1 15 1 https://www.nal.usda.gov/exhibits/speccoll/files/original/f11abf4af56863a9455a349556df7a88.pdf b4a09025dca32840bda0307cf9a00341 PDF Text Text Item ID Number °0631 Author Erickson, Mitchell D. Research Triangle Institute, Research Triangle Park, NC Ronort/ArtiClO TltlO Acquisition and Chemical Analysis of Mother's Milk for Selected Toxic Substances Journal/Book Title Year 190 Month/Day December ° Color Number of Images 168 DBSOrlptOn NOtOS Alvin L Youn 9 filcd this item under the category "Human Exposure to Phenoxy Herbicides and TCDD" Tuesday, February 20, 2001 Page 631 of 680 �J H.fc. e.V.«A. l r t * A Wl PB81-231029 Acquisition and Chemical Analysis of Mother's Milk for Selected Toxic Substances * Research Triangle Inst. Research Triangle Park, NC Prepared for Environmental Protection Agency Washington, DC Dec 80 U.S. DEPARTMENT OF COMMERCE National Technical Information Service �United States Environmental Protection Agency Office of Pesticides and Toxic Substances Washington, DC 20460 EPA-560/13-80-029 December 1980 L - 2 3 1029 Toxic Substances &EPA Acquisition and Chemical Analysis of Mother's Milk for Selected Toxic Substances REPRODUCED 3V NATIONAL TECHNICAL INFORMATION SERVICE U.S. DEPARWfNI Of COMMERCE SPRWflflELO. VA 22161 �TECHNICAL REPORT DATA (Pleat read Inttructiom on the reverie before completing) 3. R 1. REPORT NO. 560/13-80-029 4. TITLE ANOSUBTITLS 6. REPORT DATE ACQUISITION AND CHEMICAL ANALYSIS OF MOTHER'S MILK FOR SELECTED TOXIC SUBSTANCES December, 1980 S. PERFORMING ORGANIZATION CODE 31U-1521-21 + 22 '__ 7.AUTH0R(S)Mitchell D. Erickson, Benjamin S. H. Harris, III, Edo D. Pellizzari, Kenneth B. Tomer, Richard D. Waddell and Donald A. Whitaker m. PERFORMING ORGANIZATION REPORT NO. 9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT NO. Research Triangle Institute It. CONTRACT/GRANT NO. P. 0. Box 12194 Research Triangle Park, NC 27709 68-01-3849 - Task 2 12. SPONSORING AGENCY NAME ANO ADDRESS 13. TYPE OF REPORT ANO PERIOD COVERED Field Studies Branch, Exposure Evaluation Division Office of Pesticides and Toxic Substances, U. S. Environmental Protection Agency, Washington, DC 20460 Task Final 1/23/78-4/18/80 14. SPONSORING AGENCY CODE 15. SUPPLEMENTARY NOTES Project Officer: Joseph Breen . ABSTRACT RACT Samples of mother1s milk were collected from Bayonne, NJ; Jersey City, NJ; Pittsburgh, PA; Baton Rouge, LA; and Charleston, WV, and analyzed for volatile (purgeables) and semivolatile (extractable) organics using glass capillary gas chromatography/mass spectrometry/computer. In the volatile fraction, 26 halogenated hydrocarbons, 17 aldehydes, 20 ketones, 11 alcohols, 2 acids, 3 ethers, 1 epoxide, 14 furans, 26 other oxygenated compounds, 4 sulfur-containing compounds, 7 nitrogen-containing compounds, 13 alkanes, 12 alkenes, 7 alkynes, 11 cyclic hydrocarbons, and 15 aromatics were found, including major peaks for hexanal, limonene, dichlorobenzene, and some esters. The levels of dichlorobenzene appeared to be significantly higher in the samples from Jersey City and Bayonne than in samples from other sites. Jersey City samples also appeared to have significantly higher levels of tetrachloroethylene. Charleston and Jersey City samples appeared to have significantly higher levels of chloroform; however, chloroform was observed in the blanks at about 20% of that in the samples. Due to the small sample size and lack of control over the solicitation of sample donors, the data cannot be used to extrapolate to the general population. Fewer semivolatile compounds of interest were found. Polychlorinated naphthalenes, polybrominated biphenyls, chlorinated phenols, and other compounds were specifically sought and not detected (limit of detection about 20-100 ng/mL milk). Polychlorinated biphenyls (PCBs) and DDE were found. 17. a. DESCRIPTORS KEY WORDS AND DOCUMENT ANALYSIS b.lDENTIFIERS/OPEN ENDED TERMS c. COSATi Field/Croup Mother's Milk Purge and Trap GC/MS Sampling Milk Chlorinated Organics f f. It. DISTRIBUTION STATEMENT 19. SECURITY CLASS <TMs Rtpon) UNCLASSIFIED RELEASE TO PUBLIC EPA f*rm 2220.1 (R««. 4-77) 20. SECURITY CLASS <TM* page) PNCVIOU* COITION i* OMOLCTC 21. NO. Of PAGES 164 22. PRICE �EPA 560/13-80-029 ACQUISITION AND CHEMICAL ANALYSIS OF MOTHER'S MILK FOR SELECTED TOXIC SUBSTANCES by Mitchell 0. Erickson, Benjamin S. H. Harris, III, Edo D. Pellizzari, Kenneth B. Tomer, Richard D. Waddell and Donald A. Whitaker Contract No. 68-01-3849 Task 2 Project Officer: Joseph Breen Field Studies Branch Exposure Evaluation Division Office of Pesticides and Toxic Substances U. S. Environmental Protection Agency Washington, DC 20460 December 1980 / -a. �DtCLAIMER This document has been reviewed and approved for publication by the 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. ii �ABSTRACT Samples of mother's milk were collected from Bayonne, NJ; Jersey City, NJ; Pittsburgh, PA; Baton Rouge, LA; and Charleston, WV, and analyzed for volatile (purgeables) and semivolatile (extractable) organics using glass capillary gas cbromatography/mass spectrometry/computer. In the volatile fraction, 26 halogenated hydrocarbons, 17 aldehydes, 20 ketones, 11 alcohols, 2 acids, 3 ethers, 1 epoxide, 14 furans, 26 other oxygenated compounds, 4 sulfur-containing compounds, 7 nitrogen-containing compounds, 13 alkanes, 12 alkenes, 7 alkynes, 11 cyclic hydrocarbons, and 15 aromatics were found, including major peaks for hexanal, limonene, dichlorobenzene, and some esters. The levels of dichlorobenzene appeared to be significantly higher in the samples from Jersey City and Bayonne than in samples from other sites. Jersey City samples also appeared to have significantly higher levels of tetrachloroethylene. Charleston and Jersey City samples appeared to have significantly higher levels of chloroform; however, chloroform was observed in the blanks at about 20% of that in the samples. Due to the small sample size and lack of control over the solicitation of sample donors, the data cannot be used to extrapolate to the general population. Fewer semivolatile compounds of interest were found. Polychlorinated naphthalenes, polybrominated biphenyls, chlorinated phenols, and other compounds were specifically sought and not detected (limit of detection about 20-100 ng/mL milk). Polychlorinated biphenyls (PCBs) and DDE were found. iii �CONTENTS Abstract Figures Tables List of Abbreviations and Symbols Acknowledgments 1. 2. 3. 4. 5. 6. 7. Introduction Summary and Conclusions Recommendations Selection of Sampling Sites Sample Collection Sample Analysis Methods Results References Appendices A. B. C. 0. E. iii vi vii ix x 1 15 16 18 32 36 45 61 Data Collection Instruments Sampling and Analysis of Volatile Organics in Milk Analysis of Semivolatile Organics Compounds in Milk Volatile Compounds Identified in Selected Purges of Mother's Milk Semivolatile Compounds Identified in Selected Extracts of Mother's Milk Preceding page blank 68 104 112 119 144 �FIGURES Number Page B-l Diagram of headspace purge and trap system D-l Total ion current chromatogram from GC/MS analysis in sample no. 1081 (Bayonne, NJ) D-2 Total ion current chromatogram from GC/MS analysis in sample no. 1040 (Bayonne, NJ) D-3 Total ion current chromatogram from GC/MS analysis in sample no. 1107 (Jersey City, NJ) D-4 Total ion current chromatogram from GC/MS analysis in sample no. 1115 (Jersey City, NJ) D-5 Total ion current chromatogram from GC/MS analysis in sample no. 2048 (Pittsburgh, PA) D-6 Total ion current chromatogram from GC/MS analysis in sample no. 2071 (Pittsburgh, PA) D-7 Total ion current chromatogram from GC/MS analysis in sample no. 3053 (Baton Rouge, LA) D-8 Total ion current chromatogram from GC/MS analysis in sample no. 3111 (Baton Rouge, LA) E-l Total ion current chromatogram from GC/MS analysis in sample 1032 (Bayonne, NJ) E-2 Total ion current chromatogram from GC/MS analysis in sample 2121 (Pittsburgh, PA) E-3 Total ion current chromatogram from GC/MS analysis in sample 3095 (Baton Rouge, LA) E-4 Total ion current chromatogram from GC/MS analysis in sample 4093 (Charleston, WV) 107 VI for volatiles 122 for volatiles 125 for volatiles 129 for volatiles 132 for volatiles 135 for volatiles 138 for volatiles 141 for volatiles 143 for semivolatiles 146 for semivolatiles 148 for semivolatiles 150 for semivolatiles 152 �TABLES Number 1 Comparison Between Human and Cow's Milk 2 Levels of Organic Compounds Found in Human Milk in the United States 3 Ranking of Pesticides and PCBs by Reported Concentrations in Human Milk 4 Levels of Organic Compounds Found in Human Milk Outside the United States 5 Summary of PCN Concentrations Found Near Manufacturing and Use Sites 6 7 8 9 10 11 12 13 14 15 16 Prevalent Halogenated Compounds in Ambient Air and Water of Rahway/Woodbridge, Boundbrook and Passaic, NJ Estimated Daily Intake of Selected Volatile Compounds and Expected Concentrations in Blood in Northern New Jersey Total Daily Intake of Target Compounds, Pesticides, PCBs, BaP and Metals and Concentrations in Blood in Northern New Jersey . . Potential Emissions from Chemical Industry in Baton Rouge, LA. . . Prevalent Halogenated Compounds Occurring in Ambient Air and Water of Baton Rouge, Geismar and Plaquemine, LA Potential Emissions from Chemical Industry in Plaquemine, Geismar, and St. Gabriel, LA Method Validation Recovery of Selected Volatile Standards from Milk Method Validation Recovery of Semivolatile Compounds Spiked into Raw Cow's Milk Operating Conditions for GC/MS Analysis of Purgeables Operating Conditions for the GC/MS Analysis of Semivolatiles . . . Summary of Qualitative Identifications of Volatile Compounds in Mother's Milk vii 5 9 10 19 22 23 24 27 29 30 38 39 42 43 46 �TABLES CONT'D. Number Page 17 Volatiles Quantitated in Mother's Milk Samples (ng/mL) 52 18 Summary Statistics for Volatile Compounds by Site 55 19 Significance of the Differences in the Geometric Means by Site . . 56 20 Spearman Correlation Coefficients for Volatile Organics Found in Mother's Milk 57 21 Quality Control Results for Volatiles in Milk 58 22 DDE and Tetrachlorobiphenyl Levels in Selected Mother's Milk Samples B-l Instrumental Operating Conditions D-l Volatile Compounds Identified in Purge of Sample No. 1081 (Bayonne, NJ) D-2 Volatile Compounds Identified in Purge of Sample No. 1040 (Bayonne, NJ) D-3 Volatile Compounds Identified in Purge of Sample No. 1107 (Jersey City, D-4 Volatile Compounds (Jersey City, D-5 Volatile Compounds D-6 NJ) Identified in Purge of Sample No. 1115 NJ) Identified in Purge of Sample No. 2048 (Pittsburgh, PA) Volatile Compounds Identified in Purge of Sample No. 2071 (Pittsburgh, PA) D-7 Volatile Compounds Identified in Purge of Sample No. 3053 (Baton Rouge, LA) D-8 Volatile Compounds Identified in Purge of Sample No. 31]1 (Baton Rouge, LA) E-l Semivolatile Compounds Identified in Extract of Sample 1032 (Bayonne, NJ) E-2 Semivolatile Compounds Identified in Extract of Sample 3095 (Baton Rouge, LA) E-3 Semivolatile Compounds Identified in Extract of Sample 3095 (Baton Rouge, LA) E-4 Semivolatile Compounds Identified in Extract of Sample 4093 (Charleston, WV) viii 60 108 120 123 126 130 133 136 139 142 145 147 149 151 �LIST OF ABBREVIATIONS AND SYMBOLS ABBREVIATIONS DDT dpra ECD GC MS NICIMS OMB PBBs PCBs PCF PCN PLF SQ l,l-Bis(p_-chlorophenyl)-2,2-trichloroethane Disintegrations per minute Electon capture detection Gas chromatography Mass spectrometry (electron impact ionization) Negative ion chemical ionization mass spectrometry Office of Management and Budget Polybrominated biphenyls Polychlorinated biphenyls Participant Consent Form Polychlorinated Naphthalene Participant Listing Form Study Questionnaire ix �ACKNOWLEDGMENTS The authors thank the Project Officer, Dr. Joseph Breen, for his guidance and advice. Sandra P. Parks, David L. Newton, and Larry C. Michael are acknowledged for their assistance in the laboratory. Nora P. Castillo and Kent W. Thomas are thanked for their assistance with mass spectral interpretation. Pamela A. Gentry, Fred A. McKinney, Stephen P. Burke, and Barbara L. Bickford are thanked for sample analysis using mass spectrometry. Personnel who assisted in the milk collection are greatly appreciated: Elizabeth Bartholomew, Bayonne Hospital, Bayonne, NJ; Jules Rivkind and Trudy Strunk, Medical Center Hospital, Jersey City, NJ; Ian Holtzman, MageeWomen's Hospital, Pittsburgh, PA; Lewis Tracbtman, Louisiana Health Department, New Orleans, LA; Maxine Parker, Baton Rouge Area Regional Nursing Consultant, Baton Rouge, LA; Clementine Martine, Public Health Nursing Supervisor of the East Baton Rouge Parish Health Unit, Baton Rouge, LA; and N. N. Sehgal, Charleston Area Medical Center (Memorial Division), Charleston, WV. Finally we would like to thank the 42 women who so kindly donated the samples. �SECTION 1 INTRODUCTION BACKGROUND It is becoming increasingly important to correlate ambient environmental pollutant levels with human body burden. Establishment of this correlation ("exposure assessment") may provide a link between pollution and health effects. This correlation is of interest for both scientific research and regulatory risk assessment. Measurement of pollutant body burden levels generally requires invasive techniques (exceptions are breath and urine sampling) which are undesirable from the subjects' viewpoint. Some invasive techniques are generally regarded as acceptable (e.g., blood samples), while others are generally considered unacceptable from living donors (e.g. adipose tissue, internal organs, etc.). Mother's milk is an attractive medium for several reasons: (1) sample collection is reasonably straightforward; (2) milk contains a high amount of fat (about 3.5 percent, as shown in see Table 1), so fat-soluble pollutants such as DDT and polychlorinated biphenyls (PCBs) are likely to be found in higher concentrations in milk than in blood or urine; (3) large (50-100 ml) volumes are easily collected for analysis, increasing analytical reliability and detection limit; and (4) the population of nursing mothers is large relative to pathology samples such as adipose tissue. In addition, an assessment of pollutant concentrations in mother's milk may be used to predict the pollutant intake by the nursing infant. The major disadvantages of mother's milk as a human-sampling medium relate to the sampling demography: only young-to-middle-aged females are nursing. Thus, any use of mother's milk in a probability-based sampling framework extrapolated to the general population would be fraught with difficulties, such as locating donors. �Table 1. COMPARISON BETWEEN HUMAN AND COW'S MILK (1) Parameter Human Milk Cow's Milk Water and solid content Same in both; 87 to 87.5 percent is water Calories Same in both; 20 calories per ounce Protein 1 to 1.5 percent; 60 percent of this is lactalbumin and 40 percent car.ein 3.5 percent; 15 percent of this is lactalbumin and 85 percent casein Carbohydrate (in form of lactose) 6.5 to 7.5 percent 4.5 to 5.0 percent Fat(s) Variable, but both have approximately 3.5 percent. (Differs qualitatively) Contains more olein, which is Contains more volatile fatty is readily adsorbed acids, which are irritating to the gastric mucosa Digestion of fat easy Digestion of fat sometimes difficult Minerals 0.15 to 0.25 percent Vitamins 0.7 to 0.75 percent. Contains more of all minerals with the exception of iron and copper Iron content is low in both milks, approximately: 1.5 mg/1 0.5 mg/1 Varies with maternal intake (continued) �Table 1 (cont'd.) Parameter Vitamin A Vitamin B Vitamin C Thiamine Riboflavin Vitamin D Vitamin E Digestion Human Milk Cow's Milk Relative large amounts in both milks Probably adequate in both milks More is found in human milk Higher content in cow's milk Higher content in cow's milk Relatively small amount in both milks Satisfactory level in breath milk Cow's milk has a higher buffer content and can therefore adsorb much more gastric acid than breast milk before it reaches the acidity necessary for digestion. The large amount of casein on cow's milk make large, tough curds in the stomach as compared with the fine, easily broken down curds of breast milk �The purpose of this study was to measure levels of environmental pollutants in human milk by gas chromatography/mass spectrometry (GC./HS) and to evaluate the utility of using this body fluid in specific pollutant studies for populations in the vicinity of chemical manufacturing plants and/or industrial user facilities. All routes of exposure, i.-e., air, water, particulate, clothing and food were of interest. Mother's milk samples were acquired and analyzed for selected industrial chemicals. The chemicals of interest included: polychlorinated naphthalenes (PCNs), tetrachloroethylene, trichloroethane, dichloropropanes, benzene, polybrominated biphenyls (PEBs), chlorinated phenols, toluene, chlorinated benzenes, and chloroform. Where possible, any other chemicals found in the extracts were identified and quantitated. The levels of selected organic compounds in mother's milk were investigated to assess the possibility of using this medium as an indicator of body burden for a wide range of organic compounds. For this feasibility study, no attempts were made to develop a statistically valid sample; sites were selected as having a high probability of pollutant detection and subjects were selected on a volunteer basis. LITERATURE REVIEW A review of the literature concerning pollutants in mother's milk was conducted. A computer search of MEDLARS II and ORBIT—III yielded 108 citations. These citations, plus personal contacts and manual searches yielded the data discussed below. By far, most of the literature on environmental pollutants in mother's milk deals with chlorinated insecticides (e.