.Epox. .0? .09 p,p»-CDE Dieldrin — .12 ?. 8. 9. 10. 11. o,p'-DDT ~ O.A ng p,p«-DDD — .& p,pf-EBT — .30 Mian — .75 Hethoxychlor .60 u AROCIOR 1260 Figure 8, Packed column gas-liquid chromatography/electron capture detector chromatograms ill-Tistra-ting potential Interferences between, pesifcides and PCBs <Uatts, 1980). �TABLE 3. RELATIVE MOLAR RESPONSES OF ELECTRON CAPTURE AND FLAME IONIZATION DETECTORS TO SOME CHLOROBIPHENYLS3 Chlorobiphenyl 2342,2'~di 2,4-di 2,6-di 3,3'-di 3,4-di 4,4'-di 2,4,4'-tri 2,2' ,4,4'-tetra 2,2* ,6,6'-tetra 3,3' ,4,4'-tetra 3,3' ,5,5'-tetra 2,3,4,5-tetra 2,3,5,6-tetra 2,2' ,4,4',6,6'-hexa 3,3',4,4',5,5'-hexa 2,2',3,3',4,4',6,6-octa 2,2',3,31,5,5',6,6'-octa deca N Mean SD RSD ( ) % Relative molar response Electron capture Flame ionizatipn 1.00 0.20 1.10 5.16 17.7 32.0 6.10 15.2 5.97 135 106 20.6 396 320 367 259 347 726 1,180 1,150 1,410 21 310 438 140 a Taken from Hutzinger et al., 1974, and Safe, 1975. 37 1.00 0.92 0.87 0.99 0.86 0.91 0.94 0.86 0.81 0.78 0.87 0.90 0.87 0.85 0.87 0.71 16 0.88 0.07 8,3 �TAB1E 4. COMPARISOH OF RELATIVE RESPONSE FACTORS BETWEEB (GC)2-ECD, GC-EIMS (MOLECULAR ION) AJJD (GC)2-NICIMS { / 35) FOR HOMOLOGOUS SERIES OF PCBs* az Homolog series Range (GC)2-ECD3 Mean ± S.D. ( RSD) Hc % 1C1{3) 15.089-39.342 29.589 ± 12.78 (43) 2C1(12) 0.425-10.641 4.271 ± 3.83 (90) 3C1(24) 0.328-2.136 1.193 ± 0.68 (58) AC1(42) 0.385-2.229 1.074 ± 0.41 ( 8 3) 5C1(46) 0.462-8.481 1.266 ± 1.29 (102) 6C1(42) 0.391-1.912 0.973 ± 0.335 (35) 7C1(24) 0.402-2.432 1.220 ± 0.419 (34) 8C1{12) 0.925-2.602 1.514 ± 0.679 (45) 9C1(3) 1.005-1.816 1.291 ± 0.45 (35) 10C1(1) 1.168 U) 00 3 9 9 31 35 37 21 10 3 1 Range 0.456-1.787 2.881-21.199 0.721-10.901 0.102-4.267 0.465-1.216 0.369-1.440 0.236-1.192 0.241-1.116 0.066-0.565 - Overall : 0.328-39.342 ( 120:1) ~ 0.924 ± 8.343 ± 2.921 ± 2.058 ± 0.805 ± 0.817 ± 0.703 ± 0.573 ± 0.354 ± 0.418 0.75 6.17 3.64 1.02 0.27 0.29 0.30 0.26 0.26 Overall : 0.066-21.199 (y 3 0 1 2:) * From Pellizzari et al. (1982). a STI data. b Martelli et al., 1981. c N = number of PCS isomers included in measurement. A All values are relative to ottachloronaphthalene. e Responses were relative to lowest response for each group. f ( ) = number of theoretical isomers possible. (GC)2-HICIMS3 Mean ± S.D. ( RSD) N % (81) (74) (125) (50) (33) (36) (43) (46) (73) Range GC-EIMSb Mean ± S . . « RSD) N 0 3 1.000-1.090 8 1 . 000-2 . 062 7 1.000-1.627 16 1.000-2.146 12 1.000-1.013 16 1.000-1.321 13 8 1.000-1.359 3 1 1.050 1.736 1.400 1.549 1.004 1.153 ± ± ± ± ± ± 0.04 0.30 0.24 0.33 0.01 0.11 1.179 ± 0.25 - (3.8) 3 (17) 10 9 (17) (21) 11 (0.7) 3 (9.6) 7 0 2 (22) 0 0 �Flame ionization detection--Flame ionization detection (FID) is the most commonly used GC detector because of its sensitivity and universality. Although some investigators have used FID for PCB determination in samples, it has generally been used only for calibration of response factors or other method development work. FID has been used for determination of PCBs in environmental samples (Mizutani and Masayoshi, 1972; Modi et al., 1976; Lao et al., 1976; Onsuka and Comba, 1978). Biros (1971) split the GC effluent to FID for quantitation and EIMS for identification. Cook et al. (1978) and Zimmerli (1974) used FID to detect biphenyl following dehydrochlorination of PCBs; a technique termed carbon skeleton chromatography. Most of the FID applications have been in establishing response factors, characterizing Aroclors, or other method development areas (Webb and McCall, 1972; Ugawa et al., 1973; Dexter and Pavlou, 1976; Boe and Egaas, 1979; Albro and Parker, 1980; Albro et al., 1981; Stalling et al., 1982). An example of the use of FID is presented in Table 3, where the molar responses of FID and ECD were compared (Hutzinger et al., 1974; Safe, 1975). The rtna 1 conductivity (TCP)--Hirwe et al. (1974) used TCD to characterize Aroclor mixtures. This application is similar to many of the FID applications. Electrolytic conductivity--The Hall (and its predecessor, the Coulson) electrolytic conductivity detector (HECD) has been used often in PCB analysis. It is much less subject to interference from nonhalogenated compounds than ECD and the response is proportional to the number of chlorines. The high limit of quantitation and difficulty of operation are the disadvantages of this detector. Webb and McCall (1973) and Sawyer (1978) used Hall detection in the characterization of Aroclor standards. Serum et al. (1973) used it, ECD, and electron impact mass spectrometry as PGC detectors in analysis of paper products for PCBs and other compounds. Hofstaedter et al. (1974) determined that sulfur compounds in certain petroleum oils gave positive interferences in PGC/ECD determinations of PCBs. Flame photometric, microcoulo>metric, and Hall detectors were used to characterize the PCBs and interferences. Chesler et al. (1981) characterized oil products in the preparations of National Bureau of Standards standard reference materials for PCBs in oil. They used both ECD and HECD as CGC detectors. The ECD was found to be more sensitive than the HECD by two orders of magnitude and easier to maintain in a noncontaminated state. However, ECD response factors varied for different PCB isomers, whereas the molar response to chlorine which is obtained from the HECD appeared to be constant. The HECD exhibited a wider linearity range and is more selective as it responded only to halogenated compounds. An interesting, though tangential, use of HECD was presented by Dolan et al. (1972), Dolan and Hall (1973), and Su and Price (1973). By adjusting the HECD operating parameters they selectively detected organochlorine pesticides in the presence of PCB interferences. Electron impact mass spectrometry—Electron impact mass spectrometry (EIMS) ranks second only to ECD in popularity as a GC detector for PCBs. 39 �Electron impact has been and continues to be the most widely used MS ionization technique. While the chemical ionization (CI) and negative chemical ionization (NCI) techniques are often more sensitive, their operation is more complicated and variation in the spectra and response are higher. EIMS has been applied to PCB determination using both direct probe; and gas chromatography for sample introduction. Early work generally employed the then-exotic technique as a confirmation technique. In recent years, as GC/ EIMS has become more routine, more and more analysts have chosen GC/EIMS as the primary technique. Review articles—The application of EIMS to analysis for PCBs has been reviewed by Fishbein (1972), Oswald et al. (197A), Hutzinger et al. (1974), and Safe (1975). Standard methods—As listed in Table 1, several of the standard methods use GC/EIMS, either as the primary analytical technique or as the con™ firmatory technique. Primary literature—In 69 articles abstracted, EIMS was used. The applications ranged from confirmation to routine use, from direct probe to CGC, and from Aroclor characterization to analysis of dirty samples. Among the pioneers, Biros et al. (1970) used CGC/EIMS to determine PCBs in human adipose tissue; Sissons and Welti (1971) used CGC/EIMS in the characterization of Aroclor 1254; and Bonelli (1972) presented PGC/EIMS data for an Aroclor 1254/chlorinated pesticide mixture. In addition to Sissons and Welti (1971), Webb and McCall (1972, 1973), Ugawa et al. (1973), and Oswald (1974) employed GC/EIMS in characterization of commercial PCB products. Using both electron impact and chemical ionization mass spectrometry, Oswald et al. (1974) were able to differentiate some isomers in complex mixtures from their spectra. While full spectra provide the most qualitative information, the use of selected ion monitoring enhances the instrument sensitivity and seleC" tivity and simplifies data interpretation. Examples of this technique have been presented by Beggs and Banks (1976), Eichelberger et al. (1974), Martelli et al. (1981), Collard and Irwin (1982), Erickson and Pellizzari (1977, 1979) and Tressl and Wessely (1976). Especially with the more highly chlorinated homologs, several m/z values are available for monitoring. Eichelberger et al. (1974) addressed the criteria for selection—intensity and probability of interference from higher homologs or other compounds. A compromise between full scan and SIM techniques is mass chromatpgraphy. Full spectra are collected and then ion intensity versus file position plots are extracted from the data by the computer. Thus, mass chromatography has the ease of interpretation of SIM but higher LOQs since full spectra are collected. These full spectra are available for qualitative use if needed. Canada and Regnier (1976) presented a technique which used mass chromatography to monitor the ion ratios in the PCB isotopic clusters. 40 �Another compromise technique, limited njass scanning (WMS), involves (as the name implies) scanning the spectrometer only over the mass range of interest (e.g., molecular ion cluster). This permits the spectrometer to spend! more time on the ions of interest and thus achieve better sensitivity than the full scan mode. Tindall and Wininger (1980) utilized IMS in theip PGC/CIMS analysis of commercial products for incidental PCBs, Albro and Parker (1980) utilized PGC/EIMS as part of a general an^ alytical scheme for chlorinated aromatic pollutants. Positiye chemical ionization mass spectrometry—Positive chemical ioni» zation (Cl) mass spectrbmery (CIMS) is oneof the "soft" ionization techniques spectromery one of techniques which tend to produce fewer fragments. Thus, the spectra are simple and the molecular ion is generally one of the most intense peaks, However, with PCBs, the electron impact spectra generally exhibit good molecular ions, reducing the advantages of Cl. Another problem with Cl is that the ionization, process depends on a reagent gas introduced with the sample into the source. Slight changes in gas pressure, source temperature, and electronic conditions can affect the reaction conditions and thus the spectrum (both fragmentation pat* terns and overall intensity). Thus, Cl is not as reproducible as electron impact, either qualitatively or quantitatively. Several researchers have utilized GC/CIMS for determination of FCBs,* Oswald et al, (1974a), Sawyer (1978), and Cairns and Siegmund (1981) characterized standard samples. Oswald et al. (1974b), lida and Kashiwagi Stalling (1976), and Cairns and Jacobsen (1977) applied GC/CIMS to PCB tabolites , environmental samples , and food samples . Dougherty et al. (1973) reported the use of direct probe positive and negative CIMS for the analysis of human adipose tissues for PCBs. Stalling et al. (1980) reported an HPIC/MS technique for PCBs which is presumed to use the Cl mode. This preliminary report speculated that HPLC/MS could be useful as a screening technique for environmental samples. A related but often defined as separate technique, atmospheric pressure chemical ionization has been reported for PCB determination. Dzidic et al. (1975) reported subpicogram detection of 2,3,4,5,6-pentachlorobiphenyl, and Thomson and Roberts (1980, 1982) used the technique for in situ detection, of PCBfi in clay and soil. Negative chemical ionization mass spectrometry — Negative chemical tion (NCI) mass spectrometry (NCIMS) is similar to both CIMS and ECJD- The basic difference between negative and positive Cl is the polarity of the vari« ous voltage potentials in the spectrometer and the detector. Many of the chemical reactions in the NCI source and the BCD are the same. NCI and BCD exhibit similar detection limits and selectivities toward chlorinated compounds, thus the interest in NCI. The reproducibility problems of Cl are also present in NCI. The range of response factors found with ECD are also found with NCI. NCIMS, a relatively recent technique, isi still considered to be a research technique. 41 �The group led by Dougherty has published extensively on the methods iand application of (direct probe) NCIMS (Dougherty et al., 1973; Kuehl et al., 1980; Dougherty et al., 1980; and Dougherty, 1981a, 1981b), The technique is described as rapid and highly selective toward halogenated compounds. The latter advantage reduces the need for cleanup and, according to Dougherty (1981a), permits the analysis without the customary GC separation. Kuehl et al. (1980) used both CGC/EIMS and CGC/NCIMS to analyze fish samples for a variety of chloroorganics, including PCBs. The electron impact spectra were used for primary identification, although the NCI spectra were also of great value. Figure 9 presents the NCI and electron impact TICs for comparison. The NCI is much more selective toward the halogenated compounds, eliminating the broad hump which is presumably a complex mixture of lipids and oils from the fish matrix. Pellizzari et al. (1981) have used CGC/NCIMS for analysis of PCBs and have characterized the instrument operation parameters. The choice of reagent gas and its pressure markedly affect the relative intensities of the major peaks (m/z 35 and 37, molecular ion, etc.). The response factors for several PCB congeners are presented in Table 4 (Pellizzari et al., 1982). As with ECD, the range of the response factors is broad. This would probably make quantitation by extrapolation from a single calibration isomer inaccurate. While not directly used for PCB determination, CGC/atmospheric pressure negative chemical ionization mass spectrometry was shown to be both sensitive and selective for PCDDs in the presence of PCBs (Mitchum et al., 1982). Vith proper selection of masses and ionization conditions, this technique may be highly selective for PCBs. High resolution electron impact mass spectrometry--'HREIMS is capable of obtaining precise and accurate mass measurements of a peak. This known mass can correlate with only a few possible molecular formulas, As reviewed by Safe (1975), HREIMS is particularly useful for chlorinated cqmpounds because the chlorine mass defect clearly distinguishes a halocarbon from a molecule containing only carbon, hydrpgen, nitrogen, and oxygen. Safe (1976) and Safe et al. (1975) have reported the application of HREIMS to the analysis of crude goat urine extracts and other biological samples for PCB and PCT metabolites. The reported 10-ppb detection limit and the rapid analysis time (no GC separar tion is used) would appear to make this technique a suitable technique for rapid screening of samples for the presence of PCBs. The lack of work in this area, however, suggests that other considerations must reduce the applicability of HREIMS. Hass and Friesen (1979) illustrated the need for HREIMS to separate interferences (if not chromatographically separated). The spectrum in Figure 10 shows that DDE, TCDD, and PCB would have given one peak under low resolution conditions. 