£. DDT). PCBs have also been studied. Only a few references discuss the presence of other compounds in milk. Table 2 lists the levels of pollutants found in mother's milk in the United States. Table 3 summarizes these findings. Table 4 summarizes pollutants found in mother's milk outside the United States. With the exception of one reference (27) regarding 1,2-dichloroethane exposure, all of the compounds found in mother's milk are semivolatile (extractable) halogenated compounds. �Table 2. LEVELS OF ORGANIC COMPOUNDS FOUND IN HUMAN MILK IN THE UNITED STATES Compound Sample Matrix B-BHC Milk Milk Y-BHC Milk Fat Total BUG Milk Milk Milk £,p_' -DDD Milk Milk Fat Milk o,p_'-DDE Milk £,p_* -DDE Milk Milk Milk Milk Milk Fat Milk DDE Milk Milk Milk Milk Milk Mean (ppb) Range (ppb) Number of Determinations Locations References T-10 T-28 57 40 AR, MS CO 2 3 30-270 53 PA 4 6.5 7.7 6.2 <0.1-20.2 n.d.-37.0 3.6-9.0 14t 28 7 US TX Houston, TX 5 6 6 4.7 <0.1-14 n.d.-30 T-5 14t 53 40 US PA CO 5 4 3 <0.1-2.8 14t US 5 10-1720 5.2-981 13.4-236 16.7-138 790-4350 79-386 57 14t 28 7 53 40 AS, MS US TX Houston, TX PA CO 2 5 5 6 4 3 30* 4 5 1** AZ Chicago, IL Wenatche, WA Phoenix, AZ US 7 8 8 8 8 0.5 83 10.8 1.0 227 29 84.1 92.4 1766 194 60 30 30 100 74-314 20-90 <10-140 _** 70-120 (continued) �Table 2 (cont'd.) Compound o,£' -DDT Sample Matrix Milk Milk Milk Milk Mean (ppb) Range (ppb) 92 25 10 10-840 <0.1-10.8 5-36 T-13 Number of Determinations Locations References 57 AR, MS 14 1 30* 40 US AZ CO 2 5 7 3 £,£'-DDT Milk Milk Milk Fat Milk 29 114 513 7.8-89 9-383 90-2120 7-109 14t 30* 53 40 US AZ PA CO 5 7 4 3 DDT (unspecified) Milk Milk Milk Milk Milk Milk 100 60 60 70 80-130 < 10-220 50-90 10-110 n.d.-770 4 5 1 ** 40 32 Chicago, IL Wenatche, WA Phoenix, AZ US CO DC 8 8 8 8 3 9 Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk 334 20-2760 40.4-156 SD=100 SD=130 SD=100 SD=170 SD=150 SD=80 SD=120 59-1899 15-133 185-721 n.d.-770 57 14 14 20 19 27 34 6 18 38 14 7 32 AR, MS 2 Total DDT Equiv. 130 70.5 100 170 180 220 170 150 180 447 75 323 130 _** US Long Island, NY Rochester, NY Chicago, IL Lexington, KY Nashville, TN Memphis, TN Los Angeles, CA MS, AK Nashville, TN MS, AK Washington, DC (continued) 10 10 10 10 10 10 11 11 11 11 9 �Table 2 (cont'd.) Compound Sample Matrix Mean (ppb) Range (ppb) Number of Determinations 0.4 6.2 3.3 7.5 T-50 2.9-14.6 n.d,-21 1.9-21 T-ll 57 14t 28 7 40 AR, MS US TX Houston, TX CO 2 5 5 5 3 T-30 <0.1-4.4 40-460 T-5 57 14t 53 40 AR, MS US PA CO 2 5 4 3 Locations References Dieldrin Milk Milk Milk Milk Milk Heptachlor Epoxide Milk Milk Milk Fat Milk t-Nonachlor Milk 1 T-10 57 AR, MS 2 Oxychlordane Milk 5 T-20 57 AR, MS 2 PCBs Milk Milk Milk T MO T <40-100 40-100 57 39 40 AR, MS CO CO 2 12 3 Nicotine NOTES: 4 1.7 160 n.d.-195 6 Breast CA 13 Fluid BUG = benzenehexachloride (hexachlorocyclohexane) ODD a 2,2-bis(chlorophenyl)-l,l-dichloroethane DDE = l,l-dichloro-2,2-bis(chlorophenyl)ethylene DDT = l,l,l-trichloro-2,2-bis(chlorophenyl)ethane Total DDT equiv. = sum of all DDT-related peaks calculated as if all were DDT PCBs = polychlorinated biphenyls. Quantitation generally based on comparison to an Aroclor mixture T = trace n.d. = not detected SD = standard deviation t = 5 women. Separate determinations make total of 14 samples. * = 6 women. Separate samples makes total of 30 samples. ** = unspecified pool of donors in Denver and other US areas, no range given. Missing values indicate no data in original article �Table 2 (cont'd.) NOTES (cont'd.): Mean values were taken from original citation where available; otherwise arithmetic mean was calculated, counting "ND" values as zero and "T" values as 0.5 times the lowest reported value. oe �Table 3. RANKING OF PESTICIDES AND PCBs BY REPORTED CONCENTRATIONS IN HUMAN MILKa Weighted Mean Concentration (ppb) Number of Samples DDEC 99 103 DDTC 94 100 PCBsC <10 96 Oxychlordane 5 57 Dieldrin 4 92 DDDC 4 54 Hepta'chlor epoxide 4 71 BHCC 3 106 t-Nonachlor 1 57 Compound milk only. Mean value calculated from a weighted mean of values in Table 2. Where either the mean or number of samples analyzed were unavailable, the data were excluded from calculation. C A11 isomers summed. �Table 4. LEVELS OF ORGANIC COMPOUNDS FOUND IN HUMAN MILK OUTSIDE THE UNITED STATES Compound Suple Matrix a- me HI Ik t-rnc H1U Milk Hi Ik HI Ik Hi Ik Milk Y-MC HI Ik Milk Milk Fit Milk Fat HI Ik Milk Mrnn (ppb) Range <PPI>) 0.58 0.1-1.9 Number of Positive! Location Date Reference 50 17 Norwujr 1975 14 4.69 70 200 2 BO 4 2 1.2-17.8 NO -900 80-910 10-850 1-16 ND-21 50 96 22 9 SO 100 49 64 19 7 42 91 Norway Gemanjr Vienna Kuril Austria Leiden (Neth.) Canada 1975 1971 1973 1973 1969 1975 14 IS 16 16 17 13 10.91 1.0-35.8 NO 26-114 40- 100 17 0 19 7 <l-35 50 96 22 9 29 147 Norway Cenany Vienna Rural Austria Israel Canada 1975 1971 1973 1973 1975 1967-8 14 15 16 16 18 19 0.3-3.2 SO 34 Norway 197S 14 1.7-45.5 7-33 50 19 SO 19 Norway En f land 1975 1964 14 20 21 48 63 10.1 1 I-8HC Milk 1.14 Total MIC HI Ik Milk 9.4 13 Milk 9.9 £.£'-DDD Nurt.fr of Determinations 29 ODD Hi Ik 3-14 67 O.g'-DDB Milk Milk IS. 02 9.5 1.6-43.8 50 29 30 £.,>'-Doe Milk HI Ik Milk Milk HI Ik HI Ik Milk Milk Milk Milk 65.10 0.9-113.2 6-699 ND-600 SO 168 96 29 147 SO 6 9 100 19 SO 167 95 7 90 21.7 97 30 35 19 35 73 6-770 17-68 9-40 . •-I44 40-100 18 Israel 12 SO 6 100 19 Australia 1970 Norway Israel 197S 1975 14 18 Norway Portugal Ccnany Israel Canada Leiden (Neth.) N«w Irunswlck Nova Scotia Canada Enfland 1975 1972 1971 1975 1967-8 1969 2973 3973 !97S 1964 14 22 (continued) IS 18 19 17 23 23 24 20 �Table 4 (cont'd.) Compound DDE o.p_'-DDT E.P/-DDT DOT Sample Matrix HI Ik Milk Fat Milk Fat Milk Mean (PRb) IOS 3180 1920 61 HI Ik Milk Milk Milk 1S.S2 7.1 Milk Milk Milk Milk HI Ik Milk Milk Milk Hllk Milk 17.89 Milk Hllk Fat Milk Fat Milk s 3 90 7.1 12 16 13 6 6 45 36 1060 1760 10 Range <H>b) Nunber of Positives Location 67 22 9 26 67 22 9 26 Australia Vienna Rural Austria M. Australia 1970 1971 1971 1970-1 21 16 16 25 50 21 147 100 49 Honey Israel Canada Canada 1975 1975 1967-8 1975 14 16 19 24 SO 167 95 6-10 «2-ll t-21m 20-75 50 16S 96 29 147 50 6 9 100 19 Norway Portugal Gentanjr Israel Canada Leiden (N«th.) Hex Brunswick Nova Scotia Canada England 1975 1972 1971 1975 1967-8 1969 1971 1971 1975 1964 14 22 IS 18 19 17 21 21 24 20 7-160 100-2680 1030-2530 2-25 67 22 9 26 67 21 9 26 Australia 1970 1971 1971 1970-1 21 16 16 25 12-450 1930-7950 3420-5970 15-112 1.6-120.9 <1-31 ND-4B 2.1-118.1 1-145 10-250 1-144 Nudier of Detenlnationa 12 SO 6 9 100 19 Date Vienna Rural Austria M. Australia (continued) Reference �Table 4 (cont'd.) Compound Sample Matrix Mean (PPb) Milk Milk Milk Fit Milk Fat Milk F«t Milk Milk Milk Milk Milk Milk 81.74 106 1390 3480 34 BO 320 Milk Milk Milk Fit Milk Fit Milk Fat Milk Milk Milk Milk Milk Milk Milk Z.75 40 40 90 90 6 7.0 5 Aldrin Milk 21. « Heptachlor Epoxid* Milk Milk Milk Milk Milk Range (.b |p) Totil DOT Equlv. Dieldrln 141 139 71 378 12R s I 2 6 1.57 9.1 3 1.2 1 NintfMT of Determinations Nimbrr of Positives S. 2-349.0 < 10-780 220-2580 330-18800 110-11400 30-870 15-580 10-1020 19-137 3-5868 7S-170 50 160 19 34 48 96 67 147 26 290 19 0.3-3.6 5-31 <10-BO <10-170 < 10- 250 1-29 SO 168 19 34 48 67 29 147 26 50 100 19 29 50 1 50 29 147 SO 100 18 1-60 3-11 0.1-10.7 ND-6 1-13 0.6-2.6 <l-23 0.3-3.5 ND-3 50 167 19 34 48 96 67 26 290 19 6 IS 26 40 84 19 SO 69 Location Date Reference Norway Portugal Ontario Ontario Ontario Germany Australia Canada W. Australia Guatemala England 19 75 1972 1973-4 1971-2 1969-70 1971 1970 1967-8 1970-1 1973-4 1964 14 22 26 26 26 15 21 19 25 27 24 Norway Portugal Ontario Ontario Ontario Australia. Israel Canada W. Australia Leiden (Heth.) Canada England 1975 1972 1973-4 1971-2 1969-70 1970 1975 1967-8 1970-1 1969 1975 1969 14 14 26 26 25 21 18 19 25 17 24 20 Norway 1975 14 Norway Israel Canada Leiden (Heth.) Canada 1975 1975 1967-1 1969 1975 14 IS 19 17 24 (continued) �Table 4 (cont'd.) Coepound HCB KB Suple MatrU Milk HI Ik Fit Milk Fat Ml Ik Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Milk Mem (ppb) 9.1 100 1240 1670 25 2 Fit Fat Fat 1200 1200 1000 Fit Fit IS40 1290 Ring* (I) P* 1.T-60.S ND-2SO 260-4160 2140-5110 12-14 NO- 21 100-2500 200-1000 700-12000 90 22 ia 12 S80-3780 9SO-1S70 1S-JO 12-12 ND-68 HiMber of Determinations Number of Positives location Date Reference Honey Ontario Vienna Rural Austria M. Australia Canada 197S 1971-4 1973 1971 1970-1 197S 14 26 16 16 2S 24 19 34 41 64 22 9 6 9 100 Ontario Ontario Ontario Germany Vienna New Brunswick Nova Scotia Canada 1971-4 1971-2 1969-70 1971 1971 197] 1971 1971 I97S 26 26 26 IS 16 16 21 21 24 SO 19 22 9 26 100 SO 19 14 48 96 22 9 6 9 100 22 9 26 81 Oxychlordane Milk 1 KD-2 100 77 Canada 197S 24 truisNonachlor Milk 1 NO-2 100 77 Canada 197S 24 1.2-DichloroethiM Milk 60 00 1 t 2B NOTES: BUG = ODD DDE = DDT = Total PCB = benzenehexachloride (hexachlorocyclohexane) 2,2-bis(chlorophenyl)-l,l-dichloroethane l,l-dichloro-2,2-bis(chlorophenyl)ethylene l,l,l-trichloro-2,2-bis(chlorophenyl)ethane DDT equiv. = sum of all DDT-related peaks calculated as if all were DDT. polychlorinated biphenyls. Quantitation generally based on comparison to an Aroclor mixture. HCB - hexachlorobenzene ND = not detected. Mean values were taken from original citation where available; otherwise arithmetic mean was calculated, counting "ND" values as zero and "T" values as 0.5 times the lowest reported value. Missing values indicate no data in original article. Lowest value not reported. �The literature shows that mother's milk often contains seraivolatile chlorinated organic pollutants (pesticides). Presumably due to lack of analytical techniques and/or sensitivity, the presence of other pollutants has apparently not been investigated. 14 �SECTION 2 SUMMARY AND CONCLUSIONS The results show that sampling and analysis for organic compounds in mother's milk is feasible. The sample collection technique presented no significant problems. Analysis of the samples was generally satisfactory. The use of purge and trap with gas chromatography/mass spectrometry/computer (GC/MS/COMP) analysis for volatile organics was successful, although the intrusion of contaminants during analysis presented problems with some compounds. The wide range of volatile compounds found includes common air and water pollutants and possible metabolites. Thus, it may be possible to use mother's milk as an indicator of body burden if a correlation between exposure and mother's milk concentration is established. The extraction and GC/MS analysis for semivolatile organics was only marginally successful due to limited sensitivity (about 20-100 ppb milk). PCBs and ODE were the only halogenated semivolatiles found. The target semivolatile compounds (PCNs, PBBs, chlorinated phenols, and the higher chlorinated benzenes) were not present in quantities detectable by the survey techniques. The use of more sensitive (generally a factor of 100-1000) and selective methods [GC/electron capture detection (BCD), GC/negative ion chemical ionization mass spectrometry (NICIMS) or GC/single ion monitoring MS] may detect these compounds, but was outside the scope of this project. 15 �SECTION 3 RECOMMENDATIONS Further studies of the applicability of mother's milk as a matrix for assessing the human body burden of pollutants must directly compare human milk with the other available sample matrices. For example, comparison of the volatiles in breath, blood, urine, and mother's milk would determine which matrices are most suitable for measuring these compounds. It may also be advisable to use animal studies to determine the extent of environmental exposure-body burden correlation. In addition, the effects of transport of pollutants to a newborn infant should be studied. Infants may be uniquely affected by some pollutants due to their small body weight and different metabolism relative to adults. The measurement of semivolatile organics in mother's milk requires more sensitive techniques than those used in this study. For example, chlorinated compounds could best be detected using GC/ECD or GC/negative ion chemical ionization mass spectrometry and polynuclear aromatics by GC/photoionization detection. Improvement in analytical methodology could occur at several points: (1) As discussed above, more sensitive, analytical procedures could be used for specific compound classes. (2) For volatile organics, background levels could be reduced with an on-line purge and trap/GC system. Potential improvements in survey and sampling methodology include: (1) Addition of questions regarding length of nursing, age of infant, time since last nursing, etc. (2) Selection of participants according to a more statistically valid method (e.g. statistically random sampling). (3) Closer control over physical collection methodologies (e.g. all respondents gathered at one location). 16 �The 5-month time lag in the study awaiting OMB clearance was seriously detrimental to the project. The personnel and apparatus used for the validation studies had to be reassembled once OMB clearance was obtained. Restartf ing a project following a long dormant period requires retraining analytical personnel (or training new personnel if original personnel have been reassigned to other research projects), recalibration of instruments, and assembling the necessary laboratory apparatus and supplies, all of which consume government resources. Reducing this time lag is extremely important for execution of programs involving human testing. 17 �SECTION 4 SELECTION OF SAMPLING SITES Five urban areas were chosen as sampling sites. Each of these cities is a high-probability area for the presence of one or more of the chemicals of interest in mother's milk. Since many of the compounds of interest are probably specific to certain industrial sites, the samples from the other sites were intended to serve as controls for the site-specific compounds. Other compounds are considered ubiquitous and their levels in milk was probably not related to local industrial activity. The rationale for selecting the five sampling sites is discussed below. BRIDGEVILLE, PENNSYLVANIA PCNs are manufactured by Koppers Company, Inc., of Pittsburgh, PA, at the Koppers Chemical and Coatings plant in Bridgeville, about 10 km SW of Pittsburgh. (29) Reported production levels were 7 million Ib in 1956 and 5 million Ib in 1972, (29) indicating a potential long-term, relatively constant, exposure level in the surrounding area. Results from environmental monitoring in the area immediately (< 1 km) surrounding the plant indicated higher levels of PCNs in air and soil than those found near five PCN user sites, as f f\f\ O / *\ shown in Table 5. Furthermore, fish and apple samples from the same area were found to contain PCNs, indicating a potential link to the human food chain. In addition to PCNs, plants in the Bridgeville area have been reported to emit large quantities of phthalic anhydride particulate. (^5) At this plant site, Koppers is reported to manufacture chlorinated naphthalenes, phthalic anhydride, maleic anhydride, and alkyd resins. 