42 �NEGATIVE CHEMICAL IONI2ATION I 3 U c O 75 .o JL 1000 2000 Spectrum Number 3000 ELECTRON IMPACT 1000 2000 3000 Spectrum Number Figure 9. Total ion current profiles for negative chemical ionizatjion data (upper) and electron impact data (lower) obtained on a Finnigan 4000 glass capillary GC/MS system for Ashtabula River fish sample (Kuehl et al., 1980). 43 �1 322.000 321.900 T I 321.800 Figure 10. Partial high resolution mass spectrum obtained from 2.5 x 10"10 g TCDD plus matrix from 10 g human milk, illustrating potential interferences in low resolution mass spectrometry (Hass and Friesen, 1979). Nonchromatographic Methods— This section presents a variety of miscellaneous methods reported for the determination of PCBs, Nuclear magnetic resonance (NMR) spectrometry—Wilson and Anderson (1973) used both 13C and *13. nuclear magentic resonance (NMR) to characterize the chemistry of selected PCBs. No attempt at analysis of real samples was made. Levy and Hewitt (1977) reported the analysis of PCB mixtures by 13C NMR, but noted that the technique was not as useful for higher homologs. Hutzinger et al. (1974) included a discussion of the NMR characteristics of PCBs in their review book. Synthetic congeners have been characterized by proton NMR (Mullin et al., 1981). Infrared (IR) spectrometry—Hutzinger et al. (1974) discussed the infrared (IR) spectral properties of PCBs. Webb and McCall (1972) used IR and other techniques to identify 24 PCB congeners in Aroclor 1221. Radioimmunoa ssay--Albro and coworkers have reported preliminary results in the development of a radioimmunoassay (RIA) method for PCBs (Albro et al., 1979; Kohli et al., 1979; Luster et al., 1979, 1981). Suggestive evidence is presented indicating the feasibility of employing radioimmunoa$says for determining the Aroclor product number and concentration in environmental samples (Luster et al., 1979). The assay requires an antiserum for each isomer but is termed fairly specific. Other techniques—Interrupted-sweep voltametry has been applied to the identification of PCBs, yielding positive identifications (Farwell et al., 1975). Plasma chromatography has been reported to give characteristic qualitative data for PCBs (Karasek, 1971). One report utilized neutron activation analysis for the determination of PCBs in dosed rats (Mamri et al., 1971), 44 �identification and quantitation of PCBs (EPA, 1972; Brownrigg et al., 1974; Brownrigg and Hornig, 1974). The limit of detection was reported to be as low as 0.01 ppm. DATA REDUCTION Depending on the detection and output system, data may be presented to the analyst as strip chart recorder chromatograms, digitized chromatograras, numerical peak integrations, mass spectra, MS selected ion monitoring plots, MS total ion current plots, etc. Computers can easily reduce the analyst's work in data reduction and should be used for MS data acquisition and reduction. However, excessive reliance on data system output without interaction by a qualified analyst can yield spurious results. The first task in data reduction is to qualitatively identify the analyte. Quantitation can be attempted only after a positive qualitative identification. Qualitative The qualitative aspects of the analysis are all too often overlooked. Especially with PCBs, differences in the qualitative assessment of a sample can dramatically affect the quantitative results. In standard methods or other work where two or more analysts are expected to produce comparable results, the qualitative assessment of the data must be carefully specified. As an example of how qualitative interpretation of results can affect quantitation, a round robin study was recently conducted to assess the interlaboratory variability of PCB analysis in commercial products (Pittaway and Homer, 1982). Eleven data sets, generated by PGC/ECD, PGC/ EIMS, PGC/EIMS SIM, CGC/EIMS, and PGC/FID, were acquired (see Tables 5 and 6). While most of the techniques were sufficiently specific to differentiate PCBs from interferences, the PGC/FID was not. Since no attempt was made by the analyst to differentiate PCBs from interferences in this case, the PGC/FID quantitation was 28 times higher than the mean of the other analyses. Qualitative assessment of results depends to a large extent on sample type and its pretreatment. In samples where the presence of PCBs has been well-established (e.g., adipose tissue) the qualitative burden is not nearly so great as for samples in which PCBs are not expected. In many PCB procedures, the cleanup involves a rather specific liquid chromatographic separation which separates PCBs from most organochlorine pesticides. In addition, the use of specific detectors (BCD, HECD) reduces the probability of interferences and increases the confidence in identification. Better still, MS provides spectra of the eluent which may be compared with those of authentic compounds to give high confidence identifications. Finally, the retention time of the eluent should match that of a standard. CGC, and better yet high precision CGC, gives much more precise retention times than PGC and increases confidence. In the case of Aroclor (or similar mixtures) derived PCBs, a pattern of isomers usually resembles the pattern of a standard. This has been a common qualitative technique in residue analyses, especially when PGC/ECD is the analytical procedure, 45 �TABLE 5. SUMMARY OF LABORATORY TECHNIQUES USED FOR THE CMA ROUND-ROBIN STUDY (Erickson, 1982) MS calibration method GC calibration method PGC/ECb PGC/EIMS Confirmation only ? B & J Dil/Inje PGC/EIMS SIMf Autotune C Sonication/ Inj (some diluted) PGC/MSJ PFTBAJ D Sonication/ Inj (some diluted) PGC/FID E DI and Dil/Inj PGC/MS-* SIM PFTBA F Heat /Inj ; Dil/Inj; DI PGC/EIMS SIM G DI H Work- up technique Lab A DIa Analysis technique Integration technique Calculation equations LOD presented PHC No Yes EG8 (3 pts) Areas Yes Yes1 ES Ion Intensities No Yes No Yes ? ES ES (3 pts) Areas No Yes ? ES, RFk Area No Yes PGC/EIMS SIM ? ES (1 pt) Area Yes Yes Dil/Inj PGC/EIMS SIM ? RF Area Yes Yes I Dil/Inj CGCn/EIMS SIM ? RF Area Yes Yes K Acid Digest/ Extract/Inj ; Some heated CGC/MSJ IS, RF° Summed Areap No No See footnotes for Table 6. DFTPP �TABLE 6. SUMMARY OF LABORATORY TECHNIQUES USED FOR THE CMA ROUND-ROBIN STUDY (Erickson, 1982) Lab No. ions/homolog Isotope ratio mentioned Reporting units QA discussed? No. standard isomers Comments A 7 7 ppm No 18 Too many significant figures. little discussion. B &J 1 No mg/kg Yes 24 Some full scan confirmation; good discussion, good work overall. C 1 No mg/£; ppm No 10 Sample preparation is good. D " " mg/*; ppm No 5 E 3 Yes HS/8 (?) Yes 25 F 21 No H8/8 Yes iom G 4-5 Yes ppm Yes 20 Good ion/ retention time table; % recovery calculated from standard addition (were results corrected?) H I 1 1 No No ppm ppm No No 10 10 H and I are same organzation; no discuscussion of differences observed in two methods. No ppm Yes 12 Limited recovery study (•*• 100% recovery); injection precision measured for one sample. K Very Major interferences suspected — no caveats or discussion of divergent data with "Lab C." No individual isomers reported. Standard addition attempted but failed; use of Aroclor mixtures as standards is of dubious value. �FOOTNOTES FOR TABLES 5 AND 6 a Direct injection. b Packed column GC/electron capture detector, c Peak height. d Packed column GC/electron impact mass spectrometry (full scan). e Dilute and inject, f Selected ion monitoring, ^g External standard. h Details presented—two integration methods used, one designated "B"; one designted "J.1 i Estimated, no details, -P- j Unspecified operating mode, 00 k Response factor. 1 One ion from parent cluster and one ion from fragment cluster, m Aroclor mixtures. n Capillary column GC. o Internal standard (details unclear). p Areas of three (two for Cjo^Cl) most intense ions in parent cluster summed, q Limited scan technique used; all ions in parent cluster were observed. �Review Articles— Only five reviews mentioned the qualitative aspects of PCS analysis (Reynolds, 1971; Sherma, 1975; Safe, 1976; Fuller et al., 1976; and Margeson, 1977). Generally, the qualitative discussion was cursory. Reynolds (1971) advised use of pattern recognition (against the Aroclor standards). Sherma (1975) recommended a slightly more formal approach—comparison of retention times in samples and standards. Standard Methods— As noted in Table 1, less than half of the standard methods discuss qualitative analysis. In the PGC/ECD methods pattern recognition is the qualitative procedure. Often chromatography on two GC colums of different polarity is used to enhance the confidence of the verification. An example of good qualitative guidance for the analyst is found in the EPA protocol for analysis of PCBs in transformer fluids and waste oils (EPA, 1981). Locate each PCB in the sample chromatogram by comparing the retention time of the suspect peak to the retention data gathered from analyzing standards and interference free Quality Control Samples. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for each PCB can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms. In methods where GC/EIMS is specified, both mass and retention time may be used for identification. None of the standard methods adequately address the selection of ions and the permissible abundance ratios. Primary Literature— Less than half of the 38 articles abstracted contained mention of the qualitative criteria used in identification of PCBs. A representative qualitative criterion was that the chromatogram exhibits a "typical Aroclor pattern" (Gordon et al., 1982; Giam et al., 1972; Ofstad et al., 1978; Kirshen, 1981). Several publications dating back to the landmark work of Sissons and Welti (1971) concentrated on the identification of PCB isomers in commercial (Aroclor, Chlophen, etc.) mixtures (Tas and deVos, 1971; Tas and Kleipool, 1972; Armour, 1972; Willis and Addison, 1972; Paasivirta and Pitkanen, 1975; Jensen and Sundstrom, 1974; Stalling et al., 1978; Neu et al., 1978; Zell et al., 1978; Ballschmiter and Zell, 1980; Pellizzari et al., 1981; Tuinstra et al., 1981). The objective of most of these papers was to characterize the commercial mixture as an aid to quantitation in environmental samples or for toxicological information. Several researchers mentioned the comparison of retention times or relative retention time in the sample and an Aroclor standard for PCB identification (Webb and McCall, 1972; Onsuka and Comba, 1978; Pellizzari, 1982; 49 �Tuinstra et al,, 1980). A much more specific identification scheme involves use of one of the retention index (RI) (e.g., Kovats) schemes. Several publications contain tabulations of RIs (Sissons and Welti, 1971; Zell et al., 1978; Neu et al., 1978; Ballschmiter and Zell, 1980; Albro et al., 1981; Albro and Fishbein, 1972a, 1972b). Since all 209 PCB congeners are not available, a scheme of predicting RIs has been developed based on the half-RI values for the various chlorination positons on one of the benzene rings. Sissons and Welti (1971) first proposed this system, which was expanded upon and further validated by Albro and Fishbein (1972) and Albro et al. (1977), The use of half RIs permits the analyst to qualitatively identify all 209 PCBs on the basis of their retention time, although the level of confidence in this identification is low. Using state-of-the-art chromatography, RI measurement precision of ± 0.05% has been reported for PCBs (Neu et al., 1978), and with full optimization, precision of ± 0.01% has been predicted (Neu and Zinburg, 1979). Recently Dunn et al. (1982) used a computerized pattern recognition technique to evaluate CGC/ECD data on PCBs in sediments, water, benthos, and fish. The computer program can detect incorrect assignments (i.e., Aroclor 1242 instead of 1260) and abnormal samples. This appears to be a most promising technique for interpretation of large numbers of PCB determinations. When a mass spectrometer is used as the GC detector, an additional qualitative dimension is available. The mass spectra of a PCB are distinctive due to the cluster of masses generated by the presence of two chlorine isotopes in nature. If sufficient material is present to obtain full mass spectra, the unknown can be reliably identified by comparison with spectra of standards or spectral compilations (Stenhagen et al., 1974; Mass Spectrometry Data Centre, 1970; Heller and Milne, 1978). The quality of the spectrum required for identification needs to be defined (Christman, 1982). As mentioned above, the natural isotopic abundance ratios yield a characteristic pattern. The use of these ratios in selected ion monitoring can provide qualitative information when full mass spectra are not obtained. The actual ratios have been tabulated for PCBs (Rote and Morris, 1973) or may be readily calculated. This approach has been utilized (Canada and Regnier, 1976) with complex samples (Erickson and Pellizzari, 1977, 1979). Even though the natural isotopic abundance ratios are constant, instrumental variances and interferences can affect the observed ratio. Thus, tolerance criteria need to be utilized by the analyst. Tindall and Wininger (1980), in a method designed to determine PCBs even if they are not "Aroclor-derived," established qualitative criteria: Each peak in the chromatogram is evaluated to determine if it is a PCB peak. Peaks must meet these criteria to be labeled PCB peaks for quantitation: (1) the peaks of the characteristic ions must maximize at the same retention time; (2) the peak must be in the proper retention time window; and (3) the relative peak intensities of the molecular ions must be within ± 15% of the theoretical ratio. This tolerance is arbitrary and can be made larger for very low concentrations of PCBs where statistical variations in peak intensity become large. 50 �Work by Collard and Irwin (1982) and Dow (1981) established similar qualitative criteria: Identify the chlorinated biphenyl homologs by their mass ion response, relative retention time, and ion intensity ratio (± 20% relative). Secondary confirmation of trichloro-through decachlorobiphenyl may rely upon the M-70+ ion response. These two works suggest a new awareness that qualitative criteria must be stipulated in any method if the results are to have any significance. In addition to the various gas chromatographic identification methods, thin-layer chromatography and high performance liquid chromatography yield qualitative information, as discussed above. More exotic techniques such as other mass spectrometric techniques, Fourier transform infrared spectrometry, and nuclear magnetic resonance spectroscopy are not used routinely in most laboratories, so have been included as confirmatory techniques which will be discussed below. Quantitative With most organic compounds, the quantitation is relatively straightforward. The instrumental response is calibrated using standards. The amount of unknown is measured by comparison of the signal it generates with the calibration factor or curve. Quantitation of PCBs is not nearly so simple because the analyte is not a single compound but rather a complex mixture of 209 possible congeners and standards of all 209 congeners are not available for calibra^ tion. Given these problems, analysts have devised alternate quantitation methods generally based on the similarity of the sample PCB mixture to a commercial product (e.g., Aroclor). Review Articles— Most review articles mention quantitation of PCBs briefly. Safe (1976) discussed the problems of BCD response variability discussed in detail above and suggested that perchlorination would be more consistently accurate. Hutzinger et al. (1974) reviewed the quantitation methods to that date, most of which involved relating the unknown to Aroclor standards. Sherma (1975) provided a similar, but more detailed, review which included a positive assessment of the Webb and McCall (1973) procedure. The other reviews (Riseborough, 1971; Fuller et al., 1976; Reynolds, 1971; Margeson, 1977) discussed quantitation in similar but less detailed fashion. Standard Methods— As shown in Table 1, all standard methods give at least cursory instructions on quantitation. At one extreme, the general purpose protocols (EPA, 1979a, 1979b; Ballinger, 1978; EPA, 1978) contain vague direction to "integrate the area under the peak." Much more complete quantitation guidelines are given in EPA's (Bellar and Lichtenberg, 1981; EPA, 1981) protocol for analysis of PCBs in transformer fluids and waste oils. Primary Literature-It is obvious from the data presented that PCBs were quantitated in most of the references abstracted. However, many articles neglect to mention how 51 �the PGC/ECD signal was converted into a concentration value. Some 80 articles abstracted mentioned the quantitation technique, although many only made a brief mention of "integration" or "comparison with Aroclor 1260 standard." Packed column gas liquid chromatography/electron capture detector--As noted in Table 3, the response factors for the individual PCB congeners vary widely, even within a homolog. This fact has typically been overlooked in quantitation procedures based on the use of Aroclor (or other commercial mixtures) standards. The most prominent GC/ECD quantitation method was originated by Webb and McCall (1973). The weight percent and homolog identification (relative proportions where more than one homolog was present) were determined for several Aroclors, and retention times relative to £,pJ-DDE were specified. The general procedure is as follows: Chromatograph known amounts of the standards and measure the area for each peak. Using the tables of data determine the response factor (ng PCB/cm2) for each peak. Chromatograph the sample and measure the area of each peak. Multiply the area of each peak by the response factor for that peak. Add the nanograms of PCB found in each peak to obtain the total nanograms of PCB present. Samples containing one Aroclor or more than one Aroclor can be quantitated by comparison with appropriate standards. Following an interlaboratory survey, Chau and Sampson (1975) recommended that the Webb and McCall method be adopted as the uniform quantitation method. They cited the general applicability, elimination of mixed standards, the more realistic results, and simplicity of the method as reasons for their recommendations. Exact replication of the method requires reproducing the chromatography and using the same lot of Aroclor standards as Webb and McCall used. These stringent requirements have led most researchers to characterize their quantitation practice as a modified Webb and McCall (Erickson et al., 1981; Kreiss et al., 1981; Harris and Mitchell, 1981; Steichen et al., 1980; Sawyer, 1978a). The calculations required can be easily automated using common GC integrators or data systems (Erickson et al., 1981; Kirshen, 1981). Ugawa et al. (1973) devised a quantitation method similar to a Webb-McCall except it was based on the Japanese commercial PCB, Kanechlor. Unfortunately, most samples are exposed to weathering, metabolism, differential adsorption, etc., and the PCB pattern, though originally one or more Aroclors, does not closely resemble that of the standard. This has been noted repeatedly and certain correction procedures have been proposed (Beizhold and Strout, 1973; Webb-McCall, 1973). Several researchers (Collins et al., 1972; Rote and Murphy, 1971; Bellar and Lichtenberg, 1975) and standard methods (AOAC, 1980; ASTM, 1980a, 1980b) advocate comparison of the total areas under the "Aroclor region" in the sample and standard chromatograms. This is a simple approach and has been recommended 52 �by Sawyer (1973) as the most reliable method for obtaining interlaboratory precision. In a later collaborative study (Sawyer, 1978b), the individual peak height (Webb and McCall, 1973; Sawyer, 1978a), total peak height and total peak area methods were all compared and gave similar results, although the individual peak method was judged slightly better. On this basis, AOAC (1980) permits either individual peak (Webb-McCall) or total area quantitation of PCBs. Bellar and Lichtenberg (1975) used either the total peak height for samples closely resembling Aroclors or Webb-McCall for patterns "not representing a single Aroclor." Wolff et al. (1982) used 2,4,4'-trichlorobiphenyl, 2,4,5,2',5'-pentachlorobiphenyl; and 2,4,5,2',4',5'-hexachlorobiphenyl as standards for CGC/ BCD quantitation of PCBs in plasma and adipose samples of occupationally exposed people. Quantitation by this sum of individual peaks method gave comparable results to the Webb-McCall method using P6C/ECD. Both methods gave lower values than the sum of peak areas method using PGC/ECD data. Zobel (1974) devised a computer fit routine which matched the sample chrpmatogram with various "co-added" Aroclor chromatograms to obtain a best fit. "Spuriously large or small peak heights, caused by interfering compounds or metabolism, are automatically sorted and rejected." The method reports results in terms of the different Aroclors and can be modified to generate an estimate of "premetabolism" PCB content. While providing no details on how the PCBs were quantitated, Giam et al. (1973) required at least 50% of the peaks in the sample chromatogram to match those in an Aroclor standard when analyzing marine biota for PCBs. Capillary column gas liquid chromatography/electron capture detection— The application of CGC to PCB determination complicates the already difficult quantitation problems: more peaks are present. Since the peaks are ostensibly single congeners instead of the mixture obtained by PGC, much emphasis has been placed on quantitation of single congeners. Boe and Egaas (1979) devised a calibration factor system that permits the analyst to calculate the ECD response factor for a given congener, once its structure is known. More recently, the response factors for 159 congeners were measured (Table 4). As discussed above, the ranges over homologs and within a homolog indicate that calibration with each congener would be necessary for accurate results. Despite the higher resolution with CGC and therefore more available information, simplistic quantitation routines are still used, Gordon et al. (1982) used three peaks from each Aroclor standard as their method for quantitating PCBs in transformer oil by CGC/ECD. While PCBs do not weather extensively in transformer oil and are thus more likely to resemble the parent Aroclor, this method utilizes only a small portion of the available information. Schulte et al. (1976) recommend quantitation of CGC/ECD chromatograms based on two selected charactistic peaks in food extracts. Albro et al. (1981) determined the relative molar percentages of the individual components of about 100 different PCB congeners in Aroclors 1248, 1254, and 1260. They recommend using the Aroclor mixtures as secondary standards to calibrate CGC/ECD responses. 53 �Gas liquid chromatography/electron impact ionization mass spectrom.etry"The ability of EIMS to easily sort PCBs by homolog has led to a tendency among GC/EIMS users to quantitate by homolog (e.g., summing all homolog peaks). Another major difference from analog (BCD) detector quantitation is the ability to quantitate using either a single PCB-specific m/z peak or the total ion current which corresponds to the analog detector output. The first reported GC/EIMS quantitation was a simple translation of classical PCB GC/ECD quantitation: comparison of "the area under one or more of the eight peaks to the area of a known amount of a standard" (Bonelli, 1972a,b). Eichelberger et al. (1974) chose what they termed the conventional approach and assumed that the PCB mixture was identified as one of the commercial mixtures. The total peak area for each SIM mass in the sample and standard were compared using an internal standard to normalize the peak areas. Erickson and Pellizzari (1977, 1979) quantitated PCBs in sludge based on a relative molar response (RMR) of each homolog. Using SIM techniques, the RMR for one isomer of each homolog was determined. Standards of hepta- through monochlorobiphenyl were too impure to use and RMRs for these homologs were interpolated. The RMR decreased dramatically (logarithmically) with increasing degree of chlorination, presumably due to the decreasing ionization crosssection. Williams and Benoit (1979) compared the summed total integrated area for six to eight selected peaks in samples and standard for quantitation of PCBs in several household products. Tindall and Wininger (1980), in one of the few papers addressing analysis of non-Aroclor PCBs, established homolog response ratios using an unspecified number of isomers per homolog. The highest and lowest response factors for a homolog were averaged to give the average response factor used in the calculation of PCB concentration in the unknown. An internal standard (tribromobiphenyl) was used to get relative responses. Martelli et al (1981) reported the EIMS relative response factors for 45 PCB congeners (Table 4). The relative standard deviation per homolog ranged from 0.7% (3 of 46 isomers) to 21% (11 of 42 isomers). They propose using these average response factors on GC/EIMS quantitation of PCBs by homolog. Collard and Irwin (1982) used an unspecified number of isomers per homolog to establish response factors for each homolog. A daily calibration plot at three concentrations was used for comparison of the summed peak heights for one homolog. Dow (1981), in a related protocol, specified 22 congeners to be used in a similar calculation. For homologs with more than one isomer in the standard a summed intensity was used. Miscellaneous--Cairns and Jacobsen (1977) advocated the quantitation of PGC/EIMS because of the reduction in interferences by other halogenated compounds such as DDE. Eichelberger et al. (1974) also mentioned PGC/EIMS as an alternate technique for dirty samples but did not discuss quantitation. 