18 �Table 5. SUMMARY OF PCN CONCENTRATIONS FOUND NEAR MANUFACTURING AND USE SITES Air, ng/m Water, pg/L Capacitor manufacturing A Low High Mean Upstream 1 25 450 150 0.2 120 2900 1400 a 1 NDb 7.3 3.1 2 PCN manufacturer (Koppers) Sampling Period 2 Site ND 3.9 1.2 1 9.8 31 19 2 Capacitor manufacturing B 9.8 33 17 o water samples collected for period 2. Not detected. Downstream Soil, ng/kg Low High Mean 1.4 130 940 ND ND ND ND 0.6 ND 2300 7.3 470 2.0 100 �NORTHERN NEW JERSEY - STATEN ISLAND, NEW YORK, AREA (NNJ) The Northern New Jersey (NNJ) area was selected as a sampling site on two bases: production of PBBs and general chemical industrial activity. Three facilities are of interest^ ' with respect to PBBs: White Chemical Co., E 22nd St., Bayonne, NJ; Marcor, Inc., Standard T. Chemical Co., subsidiary, 2500 Richmond Terrace, Staten Island, NY; and Hexcel Corp., Fine Organics Division, 880 Main St., Sayreville, NJ. White produced 45,000 kg of FBBs (specifically octabromobiphenyl and decabromobiphenyl) between 1970 /oo^ f39} and 1973. Hexcel is reported to have produced unspecified amounts of decabromobiphenyl [as well as to have produced or used decabromobiphenyl oxide, ethylene dichloride, and l,2-bis(2,A,6-tribromophenoxy)ethane]. Standard T is thought to have been a PBB user up to about 1974. (39) Results of environmental sampling in the area surrounding these three companies (40 '41) indicated the presence of PBBs, especially the more highly brominated homologs, in sediment, water, soil, human hair, fish, turtle, and plant matter. The findings in human hair oil (18 total samples), which ranged from undetectable to 310 ppm, are especially relevant to this study, since they indicate that the PBB manufacturing in this area and the resultant environmental contamination has resulted in human exposure. Northern New Jersey has a high concentration of chemical industries, (42) many of which use or produce halogenated hydrocarbons. The list of industries and locations are summarized below. Coastal Industries, Inc. (swimming pool chemicals), Diamond Shamrock (textile processing chemicals), Scientific Chemical Processing (chemical waste disposal) and Tenneco Chemicals (synthetic foam rubbers) are located in Carlstadt. Crompton & Knowles Corp. (dyes, colors and chemicals) are located in Fairlawn. Fisher Scientific (chemicals), Conoco Chemicals are in Saddle Brook. In Bayonne are CIBA-Geigy (dyes and intermediates) and ICI America (organics). In Jersey City are Mallinkrodt (analytical reagents) and Onya Chemical Co. (textile finish compounds, water repellants, germicides, and detergents). In Kearney are Standard Chlorine Chemical Co. (chlorobenzenes), Theobald Industries (bleaches), PPG Industries (paint) and Monsanto (industrial chemicals). In South Kearney is BASFWyandotte (dyestuffs and vinylidine chloride). In Newark are American Oil and Supply Co. (surfactants and chemicals), Celanese Plastics (plastics), 20 �DuPont (pigments), Inmoat (paint), Haas & Waldstein (paint), Otto B. May (dyes, surfactants), 3M (chemicals), Benjamin Moore (paint), Sherwin-Williams (paint) and Vulcan Materials (chlorome thanes ) In Elizabeth are Perk (chlori. nated solvents) and Speciality Chemicals Division of Allied Chemical Corp. Linden Chlorine Products (chlorine) is in Linden. In Rahway are M & T Chemicals (speciality chemicals) and Merck and Co. (industrial chemicals). In Edison are Gary Page Chemicals (PVC compounds) and Mobile Chemical (paint). In Parlin, Hercules manufactures chloroform. In Passaic are Pantasote Co. of New York (PVC resin film), Stauffer (vinyl sheet and film) and United Wool Piece Dyeing and Finishing (dyes). In Patterson are several dye manufacturers. In Wayne are American Cyanamid (chemicals) and Owens Illinois (plastics). Many of these and other firms in NNJ undoubtedly manufacture or use compounds which are of interest to this study. The levels of general organic pollutants in NNJ have been found to be high due to intense chemical manufacturing in the area. Environmental monitoring by RTI under separate contracts, " has found a wide variety of organic pollutants in this area. In addition, preliminary results from ground and surface water samples indicate measurable levels of a number of 45) volatile halogenated hydrocarbons. ' These data, summarized in Table 6, are indicative of environmental levels of organics in the NNJ area to which humans may be exposed and thus are indicative of the types of compounds (45) anticipated in mother's milk. Under a separate research project, the daily intake of some selected organics was roughly estimated. These estimates are given in Tables 7 and 8. Clearly there is ample exposure to pollutants which could potentially partition into milk. The statistics for cancer in two counties of NNJ are very high. ' The overall rate for all malignant neoplasms is significantly above the national average. This cancer incidence in New Jersey has been partially linked to the chemical and allied industries located there. Northern New Jersey is a metropolitan area with a relatively static population, a well-established chemical industry, known environmental levels of organics (including PBBs) and abnormally high cancer rates. These factors make this area especially suited to this study of organics in mother's milk. 21 �Table 6. PREVALGNT HALOGENATED COMPOUNDS IN AMBIENT AIR AND WATER OF RAIIWAY/WOODBRIDGE, BOUNDBROOK AND PASSAIC, Nj( 4 <0 Occurrence Medium Ubiquitous Air ro K> tetrachloroethylene trichloroethylene 1,1,1-trichloroethane 1,2-dichloroethane chloroform carbon tetrachloride p_,m,p_-dichlorobenzenes chlorobenzene Water dichlorobenzene trichloroethane chloroform trichloroethylene dichloroethane bromodichloroethane bromodichloromethane tetrachloroethylene d ibromoch1orome thane Mean Concentration 210,000 125,000 62,000 96,000 47,000 29,000 11,000 2,700 209 42 14 7 5 5 3.7 3.6 3.3 aConcentrations for air expressed in ng/m 3 and for Area Specific Mean Concentration a 1,1,2-trichloroethane vinyl chloride 1,2-dichJoroethylene 1,1,2,2-tetrachloroethane 9,000 1,200 1,000 750 chloronitrobenzene methyl trichlorophenoxy acetate methyl dichlorophenoxy acetate bromopropyIben zene bromobenzene tetrachloroethane dichloroethylene water in pg/L. 10.7 5 3.5 3 3 2.5 1.8 �Table 7. ESTIMATED DAILY INTAKE OF SELECTED VOLATILE COMPOUNDS AND EXPECTED CONCENTRATIONS IN BLOOD IN NORTHERN NEW JERSEY(45) Foodc (ng/day) Total (ng/day) Potential Blood Concentration^ (ppb) 3,600 4,150 2,108,000 88 1,250,000 7,000 18,660 1,276,000 53 1,1, 1- trichloroethane 620,000 42,000 5,290 667,000 28 1 , 2-dichloroethane 9000 6,0 5,000 965,000 40 chloroform 470,000 14,500 14,280 499,000 21 carbon tetrachloride 290,000 1,000 12,070 303,000 13 dichlorobenzene 110,000 2900 0,0 319,000 13 chlorobenzene 27,000 1,000 28,000 1.2 vinyl chloride 12,000 12.000 0.5 3,700 0.2 7,800 0.2 6,188,200 258.2 Aira (ng/day) Waterb (ng/day) tetrachloroethylene 2,100,000 tri chloroethy 1 ene Toxic Chemical 10 u> bromodichloromethane benzene total 3,700 7,500C 300f From Ref. 44, calculated on basis of 1 , 0 L/24 h respiration rate, 000 'prom Ref. 44, calculated on basis of 1 L/24 h intake. : From Ref. 47, calculated from FDA standard diet (Ref. 4 ) 8. d,. Expected blood concentration is total daily intake divided by blood volume ( . 0 mL) assuming 4 800 half-lives/day. 'From Ref. 49, 50. From Ref. 50. �Table 8. TOTAL DAILY INTAKE OF TARGET COMPOUNDS, PESTICIDES, PCBs, BaP AND METALS AND CONCENTRATIONS IN BLOOD IN NORTHERN NEW JERSEY(45> Air Toxic Chemicals a -BUG lindane heptachlor (ng/day) 10 60 30 heptachlor epoxide chlordane 0 0 7 Total (ng/day) 1,100 1,110 62 646 92 640 647 20 20 DHR to Food (ng/day) 586 Water (ng/day) Expected Blood Concentration (ppb) 0.14 0.08 0.01 0.08 *Q 3,500 DDT/ ODD 70 lO 0.44 2,500 2,570 0.32 73 50 0 3,500 123 0.02 •x.200 <60 388 648 0.08 440 <67 8,849 9,356 1.16 2 7,800 7,823 1.0 arsenic 21 2,800 < 1,000 31,300 34,100 cadmium 50 <1,000 32,000 33,000 4.4 a 7,500 3,200 105,000 115,700 PCBs Total Halogenated Compounds benzo(a)pyrene lead Ref. 56. 'Ref. 57. <io 100-500b �Table 8 (cont'd.) Sources: Pesticides and PCBs in air — Ref. Pesticides in water -- Ref. Pesticides and PCBs in food -- Ref. PCBs in water — Ref. BaP in air -- Ref. 10 51 44 48 51 52 (US) (NJ) (US) (US) (US) - Ref. 53 (World) •- Rough estimation (from Ref. S3 [World]) Metals in air -- Ref. 54 (NJ) Metals in water -- Ref. 55 (NJ) Metals in food -- Ref. 48 (N.E. NJ) BaP in water BaP in food �BATON ROUGE, LOUISIANA Baton Rouge was selected on the basis of extensive organic chemical production (especially volatile halogenated hydrocarbons) as summarized in Table 9. (43) In addition, RTI has collected and analyzed ambient air samples from this area and established the presence of a number of compounds of interest in ambient air. (43) A summary of the levels of halogenated compounds found in water and air is presented in Table 10. In addition to the industrial production in Baton Rouge, industries in Flaquemine (15 km SSW), St. Gabriel (20 km SSE) and Geismar (27 km SSE) may emit significant levels of chemicals which may contribute to the levels observed in mother's milk in Baton Rouge. These industries and their production are listed in Table ll.(36) KANAWHA VALLEY, WEST VIRGINIA Many manufacturers of organic chemicals are located in the Kanawha Valley, WV. DuPont, near Belle, W, has a large chemical complex for the synthesis of substances such as methylmethacrylate, methylamines, ammonia, hydrogen cyanide, herbicides, and insecticides. In South Charleston are production and consumption plants (Union Carbide, and FMC). Plastics, PVC, antifreeze, chlorine, halogenated organics, carbon disulfide, peroxides, etc., are the predominant chemicals produced here. The major industrial facility in the town of Institute is Union Carbide, which also processes a broad spectrum of compounds, e.g., viscose rayon and phthalate esters. There is also a large-scale olefin processing complex and a rubber accelerator plant. A major terminal loading facility in South Charleston bandies large quantities of a variety of organic compounds. Monsanto, FMC, Allied, and Fike have plants near Nitro for the production of antioxidants, rubber accelerators, industrial chemicals, and other materials. Several other chemical manufacturers, consumers, and transporters are located in the Kanawha Valley, some or all of which may contribute to the presence of organic materials in the ambient air or water and thus contribute to human exposure. Previous RTI sampling^3>46'65>66) in the Kanawha Valley found a broad range of halogenated, ketone, aldehyde, ester, aromatic, and aliphatic 3 compounds. Quantitative results included high values in air of 11,000 ng/m 26 �Table 9. POTENTIAL EMISSIONS FROM CHEMICAL INDUSTRY IN BATON ROUGE, LAa(43) Chemical chlorodifluoromethane (101) dichlorodifluoromethane (12) dichlorotetrafluoroethane (114) ethylene dichloride polyethylene resin trichlorofluoromethane (11) 1,1,2-trichloro-l,2,2-trifluoroethane (113) vinyl chloride ethyl chloride methyl chloride perchloroethylene tetraethyl lead 1,1,1-trichloroethane trichloroethylene PVC benzene butadiene n-butyl alcohol Total Production (nimlb/yr) NA 1100 460 Raw Material Company chloroform carbon tetrachloride perchloroe thy1ene ethylene ethylene Acer ACC ACC ACC, EC ACC ACC NA perchloroethylene ACC 480 ethylene dichloride ethylene methanol ethylene dichloride ethyl chloride 1,1-dichloroethane ethylene ACC, EC 210 75 100 312 40 32 144 440 428 EC EC EC EC EC EC EC petroleum ethane, etc. EXCC EXCC, CRCC EXCC NA (continued) �Table 9 (cont'd.) Chemical Total Production (mmlb/yr) Raw Material Company EXCC EXCC decanol diisodecylphthalate NA nonene NA phthalic anhydride, isodecanol dodccene ethylene isobutylene isodecanol p isooctyl alcohol isoprene isopropanol neopentanoic acid nonene phthalic anhydride propylene resin toluene ethylbenzene styrene vinyl toluene 100 propane/propylene EXCC 700 ethane, etc. EXCC NA petroleum nonene neptene ethylene by-product propylene isobutylene propane/propylene £-xylene ethylene petroleum benzene ethylbenzene toluene, ethylene EXCC £ to 00 NA NA 10 680 5.5 300 90 320 378 900 800 NA EXCC EXCC EXCC EXCC EXCC EXCC EXCC EXCC EXCC, FGC FGC FGC FGC Data provided by the Louisiana State Air Board. ACC = Allied Chemical Corp., EC = Ethyl Corp., EXCC = Exxon Chem. Corp., FGC = Foster-Grant Co. Inc. C Involves production of other alcohols also, C,, C0, C , C ln , C._, C.,. u NA = not available. o y iu j.o it) �Table 10. PREVALENT HALOGENATED COMPOUNDS OCCURRING IN AMBIENT AIR AND WATER OF BATON ROUGE, GEISMAR AND PLAQUEMINE, Occurrence Medium Air ro vo Water Ubiquitous chloroform 1,2-dichloroethane carbon tetrachloride 1,1,1-trichloroethane trichloroethylene tetrachloroethylene 1,1-dichloroethane trichloroethylene chloroform trichloroethane dichloroethane carbon tetrachloride dichlorobenzene ch1orod ibromomethane tetrachloroethylene Mean Concentration' 5,500 1,656 Sll 605 142 118 86 96 20 11 7.7 7.1 4.2 3.5 1.9 Area Specific 1,1,2-trichloroethane 1,2-dichloroethylene dichlorobutane 1,2-dichloropropane vinylidene chloride 1,1,2,2-tetrachloroethane bromobenzene 1,2-dichloroethylene hexachloroethane aConcentrations for air expressed in ng/m 3 and for water in pg/L. Mean Concentrationa 632 472 409 306 78 70 13 4 1.6 �Table 11. POTENTIAL EMISSIONS FROM CHEMICAL INDUSTRY IN PLAQUEMINE, GEISMAR, AND ST. GABRIEL, LA(36) City Annual Capacity (million pounds) Chemical Company Plaquemine chloroform 1 , 2-dichloropropane ethylene dichloride methyl chloride methylene chloride tetrachloroethylene vinyl chloride b 10 1325 150 190 150 450 Dow it it ii M ii ii Geismar chloroform ethylene dichloride methylene chloride tetrachloroethylene 1,1,1-trichloroethane phosgene phosgene vinyl chloride vinyl chloride 46 330 VCM 80 150 65 55 125 300 300 BASF RCC BOR MCJ phosgene NA SCC St. Gabriel Dow « Dow Chem. USA VMC ~ Vulcan Materials Co. BASF = BASF Wyandotte Corp. RCC «= Rubicon Chems., Inc. BOR « Borden, Inc. MCI « Monochem, Inc. SCC « Stauffer Chem Co., Agric. Chem. Div. 200 million pounds combined capacity in Plaquemine and Freeport, TX plants. 30 �for methylene chloride, 1500 ng/m 3 for tetrachloroethylene, and 72,000 ng/m 3 for benzene. Compounds identified in the air particulate fraction included .long-chain alkanes, polycyclic aromatic hydrocarbons (PAH) from naphthalene through anthanthrene (or an isomer), alkyl-PAH derivatives, and nitrogen-containing heterocycles. 31 �SECTION 5 SAMPLE COLLECTION At each of the five sites, arrangements were made to work through clinical facilities to recruit a suitable panel of respondents. These facilities included the Bayonne Hospital in Bayonne, NJ; the Medical Center Hospital in Jersey City, NJ; Magee-Women's Hospital in Pittsburgh, PA; Charleston Area Medical Center in Charleston, WV; and the East Baton Rouge Parish Health Clinic in Baton Rouge, LA. Advance arrangements were made through a contact person at each facility. This person was responsible for recruiting a professional member of the facility's staff to serve as the data collector. The data collector was usually & registered, licensed practical, or public health nurse associated with the facility. Respondents were paid $5 for their assistance in providing a milk sample and completing the survey questionnaire. The data collection effort is discussed in the following sections. OMB CLEARANCE Under the Federal Reports Act, clearance for the study of human subjects must be obtained from the Office of Management and Budget. This clearance was obtained on October 18, 1978. The OMB number is 158-578010. This study was approved with the understanding that: (1) the surveys were conducted as a pretest of the feasibility of information collection procedures; (2) the information collected will not be used to generalize to either local areas or the nation as a whole. These two caveats were invoked since the sample size was small and a nonprobability sampling method (subject selection) was used. 32 �TRAINING Before data collection began at a site, a training session was held to acquaint the facility contact person and data collector(s) with the survey. The session addressed the study objectives; use of the data collection instruments; administrative instructions; quality control procedures; and instructions for collecting, packing, and shipping milk samples to RTI. The training was conducted by an RTI survey specialist from the Survey Operations Center. A detailed manual and necessary field reporting forms were developed for use in these sessions. All training was conducted at the participating facility and lasted approximately 4 hours. SURVEY INSTRUMENTS Three data collection instruments (see Appendix A) were developed for use by the data collectors. The Participant Consent Form (FCF) was used to introduce the study, explain the study objectives and requirements of participation, present the confidentiality procedures, and obtain consent of participant. This form was signed by the respondent, who retained a copy for her files. The original was attached to the data collection instrument and a second copy was filed in the respondent's hospital record. The Participant Listing Form (PLF) provided a means of assigning unique numbers to participants at each performance site. The data collector completed this form as each participant was solicited; the form was returned to RTI with the completed questionnaires when work at the site was finished. The Study Questionnaire (SQ) was the primary data collection instrument. Information concerning participant demographic characteristics, residence information, health data, use of medications, and personal characteristics was obtained through this document. The SQ was administered after patients had been screened and prior to collection of the milk sample. PARTICIPANT SCREENING Potential participants (lactating women) were screened by the data collector to determine whether or not they met certain study criteria, which included: 33 �ability and desire to provide a milk sample of approximately 100 ml. permanent residence within the area of interest for at least the preceding 12 months, and no travel outside the area of interest for the seven days preceding sample collection. After potential participants were screened, 10 women who met all the criteria for participation were asked to provide a milk sample and complete the SQ. PLF, PCF, AND SQ COMPLETION PROCEDURES When an eligible person agreed to participate, her name was listed on the PLF anci she was assigned a unique participant number. The data collector then read the information contained on the PCF to the participant while she followed along using a second copy. After answering questions or handling problems, the data collector asked the participant to sign the PCF prior to administration of the SQ. The data collector then completed the SQ by asking the questions directly to the participant. Completion time averaged 15 minutes. An adhesive, computer-generated ID label was affixed to the SQ; a duplicate label was provided to be used for identifying the milk sample bottle. Each participant was a self-respondent unless she was under 18 years of age, in which case the SQ could have been administered in whole or part to the parent or guardian, but in the participant's presence. SAMPLE COLLECTION PROCEDURES After completion of the SQ, the data collector made the necessary arrangements for the participant to provide the milk sample. A collection bottle was taken from the shipping box and the adhesive ID label was affixed to the bottle. The milk was manually expressed directly into the bottle; no breast pumps or other devices were allowed. Immediately after the milk was collected, the bottle was capped and the sample frozen until all ten samples were collected and ready for shipment to RTI. A minimum of 60 ml (half-full bottle) was required for each sample. If insufficient milk was collected, the sample was discarded and an additional subject was added to the study. 34 �SHIPPING PROCEDURES Sample bottles were packed in the shipping container, cooled with dry ice, and sent directly to RTI via Federal Express. 35 �SECTION 6 SAMPLE ANALYSIS METHODS The milk samples were analyzed using gas chromatography/mass spectrometry/cornpute:r. Due to the broad range of volatilities, the samples were partitioned into two general classes of compounds: volatiles (e.g. benzene, chloroform) and semivolatiles (e.g. PCNs, PCBs, pesticides). The analytical protocols developed for the volatile and semivolatile components in mother's milk are reproduced in Appendices B and C, respectively. The experiments conducted which led to these protocols are discussed below. DEVELOPMENT OF ANALYTICAL PROTOCOL FOR VOLATILES The headspace purge technique was validated by determining the recovery of four model compounds from raw cow's milk samples. Compounds labeled with carbon-14 were chosen in order to examine both the amounts recovered on Tenax GC and the amounts remaining in purged samples. Twelve 50 mL cow's milk samples were spiked with methanol solutions of 14 the C-compounds. The analysis for each of the four model compounds was performed in triplicate. In addition, standards were prepared in triplicate by adding the appropriate amount of each compound in solution to a scintillation-counting vial containing 15 mL of Triton X/toluene/Omnifluor scintillation "cocktail." Milk samples were purged as described in Appendix B; Tenax cartridges were stored, and aliquots of the purged samples were retained for oxidation and counting. Tenax cartridges were desorbed at 270°C and 30 mL/min N. for 10 minutes into 15 ml, of Triton X cocktail in tandem scintillation vials. The vials were capped and refrigerated until scintillation counting. An aliquot (1 mL) of each purged milk sample was oxidized in the Packard Tricarb Sample Oxidizer, which converted all carbon-containing compounds to carbon dioxide and water. The 14C-carbon dioxide was collected in a trapping solution and 36 �referenced to a quench correction curve. All standards, Tenax samples and oxidized milk samples were counted on a Packard Liquid Scintillation Counter with automatic standardization. Counting data was analyzed by computer to obtain the number of disintegrations per minute (dpm) for each vial. The percent recovery was calculated for each milk sample as shown below: 1 rocov-rv - dpm in first vial + dpm in second vial * ^ ~ average dpm added to triplicate standards .~ * The second of the tandem scintillation vials contained <2 percent of the radioactivity in every case. The amounts of 14C compounds retained in the purged sample was calculated: v retained = dpm in oxidized, purged sample ,QQ« * average dpm added to triplicate standards * x * The data are tabulated in Table 12. The recoveries for the volatile chloroform and carbon tetrachloride were about 90 percent, as expected. The less-volatile chlorobenzene and bromobenzene exhibited correspondingly poorer recoveries. These compounds are generally considered only marginally purgeable from water, so these results from milk are not surprising. The methodology validation experiment indicated that the proposed method of analyzing human milk for volatile organic compounds was adequate. Sensitivity and detection limits were determined by the capabilities of the GC/MS/COMP system. DEVELOPMENT OF ANALYTICAL PROTOCOL FOR SEMIVOLATILES The extraction and cleanup method was validated using six model compounds (2,4-dichlorophenol, pentachlorobenzene, 1,2,3,4-tetrachloronaphthalene, 4,4'-dibi:omobiphenyl, 2,2',5,5'-tetrabromobiphenyl, and octachloronaphthalene) which were representative of the semivolatile (nonpurgeable) compounds of interest. The compounds were spiked into raw cow's milk at a level of about 1 pg/mL. Raw cow's milk was chosen as the closest readily available analog to mother's milk. The results are presented in Table 13. The overall mean recovery was about 70 percent and the mean of the relative standard deviations was 22 37 �Table 12. METHOD VALIDATION RECOVERY OF SELECTED VOLATILE STANDARDS FROM MILK Compound 14 a C- chloroform 14 C-carbon tetrachloride 14 C- ch lorobenzene 14 C-bromobenzene CO Percent . Recovered Percent. Retained Percent Accounted for 62 88 + 5 6 + 0.3 94 12 76 88 + 6 3+ 3 91 ±3 132 63 + 2 26 + 3 89 +_ 1 156 35 + 3 51 + 13 86 1 10 80,000-94,000 dpm added to each sample. Mean +_ standard deviation of three replicates. •* "Sum of percent recovered and percent retained. 3 00 b.p. ( C °) �Table 13. METHOD VALIDATION RECOVERY OF SEMIVOLATILE COMPOUNDS SPIKED INTO RAW COW'S MILK Compound Concentration in Milk mp ( C bp (°C] °) 1 (ng/mL) Mean Standard Recovery Deviation Relative Standard , Deviation 2,4-Dichlorophenol 45 207 1.12 59 12 20 Pentachlorobenzene 85 277 1.24 76 19 24 1.37 59 15 25 1.04 58 19 33 0.93 94C 10 11 1.08 78C 14 17 1,2,3,4-Tetrachloronaphthalene 4,4'-Dibromobiphenyl ig_ 164 357 2 , 2 ' , 5 , 5 ' -Tetrabromobipheny 1 vo Octachloronaphthalene 198 441 Seven replicates. 'standard deviation divided by mean multiplied by 100. replicates. �percent. These results indicated that refinements in the method should be considered prior to a large-scale study. Two methods were available for removing fat and other nonvolatile components of the milk extract: Florisil column chromatography and gel permeation chromatography (GPC). Evaluation of the two techniques indicated that the Florisil method was more suitable to this project. The Florisil method was faster and had greater sample capacity than the GPC. In addition, the GPC procedure required the use of a pumping system, UV detector, and expensive, fragile GPC columns. Initial tests with both methods revealed interference problems, although those with GPC were more severe. Using GPC, decabromobiphenyl and hexabromobiphenyl eluted with the fat peak. This was judged totally unsatisfactory. Using Florisil, some fat eluted in the fraction with the compounds of interest, but repetition of the procedure yielded samples sufficiently clean for analysis. DEPARTURES :FROM THE ANALYTICAL PROTOCOLS Emulsions The formation of an emulsion during the toluene-acetone extraction of semivolatiles (step 6, Appendix C) was an area of concern. Approximately 80 percent of the time an emulsion occurred. To eliminate this, three approaches were taken with reasonable success. The first was to avoid the emulsion formation by swirling rather than shaking the toluene and acetone extracts. The second approach was to break the emulsion by adding Na.SO, and waiting. Both the amounts of Na-SO, and the time required varied. In severe cases emulsions were broken by filtering through glass wool wetted with toluene. Lipid Removal Using Florisil Problems were also encountered during the Florisil cleanup. Some samples had a tendency to solidify while concentrating the ether/pentane eluate, apparently due to abnormally high fat content. This usually occurred when the sample volume reached 1-3 mL. The samples to which this happened were diluted with pentane and eluted through another Florisil column. The Florisil cleanup was repeated until the samples remained liquid at small (<1.0 mL) volumes. Three cleanups was the maximum required for any sample. 40 �GC/MS ANALYSIS PROCEDURES Samples were analyzed by gas chromatography/mass spectrometry using an LKB 2091 EI/CI GC/MS. Operating conditions for the analysis of purgeables is given in Table 14 and the operating conditions for the extractables is given in Table 15. Analysis of the purgeables involved the use of the desorption apparatus described in Appendix B. Quantitation of the unknowns was accomplished using relative molar responses (RMRs) as discussed in Appendices B and C. The RMRs were calculated from replicate determinations of known amounts of standards and analytes. Qualitative Analysis Initial identification of compounds by GC/MS involved comparisons of unknown spectra with data compiled in the Eight Peak Index of Mass Spectra^ . If the peaks present in the unknown spectra clearly matched the peaks of the standard compound in the tables and the intensities were about the same, then a positive identification was usually made. If peak intensities of unknowns varied from those of the standards, and there were isomers of the compounds that were not listed in the Eight Peak Index, then the compound was listed as an "isomer." Whea the background peaks interfered with the spectrum of an unknown to an extent that made identification uncertain, the compound identification was labeled as "tentative" (tent.). If no standard spectra similar to those of the unknowns appeared in the mass spectral references, but fragments characteristic of a certain class of compounds were identified, tentative identifications were made on the basis of the characteristic fragments and apparent molecular weights. These identifications were also labeled "tent". Usually tentative identifications involved alkyl derivatives or homologs of classes of compounds that were positively identified in the same sample. Positive identifications, as well as some tentative identifications, often required more detailed investigations of standard spectra in the Registry of Mass Spectral Data or standard spectra found in other literature such as scientific journals. The Registry of Mass Spectral Data presents data in the form of histograms rather than as a list of peaks and their intensities. This type of format allowed more subtle differences in mass.spectra to be considered when several similar standard spectra in the �Table 14. OPERATING CONDITIONS FOR GC/MS ANALYSIS OF PURGEABLES Instrument Coluxnn Flow LKB 2091 80m - SE-30 WCOT Capillary Column Desorption Temperature Desorption Time 270°C 8 min Desorption Flow Column Temperature 15 mL/m"in He 30°C for 2. min programmed to 240°C at 4cC/min Scan Range Scan Speed Scar Cycle 5 •* 490 Dalton 0 •*• 670 in 2 sec 1.7 mL/imtn He 1.7 sec Injector Temperature Accelerating Voltage Ionizing Energy 250°C Trap Current 50 yA Source Temperature 210°C 3500 V 70 eV 42 �Table 15. OPERATING CONDITIONS FOR THE GC/MS ANALYSIS OF SEMIVOLATILES Instrument GC Column LKB 2091 25m SE-52 WCOT capillary column Flow Column Temperature 1.5 mL/min with 15:1 split 80°C for 3 min then 8°C/min to 265°C Scan Range Scan Speed 5 •»• 530 Dalton 2 sec 0 -*• 670 Dalton Scan Cycle 2.4 sec Injector Temperature 240°C Accelerating Voltage Ionizing Energy Trap Current 3500 V 70 eV 50 UA Source Temperature 210"C �Eight Peak Xndex appeared to represent possible candidates for unknown identifications. A large number of sample components remained unidentified. These unidentified components were labeled "unknown." In order to quantify the degree of certainty with which a compound has been identified, a "level" heirarchy has been established. The compound identification criteria are listed below: Level I Computer Interpretation. The raw data generated from the analysis of samples are subjected to computerized deconvolution/library search. Compounds identified using this approach have the lowest level of confidence. In general Level I is reserved for only those cases where compound verification is the primary intent of the qualitative analysis. Level II Manual Interpretation. The plotted mass spectra are manually interpreted and compared to those spectra compiled in a data compendium by a skilled interpreter. In general a minimum of five masses and intensities (±5 percent) should match between the unknown and the library spectrum. This level does not utilize any further information such as retention time since the authentic compound may not be available for establishing retention times. Level III Manual Interpretation Plus Retention Time/Boiling Point of Compound. In addition to the effort described under Level II, the retention time of the compound is compared to the retention time that has been derived from previous chromatographic analysis. Also the boiling point of the identified component is compared to the boiling points of other compounds in the near vicinity of the one in question when a capillary coated with a nonpolar phase has been used. Level IV Manual Interpretation Plus Retention Time of Authentic Compounds. Under this Level, the authentic compound has been chromatographed on the same capillary column using identical operating conditions and the mass spectrum of the authentic compound is compared to that of the unknown. Level V Level TV Plus Independent Confirmation Techniques. This Level utilizes other physical methods of analysis such as GC/Fourier transform infrared spectrometry, GC/high resolution mass spectrometry, or nmr analysis. This Level constitutes the highest degree of confidence in the identification of organic compounds. Unless otherwise stated, all identifications in this report were Level II. 44 �SECTION 7 RESULTS VOLATILES All 42 of the purged samples were analyzed by thermal desorption/GC/MS. The mass spectra from selected samples were interpreted manually to determine which compounds should be quantitated. From these data, selected compounds were quantitated in all samples. All data were stored on magnetic tape for subsequent processing and are routinely archived for at least 5 years. Qualitative Identifications Eight samples were interpreted. The results are presented in Appendix D. Samples were selected according to the following criteria. At least two samples were required from each collection site (Jersey City and Bayonne, NJ, were counted as two separate sites). The total ion current chromatograms were inspected and the samples with the greatest number of peaks or those containing very intense unique peaks (not observed in other samples) were selected. For those samples selected, all of the mass spectra were printed and interpreted manually by experienced spectroscopists. Table 16 summarizes the compounds found and their frequency of occurrence. It is interesting to note that some compounds (e.£. 1,1,1-trichloroethane and hydrocarbons.) are common air pollutants, others (e.g.., dibromochloromethane) are common water pollutants, others (dimethyldisulfide, furans, aldehydes) appear to be metabolites, others (chlorofluorocarbons, siloxanes) are known background interferents, and others (iodopentane) are of unknown source. Quantisation Based upon the qualitative identifications summarized above, nine coopounds were selected for quantitation in all of the samples. The results for four compounds are summarized in Table 17. As discussed below, the 45 �Table 16. SUMMARY OF QUALITATIVE IDENTIFICATIONS OF VOLATILE COMPOUNDS IN MOTHER'S MILK Sample Number Compound 1081 1040 1107 1115 2048 2071 3053 3111 Halogenated Compounds _ _ 4 - . _ chlorodif;.uoromethane chlorotrlfluoromethane dichlorodifluorome thane chlorome thane chloroethane trichlorofluoromethane dichloroei:hylene Freon 113 methylene chloride chloroform 1,1, 1-trichloroethane carbon tetrachloride trichloroethylene chloropentane dibromochloromethane tetrachloroethylene dichloropropene chlorobenzene chlorohexzine iodopentarie 3-methyl-3.-iodobutane chloroethylbenzene dibromodichloromethane dichlorobenzene chlorodecane trichlorobenzene 4 — 4 4 4 — _ 4 . - 4 . 4 - - - - 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 - 4 4 4 4 4 4 4 4 - . 4 4 - 4 - - 4 4 4 4 4 - 4 4 4 4 4 4 4 4 4 4 4 4 . . . 4 4 4 4 4 - 4 4 - 4 4 . 4 - 4 4 4 4 4 4 - 4 4 4 4 - - - - - 4 4 4 4 4 - - - 4 - - 4 4 4 . 4 4 4 - 4 4 4 - - - - 4 4 4 4 4 . 4 . 4 . - . . . . . - - 4 4 - - - Aldehydes _ acetaldehyde methylpropanal n-butanal methylbutanal crotonaldehyde nj-pentanal £-hexanal furaldehyde n-heptanal benzaldehyde n-octanal phenyl acetaldehyde 4 4 4 4 - 4 4 - 4 - 4 - - - . 4 - - - - 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 - 4 4 4 4 - 4 - . - 4 4 4 - 46 4 4 4 - 4 4 4 4 - 4 4 4 - 4 - 4 4 4 . - 4 - - - - (continued) �Table 16 (cont'd.) Sample Number Compou-id n_-nonanal methyl furaldehyde n-decanal n_-undecanal iv-dodecanal 1081 1040 1107 1115 + + . _ . . _ _ _ _ _ + . . . . . - + + + + + . _ _ . + _ + . + + + + + . _ + + + + + . . 2071 3053 + . + + . + . _ 2048 3111 + + . _. _ _ . . . * + . . + . + + + - + + . + . . _ . . + _ . , _ . . . . . _ . . + . _ . _ . + . . _ Ketones acetone methyl ethyl ketone methyl isopropyl ketone methyl vinyl ketone ethyl vinyl ketone 2-pent£inone methyl pentanone methyl hydrofuranone 2-methyl-3-hexanone 4-heptanone 3-heptanone 2-heptanone methyl heptanone furyl methyl ketone octanone acetophenone 2-nonanone 2-decanone alkylated lactone phthalide + + . + + _ . . _ + + . + + + _ . . + H+ > . + + + + + _ + . _ . . . + . + + + - . . _ _ . + + _ + _ _ . _ . + - h + . _ _ _ _ + + + . + + _ _ _ _ - Other Oxygenated Isomers C 5 H 10 0 C6H80 C 6 H 10 0 Ci,H602 C 6 H 12 0 C 7 H 12 0 C 7 H 10 0 C6H602 C^mOj C8H150 (continued) �Table 16 (cont'd.) Sample Number Compound 1081 1040 1107 1115 2048 2071 3053 3111 Other Oxygenaced Isomers (continued) C10H120 C10HU0 . C10H160 - C1£)H180 - C 10K20° C10H220 . - _ + _ + _ + - C H 9 8°2 CUH200 . . . . . . . . . . . . C . . . . . . + 10E10°2 Alcohols methanol isopropanol 2-methyl-2-'?ropanol n.