54 �As discussed in a separate section, perchlorination and dehydrochlorination, followed by PGC/ECD and PGC/FID determinations, respectively, have been proposed as PCB quantitation methods which eliminate the congener variability problems. TLC and HPLC have also been employed as quantitative techniques and are discussed in separate sections above. CONFIRMATION Confirmatory techniques have been frequently used in PCB analysis. The term confirmation may be loosely defined as any operation performed to increase the confidence of the results beyond the primary analysis. Qualitative confirmation is much more often reported than quantitative confirmation. Confirmatory techniques involve variation of the same technique (PGC/ECD on two dissimilar columns), confirmation by a lesser technique (PGC/ECD with TLC confirmation), or confirmation by a more advanced technique (PGC/ECD with PCG/ EIMS confirmation). Review Articles Hutzinger et al. (1974) devoted about two pages to the subject of confirmation. While mass spectrometry was briefly mentioned, most of the discussion centered on perchlorination. Standard Methods Table 1 listed all of the standard methods and notes the type of confirmation suggested. All of these confirmations are optional and qualitative. Primary Literature As early as 1969, the need for confirmation of findings was discussed (Reynolds, 1969). An exchange of comments following a presentation by Riseborough (1971) led to a proposal for confirmation by P. L. Diosady, covering, mass spectrometry, dechlorination, and perchlorination. Price and Welch (1972) are typical of many early investigators who backed up their PGC/ BCD analysis with a TLC confirmation (see also the standard methods: AOAC, 1980; FDA, 1977). Hannan et al. (1973) utilized a cumbersome ultraviolet irradiation method to confirm PGC/ECD results. Mes and coworkers have utilized a variety of confirmatory techniques, generally in concentration, in the analysis of adipose and milk samples (Mes et al., 1977; Mes and Davies, 1979; Mes et al., 1980). The methods include two dissimilar GC columns, perchlorination, and GC/EIMS. GC/EIMS was used by Biros et al. (1972) to confirm TLC results. GC/EIMS confirmation has also been reported (Musial et al., 1979; Teichman et al., 1978; Lucas et al., 1979; Rodriguez et al., 1980; Haile and Baladi, 1977; Erickson et al., 1981). HREIMS has been reported as a confirmatory technique (Safe et al., 1975; Safe, 1976; Musial et al., 1974). Kuehl et al. (1980) used CGC/NCIMS to qualitatively confirm their CGC/EIMS PCB identifications in 55 �fish. Mass and Friesen (1979), placing particular emphasis on polychlorinated dibenzodioxins, reviewed the advanced mass spectrometric techniques for both high sensitivity and high reliability analysis: HREIMS and NCIMS. SCREENING TECHNIQUES Screening techniques in this text are defined as methods used to identify the presence of PCBs qualitatively, semiquantitatively, or quantitatively without specification of the homologs in a sample extract. Screening techniques under this definition could include thin-layer chromatography, high performance liquid chromatography, and gas-liquid chromatography. These methods have been discussed in detail earlier in this review. Perchlorination and carbon-skeleton chromatography, however, are screening methods that have not been mentioned, although Table 1 indicates that perchlorination has been used as a quantitative method or PCB confirmation technique in several of the standard procedures. Perchlorination Perchlorination methods are based on the exhaustive chlorination of the biphenyl ring of the PCB congeners. The major disadvantage of the perchlorin1ation reactions is that biphenyl can also be perchlorinated. Thus, the presence of biphenyl can lead to erroneously high levels of quantitation. Quantitative analysis is typically accomplished by GC/ECD systems although GC/MS identification has been used in some instances. Perchlorination reactions are reportedly troublesome because of contamination of reagents with decachlorobiphenyl or brominated compounds (Trotter and Young, 1975). Perchlorination reaction methods were first studied using antimony pentachloride (Berg et al., 1972; Matsumoto, 1972; Armour, 1973) and thionyl chloride in the presence of aluminum chloride (Nose, 1972). Armour (1973) reported greater than 90% recovery of PCBs by perchlorination and found the technique comparable to PGC/ECD comparison with Aroclor standards. Nose (1972) reported approximately 100% conversion of tri-, tetra-, and hexachlorobiphenyls to decachlorobiphenyl with the thionyl chloride system. Antimony perchloride is apparently the most frequently used reagent as indicated by a review of the literature. Hutzinger et al. (1973) studied trichlorosulfur-tetrachloroaluminate to quantitatively convert Aroclor 1254 to decachlorobiphenyl. One of the major disadvantages of perchlorination arises from blank problems (Trotter and Young, 1975). This has resulted in the need to carefully characterize perchlorination reagents prior to reaction (Huckins et al., 1974). The other major disadvantage of perchlorination is the conversion of biphenyl to decachlorobiphenyl. Chlorine-37 labeled perchlorination reagents have been studied as a means to clarify this problem and at the same time distinguish the contribution of various PCB homologs to the final decachlorobiphenyl by computer assisted isotope dilution interpretation (Burkhard and Armstrong, 1982). This technique, although unique in approach, requires optimum reaction and MS conditions for successful analysis. Perchlorination has been used successfully for numerous studies in recent years (Kohli et al., 1979; Sherma, 1981; Stratton et al., 1978; Fulton et al., 1979; Crist and Moseman, 1977; Robbins and Willhite, 1979; Mes et al., 1977; Mes and Davies, 1979; Haile and Baladi, 1977; Vannuchi et al., 1976; Margeson, 1977; Brinkman et al., 1978; Kohli et al., 1979; Albro et al., 1980; Leoni et al., 1976; Trevisani, 1980), 56 �Carbon Skeleton Chromatography Carbon skeleton chromatography is based on the dechlorination of PCBs to biphenyl. Catalysts for the dechlorination are typically platinum or palladium. The disadvantage of carbon skeleton chromatography is that background levels of biphenyl in the sample extract will yield erroneously high concentrations of total PCBs as noted for perchlorination. Also, since the product of dechlorination is biphenyl, mass spectrometry must be used to reliably identify the compound, especially in extracts from complex matrices. Quantitative carbon skeleton chromatography by catalytic decomposition of the PCBs over platinum or palladium to biphenyl has been discussed in three articles (Berg et al., 1972; Zimmerli, 1974; Cooke et al., 1978). Zimmerli (1974) and Cooke et al. (1978) studied conversion of PCBs as well as halogenated terphenyls, napthalenes, dioxins, furans, and DDT. Effective catalysts were found to be effective as 3% palladium at 305°C and 5% platinum at 180°C. Reaction products for the various compounds were identified by GC/MS. On the other hand, false negative results have been observed using this technique for analysis of chlorinated bottoms (personal communication, M. D. Crouch, Toxicon Laboratories, Baton Rouge, Louisiana, 1982). QUALITY ASSURANCE A strong quality assurance (QA) program for PCB analysis should include use of pure standards, solvents, and glassware; an evaluation of method blanks for background PCB and interference levels; calibration of instrumental equipment; validation of the individual method steps as well as the overall method; and an evaluation of the overall performance of a method through replicates, interlaboratory comparisons, and/or standard reference materials. The data that should be provided by a strong QA program should include at a minimum, precision and accuracy measurements for each sample matrix. These parameters have been previously outlined by MacDougall et al. (1980) in an attempt to clarify needs for general data quality evaluation for comparison of trace organic results among numerous laboratories. The guidelines for data acquisition and data quality evaluation presented by MacDougall et al. (1980) were provided under the direction of the Americal Chemical Society Committee on Environmental Improvement and the Subcommittee on Environmental Analytical Chemistry. The guidelines were based on good analytical practices to assist analysts in obtaining data of requisite quality and to aid in the evaluation of the quality of the reported data. In addition to the QA parameters previously listed, MacDougall et al. (1980) have presented requirements for sampling to adequately characterize a sample and enhance reliability in the final result. These guidelines also discuss the necessity of detailed documentation of sample preparation and actual analysis such that other qualified analysts may duplicate the work. The demonstration of precision and accuracy of measurements through good laboratory practices, proven methodologies, low noise instrumentation, the use of standard reference materials, and participation in collaborative studies were also discussed as essential to strong QA programs. The guidelines also presented definitions of and criteria to establish limits of detection (LOD) and limits of quantitation (LOQ). Method validation, qualitative confirmation of validated measurements, risks in data interpretation from low recovery methods, reporting of interferences, and the 57 �appropriate presentation of the analytical results were discussed with respect to evaluation of data quality. Quality assurance in some form has been practiced in many of the studies abstracted for the PCB analysis literature review. However, few of the studies have implemented enough QA to allow comparison of the data from one matrix to the next. The EPA has taken steps to implement strong QA programs in various standard methods of analysis and as part of long-term project goals (EPA, 1979a, 1980a, 1980b, 1981; Bellar and Lichtenberg, 1981). Table 1 lists the standard methods that acknowledge the need to follow some type of QA program. Other than the standard methods and EPA guidelines, QA programs have been practiced for collaborative method studies for PCBs in different matrices (DCMA, 1981; Sawyer, 1973, 1978; Delfino and Easty, 1979; Devenish and Harling-Bowen, 1980). The QA program for the Dry Color Manufacturers Association (DCMA, 1981) round robin study included instrument calibration specifications, performance evaluation of the gas chromatography column with a standard mixture of PCBs, and measurement of sensitivity for PCBs by serial dilution of the standard, methods blanks, specification of quantitation procedures and validation of sample preparation procedure. The validation of sample extraction, cleanup and analysis included workup of blind and known spike samples. The results of the DCMA study indicate that variance in reported PCB levels between laboratories was signficantly reduced when a commercially prepared quantitation standard was used by all participating laboratories. Data from the DCMA report indicated relative standard deviations of 3.1 to 9.1% within a laboratory, 2.4 to 40% between laboratories, and values ranging from 7.3 to 41% representing the total reproducibility for analysis of three different pigments. The Chemical Manufacturers Association sponsored a round-robin study of PCB concentrations in five different samples that are indicative of matrices that will be regulated by the PCB Remand Rule (Pittaway and Horner, 1982). Eight different laboratories participated in the study. In contrast to the DCMA study, no defined protocol or QA programs were specified for analysis of the matrices. Each laboratory was allowed to choose the method of extraction, cleanup, instrumental determination and quantitation, and QA program if desired. This study indicated that there are many sources of potential error in the quantitative analysis of PCBs. A comparison of the reported levels of PCBs and precision of measurements between laboratories indicated a true need for a strong QA program that might allow some normalization of the data, The collaborative study reported by Delfino and Easty (1979) focused on the analysis of PCBs in paper mill effluents. The study consisted of two phases. The first phase was used to determine the comparability of PCB methodologies between six different laboratories and the abilities of the participating analysts to perform the basic operations required for PCB analysis. These factors were determined by direct injection and quantitation of a performance standard and the simple extraction and analysis of a spiked aqueous solution. The second phase required an actual validation of a sample method using known and blind samples. A modified EPA wastewater analysis protocol 58 �was followed by all participating laboratories. Some flexibility to the method protocol was allowed for column materials and exact quantitation procedures. The results of the first phase extraction from distilled water yielded an average recovery of 95.6% with a relative standard deviation of 14,7%. The relative standard deviation for direct injection of a standard solution was 15.6%, thus indicating that gas chromatographic analysis was the principle source of variance. The results for paper mill effluent yielded similar results with 