-propanol 1-butanol 1-pentanol o-furfuryl alcohol 2-ethyl-l-hexanol phenol 2,2,4-triiaethylpentyl1,3-diol a-terpineol _ + _ _ _ _ _ _ _ + _ _ + . _ . _ _ + _ _ + _ _ + _ . + _ _ + + + _ _ + _ + _ _ + + _ + _ _ + + + + + _ _ + _ + _ _ + _ _ _ , • , . • • . . . . _ _ . _ + - - . _ _ . _ _ _ + _ _ + _ _ + _ . . _ + _ _ _ + + _ _ -f + . _ + + + _ + _ _ . + + _ + + _ • Acids acetic acid decanoic acid Sulfur Compounds sulfur dioxide carbon disuLfide dimethyl disulfide carbonyl sulfide • . (continued) 48 �Table 16 (cont'd.) Sample Number Compound 1081 1040 1107 1115 2048 2071 3053 3111 Nitrogen Compounds nitrome thane C5H6N2 C5H8N2 _ + . . . . . . C.H.N-0 442 methyl acetamide benzonitrile methyl cinnoline _ _ - + _ _ - _ _ + + - . _ • * • _ + . _ + _ _ _ - . _ - + + _ _ . . . . . . . . - _ + - _ _ _ - _ _ Esters vinyl propionate ethyl acetate ethyl-n-caproate methyl caprylate ethyl caprylate isoamyl formate methyl decanoate ethyl decanoate _ _ . _ . - _ + _ _ + _ _ _ _ . _ _ . _ _ _ . f _ _ _ _ _ - - + + + + + + - _ . _ , _ - _ _ - - Ethers dimethyl ether £-dioxane dihydropyran _ + . . . _ . + + _ _ + . - + - - _ _ _ _ _ _ - _ _ + _ + _ + + _ + + _ + _ - _ - _ _ Epoxide l,8-cin«ole . _ _ _ . _ _ _ . . + _ . _ . . _ _ _ . + + + _ _ _ _ _ _ - _ + _ _ + _ _ _ _ + _ Furans furan tetrahydrofuran methyl furan methyl tetrahydrofuran ethylfuran dimethylfuran 2-vinylfuran furaldehyde 2-n-butylfuran 2-pentylfuran methylifuraldehyde furyl xaethyl ketone a-furfuryl alcohol benzofuran ,_ . + _ + + 4 _ . _ 4 _ _ . . + + + + _ _ _ + _ _ - _ _ . _ + _ . + _ _ _ _ - - (continued) �Table 16 (cont'd.) Sample Number Compound 1081 1040 1107 1115 2048 2071 3053 3111 Alkanes C3H8 C4H1Q + C5H12 CfiH14 + C7E16 + C8H18 + C9H2Q C10H22 + + CUH24 C12H26 + + r u L H _ C . . . 13 28 14H30 C15K32 + 4 - * _ + _ J + + + . _ 4+ . . . + _ . Alkenes C3H6 C H 48 C5H1Q + . . . . + + CgH18 C1QH20 + _ + + + T J C 11H22 12K24 + . . . + . . + + + + + - - - + _ - 4 + C - C - 13K26 isoprene . + CfiH12 CyHu CgH16 p . J + _ + L + + _ + + l _ + + _ f _ _ + L _ * L * . + . -f _ „ . . _ . . - . . _ Alkynes C5Hg C6H1Q . . . . . + + . + ... C H 7 12 50 (continued) �Table 16 (cont'd.) Sample Number Compound 1081 1040 1107 1115 2048 2071 3053 3111 Alkynes (continued) C8H14 C9Hlfi + + - - + + . . H- C - . + - + + . . + + + + + _ + + + + + _ - _ . . + + + + _ + + + - + _ + _ _ . + + _ + + _ _ • - + + + + + _ _ + + + + + + + + + + + + + 4 + + + _ + + _ + + - + + + + + + + + + + - + + •)• + + + •<• + + * + -«+ + + + + . + + . » . + + + - + + + + + + + + + + 10H18 C H 12 22 . + . . . . Cyclic Hydrocarbons cyclopentane methylcyclopentane cyclohexane ethylmethylcyclohexane C 10H14is"mers C-0H.,isomers (other) limonene methyldecalin a-pinene canphene camphor + + _ . + + -_ _ _ + _ _ _ Aromatics benzene toluene ethylbenzene xylene phenylacetylene styrene benzaldehyde C,-alkylbenzene C4-alkylbenzene methylstyrene dimethylstyrene C5-alkylbenzene naphthalene Cg-alkylbenzene isomers isomers isomers isomers _ . + - + + + + + + + + . + + + + + ' + + . . _ _ + - Arranged by class in approximate elution order. See Appendix D for sampleby-saaple identifications. + - present; - - not identified in sample. b Participant code number. 51 �Table 17. VOLATILES QUANTITATED IN MOTHER'S MILK SAMPLES (ng/ml.) Site Bayonne, NJ Sample Number' 1016 1032 1040 1057 1073 Chloroform1' d Tetrachloroethylene Chlorobenzene Dichlorobenzenec 0.2 0.1 1081 0.3 0.1 0.7 0.7 1.3 1.5 1.5 1.1 0.9 3.8 6.3 0.1 0.1 0.1 0.1 6.7 9.1 66 0.2 2.2 32 Jersey City, NJ 1024 1107 1115 1123 1164 13 17 1.7 20 65 43 7.4 8.1 17 4.0 0.1 0.2 0.3 0.1 0.1 2.8 68 49 2.2 0.9 Pittsburgh, PA 2014 2022 2048 2055 2063 2071 2089 2097 2105 2113 2121 2139 0.9 1.5 0.6 0.8 0.6 1.2 0.7 6.7 2.8 1.2 0.8 0.6 0.8 1.8 1.8 1.0 1.6 1.0 26 1.8 1.3 0.7 2.4 0.7 0.2 0.1 0.1 0.05 0.1 0.1 0.2 0.4 0.1 TRe 0.1 0.2 1.1 8.9 0.7 3.1 1.4 0.5 0.3 1.1 0.4 2.0 ' 0.9 Baton Rouge, LA 3012 3020 3038 3046 2.9 0.7 0.8 21 0.1 0.5 1.7 2.5 0.3 0.1 0.2 0.1 4.2 0.6 1.3 2.2 tn (continued) �Table 17 (cont'd) Charleston, WVg OJ £* Sample Number3 Chloroform Tetrachloroethylene 3053 3079 3087 3095 3103 3111 Site 0.3 0.8 0.7 1.3 0.6 1.8 0.4 0.6 0.4 1.0 0.2 0.5 4010 4028 4036 4051 4069 4085 4093 4101 4119 5.0 7.2 1.2 1.4 3.9 0.6 0.4 0.4 1.0 1.0 >19f 7.5 8.2 5.3 12 8.7 11 Participant code number. See text for caveats with respect to chloroform. All isomers summed. Not detected. Trace. Instrument saturated. p Sample 4044 lost due to instrumental malfunction. CMorobenzene 0.2 0.1 0.2 0.3 0.1 0.1 0.2 10 0.2 0.1 0.1 0.1 0.04 Dichlorobenzenec 1.8 0.2 5.2 4.2 >22 44 0.7 1.9 0.2 1.1 3.6 3.8 0.04 26 1.4 �quantitation of the other five compounds is not reported, since the levels in milk were not judged sufficiently greater than background to be reliable. Upon inspection, it is obvious that most values are low relative to only a few high "outliers." These high values suggest that there is a range of levels of these compounds which may correlate with exposure. These results were analyzed statistically to determine if any of the values correlated significantly. As can be seen in Table 18, the arithmetic mean and median values generally are quite different. The arithmetic mean is skewed toward the high end, generally due to one or two relatively high values. mean. A more realistic representation of the central data is the geometric These geometric mean values were tested for their significance (^.6., are the geometric means significantly different from site to site?). Table 19 summarizes this data, prom this table, it appears that samples from Jerse}' City have significantly higher levels of chloroform, tetrachloroethylene, and dichlorcbenzene than the other study samples. Charleston samples appear to have significantly higher levels of chloroform, and Bayonne samples appear to have significantly higher levels of dichlorobenzene. To test if any of the compound levels were related, the Spearman correlation coefficients (nonparametric correlation based on the sample, designed to lessen the weight of a single high outlier) were determined as shown in Table 20. There does not appear to be any compound-to-compound correlation among the subjects. In interpreting these data, it must be remembered that this is a very small data set. Therefore these data should not be used to extrapolate to the city or area from which the samples were collected. Quality Control Table 21 presents the quality control results for chloroform, tetrachloroethylene, chlorobenzene, and dichlorobenzene. The very high recovery of chloroform from the controls indicates either a miscalculation of the amount actually spiked or contamination of the samples used as controls. Since the procedural blanks contained about 15 times less chloroform, the former explanation is most reasonable. However, the chloroform values reported in Table 17 must be interpreted subject to the following 54 �Table 18. SUMMARY STATISTICS FOR VOLATILE COMPOUNDS BY SITE Site Bayonne, NJ Maximum Meanb Median S.D. n Jersey City, NJ Maximum Meanb Median S.D. n Pittsburgh, PA Maximum Meanb Median S.D. n Baton Rouge, LA Maximum Msanb Median S.D. n Charleston, WV Maximum Meanb Median S.D. n Overall Maximum Mean Median S.D. n Tetrachloroethylene Chloroform 1.3 0.52 0.5 0.48 6.3 2.52 1.5 6 6 2.13 Chlorobenzene 0.2 0.12 0.004 0.1 6 66 19.37 7.9 68 24.48 31.69 8.1 0.3 0.16 0.1 24.3 15.9 0.089 5 5 65 23.34 43 15.9 17 6.7 1.53 0.85 1.74 26 3.41 1.45 7.13 12 12 21 3.09 2.5 0.79 0.8 0.5 6.34 0.75 10 Dichlorobenzene 25.54 6 2.8 5 5 0.4 0.12 8.9 1.71 0.1 1 0.11 2.41 12 0.3 0.16 0.15 0.096 12 44 8 3.2 13.98 10 10 >19 3.21 10 1.20 26 4.30 10 12 7.21 7.5 1 0.1 1.4 3.55 6.02 8.25 9 9 3.30 9 9 65 5.57 1.25 10.9 43 4.10 1.25 8.15 10 0.37 0.1 1.53 68 9.15 1.95 17.3 42 42 42 42 Tlaximum, mean and median values are ng/mL. Arithmetic mean. 55 �Table 19. SIGNIFICANCE OF THF. DIFFERENCES IN THE GEOMFTRIC MEANS BY SITE Geometric Mean (ng/mF,) Ch loroform Site 0.45 Nayonne 14.7 Jersey City Tetrach loroethylcno Chlorobcnzene Di ch lorobcn zene 2.09 0.12 8.33 11.5 0.16 8.55 Pittsburgh 1.23 1.82 0.12 1.21 Baton Rouge 1.53 0.67 0.15 3.83 Charleston 5.92 1 . 65 0.42 1.98 0.01 0.01 N.S.b 0.05 rt Significance g 0.01 implies 99 percent confidence that the numbers are statistically different, while 0.05 implies 95 percent confidence. Not significant. �Table 20. SPEARMAN CORRELATION COEFFICIENTS FOR VOLATILE ORGANICS FOUND IN MOTHER'S MILK .. , , . Chloroform Chloroform Tetrachloro. . ethylene „. , , Chlorobenzene Dichloro, benzene 1.0 0.37a -0.02b -0.13b 1.0 Chlorober.zene Dichlorobenzene 0.007b 0.05b 1.0 Tetrachloroethylene 0.03b 1.0 Significant at 0.05 level (95 percent confidence). b Not significant Sample size - 42 57 �Table 21. Type of Sample Chloroform QUALITY CONTROL RESULTS FOR VOLATILES IN MILK Tetrachloroethylene Chlorobenzene Dichlorobenzene 17 0.12 0.19 159 Blanksa Mean (ng/mL) b S.D. RSD (Z) 7 1.2 1.3 108 7 0.22 0.11 49 7 0.03 0.025 84 14.02 8.20 58 8 1.12 0.41 37 8 0.62 0.34 55 Controls 0 Mean Recovery® Vn oo S.D. RSD (Z) Blanks consisted of two field water blanks and five water blanks purged with the milk samples to monitor procedural background. No difference between the two types of blanks was observed. Arithmetic mean. Controls consisted of two spiked raw cow's milk samples carried to the field and returned, two spiked raw cow's milk samples stored in the laboratory, two spiked water samples carried to the field and returned, and two spiked water samples stored in the laboratory. No major differences were observed between the four types of samples. Samples were spiked at 30-90 ng/volume purged (or about 1 ng/mL). Not included in control spiking solution. 1.0 • 100 percent recovery. Extremely high recovery probably a result of improper loading of controls. �considerations: the mean reported levels in the samples were only 4.9 times the blank levels; the recovery from controls was about 1400 percent, invalidating the recovery study; and chloroform is known to be a laboratory atmospheric contaminant. The compounds presented in Table 17 represented significant levels above the background in blanks. Several other compounds were quantitated that did not exhibit substantial concentrations. These compounds, with the ratio of the mean in the samples to the mean in the background given in parenthesis, were: 1,1,1-trichloroethane (1:1), benzene (2:1), toluene (2:4), trichloroethylene (1:2) and carbon tetrachloride ( : ) These levels 14. in the samples cannot be reliably assigned to either the milk sample or to laboratory contamination. If these compounds are present in milk, they are very low and cannot be regarded as significant, given the limitations of the technique employed. Apparently, mother's milk does not represent a bioconcentration matrix for these compounds. SEMIVOLATILES Three samples were fully interpreted, as presented in Appendix E. As can be seen from the data, few compounds of interest were observed in the mass spectra. The data were searched on the GC/MS data system for target compounds (PCNs, PBBs and PCBs) using single ion plots called up from the full data set. No evidence for any of these compounds was observed at a detection limit of about 20 ppb. DDE was quantitated in five samples as shown in Table 22. These values were in the range generally reported by previous investigators (see Tables 2-4). Since none of the target compounds were present in detectable quantities, no further identification or quantitation was attempted. 59 �Table 22. DDE AND TETRACHLOROBIPHENYL LEVELS IN SELECTED MOTHER'S MILK SAMPLES Sice Sample Number DDE ng/mL Milk Tetrachlorobiphenyl Pittsburgh 2105 45 NDb Pittsburgh 2121 73 Tc Charleston, WV 4069 107 ND Charleston, WV 4085 38 ND Charleston, WV 4093 d Mean 91 ND 71 S.D. 29 RSD (2) 42 Median 73 Samples selected as having the most intense total ion current chromatograms. Not detected. Trace. Arithmetic mean. 60 �REFERENCES 1. Ziegel, E. and C. C. Van Blarcom, Obstetric Nursing, 6th ed., Macmillan, New York, 651 ( 9 2 . 17) 2. Strassman, S. C. and F. W. Kutz, "Insecticide Residues in Human Milk from Arkansas and Mississippi, 1973-74," Pest. Moo. J., 10, 130-133 (97. 17) 3. Savage, E. P., et. al., "Organochlorine Pesticide Residues and Polychlorinated Biphenyls in Human Milk 1971-72," Pest. Mon. J., 7_, 1-3 (1973). 4. Kroger, M., "Insecticide Residues in Human Milk," J. Pediat., 80, 401405 ( 9 2 . 17) 5. Curley, A. and R. 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P., et al., "A Search for Polychlorinated Biphenyls in Human Milk in Rural Colorado," Bull. Environ. Contamin. Toxicol., 9, 222-226 (1973). 13. Petrakis, N. L., L. D. Gruenka, T. C. Beelen, N. Castagnoli, Jr., and J. C. Craig, "Nicotine in Breast Fluid of Nonlactating Women," Science, 199. 303-305 (1978). 14. Bakken, A. F. and M. Seip, "Insecticides in Human Breast Milk," Acta Paediatr. Scan., 65, 525-529 (1976). 15. Knoll, W. and S. Jayaraman, "Zur Kontamination Von Humanmilch tnit chlorierten Kohlenwasserstoffer," Die Nahrung, 17, 599-615 (1973). 16. Psendorfer, Von H., "Ruchstande von Organochlorpestiziden (DDT u.a.) und polychlorierten Biphenylen (PCBs) in der Muttennllch," Wiener Klinische Wochenschrift, 87, 731-736 (1976). 17. Th. TuLustra, L. G. M., "Organochlorine Insecticide Residues in Human Milk ia the Leiden Region," Neth. Milk Diary J., 25, 24-32 (1971). 18. Polishiik, Z. W., M. Ron, M. Wasserman, S. Cucas, 0. Wasserman, and C. Lemesca, "Organochlorine Compounds in Human Blood Plasma and Milk," Pest. Mon. J., 10, 121-129 (1977). 19. Ritchy, W. R., G. Savary and K. A. McCulley, "Organochlorine Insecticide Residues in Human Milk, Evaporated Milk, and Some Milk Substitutes in Canada," Can. Publ. Health J., 63, 125-132 (197?.). 20. Egan, H., R. Goulding, J. Roburn and J. O'G. Tatton, "Organo-chlorine Pesticide Residues in Human Fat and Human Milk," Bxit. Med. J., 2, 6669 (1965). 21. Newton, K. G. and N. C. Greene, "Organocblorine Pesticide Residue Levels in Human Milk — Victoria, Australia 1970," Pest. Mon. J., 6, 4-8 (1972). 22. Graca, I., A. M. S. Silva Fernandes and H. C. Mourao, "Organochlorine Insecticide Residues in Human Milk in Portugal," Pest. Mon. J., 8, 148-156 ( 9 4 . 17) 23. Musial, C. J., 0. Hutzinger, V. Zitko and J. Crocker, "Presence of PCB, DDE, and DDT in Human Milk in the Providences of New Brunswick and Nova Scotia, Canada," Bull. Environ. Contamin. Toxicol., 12, 258-267 (1974). 62 �24. Hes. J. and D. J. Oavies, "Presence of Polychlorinated Biphenyl and Organochlorine Pesticide Residues and the Absence of Polychlorinated Terphenyls in Canadian Human Milk Samples," Bull. Environ. Contain. Toxicol., 21, 381-387 ( 9 9 . 17) 25. Stacey, C. I. and B. W. Thomas, "Organochlorine Pesticide Residues in Human Milk, Western Australia — 1970-71," Pest. Mon. J., 9, 64-66 (1975). 26. Van House Holdrinet, M., H. E. Braun, R. Frank, G. J. Stopps, M. S. Smout, and J. W. McWade, "Organochlorine Residues in Human Adipose Tissue and Milk from Ontario Residents," Can. J. Pub. Health, 68, 74-83 ( 9 7 . 17) 27. Winter, M., M. Thomas, S. Wernick, S. Levin and M. T. Farver, "Analysis of Pesticide Residues in 290 Samples of Guatemalan Mother's Milk," Bull. Environ. Contamin. Toxicol., 16, 652-657 ( 9 6 . 17) 28. "Criteria for a Recommended Standard...Occupational Exposure to Ethylene Bichloride (1,2-dichloroethane)," HEW Publ. No. (NIOSH) 76-139 (March 1976). 29. Kover, F. D., Environmental Hazard Assessment Report. Chlorinated Naphthalenes. EPA 560/8-75-001 (December 1975). 30. Erickson, M. D., R. A. Zweidinger, L. C. Michael and E. D. Pellizzari, "Environmental Monitoring Near Industrial Sites: Polychloroaaphthalenes," EPA-560/6-77-019 (1977). 31. Erickson, M. D., L. C. Michael, R. A. Zweidinger, and E. D. Pellizzari, "Development of Methods for Sampling and Analysis of Polychlorinated Naphthalenes in Ambient Air," Environ. Sci. Techno1., 12, 927-931 (1978). 32. Erickson, M. D., L. C. Michael, R. A. Zweidinger and E. D. Pellizzari, "Sampling and Analysis for Polychlorinated Naphthalenes in the Environment," JAOAC, 61, 1335-1346 (1978). 33. Erickson, M. D., L. C. Michael, R. A. Zweidinger, and E. D. Pellizzari, "Development of Methods for Sampling and Analysis of Polychlorinated Naphthalenes in Ambient Air," 1977 Annual Meeting, American Chemical Society, Chicago, IL (August 31, 1977). 63 �34. Erickscn, H. D., L. C. Michael, R. A. Zweidinger, and E. D. Pellizzari, "Sampling and Analysis for Polychlorinated Naphthalenes in the Environment," 1977 Annual Meeting AOAC, Washington, DC (October 20, 1977). 35. Unpublished data, E. Roessler, Borough of Bridgeville, PA (1976). 36. 197? Directory of Chemical Producers-USA, Chemical Information Services, Stanford Research Inst., Menlo Park, CA (1977). 37. Environmental Sciences and Engineering, "Trip Report for Sampling of Polybrominated Biphenyls (PBBs)," submitted to OTS, EPA, Washington, DC, Contract No. 68-01-3248 (April 1977)). 38. Mumma, C. E. and D. D. Wallace, "Survey of Industrial Processing Data. Task I - Pollution Potential of Polybrominated Biphenyls," EPA-560/375-004 (June 1975). 39. Unpublished data, E. J. Londres, New Jersey Dept. of Environmental Protection via G. E. Parris, OTS, EPA, Washington, DC (1977). 40. Erickson, M. D., R. A. Zweidinger, and E. D. Pellizzari, "Analysis of a Series of Samples for Polybrominated Biphenyls (PBBs)," EPA-560/6-77-020 (Augus-: 1977). 41. Environmental Science and Engineering, "Data Report for Polybrominated Biphenyl Near Manufacture (sic) in the Northeast," submitted to OTS, EPA, Washington, DC Contract No. 68-01-3248 (June 16, 1977). 42. 1974 New Jersey State Industrial Directory, New Jersey State Industrial Directory, 2 Perm Plaza,. NY, 10001 (1974). 43. Pellizzari, E. D., "The Measurement of Carcinogenic Vapors in Ambient Atmospheres," EPA-600/7-77-055 (June 1977). 44. Pellizzari, E. D., M. D. Erickson, and R. A. Zweidinger, "Formulation of a Preliminary Assessment of Halogenated Organic Compounds in Man and Environmental Media," EPA-560/13-79-006 (July 1979). 45. Pellizzari, E. D., M. D. Erickson, T. D. Hartwell, S. R. Williams, C. M. Sparacino and R. D. Waddell, "Preliminary Study on Toxic Chemicals in Environmental and Human Samples. Part I: Formulation of an Exposure and Body Burden Monitoring Program," submitted to IT. S. Environmental Protection Agency, Washington, DC, Contract No. 68-01-3849 (June 1980). 64 �46. Pellizzari, E. D., "Analysis of Organic Air Pollutants by Gas Chromatography and Mass Spectrescopy," Publication No. EPA-600/2-77-100, Contract No. 68-02-2262, (June 1977). 47. McDonnell, G., D. H. Ferguson and C. R. Pearson, "Chlorinated Hydrocarbons and the Environment," Endeavour, 34, 13-18 ( 9 5 . 17) 48. FDA Compliance Program, Evaluation, "FY 74 Total Diet Studies (7320.08)," Date accepted: January 21, 1977. 49. State of New Jersey Department of Environmental Protection, "Initial Report on the Findings of the State Air Monitoring Program for Selected Volatile Organic Substances in Air," (October 1979). 50. Zweidinger, R. A., A. Sherdon, B. S. Harris, III, H. Zelon, T. Hartwell, and E. D. Pellizzari, "Measurement of Benzene Body Burden of Potentially Environmentally Exposed Individuals," Final Report, EPA Contract No. 68-OL-3849, Task 1 (May 1980). 51. Hartwell, T., P. Piserchia,.S. White, N. Gustafson, A. Sherdon, R. Lucas, D. Lucas, D. Myers, J. Batts, R. Handy, and S. Williams, "Analysis of E?A Pesticide Monitoring Networks," Office of Toxic Substances, Washington, DC. Draft Report (1979). 52. U.S. Environmental Protection Agency, Office of Research and Development, "Health Assessment Document for Polycyclic Organic Matter," (May 1978). 53. Stanford Research Institute, "The Environmental Fate of Selected Polynuclear Aromatic Hydrocarbons," Prepared for U. S. Environmental Protection Agency (February 1976). 54. State of New Jersey Department of Environmental Protection, "Initial Report on the Findings of the State Air Monitoring Program for Selected Heavy Metals in Air," (October 1979). .55. Unpublished'data, William J. Librizzi, U.S. Environmental Protection Agency, Region II (October 1977). 56. Fribers, L., M. Piscator, G. F. Nandberg and T. Kjellstrom, "Cadmium in the Environment," CRC Press, Cleveland, OH (1974). 65 �57. National Academy of Sciences, "Lead," Washington, DC ( 9 2 . 17) 58. Mason, T. J., F. W. McKay, "U.S. Cancer Mortality by County: 1950-69," DHEW Publ. No. (NIH), 74-615, Washington, DC, U.S. Govt. Printing Office (1974). 59. Mason, T. J., F. W. McKay, J. R. Hoover, W. Blot and J. F. Fraumeni, Jr., "Atlas of Cancer Mortality for U.S. Counties: 1950-69," DHEW Publ. No. (NIH) 75-780, Washington, DC, U.S. Govt. Printing Office (1975). 60. Greenberg, Michael R., "The Spacial Distribution of Cancer Mortality and of High and Low Risk Factors in the New Jersey-New York-Philadelphia Metropolitan Regions, 1950-1969, Part I," New Jersey Dept. of Environmental Protection, Program on Environmental Cancer and Toxic Substances (January 1979). 61. Greenberg, M., F. McKay, and P. White, "A Time-Series Comparison of Cancel Mortality Rates in the New Jersey-New York-Philadelphia Metropolitan Region and the Remainder of the United States, 1950-1969," Am. Jour, of Epidemiology, 111. 166 (I960). 62. Greenberg, M. R., P. W. Preuss, and R. Anderson, "Clues for Case Control Studies of Cancer in the Northeast Urban Corridor," Soc, Sci. & Med., 14D, 37-43 (1980). 63. Greenberg, M. R., J. Caruana, B. Holcomb, G. Greenberg, R. Parker, J. Louis, and P. White, "High Cancer Mortality Rates from Childhood Leukemia and Young Adult Hodgkin's Disease and Lymphoma in the New Jersey-New York-Philadelphia Metropolitan Corridor, 1950-1969," Cancer Research, 40, 439-443 ( 9 0 . 18) 64. Cross, J. and G. B.tWiersma, "Preliminary Analysis of Cancer Rates in Organic Chemical-Producing Counties," EPA-600/1-79-022 (June 1979). 65. Pellizzari, E. D., and M. D. Erickson, "Analysis of Organic Air Pollutants in the Kanawha Valley, WV and the Shenandoah Valley, VA," Publication No. EPA-903/9-78-007, Contract No. BOA 68-02-2543 (June 1978). 66. Erickson, M. D., S. P. Parks, D. Smith and E. D. Pellizzari, "Sampling and Analysis of Organic Air Pollutants in Two Industrialized Valleys," FACSS V, Boston (October 30 - November 3, 1978. 67. McLafferty, F. W., E. Stenhagen, and S. Abrahammson, Ed., Registry of Mass Spectral Data, John Wiley and Sons, New York (1974). 66 �68. Eight Peak Index of Mass Spectra. Vol. I (Tables 1 and 2) and II (Table 3), Mass Spectrometry Data Centre, AWRE, Aldermaston, Reading, RG74PR, UK (1970). 67 �APPENDIX A DATA COLLECTION INSTRUMENTS 68 �STUDY OF ORGANIC COMPOUNDS IN HUMAN MILK EPA Contract No. 68-01-3849 RTI Project No. 31U-1S21-22 DATA COLLECTION INSTRUCTIONS Performed for Office of Toxic Substances Environmental Protection Agency Washington, DC 20460 69 �1.0 Introduction Under contract to the Office of Toxic Substances, Environmental Protection Agency (EPA), the Research Triangle Institute (RTI) is conducting a limited study designed to measure environmental pollutant levels in human Bilk and to evaluate the utility of using this body fluid it. specific pollutant studies for populations in the. vicinity of manufacturing plants and/or industrial user facilities. RTI is responsible for all phases of the study, including study design, subject recruitment, chemical analysis of milk samples, and report writing. RTI is a not-for-profit contract research organization located in North Carolina's Research Triangle Park between Raleigh, Durham, and Chapel Hill. The Institute was incorporated as a separate operating entity in 1958 by the University of North Carolina (UNO at Chapel Bill, Duke University at Durham, and North Carolina State University at Raleigh, and is still closely affiliated with the three universities. 2.0 Overview Four urban areas have been chosen as performance sites; they are Bridgeville, Pennsylvania; the area which includes Linden and Bayonne, New Jersey and western Staten Island, New York; Baton Rouge, Louisiana; and South Charleston and Nitro, West Virginia. These sites represent high-probability areas for the presence of one or more of the chemicals of interest in human milk. The selected industrial chemicals of interest include polychlorinated naphthalenes, tetrachlorethylene, trichloroethane, diehloropropane, benzene, polybrominated biphenyls, chlorinated phenols, toluene:, chlorinated benzenes, and chloroform. 70 �At each of the four sites, arrangements will be made to work through clinical facilities such as hospitals, clinics, or physician's offices, In order to recruit a panel of respondents. At each site ten participants will be recruited, for a total of 40. Potential participants (lactating females) will be screened to determine that they live in one of the areas of interest and are willing and able to provide the milk sample. A questionnaire will be administered for each participant to obtain information on demographic variables, residence histories, and potential exposure situations; for each participant, a sample of milk will be collected and analyzed for the compounds of interest by gas chromatography/mass spectrometry or high pressure liquid chromatography. A professional member of the facility's staff, such as a registered nurse, will be trained in the proper procedures to administer the questionnaire and obtain the milk sample, To try to reduce the non-participation rate due to refusals, and to reimburse the subject for the time spent on the study, volunteers will be offered a $5.DO incentive for participating. 3.0 Data Collection 3.1 General Remarks Data collection for this research effort consists of the following steps: 1. Screening of potential participants (lactating women) to determine that they live in one of the areas of interest (see below), that they have resided in that area for at least the preceding 12 months, that they have remained in that area continuously for the preceding week, and that they are willing and able to provide a milk sample. 71 �2. When an eligible person is encountered, the nature and purpose of the study will be explained and their participation solicited. 3. When an eligible person agrees to participate, the person will be required to sign a Participant Consent Form (PCF) in order to participate in the study. 4. Once the participant has signed the PCF, the person should be listed on the Participant Listing Form (PLF), a Patient Number assigned, and the data collector will proceed to administer the Study Questionnaire (SQ) and collect the tr.Uk sample. 5. Once the SQ has been administered and the milk sample collected, the participant will be offered a $5.00 incentive for participating. * 6. Milk samples and completed data collection instruments will be returned to RTI. 3.2 Survey Instruments As indicated in the preceding section, there are 3 data collection instruments for this research effort, the PCF, the PLF, and the SQ; subsequent sections contain instructions for the use of each instrument as well as item-by-tiem explanations for their completion, and general descriptions are provided below. The survey instruments have been designed hopefully to provr.de an efficient means of collecting and recording the requisite data for the study. It is imperative that all s-urvey instruments be completed accurately. The success and reliability of the study and its results are dependent upon the quality of data collected, which will be fully dependent 72 �on the accuracy of your execution of your assignment. As you complete a fora, conduct a thorough edit to verify that required data have been entered and entered correctly. Copies of the data collection instruments appear in Attachment 1. 3.2.1 Participant Consent Fora (PCF) • Purpose; The purposes of the PC? are to introduce the study; explain its objectives, sponsorship (the relationship and roles of 811 and EPA), and requirements of and risks, burdens, and benefits to participants; and stress that participation is completely voluntary and that all data collected will be kept confidential. . General Description; The PCF is a single page fora printed on special paper which makes three copies from a single impression. The survey title appears at the top, along with the name of RII; spaces for necessary identifying information appear at the bottom. . Administration; The PCF will be signed by the participant and contains an agreement to provide the necessary information and milk sample. Participants may freely withdraw from the study at any time; however, in order to encourage participation RII offers an incentive of five dollars to each participant to be paid after each data set (PCI, SQ, and milk sample) is obtained. Again, confidentiality of data is stressed, including steps 73 �taken to disassociate the name of the participant from the data once collected; for example', the PCF is the only data collection instrument which bears the name of the participant and allows its association to study identification numbers, but will be maintained in hard copy only and stored in a restricted area. To further emphasize this disassociation, the incentive will be paid in cash rather than by check or money order, although the participant will sign the PCF indicating that the incentive was received. A signed PCF must be obtained for each participant before proceeding with Study Questionnaire (SQ) administration and collection of the milk sample. • Disposition; The top (white) copy will be attached to the appropriate SQ until it is received at RTI and verified; the yellow copy will be provided to the participant; the pink copy will be retained by the data collector. 3.2.2 Participant Listing Fora r(PLF) . Purpose; The purpose of the FLF is to provide a means of assigning unique numbers to participants at each performance site. . General Description; The PLF is a single page form printed on pink paper; space for Comments is provided on the reverse side. The survey title appears at the top, along with the names and addresses of RTI and EPA/OTS and a confidentiality statement. 74 �. Administration; Aa each participant is enlisted up Co the required number ( 0 , that participant should 1) be listed on the PLT. . Disposition; When data collection at a site or facility is completed, the FLF (or a copy) should be sent to RTI. 3.2.3 Study Questionnaire (SQ) : The purpose of the SQ is to obtain information on participants, Including demographic characteristics such as age, sex, race, and occupation; residence information; health information such as current health status and prescription medications; and personal characteristics such as hobbies. . General Description; The SQ is divided into six sections, dealing respectively with demographic characteristics, occupation, health and personal habits, residence and household information, information on the interviewer and respondent, and information regarding the milk sample, including an indication as to whether or not the milk sample was obtained, the date and time of acquisition of the sample, and the date the sample was shipped to RTI. Participants will be identified by a unique study number used to correlate and cross-identify the questionnaires and samples by way of pre-printed self-adhesive labels. The SQ is 5 pages long, with space provided for comments, 75 �. Administration; An SQ is to be completed for each participant for whoa a signed PCF is obtained. • Disposition! The SQ1* are to be sent to RTI as instructed. 3.3 Screening As indicated in section 3.1, potential participants (lactating women) should be screened to determine that they meet certain study criteria for participation: 1. That they are willing and able to provide a milk sample of sufficient quantity (approximately 100 ml.), 2. That they live in one of the areas of interest (see below), 3. That they have resided in that area for at least the preceding 12 months, and A. That they have remained in that area continuously for the preceding 7 days. As indicated in section 2.0, four areas have been chosen as performance situs, with a specific Site Number assigned to each which will remain constant ilor each site and is to be entered where appropriate on data collection instruments as follows: Site Site Number Northern New Jersey/Staten Island, New York Bridgeville, Pennsylvania Baton Rouge, Louisiana Nitro/South Charleston, West Virginia 1 2 3 4 With the exception of Bridgeville, Pennsylvania, participants residing in some areas at each site are of considerably more interest to the study than those living in others, as discussed in the following sections. 76 �3.3.1 Northern Sew Jersey/Staten Island. New York Within the Northern New Jersey/Staten Island area, potential participants residing in some communities are of more interest than those residing in others, more or less in the order listed below: 1. Bayonne, NJ 2. Northern Staten Island (Port Richmond), NY 3 ' Linde0' » 4. Carlstadc, NJ 5. Saddle Brook, NJ 6. Jersey City, NJ 7. Kearney, NJ 8. Newark, NJ 3.3.2 9. Elizabeth, NJ 10. Sayreville, NJ ,, _ . ... 11. Rahway, NJ 12. Edison, NJ ^ Parlin> NJ ^ Patterson, NJ ^ Wayne> HJ Baton Rouge, Louisiana Potential participants residing in Baton Rouge are of primary interest to this study; other communities in the Baton Rouge area of interest are Placquemine, St. Gabriel, and Geismar. 3.3.3 Nitro/South Charleston, West Virginia Potential participants residing in Nitro and South Charleston are of primary interest to this study; other communities of interest in the area are Belle and Institute. 3.4 Participant Listing Fora When an eligible person is encountered who agrees to participate, that person should be listed on a PLF in order to be assigned a unique Participant Number. The PLF is completed by entering the appropriate Site Number (see section 3.3 above); then, each time that an eligible participant is encountered who agrees to participate, up to the number required, enter the Participant's Name (Last, Firstt Middle) on the PLF and assign a Porticipois Number in the left-hand column, beginning with 0001 at each site unless other77 �vise instructed. Assign Participant Numbers consecutively for all study participants. Where appropriate, enter the participant's Medical Record Kuniber in the right-hand column. When making numerical entries, right-adjust and enter leading zeros. 