93.6% average recovery with a 16.0% relative standard deviation, and indicated that the method was satisfactory for paper mill effluents . Sawyer (1978) conducted a collaborative study of PCB quantitation with BCD as the detector. Ten independent laboratories took part in the study and used existing AOAC methodology to study three ECD quantitation procedures. The average combined recovery in this study was approximatley 85% with a coefficient of variation of 15%. No significant difference was noted for the three different quantitation operations. A large void in most QA programs has been filled by the provision of standard reference materials of known PCB concentration (Chesler et al., 1982). Although the standard reference material will only be available as an oil, it leads the way in establishing further QA criteria for the analysis of PCBs in other media. The preparation of additional PCB standard reference materials as wet and dry reference materials has been discussed by Chau and Lee (1980), Chau et al. (1979), and Addison and Nearing (1982), although these materials are not currently available. Other policies that are of considerable concern and reflect the current attitudes toward QA have been presented by Glaser et al. (1981) concerning method detection limits based on confidence levels and the guidelines presented by Environmental Science and Technology (Christman, 1982) outlining information required to label compounds identified by mass spectrometry as "tentative" or "confirmed." BY-PRODUCT PCB ANALYSES Historically, analysis of PCBs has been concerned with commercial mixtures , such as Aroclors, and their dispersal in the environment and certain commercial products (packaging materials, paper products, transformer oils, etc.). The analytical approaches to identification and quantitation of these commercial PCB mixtures has already been discussed in this literature review. Health and environmental concerns have resulted in an increasing number of federal regulations (EPA, 1979d) controlling the manufacture, use, and disposal of PCBs. A recent report prepared by the Chemical Manufacturers Association for EPA (Pittaway et al., 1981) documents numerous commercial processes that will be affected by proposed federal regulation of by-product PCBs, These by-product PCBs are produced by diverse processes, few of which resemble the commercial PCB synthesis routes. Thus, the resultant PCB mixtures do not resemble the familiar Aroclors. The analysis of by-product PCBs was reviewed by Hodges et al. (1982). 59 �An extremely limited number of articles are available for review of byproduct analysis (Tindall and Wininger, 1980; Collard and Irwin, 1982; Pittaway and Horner, 1982; DCMA, 1981; Dow, 1981). These few references, however, describe some of the problems encountered in by-product analysis of commercial products as discussed below. Dry Color Manufacturers Association Pigment Analysis A major study was conducted by the Dry Color Manufacturers Association (1981) for the analysis of by-product PCBs in three different pigments. This study concluded that a universal cleanup procedure was not possible for accurate PCB analysis from all of the pigments. The use of GC/MS was recommended for establishing positive identification of the PCBs. Two of the pigments studied contained only one PCB isomer, while the third pigment was contaminated with several different isomers of the penta- and hexachlorobiphenyl homologs. A thorough quality assurance program was developed for the purpose of reducing interlaboratory variability. The quality assurance program included validation of each step of sample preparation, gas chromatographic performance standards, and mass spectrometer calibration and performance appraisal, as well as requirements for analysis of spiked blanks, replicates, and standard additions. Round-robin experiments were conducted under this study. The DCMA found that a large portion of the interlaboratory variance was due to the differences in preparation of the standard mixtures of PCB isomers used for establishing response factors. A calibration mixture obtained from a single source was found to greatly reduce interlaboratory variance. In addition, specification of PGC criteria with respect to retention times and resolution of specific isomers was required to promote comparability of results between laboratories. Chemical Manufacturers Association Round-Robin The Chemical Manufacturers Association has conducted a round-robin experiment for analysis of by-product PCBs (Pittaway and Horner, 1982) in chlorinated benzene waste streams, mixtures of chlorinated benzenes, blind spikes in the chlorinated benzenes, composite waste streams from a chlorinated aliphatic process, and a benzene column bottom sample. The round-robin studies defined some of the problems of by-product PCB analysis in commercial products and process waste streams. Many sources of potential error in the quantitative analysis of these samples were identified and include unknown interferences, inappropriate use of reference standards, inappropriate protocols, day-to-day variations in instrumental responses, calibration, and execution of analytical procedures, inappropriate collection of samples, contamination of samples, and limitations in instrumental methods. The round-robin study measured differences in analytical results between laboratories, differences due to variation in analytical methods, limitations of instrumental methods, and impact of analysis by random laboratories 60 �(Pittaway and Homer, 1982; Hodges et al., 1982). A total of eight laboratories (six industrial and two EPA) participated in the study, using a variety of techniques as shown in Tables 5 and 6. Guidelines were not given for methods of sample preparation, instrumental analysis, quantitation measurements or quality assurance practices. The results from the round-robin study showed a significant variance in data among laboratories, which one might expect from the lack of written protocol and quality assurance. This study demonstrated that there is a need for a common denominator in analytical protocol for analysis of by-product PCBs from a wide variety of simple to complex matrices. Other Studies Tindall and Wininger (1980), Collard and Irwin (1982), and Dow (1981) studied PGC/MS methods for analysis of by-product PCBs in commercial and environmental samples. The MS analysis method was based on limited mass scan ranges to qualitatively identify and quantitate any of the possible 209 PCB congeners by homologs. Tindall and Wininger (1980) reported that the criteria for PCB quantitation must include matching of characteristic ions at proper retention time windows. In addition, characteristic ions must maximize at the same retention time and the relative peak intensities must be within ± 15% of the theoretical ratio. The accuracy limiting step of the PGC/MS (limited mass scan range) methods (Tindall and Wininger, 1980; Dow, 1981; Collard and Irwin, 1982) is the selection of standards. In each case response factors were determined for a limited number of isomers for each PCB homolog with the underlying assumption that all PCBs of the same homolog have nearly the same response factor, Quantitation procedures varied between the studies. Tindall and Wininger (1980) used an internal standard, tribromobiphenyl, which responded to MS source changes much like a PCB. In addition, its molecular weight was great enough that interferences were rarely encountered. Collard and Irwin (1982) and the Dow method (1981) quantitated versus a calibration curve established at various concentrations using 10 congeners to represent each PCB homolog. No internal standards were used. The accuracy and precision of these PGC/MS methods are dependent on frequency of instrumental calibration and the extent that other compounds in the ion source of the MS affect the sensitivity during the course of an analysis. 61 �SECTION A APPLICABLE TECHNIQUES The objective of this section is to outline the best possible approaches for by-product PCB analysis in commercial products that will be regulated under the PCB Remand Rule. The proposed procedures are a result of the review of the available literature presented in the previous section. The analytical approaches provide versatility in terms of the wide spectrum of matrices represented by the proposed regulated products. The success of the proposed rule will rely heavily on a strong quality assurance (QA) program to monitor sample preparations and instrumental analysis. The proposed QA program will provide sufficient data to determine the quality of the quantitation data for each specific sample matrix encountered. Sample extraction, cleanup, instrumental determination, quantitation and data reduction, confirmation, screening, and the overall quality assurance program are discussed. EXTRACTION The literature review of extraction techniques describes several approaches to isolation of PCBs from various matrices. The extraction may be as simple as dilution of an organic liquid, batch extraction of aqueous solutions , or Soxhlet extraction of solids; or as complex as matrix destruction via saponification or with concentrated acid before extraction of the PCBs with an appropriate organic solvent. However, the analyst must keep in mind that totally unexpected reactions produced the trace levels of the by-product PCBs being determined. Hence, the use of vigorous or harsh chemical reactions may generate or destroy PCBs (L. F. Hanneman, Dow Corning Corporation, personal communication, 1982). Suitable organic solvents will include petroleum ether, hexane, and methylene chloride. The exact extraction procedure, however, is dependent on the specific matrix. The alternative to designating a specific extraction procedure for all solid and liquid samples that are of highly dissimilar matrices both chemically and physically is to formulate a rigid QA protocol before the extraction step and to continue it through all aspects of analysis. The QA protocol will require extensive homogeniaation of samples (solids, suspensions, liquids) by grinding and mixing. An aliquot of each homogenized sample will be spiked with a series of surrogate compounds. Final analysis of the sample extract for the surrogate compound recoveries will provide sufficient quantitative information to evaluate the effectiveness of the extraction procedure and or cleanup technique. The choice of surrogate compounds is critical for exact performance measures of any method. The surrogate compounds must maintain the exact chemical characteristics of the PCBs for extraction, cleanup, and quantitation purposes. The surrogates may be either a series of PCB congeners representing 62 �each of the chlorinated homologs or a selected number of stable massrlabeled (carbon-13 or chlorine-37) PCB isomers. The series of unlabeled PCB congeners surrogates would necessitate independent measures of spike recovery and analyte concentration, whereas the mass-labeled PCB surrogates would allow simultaneous determination and quantitation of the analyte PCBs and the surrogate compounds if EIMS is used as the GC detection. The implementation of the use of the mass-labeled surrogates would provide a strong QA program since recovery could be monitored for each sample analyzed and consistency between analytical laboratories and different sample matrices could be compared more readily by a regulatory agency. Mass-labeled PCB isomers as surrogates could be provided at a reasonable cost per sample analyzed (W. Duncan, Midwest Research Institute, personal communication, 1982). A series consisting of mono-, tetra-, octa-, and decachlorobiphenyl mass-labeled isomers would provide a sufficient set of surrogates. Carbon-13 labeled isomers of 99% purity for these homologs would provide sufficient differences in mass spectra patterns for differentiation from isomers of natural abundance. The major problem to consider in adding surrogate compounds is whether the incorporation of these compounds in a matrix will mimic the true analytes. Incorporation cannot always be achieved, especially with matrices that require exhaustive extraction methods. However, the measured recovery of surrogates from an extraction and cleanup procedure will provide information on degradation of PCBs by the analytical procedure. It may be desirable to design small scale experiments to incorporate the surrogate PCBs during a product process (L. F. Hanneman, Dow Corning, personal communication, 1982). Solid matrices, expecially those that may be intractable, should be of prime interest for this approach. The surrogate compounds could be incorporated before polymerization, vulcanization, curing, precipitation, or other processes. The recoveries of the surrogates could be used to determine if the proposed extraction technique is applicable for routine analysis of particular solid matrices. Exact extraction protocols could be designated for air and simple aqueous samples as shown in Table 1. Exact extraction protocols for commercial products could also be designated, but optimum performance for all matrices is highly unlikely. A specified extraction protocol would require rigorous methods for all samples and must consider possible adverse reactions of certain products to sulfuric acid digestions and alkaline saponification. Independent extraction procedures for different matrices combined with the use of surrogate compounds and thus validation of the method would be an effective alternative. Each independent laboratory, however^, must certify that an effective extraction procedure is practiced. The level of recovery considered sufficient and method of addition of internal standards for final quantitation are yet to be determined. 63 �CLEANUP Many cleanup techniques are applicable to commercial products. The nature of the sample, complexity of the matrix, and the chemical characteristics of other components dictate the requirements for any sample preparation. Cleanup for air and aqueous samples in effluents from commercial production facilities is achievable by applying standard methods (Table 1). However, cleanup of a wide range of product matrices will require application of many different techniques. A generic cleanup procedure may not suffice or be necessary in the majority of analyses because of the different chemical characteristics in the sample matrix. For example, sulfuric acid may provide sufficient cleanup and quantitative recovery of one product that contains only decachlorobiphenyl. However, this procedure will not be sufficient for a matrix that contains mono- through trichlorobiphenyl isomers, which may not be recovered quantitatively, likewise, designated adsorbent columns may not provide the separation of interferences necessary for good quantitative analysis for a large majority of matrices. As with the extraction step, one alternative is to allow the individual laboratory to develop the necessary cleanup procedure. Each laboratory, however, must follow the stringent QA program using spiked samples or surrogate compounds to validate the method at a determined level of proficiency. This will meet the special analytical needs of the individual analyst and at the same time provide the data necessary to determine analytical proficiency of the method and consistency between laboratories and matrices. DETERMINATION Gas-liquid chromatography is judged to be the only acceptable primary separation method. Capillary GC is preferred over packed GC. The injection system, type of liquid phase, column dimensions and operating conditions should not be specified, but performance should be maintained within established criteria. Electron impact mass spectrometry is the primary Operating conditions (SIM, full-scan, or limited mass teria, and other variables are still to be specified. BCD and HECD are considered too nonspecific for these for general application (NCIMS, MS/MS, FTIR). detection candidate. scan), performance criOther detection options, matrices or too uncommon Separation As clearly evidenced in the review of the literature, GC is by far the most popular technique for PCB determination. The relative merits of PGC and CGC are well-known and apply to the separation of PCBs. CGC provides better resolution, retention time precision, and higher qualitative reliability. PGC yields a simple chromatogram (less data reduction), permits higher sample loading (and therefore possibly lower LOQs), and is generally considered easier to use. Historically, PGC quantitation has been more precise, although it has not been established how much of the imprecision attributed to CGC was due to poor technique on the part of the analyst. �The high resolution of CGC is not required in this application for separation and identification of the individual PCB congeners since the final result needed is total PCB. However, the high resolution of CGC should aid the analyst in separating PCBs from interferences. In this respect, CGC is preferable. In many cases when the sample is amenable to "dilute and shoot" techniques, very high levels of matrix materials may be present, which will overload the column. Although CGC is more sensitive to column overloading, both CGC and PGC will overload with percent levels of matrix materials. The advantages of CGC, therefore, make it the technique of choice. However, PGC should also be allowed. Nearly every GC phase has been reported in PCB analysis. The most satisfactory separations have been achieved on nonpolar and semipolar phases (Apiezon L, methyl silicone, Dexsil, etc.). Since enforcement of very specific column parameters is difficult and since rigorous stipulations do not appear warranted, it is recommended that any nonpolar and semipolar capillary column be permitted. The choice of CGC injector (split, splitless or "Grob," and on-column) can substantially affect the amount of material transmitted through the system. Since enforcement of use of a particular injection would be difficult and since no clear choice is presented, any injector which meets performance criteria should be permitted. As part of the quality assurance program, a set of GC performance criteria should be established. The criteria should include number of effective plates, separation number (Tz), resolution, and peak asymmetry. Since PCBs are neutral, the acid/base characteristics of a column are of little interest; however, some measure of compound transmission through the system must be used. This may be achieved by monitoring the overall system response. Other options would entail additional work and are thus less favored. Detection The electron capture detector is the most sensitive candidate detector. However, it suffers from large differences in response factors for PCB congeners, which would result in very poor precision (Tables 3 and 4). Even more serious is its lack of specificity. Since many of the sample matrices will contain large amounts of halogenated nonPCB compounds, BCD would be overloaded throughout much of the chromatogram, making PCB identification and quantitation impossible. In certain cases, ECD may be a satisfactory detector, especially as a semiquantitative technique for screening samples prior to CGC/EIMS analysis. Electron impact mass spectrometry (EIMS) appears to be the method of choice. Mass spectrometry has sufficient selectivity that a chlorinated organic matrix will not generally interfere with PCB determination. While the El mode is not the most sensitive (NCI is much more sensitive), it is the most common ionization technique for GC/MS and, most importantly, is the most reproducible quantitatively. The precision of the EIMS depends upon the precision of the response factors. The most thorough evaluation of PCB response factors 65 �(Martelli et al., 1981) found up to + 20% RSD in selected isomers of one homolog. Since only 45 of the 209 congeners were characterized, the magnitude of the variation in the remaining response factors is not known. DATA REDUCTION Qualitative Since most matrices subject to regulatory analysis contain substantial amounts of halogenated compounds in addition to PCBs and since an "Aroclor pattern" will not usually be present, identification of PCBs is very important. Any misidentification of a nonPCB as a PCB will yield an erroneously high value. From the EPA's viewpoint, this poses no regulatory problem. However, it may result in needless effort and cost to the regulated manufacturers. In most cases, the EIMS data should provide sufficient confidence in the identification of PCBs for action. For those laboratories which choose to employ an equivalent technique for routine analysis, any samples with PCB values near the regulatory cutoff ("near" has not been defined) would have to be reanalyzed by the primary technique before a regulatory decision could be made. In cases where there are some doubts as to the identity of a peak as PCB by CGC/EIMS, any available confirmatory technique should be allowed, provided that the LOQ is equivalent to or lower than the CGC/EIMS LOQ. Positive confirmations present no regulatory problems to EPA. Any confirmations which show that a peak is not PCB must be well-documented with appropriate QA (for example, a spectrum of a PCB standard spiked into the matrix). In many cases, instrument responses are highly dependent on the matrix, so the response to standards in clean solvent cannot be equated with the response in the sample. In cases where a peak is shown to contain both a PCB and an interference, regulations should state that the entire peak must be quantitated as PCB unless the level of the interference can be precisely shown. The qualitative criteria for the EIMS data should address the following points: 1. Full spectra a. Number of ions which must be present. b. Background subtraction techniques permitted. c. Ion intensity tolerances. d. Relative retention time windows. 2. SIM a. Number and mass of ions to be monitored per homolog. b. Tolerance of ion intensity ratios. 66 �c. Relative retention time windows. d. Signal-to-noise ratio. 3. LMS a. Mass range to be scanned. b. Tolerance of ion intensity ratios. c. Relative retention time windows. d. Signal-to-noise ratios. Quantitative Assuming that GC/EIMS is to be used, digitized data will be obtained for use in quantitation. The areas or intensities of individual mass ions must be measured, compared with those for a standard, and converted to a concentration value. This process is complicated in PCB analysis by several factors: 1. Previous schemes based on Aroclor standards are not applicable to incidentally generated PCBs. 2. PCBs are a complex mixture, so the problem really involves up to 209 separate quantitations. 3. All 209 congeners are not available as standards. 4. Two or more congeners may co-elute. The ions for quantitation, selection of standards, and calculation procedures are discussed below. Quantitation Ions— The highest signal-to-noise ratio and therefore precision is a compromise between absolute ion intensity and background signal. Most analysts have chosen an ion in the molecular cluster for quantitation. Even though other ions may be more intense, the molecular cluster is at the highest mass and the background is generally lower. The use of the most intense ion in the molecular cluster is recommended for quantitation, with options of less intense ions from that cluster if interferences are encountered for the primary ion. Calibration— Four calibration methods are available: external standard, internal standard response factors, internal standard multi-point calibration, and direct use of the surrogates. External standard calibration—Calibration of the analysis system versus an external standard and then quantitation using the absolute intensities or areas of the peaks lacks precision (Haefelfinger, 1981) and is not recommended for gas chromatographic analysis. Often, the greatest source of imprecision is the reproducibility of injection volume. 67 �Internal standard response factors — In this method, internal standard(s) are added to the sample extract immediately prior to the instrumental deter" mination, and the analytes are quantitated using the ratio of the peak height or area of the analyte and internal standard. A previously determined response factor (essentially a two-point calibration curve, with an assumed intercept at the origin) is used in converting the response ratio to mass. For PCBs, which can span a large chromatographic range, three or four internal standards are recommended since the precision of the response factors, and therefore the final quantitation, is related to how close the analyte peak and internal standard elute (Haefelfinger, 1981; Bickford et al., 1980). Other factors to be considered in the selection of internal standards are chromatographic resolution from analytes and interferences, different mass spectral properties to assure identification in GC/MS analysis, chemical similarity to analytes (to minimize effects of changes in system selectivity), very low probability of occurring in samples, and chemical stability. Candidates for internal standards in PCB analysis include other halobiphenyls (e.g., fluorononachlorobiphenyl or dibromobiphenyl), related haloaromatics (e.g., chloronaphthalenes), and isotopically labeled PCBs (e.g., d6-3,4,3',4'-tetrachlorobiphenyl). Given the complexity of the matrices in which by-product PCBs may need to be determined, related chloroaromatics should not be used and halobi-^ phenyls must be selected judiciously. Since this technique is in essence a one-point calibration, the response factors must be determined at a concentration close to that of the analyte. Differences of more than one order of magnitude may induce significant errorRecovery surrogates added prior to any sample treatment may also be quantitated against the internal standard and, since the amount added is known, their recovery can be calculated. Knowledge of the percent recovery is useful in monitoring extraction/cleanup performance. The final number reported may be corrected for recovery if desired (or required), or the value found and percent recovery reported separately. It should be noted that if the recovery surrogates and analytes are not, in fact, equally recovered, then the reported recovery is meaningless. This will happen if the surrogates are not fully incorporated into the matrix. Internal standard multi-point calibration—This technique is essentially the same as the response factor technique, above, except multiple calibration points (typically three, spanning up to two orders of magnitude) are used to establish a calibration curve. This has the potential for greater precision, but requires much more time and several solutions. In cases where detector sensitivity (signal response versus amount or concentration) is either nonlinear or the curve does not intercept close to the origin, a multi-point curve is advisable. Surrogate calibration—Surrogates may be used as internal standards for quantitation. Using previously determined response factors (or calibration curves), the response ratio of the analyte and surrogate, and known masses and volumes, the mass of the PCBs may be calculated. When the surrogate recovery is less than 100%, this method automatically corrects for this loss and provides a built-in recovery correction. This method has the advantage of simpler 68 �calculation and requires fewer solutions. This technique is often referred to as isotope dilution. As with the internal standard technique, the surrogates must be incorporated into the matrix to assure equivalent recovery between the surrogate and analyte. Selection of Compounds for Calibration— Clearly, most of the reported quantitation methods which rely on relation of the sample peaks to those in an Aroclor standard are not applicable to by-product PCB determination. The options for compounds to be used in calibration are: 1. Establish and use relative responses for all 209 congeners. 