3.5 Participant Consent Fora Potential participants must understand exactly -what is involved in participation in the study and what benefits may be realized by participation; this understanding and agreement must be documented by a signed PCF. In the event that the potential participant is under the age of 18 years, the person's parent or other legal guardian must sign the PCF in order for the designated eligible to participate. More specifically, the potential participant and/or that person's parent, guardian or other spokesman, must understand that full participation in the study consists of providing answers to a questionnaire related to environmental exposure, part of which relates to the individual's household in general and part of which is related to the individual participant (be prepared to show the person the SQ), and providing a ntf.lk sample of approximately 100 ml. (be prepared to show the person one of the collection bottles.) The individual must further understand that she will only enjoy certain limited benefit.1! in return for her time and inconvenience, primarily a $5.00 incentive to be disbursed after administration of the questionnaire and collection of the milk sample. The individual must understand that participation in the study iu completely voluntary and that she may withdraw at any tine, but that payment of the incentive is dependent on full pcrtiGipavion. The individual must also understand that all data collected in the study will be held strictly confidential, and that names will not be disclosed. 78 �If the participant or that perons's parent, guardian or other spokesman agrees to participate, read through the PC? with then and make entries where appropriate. At the bottom, record the Date (month, day, aid year) that the PCS' is signed and print the Participant's full Same (First, Middle or Maiden, Last - do not abbreviate); record the appropriate Site Sianber (see section 3.3 above) and Participant Number (from the PLF); have the participant (or other appropriate person) sign the PCF; enter jour signature as witness; and record the participant's home Address (Street Number and None, City, State, and Zip Code) in the spaces provided. After data collection (administration of SQ and collection of milk sample) is completed, the participant (or that person's parent or guardian) should be given $5.00. The recipient must sign in the space provided at the bottom of the PCF to indicate receipt of the incentive. Should the signatures on the PCF for Participant and Recipient be other than the participant's, please explain in the Comments section of the SQ. Finally, as indicated in section 3.2.1, the top (white) copy of the PCF is to be attached to the appropriate SQ; the yellow copy is to be provided to the participant or her guardian; and the pink copy is to be retained by the data collector. 3.6 Study Questionnaire Before proceeding with administration of the SQ, read the justification and confidentiality statement in the box on the cover. Enter the appropriate Site (see section 3.3 above) and Participant (from the PL?) Numbers. Stapled inside the SQ you will find a set of pre-printed, selfachesive labels which are necessary to identify corresponding SQs and samples. Each label contains a unique Study Number, which should be the same on all 79 �labels in a set, and an indication of what the label is for. You should also have some labels that have Cj.ly a Study Number and a few that are completely blank; these are for your use in the event that a label is damaged or missing. If you use a label that has a Study Number only, you will have to write on the label what it is intended for, such as MILK; if you use a blank label, you must write on the label the Study Number and what i'C is intended for. Check to be sure that all the labels in a given SQ contain the same Study Number; if not, do not use the SQ and return it to RTI. If the Study Number is the. same on all labels, remove the one for the QUESTIONNAIRE and place it on the cover of the SQ over the spaces provided for the Study Number. Space for Comments is provided on page 5. If the.participant is under 18 years of age, the SQ may have to be administered in whole or part to the parent or guardian, and must be administered in that person's presence.- If the participant suffers from a speech or hearing deficit, or is otherwise incapacitated, the SQ may have to be administered to the spouse or some other spokesman. Item 1 - Race; Indicate the participant's race by placing an X in the appropriate box. This question may be answered by observation; however, if there is any doubt whatsoever, ask. Item 2 - Age; Determine and enter the participant's age in years as of the last birthday. Item 3 — Birthdate; Determine and enter the participant's exact birthdste (month, day and year). Again, remember to rightadjust and enter leading zeros. A note on dates: accept and record partial datest if that is all that the respondent can provide; in that case, indicate missing elements of the date 80 �with • dash ( ) — for example, April 1977 would be recorded as |01AJ - H j - |7|7j . Item 4 - Weight; Determine and enter the participant's approximate weight In pounds (to the nearest pound—no fractions!) or kilograms, in which case observe the decimal. Item 5 - Height; Determine and enter the participant's approximate height in inahea or centimeters. Item 6 - Current Employment; Determine if the participant is currently employed in any capacity and place an X in the appropriate box. If the answer is Yes, continue to Item 7; if the answer is No, skip to Item 10. Item 7 - Length of Present Employment: Determine and record the length of time that the participant has been employed by her•present employer; enter the units in the spaces provided and then place an X in the appropriate box to indicate whether the units represent days, months, or years. Item 8 - Occupation Away From Home; Determine if the participant's occupation usually takes her away from home and place an X in the appropriate box. If Yes, continue to Item 9; if No, skip to Item 11. This question, and Item 9 below, are aimed at eliciting information regarding the location of the participant's various exposure to the environment. Item 9 - Location of Present Employment; If the participant is currently employed, determine the nature (not the name) and location (street address, city, state, and Zip Code, if known) 81 �of Che employer. By naturet we mean Che type of business, such as service station, school, hospital, grocery store, doctor's office, hotel, restaurant, etc. Item 10 - Employment Statusr If the participant is not presently employed, determine which of the provided categories best describes the participant's status and place an X in the appropriate box. If the response is choice 1 or 2, skip to Item 15; if the response is choice 3-5, continue to Item 11. Itec 11 - Usual Occupation; Determine and record the participant's usual (or most common) occupation (when employed); be succinct e.g., high school coach, waitress, hotel desk clerk, taxi driver. Item 12 - Present Occupation; Determine if the participant is presently employed in her usual occupation (indicated in Item 11) and place an X in the appropriate box. Items 12 and 13 may be skipped for unemployed, retired and disabled persons. Item 13; If the response to Item 12 was positive, determine how long the participant has been employed in her usual occupation (recorded in Item 11) and record; enter the units in the spaces provided and then place an X in the appropriate box to indicate whether the units represent days, months or years. Item 14; Determine if the participant presently works at or in any of the listed occupations or establishments and place an X in each appropriate box. Item 15 - Present JSmoking Status.; Ascertain if the participant currently smokes cigarettes, and place an X in the appropriate box. If YES, continue to Item 16; if NO, skip to Item 18. 82 �*• I_ten_16 -_ Age at First Smoke; If the participant is a smoker (a positive response to Item 15), ascertain the age (in years) at which the participant started smoking and record in the spaces provided. Item 17 - Smoking Frequency: Ascertain how many cigarettes the participant smokes per day, an the average, and place an X in the appropriate box. If the participant uses tobacco in some form other than cigarettes, such as snuff, record in the space provided. Item 18 -Time Outdoors; Ascertain the average number of hours that the participant spends out of doors each day and record in the spaces provided — another indication of environmental exposure. Item 19 "Time Away From Hornet Determine how many hours of the day on the average the participant normally spends more than 2 miles away from home, and record in the spaces provided. This determination should be done separately for weekdays and weekends. Item 20 - General Health Status; Using the four qualifiers provided, ascertain the participant's general current health status and place an X in the appropriate box. Item 21 - Prescription Medications; Inquire as to whether the participant is currently taking any prescription mediaavionfs) on a regular daily basis and place an X in the appropriate box; if YES, determine and record the drug name - e.g., penicillin, oral contraceptives, Vallum, phenobarbital, etc. 83 �Item 22 - Non-prescription Medications; Inquire as to whether the participant has taken any non-prescription medications in the past 24 hours, and place an. X in the appropriate box; If YES, determine and record the drug name -e.g., aspirin, vitamins, Dristan, Bufferin, Alka-Seltzer, etc. Item 23 - Gasoline; Inquire as to whether the participant pumps her own gasoline, for example at self-service pumps, and place and X in the appropriate box. Item 24 - Egg Consumption; Determine and record the approximate number of -eggs that the participant has eaten in the past 48 hours. Again, in recording numerical entries, remember to right-adjust and enter leading zeros. Item 25 - Hobbies; Determine if the participant pursues any of the listed avocations and place an X in each appropriate box. Item 26; Determine if the participant pursues any activity that includes regular use of solvent glue or model airplane cement, and place an X in the appropriate box. Item 27 - Length of Residence in Area; Determine hew many years the participant has lived in the area, of interest, and record in the spaces provided. Round to the nearest year, except that if the response is less than one year record as [ < ! I I and terminate the interview; the individual is ineligible to participate further in the study. This situation should be detected during the screening process. 84 �Item 28 - Length of Residence at Current Address; Determine how long Che participant has lived at her current address; record the units in the spaces provided and place an X in the appropriate box to indicated whether the units represent days, months, or years. Use the most appropriate units and round to the nearest appropriate unit. For example, more than 28 days should be expressed in months and more than 11 months should be expressed in years. If the participant has resided at her current address for less than 12 months, but has lived in the area of interest for at least 12 months, record any previous addresses during the preceding 12 months (city and state is sufficient) in the Comments section. Item 29 - Cooling Appliances; Determine whether any of the indicated appliances or others, in which case specify, are used to cool the participant's home and place an X in the appropriate box(es) for all that apply. Item 30 - Home Garden; Determine if the participant's household consumes food grown in a home garden and indicate the response by placing an X in the appropriate box. If a positive response is obtained, determine the location of the garden and record. Location could be participant's backyard, or another community, in which case specify city and state; be as specific as possible. Item 31 __- Commercial Food Source; Determine where the participant's household usually obtains fruit and/or vegetables and record. 85 �Again, be as specific as possible. For example, if Che city or town has more than one store by the same name, the store name alone would not be an adeuqate answer; as a matter of course, record the name and location of the store, market, or vendor. Items 32-34 - Water Sources; In Item 32, try to determine the primary source of drinking water for the participant's household and place an X in the appropriate box. In Item 33, determine if the same primary drinking water source indicated in Item 32 is used for drink mixes such as coffee and tea; if it differs, indicate how. In Item 24, try co determine the primary source of water for cooking in the participant's household and place an X in the appropriate box. For example, some households in some areas of the country use bottled water for drinking and drink mixes but tap water (from whatever source) in cooking. Itea 35 - Other Household Tobacco Use; Inquire as to whether other members of the participant's household smoke, and place an X in the appropriate box; if YES, dpr.ernine if the other members smoke cigarettes, cigars, a pipe, etc. and place an X in each appropriate box. Item 36 - Occupation of Other Household Members: Determine if any other members of the participant's household work at any of the listed occupations or businesses, and place an X in each appropriate box. 86 �Item 37 - Hobbies of Other Household Members; Determine if any other members of the participant's household pursue any of the listed avocations, and place an X in each appropriate box. Respondent/Interviewer Information Item 38 - Respondent; Indicate, by placing an X in the appropriate box, whether the person who served as the primary respondent was the participant or some other person, in which case specify in the space provided. Iten 39 - Interviewer Number; Enter your assigned 3-digit Interviewer identification Number. Item 40 - Date of Interview; Enter the date (month, day and year) that the interview was conducted and the questionnaire completed. Item 41 - Interviewer Name; The name of the person administering the questionnaire should be printed in the space provided. Sample Information Item 42; Indicate, by placing an X in the appropriate box, whether or not a milk sample was collected; if not, explain in the • Comments section below. Item 43 - Date, and Tine of Milk Saaple Collection; If a milk sample is collected, record the date (month, day and year) and approximate time (using a 24-hour clock) of such collection. The time should correspond to the time that collection was completed; on a 24-hour clock, add 12 to the p.m. hours - e.g., 1:00 p.m. would be 13:00, 5:30 would be 17:30, etc. 87 �Iten 44 - Date Shipped to RTI; Record the date (month, day and year) that the respective milk sample was shipped to RTI, or turned over to an RTI representative. 3.7 Collection of the Milk Sample 3.7.1 General Remarks As indicated in section 1.0 above, the milk samples are being collected for chemical analysis by RTI as part of an EPA study to measure pollutant levels in human milk and evaluate the utility of using this body fluid in specific pollutant studies. The chemical compounds for which the samples will be analyzed are present in extremely low levels, so the utmost care and cleanliness must be used to prevent either contamination or loss. The instructions below are designed to preserve the integrity of the sample and should be followed precisely. 3.7.2 Sample Collection Instructions 1. The bottles provided have been thoroughly cleaned and should be kept tightly closed, except during sampling; do not wash or otherwise clean them. 2. Remove the MILK SAMPLE label from the sheet of labels in the appropriate SQ and place on one of the collection bottles. 3. The milk should be manually expressed directly into the the bottle; do not use breast pumps or other devices as the plastics in such devices would contaminate the sample. Hands should be cleaned and thoroughly rinsed to remove any residual soap; do not use rubber gloves. 88 �4. Collect as ouch milk as possible. Unless the mother has recently nursed her infant, at least half a bottle should be easily obtainable. Less than half a bottle is unuseable and does not constitute a sample. The ability of the participant to provide an adequate sample should be determined during the screening process. 5. Immediately cap the bottle and double check to see that the study numbers on the bottle and questionnaire match. 6. The milk sample should be immediately frozen following collection and remain so until shipping. 7. Note any deviations from this procedure in the Comments . section of the appropriate SQ. 3.7.3 Shipping Instructions 1. Pack the container as it was received. 2. Fill the can with dry ice. 3. Make sure that there is adequate padding to prevent breakage, that all excess space is filled with packing material. 4. Fill out enclosed Federal Express forms, attach to the outside of the box, and seal the box. 5. Call Federal Express and have them pick up the package. 6. When Federal Express picks up the package, call Dr. Mitch Erickson at RTI (see below) to notify him that Federal Express has picked up the package; if Dr. Erickson is ouc, leave an appropriate message with his secretary. 89 �7. Mail Che corresponding questionnaires to RTI in one of the envelopes provided. 