2. Establish and use relative responses for all available (about 80) congeners and extrapolate the responses for the other isomers. 3. Establish and use relative responses for several congeners and extrapolate the responses for the other congeners. 4. Characterize a secondary standard using all available congeners. The secondary standard would be prepared from commercial mixtures to span the range of congeners. Option 1 is the ultimate technique. However, all 209 congeners are not available and synthesis/acquisition would be extremely expensive and require well more than a year for completion. Thus, even if this approach is to be pursued, an interim approach must be specified. Options 2 and 3 are compromises. Option 2 could be termed the best available method. Option 3 is easier to implement and utilizes a reasonable number of quantitation congeners. Option 4 would generate a well-characterized mixed Aroclor or similar mixture. This has the advantages of low cost (oace the characterization has been completed) and uniformity. The disadvantages are that (a) the concentrations of the congeners range over two or more orders of magnitude, so calibration of the instrument would be difficult and (b) many users will have only a limited range of PCB homologs (e.g., only dichlorobiphenyls) and would not want to use a standard requiring a full GC temperature program. Options 2 and 3 appear to be the most applicable. Whether Option 2 or 3 is more appropriate depends on the variability of the response factors and the precision desired by EPA. This area needs to be further investigated. Assuming that all 209 congeners are not characterized and used as calibration standards, analysts will have to extrapolate response factors from the standards used to other isomers. Guidelines for these extrapolations must be specified. A preliminary investigation by at least one laboratory to define the response factor variability among all available congeners is recommended. An estimate of the error associated with the extrapolation would be available from statistical evaluation of the resulting data. 69 �LIMIT OF QUANTITATION Extrapolation of the data in Table 2 to a proposed LOQ for the PCB Remand Rule is difficult because of several uacharacterized variables. The levels of interferences will vary widely. In addition, recoveries will vary, also affecting the LOQ. A major variable is the concentration factor in the workup (number of grams of sample concentrated or diluted to a given sample volume for injection on the GC). If the method works with a 1-g sample, an order of magnitude decrease in LOQ can be effected by using a 10-g sample. This requires additional effort and therefore cost. Taken to the extreme, it is possible to use very large samples (many kilograms) to lower the LOQ. On the other hand, the customary volume to concentrate a sample extract is 1 ml. One can, with some difficulty and loss of volume precision, further concentrate the extract to 100 pi, effecting a 10-fold decrease in LOQ. However, if the sample is still dirty, this further concentration can lead to solidification, which prevents injection onto a GC column. DATA REPORTING The final data report should list total PCB as the bottom line number, since this is the value of regulatory interest. The analytical reporting format should be specified to eliminate any ambiguity and should address the following issues: 1. Tabulation of individual congener quantitation. This may be difficult to achieve since congener identifications may not be available for more than a few congeners. 2. Tabulation of individual homolog quantitation. quired so that data reviewers can assess the data. This should be re- 3. Reporting units. These must be specified. Units such as micrograms per gram (solids), micrograms per liter (water), and micrograms per cubic meter (air) are recommended. 4. Recovery correction. If the final protocol specifies use of surrogates to monitor recoveries and if the method is validated, then recovery correction would be appropriate. While this conflicts with the customary practice in pesticide residue, priority pollutant, and other analyses, it is con~ sistent with the practice in many other fields (e.g., clinical analyses). Since near quantitative (> 70%) recovery cannot be assumed, recovery correction is strongly recommended. Although high recoveries may not be guaranteed, very low recoveries cannot be tolerated. The lower the recovery, the higher the overall method LOQ. In addition, very low recoveries are generally accompanied by poor precision. If, for instance, 10 ± 5% recovery is achieved, the uncertainty in the nominal 10X correction factor is huge (6.7-20X). Thus, a lower acceptable limit of recovery (e.g., 30%) must be stipulated for acceptable data. 5. Standard reporting format. A standard reporting form, including all equations to be used, intermediate calculations, etc., should be required. This improves quality assurance since the chance for error (e.g., using the 70 �wrong conversion factor) is reduced, and any errors would be detected more easily. In addition, data presented to regulatory personnel on standard forms are much easier to review. 6. Internal standards. If no recovery surrogates are available, internal standards would most certainly be advocated. Their use generally improves precision, and thus data quality, over the use of external standards. If surrogates are used, the need for internal standards is not so clear. One can use the surrogate response in the calculation of unknown concentrations. In this case, instrument response variability, losses in the instrument, and workup recovery are taken into account, all in one calculation. Thus, recoveries are corrected without any real knowledge of the percent recovery. On the other hand, the use of both internal standards and recovery surrogates would yield a fairly accurate assessment of the recovery and permit the analyst (or regulator) to decide if the recovery is unacceptably low. While knowledge of recoveries is not of central regulatory concern, it does provide the analyst with an estimate of the method performance. Therefore, if no internal standards are used, a seraiquantitative estimate of recovery must be made using the CGC/EIMS response (area counts or similar measure) to the surrogates. If this is below a certain threshold (say 30% of expected), then the sample preparation must be repeated or changed. The use of the surrogate compounds as standards for both workup and instrumental analysis is simple-, and since it is one step instead of two, it should be more precise. The price paid for this simplicity is that recoveries are not well characterized. In the interest of simplicity and better precision, the use of internal standards in addition to recovery surrogates is not recommended. CONFIRMATION TECHNIQUES Qualitative Alternate columns, detectors (HREIMS, FTIR, NCIMS, HECD, etc.), and techniques such as MS/MS, direct probe HREIMS, NMR, FTIR, HPLC, etc., will be permitted for confirmation of PCBs. Proper validation and demonstration of comparable or lower detection limit must be provided with any confirmation which overrules the GC/EIMS identification and eliminates the compound from quantitation as a PCB. Quantitative As part of the overall QA, quantitative confirmation is required. The options proposed include duplicate analyses and standard addition. Acceptance criteria for these confirmatory techniques are discussed in more detail in the Quality Assurance subsection. SCREENING/EQUIVALENT METHODS Alternate procedures to the designated protocol may be necessary to obtain rapid estimates of PCB concentration for commercial facilities operating on a continuous process basis or for small businesses relying on contract laboratories for analyses. The alternate procedures could possibly include perchlorination, dechlorination, TLC, PGC/ECD, PGC/HECD, CGC/ECD, CGC/HECD, etc. 71 �The data generated by these methods would be for the individual industry's use to determine if changes in process design or initial reactants are necessary to lower the levels of PCBs in the final product. However, compliance with the regulations must still be determined with the designated protocol unless EPA accepts the screening technique as equivalent to the protocol. Equivalency must be demonstrated in terms of sensitivity and selectivity for PCBs, limits of detection and quantitation, and interferences. A strong QA program must be implemented to establish and monitor the equivalency of an alternate method. The quality control program should include measurements of blanks, spiked blanks, and spiked samples (blind and known) to establish limits for precision, accuracy, and recovery of analyses from the sample matrix. Equivalent methods would be most applicable to continuous process operations with little system variance. Gross changes in any parameter of a continuous operation process should require further verification of equivalency of the alternate method. The levels of PCBs in a fraction of all samples should still be analyzed according to the proposed primary protocol for quality assurance. 72 �SECTION 5 POSSIBLE ANALYTICAL SCHEMES The purpose of this section is to discuss how all the analytical com" ponents presented in Section 3 can be integrated to produce an effective overall protocol. For discussion purposes, it is presumed here that a primary protocol will be established and that it will contain the following steps: 1. Homogenize sample and subsample if necessary. 2. Incorporate surrogate compounds (e.g., four 13C PCB congeners). 3. Dilute, extract, or clean up as required. 4. Concentrate or dilute to a known volume. 5. Analyze a known aliquot by CGC/EIMS. 6. Identify PCBs by relative retention time and mass spectral characteristics. 7. Integrate the PCBs by homolog and calculate amounts of each homolog by normalizing the responses to responses for the surrogate compounds, using one or more homolog response factors. 8. Sum all 10 homolog concentrations to obtain a total PCB value. 9. Report on standard reporting form. 10. Follow specified routine quality assurance (blanks, controls, duplicates, standard addition, instrument performance criteria, etc.). 11. Maintain appropriate records. ISSUES TO BE ADDRESSED If this or a similar protocol is specified, several issues must be addressed. Method Flexibility Some flexibility must be permitted in the method details (GC columns, solvent evaporation techniques, etc.) to accommodate different apparatus and 73 �laboratory practices. However, excessive flexibility will adversely affect the data quality since many operations are uncontrolled. With proper QA practices, the method can be flexible while still generating acceptable results. Thus, it appears that the best approach is to provide options and suggest rather than require for most method details. As long as the laboratory demonstrates it is within the performance boundaries specified by the QA guidelines, the optional approaches should be allowed. Substitute Methods Except when validated and routinely confirmed by CGC/EIMS, no substitute methods should be permitted. Equivalent Methods Equivalent methods should be permitted. Equivalent methods (TLC, GC/ECD, etc.) are defined as methods which have been validated against the primary method and yield comparable quantitative results and have LOQs comparable to the primary method or lower LOQ than the regulatory cutoff. Results obtained by an equivalent method must be confirmed by the primary method if significant interferences are suspected or the levels found are near the regulatory cutoff ("near" must be defined). Any use of an equivalent method would be subject to the additional QA provision that a specified number (e.g., every tenth) of samples be routinely run by the primary method and that the two results agree within specified tolerances (the agreement should be specified by homolog, not simply by total PCB, to avoid any method bias toward one end of the homolog lines). Since an equivalent method would be subject to validation and additional QA, it would be applicable only to routine monitoring of a process. Obviously any single batches or one-shot analyses would have to be done by the primary method. The major application of equivalent methods is projected for the company with a process at several plants which must be monitored periodically. Since most plants do not have GC/MS instrumentation and a slow turnaround from central research would either delay product shipping or permit untested product to be released to customers, use of an equivalent method appears to be the only acceptable alternative. QUALITY ASSURANCE The QA options to be addressed include: 1. Round robins: One or more round robins appear to be a good mechanism for improving the methodology and predicting the data quality. The objectives and execution of the round robin need to be addressed. Whether periodic round robins should be required is also of interest. 2. QA organization: Some organization must be designated to administer QA. The responsibilities and authority of the organization need to be specified. At one extreme, the QA organization periodically reviews the data submitted. On the other extreme, the QA organization would have laboratory 74 �facilities and confirm results on selected samples, prepare and send out performance audit samples, organize and execute round robins, conduct systems audits, and conduct method development efforts when necessary. Clearly the data quality and cost are roughly proportional to the amount of QA. A sensible compromise must be reached. 3. Systems audits: One standard QA practice is the systems audit. This is especially valuable in that the QA officer observes the personnel and facilities in operation and assesses their competence and performance. This is the only way the QA office can monitor the laboratory practices and review the raw data (chromatograms, mass spectra, magnetic tapes, etc.). The use of systems audits is desirable, but it requires personnel and travel fund commitments . 4. Performance audits: A performance audit is a quantitative analysis with a material of known PCB content. Performance audits consist of blanks and samples, blind or known, submitted by the QA lab and are generally analyzed along with routine samples. A performance audit system is mandatory as part of the overall laboratory certification program. 5. Laboratory certification; A laboratory certification program is recommended. The quality of the data and therefore the laboratory capabilities and performance must be assured. There are several methods for laboratory certification: round robin participation, performance audit participation, or submission to a systems audit. Most likely a combination of the three would be the most reasonable certification route. Following initial certification, all participating laboratories must be periodically recertified. Performance audits and systems audits are the most appropriate recertification methods. 75 �APPENDIX A PERSONAL CONTACTS Note; In preparation of this document, telephone, written, or personal discussions were held with the individuals listed. 76 �Ahmed, Karim. Natural Resources Defense Council, 122 E. 42nd Street, New York, New York 10169. Alford-Stevens, Ann. Environmental Monitoring and Support laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio 45268 Bell, Robert A. Corporate Research and Development, General Electric Company, 1 River Road, K-l, 3B15, Schenectady, New York 12301, (518) 385-8505. Albro, Phillip. NIEHS, Research Triangle Park, North Carolina 27711, FTS 629-3264. Bellar, Thomas A. Environmental Monitoring and Support Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio 45268, FTS 684-7311. Bidleman, Terry F. Department of Chemistry, University of South Carolina, Columbia, South Carolina 29208, (803) 777-4239. Breen, Joseph J. Office of Toxic Substances, U.S. Environmental Protection Agency, 401 M St., Washington, D.C. 20640, FTS 382-3569. Budde, William. Environmental Monitoring Support Laboratory, U.S, Environ" mental Protection Agency, Cincinnati, Ohio 45268, FTS 684-7309. Burgess, Ken. Dow Chemical Company, 1803 Building, Midland, Michigan, 48640, (517) 636-3177. Bursey, Joan T. Analytical Sciences Division, Research Triangle Institute, Research Triangle Park, North Carolina 27709, (919) 541-5928. Bumgarner, Joseph. Environmental Monitoring and Systems Laboratory, U(S. Environmental Protection Agency, Research Triangle Park, North Carolina 27711, FTS 629-2434. Carey, Ann E. Office of Toxic Substances, U.S. Environmental Protection Agency, 401 M St., Washington, D.C. 20460, FTS 382-3569. Carra, Joseph. Office of Toxic Substances, U.S. Environmental Protection Agency, 401 M St., Washington, D.C. 20460, FTS 382-3900. Caspers, Horst. Stauffer Chemical Company, Dobbs Ferry, New York 10522, (914) 673-1200. Chesler, Stephen N. Organic Analytical Research Division, National Bureau of Standards, Washington, D.C. 20234, (301) 921-2153. Christman, Mark H. E. I. DuPont de Nemours, Wilmington, Delaware 19898, (202) 774-6443. Crouch, Michael D. Toxicon Laboratories, 3213 Monterrey Boulevard, Baton Rouge, Louisana 70814, (504) 925-5012. DaRoche, Maria. Sun Chemical Corporation, 441 Tompkins Avenue, Staten Island, New York 10305, (212) 981-1600 ext. 215. 77 �Dougherty, Ralph C. Department of Chemistry, Florida State University, Tallahassee, Florida 32306, (904) 644-5725. Ewald, Fred. PPG Industries, Inc., P.O. Box 31, Barberton, Ohio 44203, (216) 848-4600. Fensterheim, Robert J. (202) 887-1189. Gebhart, Judy. Ohio 43201. CMA, 2501 M Street, NW, Washington, B.C., Battelle Columbus Laboratories, 505 King Avenue, Columbus, Gunter, Bill. CCD, Office of Toxic Substances, U.S. Environmental Protection Agency, 401 M Street, SW, Washington, D.C. 20460, (202) 382-3933. Haile, Clarence L. Midwest Research Institute, 425 Volker Boulevard, Kansas City, Missouri 64110, (816) 753-7600. Hanneman, Larry F. Dow Corning, P.O. Box 1592, Midland, Michigan 48640, (517) 496-5003. Hass, J. Ronald. FTS 629-3463. NIEHS, Research Triangle Park, North Carolina 27711, Heggem, Daniel T. Field Studies Branch, Office of Toxic Substances, U.S. Environmental Protection Agency, TS-798, Washington, D.C. 20460, (202) 382-3584. Hensler, Charles. DuPont, Jackson Lab, Deepwater, New Jersey 08023, (609) 299-5000, ext. 3611. Hodges, Kent L. Dow Chemical Company, 574 Building, Midland, Michigan 48640, (517) 636-6544. Johnson, Larry. Industrial Environmental Research Laboratory, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina 27711, FTS 629-7943. Kaley, Robert. Monsanto Company, 800 North Lindbergh Boulevard, St. Louis, Missouri 63166, (314) 694-4964. Kingsley, Barbara. SRI International, 333 Ravenswood Avenue, Menlo Park, California 94025, (415) 326-6200. Kleopfer, Robert D. Region VII, U.S. Environmental Protection Agency, 1735 Baltimore Avenue, Kansas City, Missouri 64108, (816) 374-4285. Kutz, F. W. Field Studies Branch, Office of Toxic Substances, U.S. Environmental Protection Agency, TS-798, Washington, D.C. 20460, (202) 382-3569. Lewis, Robert G. Environmental Monitoring and Systems Laboratory, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina 27711, FTS 629-3065. 78 �Lopez-Avila, Viorica. Acurex, 485 Clyde Avenue, Mountain View, California 94042, (415) 964-3200. Moll, Amy. Regulatory Impacts Branch, Office of Toxic Substances, U.S. Environmental Protection Agency, TS-779, Washington, D.C. 20460 (202) 382-3715. Mullin, Michael D. U.S. Environmental Protection Agency, Large Lakes Research Station, 9311 Groh, Grosse lie, Michigan 48138, FTS 226-7011. Parris, Reenie. Organic Analytical Research Division, National Bureau of Standards, Washington, D.C. 20234, (301) 921-2153. Pellizzari, Edo D. Analytical Sciences Division, Research Triangle Institute, Research Triangle Park, North Carolina 27709. Petty, James D. Fish-Pesticide Research Laboratory, Fish and Wildlife Service, U.S. Department of Interior, Columbia, Missouri 65201, FTS 276-5399. Pfaffenberger, Carl D. Division of Chemical Epidemiology, School of Medicine, University of Miami, 15655 S.W. 127th Avenue, Miami, Florida 33177, (305) 255-3300. Redford, David. Office of Toxic Substances (TS-798), U.S. Environmental Protection Agency, Washington, D.C. 20460, FTS 382-3583. Robinson, J. Lawrence. Dry Color Manufacturers' Association, Suite 100, 1117 North 19th Street, Arlington (Rosslyn), Virginia 22209, (703) 525-9483Robinson, Thomas. Vulcan Materials Company, P.O. Box 7689, Birmingham, Alabama 35253, (205) 877-3556. Ronan, Richard. Versar, Inc., 6621 Electronic Drive, Springfield, Virginia 22151, (703) 750-3000. Safe, Stephen, Department of Physiology and Pharmacology, College of Veterinary Medicine, Texas A & M University, College Station, Texas 77843. Sawyer, Leon D. Food and Drug Administration, 240 Hennepin Avenue, Minneapolis, Minnesota 55401, FTS 725-2121. Slevon, Larry. Battelle Columbus Laboratories, 505 King Avenue, Columbus, Ohio 43201 Smith, John. DDB, Office of Toxic Substances, U.S. Environmental Protection Agency, Washington, D.C. 20460, FTS 382-3900. Sonchik, Susan. Versar, Inc., 6621 Electronic Drive, Springfield, Virginia 22151, (703) 750-3000. Stalling, David L. Fish-Pesticide Research Laboratory, Fish and Wildlife Service, U.S. Department of Interior, Columbia, Missouri 65201, FTS 276-5399. 79 �Underwood, Joseph. Food and Drug Administration, 1009 Cherry Street, Kansas City, Missouri 64106, (816) 374-5524. Warren, Jackie. Natural Resources Defense Council, 122 East 42nd Street, New York, New York 10168. 80 �APPENDIX B BIBLIOGRAPHY 81 �BIBLIOGRAPHY Aaronson, M. J., J. D. 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Veith, G. D., and L. M. Kiwus, "An Exhaustive Steam-Distillation and SolventExtraction Unit for Pesticides and Industrial Chemicals," Bull. Environ. Contam. Toxicol., jj, 631-636 (1977). 122 �Veith, G. D., D. W. Kuehl, E. N. Leonard, K. Welch, and G. Pratt, "Polychlorinated Biphenyls and Other Organic Chemical Residues in Fish from Major United States Watersheds Near the Great Lakes, 1978," Pestic. Mon. J., 15, 1-8 (1981). Wakimoto, T., M. Fukushima, R. Tatsukawa, and T. Ogawa, "Separation of PCBs [Polychlorinated Biphenyls] from p,p'-DDE and Other Organochlorine Pesticides by a Newly Developed Silica Gel," Nippon Nogei Kagaku Kaishi, 49(10), 499-503 (1975); Chem. Abst.. 84, Il6448r (1976). Wakimoto, T., R. Tatsukawa, and T. Ogawa, Kogai to Taisaku, 7, 517 (1971); Fish Res. Bd. Can., Translation No. 2185. Ward, R. S., and A. Pelter, "The Analysis of Mixtures of Closely Related Naturally-occurring Organic Compounds Using High Performance Liquid Chromatography," J. Chromatogr. 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Choi, "Determination of Pentachlorophenol and Chlorobiphenylols in Biological Samples," Bull. Environ. Contam. Toxicol., 12(6), 649-653 (1974). Zitko, V., "Levels of Chlorinated Hydrocarbons in Eggs of Double-Crested Cormorants from 1971 to 1975," Bull. Environ. Contam. Toxicol., 16(4), 399405 (1976). Zobel, M. G. R., "Quantitative Determination of Polychlorinated Biphenyls— A Computer Approach," J. Assoc. Offic. Anal. Chem., 57(4), 791-795 (1974). 125 �TECHNICAL REPORT DATA (Please read Instructions on the reverse before completing) 1. REPORT NO. 3. RECIPIENT'S ACCESSION NO, EPA-560/5-82-005 4. TITLE AND SUBTITLE 5. REPORT DATE Methods of Analysis for By-Product PCBs—Literature Review and Preliminary Recommendations 7. AUTMQR(S) October 1982 6. PERFORMING ORGANIZATION CODE 4901-A(51) 8. PERFORMING ORGANIZATION REPORT NO. Mitchell D. Erickson John S. Stanley Interim Report No. 1 9. PERFORMING ORGANIZATION NAME AND ADDRESS Midwest Research Institute 425 Volker Boulevard Kansas City, Missouri 64110 10. P R O G R A M E L E M E N T NO. 11. CONTRACT/GRANT NO, 68-01-5915 Task 51 12. SPONSORING AGENCY NAME AND ADDRESS U.St Environmental'Protection Agency Office of Toxic Substances Field Studies Branch, TS-798 Washington. D.C. 20460 13. TYPE OF REPORT AND PERIOD COVERED Interim (March-April 1982) 14. SPONSORING AGENCY CODE 15. SUPPLEMENTARY NOTES Frederick W. Kutz, Project Officer David P. Redford, Task Manager 16. ABSTRACT A review of the literature on polychlorinated biphenyl (PCB) analysis and recommendations for methods to determine by-product PCBs in commercial products and other matrices is presented. This report was prepared to assist EPA in formulating a rule regulating by-product PCBs. The published literature on PCB analysis is critically reviewed. Several hundred references are cited in a bibliography. The review if subdivided into extraction, cleanup, determination, data reduction, confirmation, screening, quality assurance, and by-product analysis sections. The determination section includes TLC, HPLC, GC (POC and COC) , GC detectors (ECD, FID, HECD, EIMS, and other MS) and nonchromatographlc analytical methods (NMR, IR, electrochemistry, NAA, and RIA). Techniques applicable to analysis of commercial products, air, and water for by-product PCBs are discussed. The final section of this report presents a recommended overall primary analytical scheme. KEY WORDS AND DOCUMENT ANALYSIS IZ: DESCRIPTORS 3. b.lDENTIFIERS/OPEN ENDED TERMS C. COSATI Field/Group 19. SECURITY CLASS (This Report) 21. NO, OF PAGES PCBs Polychlorinated Biphenyls Analysis By-product PCBs Review 18. DISTRIBUTION STATEMENT Unclassified 20. SECURITY CLASS (This page) Unlimited Unclassified EPA Form 2220-1 (Rev. 4-77) PREVIOUS EDITION is OBSOLETE 135 22. PRICE � Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 186 Folder The folder containing the original item. 5384 Series The series number of the original item. Series VIII Subseries I Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Creator An entity primarily responsible for making the resource Erickson, Mitchell D. John S. Stanley Description An account of the resource <strong>Corporate Author: </strong>Midwest Research Institute Date A point or period of time associated with an event in the lifecycle of the resource October 12 1982 Title A name given to the resource Methods of Analysis for By-Product PCBs - Literature Review and Preliminary Recommendations ao_seriesVIII