8. When the questionnaires are in the. mail, call Ben Harris at RTZ (see below) to notify him that the questionnaires are in the mail; if Mr. Harris is out, leave an appropriate message with his secretary. 4.0 Confidentiality All survey research conducted by RTI is based on highest ethical standards, including those related to confidentiality. These standards are applied from the earliest steps of deciding whether or not RTI should participate in a proposed survey to the final steps of analyzing and reporting the information obtained. Strict precautions must be observed at all times to protect the rights of those whom we interview or about whom we collect data. Such 9 precautions are built into the study design, so that promises of confidentiality and anonymity will be upheld during all phases of data handling and analysis. Ho amount of effort to insure confidentiality will be successful, however, unless those responsible for data collection in the field maintain equally rigid standards, treating with utmost confidence all information offered or observed during data collection. Successful and meaningful survey research is dependent on the establishment of trust between individuals engaged in data collection and sources of information, and maintaining this sense of responsibility to the public throughout all survey activities. Each data collector will be required to sign in duplicate a contractual agreement which Includes provisions on confidential treatment of data. This agreement is designed to protect you as well as RTI and participating institutions and individuals. A copy of this agreement appears in Attachment 2. 90 �The Importance of cotal confidentiality cannot be over-emphasized. Any breach of confidence could result in litigation. 5.0 Contacts with Project Staff During the data collection period it will be necessary for data collectors to maintain regular contact with RTI project staff by telephone. While you are collecting data, problems or confusing issues may arise that are not addressed in these instructions. You are encouraged to telephone RTI whenever you experience a problem or encounter a situation which you feel you cannot adequately handle. All supplies required for data collection will be furnished by RTI. Should you require additional supplies during the conduct of data collection, inform your RTI contact so that proper arrangements can be made. Need for additional supplies should be anticipated so that your work will not be delayed while you await receipt of needed items. All study-related items that are in your possession at the conclusion of data collection are to be returned to RTI or disposed, of according to instructions from your RTI contact. Calls to RTI should be made between the hours of 8:30 a.m. and 5:00 p.m. (Eastern Time), Monday through Friday, to RTI'3 toll-free number, 800-334-8571. Request to speak to the appropriate project staff member listed below: Or. Mitch Erickson Extension 6505 (regarding milk sample collection) MX. Ben Harris Extension 6055 (regarding participant selection and questionnaire administration) 91 �If che problem is particularly acute, and you have trouble getting through on .the toll-free line, call collect 919-541-6505 (Dr. Erickson) or 919-541-6055 (Mr. Harris). After 6:00 p.m. Eastern Time you may call Mr. Harris collect at work (919-541-6055) or person-to-person at home (919-942-6988). 92 �Attachment 1 Data Collection Instruments 93 �OMVNo. IM-ITtOI im Snnmoir 1H RESEARCH TRIANGLE INSTITUTE STUDY OF ORGANIC COMPOUNDS IN HUMAN MILK PARTICIPANT CONSENT FORM I jndtrttand thit Rntireh Triangla Innitutt ii angagad in * nudy of vinous organic compounds u thtv aopaar in hunan milk. I undantand th*t tha wrvty ii baing eonduettd in onitr to maBura th» Itvili of various organic compciundi in human milk, and it limittd to tha purpota natad. I hirthar undamtnd thit thi lurvtv '« baing conductad undar tht autpica* Of thi Unitld Stitu EnvironmantaJ Protaetion Agtnev in emmmion with [Kaae of Local Agency] • I do htnfav fncly eonunt to piriieiott* in thit nudy of ergviie compound* in human milk ind undtnond thai my airbcipttion will contiit of eroviding miwtn to a sutiuonnain ralawd to tnvironmtntai txpotun and providing a milk tampia of aopraximtttlv 100 ml. I undtrnand that an agtnt of Rmareh Tnanolt Initituta will acmm ttar tha auaitionnaira and collact tfw milk tampia, aftar which I will nMtint an incannva of hva dollara for my participation. I unaarnand thai my na.1"* will not bt voluntarily ditdoiad. or raltrrad to in any way whan compiling and avaluating tni nrauln of th* nxdy. I undarnand tfiat oarticipation in tfiii ttudy may rawlt in no dirtet banafia to rrn. om«r tnan tnou datcribad harain. and that I am fraa to wi^draw from thii nudy at any tima. It hat bnn axpiainad to m« that than ara no lignificant nik: to ma from participation in thii ttudy. I funtiar undarnand that whila panicioating in thi itudv I will b* frat to atk any quattiont eoncaming ma nudy: if I hava any funnar Ouanioru about trw projaet, I know that I am fra« to contact or Mr Banjamin S. K Harrit, III, Survay Ooarationi Canttr, Haaarch Triangla Innituta, Raiaarch Triangli Park. Norm Carolina Z770S, vlaphona numbtr 91S-S*1-605S. One . , " • , i . ' " Ifinml u D SIGNATURES: ISotti Htimetr mt Html Karl Oaal 94 TTTI t£p Can; �STUDY OF ORGANIC COMPOUNDS IN HUMAN MILK Conduced by: *nmtra\ ~rmrq* Inuai* Off to e/ To«« SUHWMM IfwRuinwitM PmnctKNi tyitt 2MW _ RnHn« Trian«i« fw*. Norti CmliiM 2T708 PARTICIPANT LISTING FORM I on 4i* c NOT1CI!: All i ta K«d in wict eenfldinei. mil « MM only by gmoni rmit Mnnfladon «f HI indn^uw or m •DDil«uiMni mil in md tor ow purpoMi IORM (or *• mrtv. m) will net M tfiKlOMtl Of (VWUMl TO OCflVT PWtt Of UMd "Of OAV OCflOf D 95 �COMMENTS 96 �OMINO. 1U-S7W Aoorewi txeirn StmrnMt 19 STUDY OF ORGANIC COMPOUNDS IN HUMAN MILK Iponmtf by. Conam.ua by: <MiM of Ton tmiromwnul Prannion A^aiQ NMAinfton. O.C. «M«0 ft«Mrah Triwigto Imtaiu fttMKft Triwifli Nrt. Nam Cwaiw 27709 QUESTIONNAIRE THE RESEARCH TRIANGLE INSTITUTE OF RESEARCH TMIANCLE PARK. NORTH CAROLINA. IS UNDERTAKING A RESEARCH STUDY FOR THE U.S. ENVIRONMENTAL PROTECTION AGENCY OF LEVELS OF VARIOUS ORGANIC COMPOUNDS IN HUMAN MILK. THE INFORMATION RECORDED IN THIS QUESTIONNAIRE WILL BE HELD IN STRICT CONFIDENCE AND WILL BE USED SOLELY FOR RESEARCH INTO THE EFFECTS OF ENVIRONMENTAL FACTORS ON PUBLIC HEALTH. ALL RESULTS WILL BE SUMMARIZED FOR GROUPS OF PEOPLE; NO INFORMATION ABOUT INDIVIDUAL PERSONS WILL BE RELEASED WITHOUT THE CONSENT OF THE INDIVIDUAL. THIS QUESTIONNAIRE IS AUTHORIZED BY LAW (P.L. 94-469). WHILE YOU ARE NOT REQUIRED TO RESPOND. YOUR COOPERATION IS NEEDED TO MAKE THE RESULTS OF THIS SURVEY COMPREHENSIVE. ACCURATE. AND TIMELY. Stu*.r nuflitar: • D Stanumbtn 97 Prttetpim number: �Fint, I would Ilk* to «k torn* gutmi qu*ftiom obout you. 1. Mm: QHWWI. [[]j f"*™^ I ™ fl|»'«*-""*( p. E "'•«••>«*•''•'« B I I Hlventa *ri*ifi I m-m-cn I l«(« 2. Whn «•» your •(• in y«n K IBM hirtm»y7 1 Whn • your htightr | j |ircn« | | DID- n j | I ureuld like to uk lomt quottiem about your oeeupnien. B. An vou priMRily *mDlov*ri IK Wf cmehy? | ' | Vot ICamtnni \ t ] No <0e ta 0. 101 7. How long hw*you bion unploy** Bv your prownt unployir? [__JU|»K» LlJt>*v' LiJMDmn uJ1>Mr> (. Doo) your eecupttion iou*liy t>k* you M*V from horn*? jjj Voi ICotmnutl \ * |No/6«io 0. Ill I. flhf. a Vw nnurt *nd loe*>.?n Ittrxt iddr»«l of *<• compmy for whWi you wort? 1C. If net prmntlv •mpley*a. whteh of «u foUONin) b*n d*Briboi your n*B»7 HOUHWlt* ICc u a »» 11. Whn atwm youruwd occuorton? tSe*aty> . 12. Art von prmnoy •mplt^Bl in thto <xcuORien7 [ < [Y» a No 13. If y«i to ibon ouMOon, haw long hm you bun vnoloyid In Ml i PT~| 1 I I I" "" lCh«e*«oteri . Do you work n of in «ny of *• following oeeupni I ' I 'wrong [_SJ Dry dwung ITIrwL_J°"" [T • I Serve*ration/pr*j»/«nj>««r»p*» PnralMii pteni hirnlBira r«f hiMikii or rap** 98 EV- �tteit I would Ilk* to «k urn* quarternragudlno,your hctltti wd pononol tabta. 11 Oo you motor Ifc H Voi ICum^MJ I {TJNo»o«af« HQW old won you Mritvn you flnn icmtd 17. On On oiorin. haw m«ny cltirvRM do you ««oti oor ON' QJ LM ttun M port (M «praMd QJ About 1H p«la I2M4 c*nml [jj About » OMk 15-14 lifBuart Qj About J p«ki O8-49 clpnmi) I pock I1H4 iljatnoJ NCTh QMor(*in2poela(SQarfflara*itnttHl /f *w ttneiptn tarn Mawco /« »<n» MMr ftm feoXr MM 11 Win it «M n«raai numew o< houn am you omd out ol doon forii doy? 19. Haun Mowfflmyhaun of *• diy. M *• »mi|lL do you namully OMI* unv from Kamnf Mmnaf •**»!•» «x n»i«unt Mount ~" [ | ~"l ». H.*-"* ( f| Wan do you eoniov «M eumm lonii ol your koil«7 ffiktv* ancj QfaortomQ Hood Qj »>* 21. Ait you aurrwrty «Ui«j ony »i«u»iloa modkabodUl on * rojulv <My br^tf J2. M««you t^w*nvnon«>«BrioitoniMdlador«kl«M»on4«lH)un7 33. Oo you puma yaufoMipir X. 8L Voi How mony *)gi h*x you «on * M pon < Oo you punuo «iy of tn MHo«Hn| hobela? tttac* o« otn ojp^rJ |»umHuioro)lnWiini XL Q] Yoi | « | PUnant Q] Q] leoto mod^i Oo you purojo ony onMiy «in Indudoi ropilor ino of tolvtm gluo or « [JJYoi Q]"*o 99 QJ Voi Q Q No �L*rty, I would Ilk* to mk lomt quortc™ (bout your rodrianc* md houMhoJd. 27. HIM mony y«n hw* you «•* <" «* "»^ I I ~| Vnn a. Now lor* hm yen IM n your cwnm oddraorf 9. DC TOM ceo! your norm with Mr of Ow hXlc«rln» •ollvotf ffikM* •» Ultr •Pft'J \ \ | Unta [_jj ten [* I » | Window *Jr oondltKmrli) | » | C*imt oihoyn hnUI |_jj Do AM know [T] EvoBomw* MOtorta) jjjj Other f* Q Cirwtatlni Mi) Don your heu«*old ore* ony of la OMI food In a hem, pr4«n? Qj V« 31. Do mn know Q WK« dew v«uf heu»HcW etoin fmti tntt milt, MoratHM? Ootdtrl 12. Whit • 9li pnmw mm 0f ytur nmr tar dnnkinf? [»JT«p.i [TJ Tip • municipil wppi, n [Tj »c If no. how *o« h dlttorr «3iMBnV/ Whit a Bit prirMry mm* of your «•»» for cooking? [ * I Top • munlekHl wpery }& | * | Top - DnVoo wdl Com xvon. MM m your imMMd motor If ytr. duct til Mff MPV/ M. Qj Voi | * | Oo not [JJ No Qj Oo not know JjJ QoHitai Qj OpMl [JJ p|p,| «] OOw t&atityl Oo» onyom •• In your houMhaW work • ony of th« followini oceuoKurK/buvnMir*? lOuet off Kwr oppryj Q feimlni [ * | Chomal ptam [_^1 Dry elo»n| | * | Nmlowii plwn 17. [_*J Oa Ml know li that th« ovnt prinury mm ft xnor nx dnnk mi»« ueri • eoffoi. iov KookAid. me' Q]VII 34. | « | T«s> • prMB Mil [_»J fonriei n»don/oii»oi/>noino npoir ( * | •vmnur* wflnWilnH or n»lr Do* invent *IM if your ttaafheU pumn ony of «MtoMowmthobbW /Due* *» «Ht*&Y.> r~i r—I r—i IJJ.rHirnhun nftnMiki| I » I la RESPONDENT/INTERVIEWER INFORMATION M. Movendonc [j] [_»J »« 41. I0*rl lYmrl en - CD - nn I 100 �SAMPLI INFORMATION 43. W» i n*k wnpi* mUmuit M V« I I No «. ,,^-» en-nn-en —• Won*/ 44. On *«Md » I (Dnt -m-m COMMENTS 101 Houn : Minuw I : �Attachment 2 Research Triangle Institute Data Collection Agreement 102 �for Research Triangle Institute DATA. COLLECTION Project Mo. AGREEMENT X, . agree to provide, as in employee of Poverforee Company, Inc., field data collection services for Research Triangle Institute in connection with the project named above. a. X agree to provide services within the guideline* aod •pacifications for project data collection activities provided by Research Triangle Institute; b. X an aware that the research being conducted by the Institute is being perfomed under contractual arrangeaent with t c. X agree to treat as confidential all information secured during interviews or obtained la any project-related way during the period X aa providing services to the Institute; d. I shall at all tines recognize and protect the confidentiality of all information secured while providing ay services throughout the conduct of this research project; e. I aa aware that the survey instruments completed fora the-basis from which all the analysis will be dravn. and therefore agree that all work for which X subait invoices will be of high quality •and la accordance with project specifications; and f. X fully agree to conduct myself at all tlaet in a manner that will obtain the respect and confidence of all individuals from whom data will be collected and I will not betray this confidence by divulging information obtained to anyone other than authorized representatives of Research Triangle Institute. Dated at (City/Town) (State) thia . day of 19_ Employee For Research Triangle Institute Disposition: Original to KTX; yellow copy retained by Employee. 103 �APPENDIX B SAMPLING AND ANALYSIS OF VOLATILE ORGANICS IN MILK 104 �SAMPLING AND ANALYSIS OF VOLATILE ORGANICS IN MILK 1.0 Principle of the Method Volatile compounds are recovered from an aqueous or solid sample by warming the sample and purging helium over it. The vapors are then trapped on a Tenax cartridge which can be introduced by thermal desorption directly into the GC/HS for analysis. This protocol is the result of extensive development efforts.(1'9) 2.0 Range and Sensitivity For a typical organic compound approximately 30 ng is required to obtain mass spectral identification using high resolution gas capillary GC/MS analysis. Based on a 50 g milk sample, a detection limit of about 0.6 JJg/kg would be possible. The dynamic range (limit of detection to saturation on the mass spectrometer) for a purged sample is M.O ; however, smaller samples may be purged and the upper end of the range increased commensurately. 3.0 Interferences Two possible types of interferences must be considered: (1) material present in the sample which physically prevents the effective purge of the •ample, and (2) material which interferes with the analysis of the purged sample. In the former case, several techniques have been developed to . handle such problems (e.g., foaming) by diluting and stirring the sample. The second case is minimized by the use of GC/MS for the analysis, since unique combinations of m/£ and retention time can be selected for most compounds. This permits the evaluation of compounds even though chromatographic resolution is not obtained. 4.0 Precision and Accuracy The purge and trap technique has been evaluated for a variety of matrices using model compounds which are expected to be typical of volatile halogenated compounds. 105 �The recovery of the purge step was validated using cow's milk samples spiked w-'th 14C-chlorofonn, 14C-carbon tetrachloride, 14C-chlorobenzene and 14C-bromobenzene. The average recoveries were 88, 88, 63, and 35 percent, respectively. The recoveries correlate roughly with volatility (inversely with boiling point), so anticipated recovery for other compounds may be interpolated from these data. 5.0 Apparatus 5.1 Purge Apparatus The purge apparatus is shown in Figure 1. 5.2 Sampling Cartridges The sampling tubes are prepared by packing a 10"en long x 1.5-cm i.d. glass tube containing 6 cm of 35/60 mesh Tenax GC with glass wool in the ends 3} to provide support. (2 ' Virgin Tenax is extracted in a Soxhlet extractor for a minimum of 24 h with redistilled methanol and pentane prior to preparation (•> 3) of cartridge samples. ' After purification of the Tenax GC sorbent and drying in a vacuum oven at 100°C for 2-3 h all of the sorbent material is meshed to provide a 35/60 mesh-size range. Sample cartridges are then prepared and conditioned at 270°C with helium flow at 30 ml/min for 30 minutes. The fit conditioned cartridges are transferred to Kiroax (2.5 cm x 150 cm) culture tubes, immediately sealed using Teflon-lined caps, and cooled. This procedure is performed in order to avoid recontamination of the sorbent bed. (2' 3) 5.3 GC/MS/COMP The volatile halogenated hydrocarbons purged from water are analyzed on either an 1KB 2091 GC/MS with an LKB 2031 data system or a Varian HAT CH-7 GC/MS with « Varian 620/i data system. The sample, concentrated on a Tenax GC (2 4) cartridge, is thermally desorbed using an inlet manifold system. ' The operating conditions for the thermal desorption unit and the analysis Tenax GC cartridges lire given in Table 1. 6.0 Materials 6.1 Sampling Clean, 120 ml, wide-mouth glass bottles with Teflon-lined caps are used for the collection of milk samples. 106 �TENAX CARTRIDGE THERMOMETER -20tcl50°c HELIUM 'PURGE THERMOMETER ADAPTER -with 0-ring HELIUM INLET TUBE ¥ 10/18 LIQUID LEVEL 100 ml ROUND BOTTOM FLASK MAGNETIC STIRRING BAR Figure B-l. Diagram of headspace purge and trap .yatea. 107 �Table H-l. INSTRUMENTAL OPERATING CONDITIONS UC* 2091 Deaorptlon chamber temperature 265 IS *L/»ln 10 HlVmia Deaorption tlM 8.0 Bin 8.0 mla Capillary trap temperature during deeorptlon -196»C -196"C Temperature *f capillary trap darlag injection onto rolMui -196*C to 2SO*C - tbea held at 190*C Tiae of He flow through capillary trap 12 3/4 •• ! 12 3/4 ail. He flow through column laveep time] 00 270 Deaorptloa chamber Re flew o VarUn HAT CH-7 f .5 »tn 4 •• ! Carrier flow 2.0 BL/.ln 1.0 ml/mlo Capillary column 100 • SK-30 SCOT 20 • 8C-30 VCOT Column temperature 30*C for 2 »1«, then « / ! to 2*0* ••• 20 •» 240* at 4»/»ln Bcaa range 5-490 dalton 20 * 500 dalton Scan rate 2 aec full acale 1 aec/decade Scan cycle tl«* 2.4 aec 4.3 aec Scan • 4 oe parabolic eiponeatial Trap current 4A Fll«Bent current SO|iA 30i 0|A Accelerating Tolctage 3.5 kV IkV �6.2 Purge Teuax cartridges - 16-mm o.d. x 10.5 cm glass tubes filled with 6 cm of Tenax with 1-cm glass-wool plugs in each end. Charcoal cartridges - 16-mm o.d. x 6 cm filled with 4 on of charcoal and glans-wool plugs in each end. Glass culture tubes with Teflon-lined screw caps. 7.0 Procedure 7•1 Collection of Field Samples Milk (60-120 ml) is expressed directly into the wide-mouth bottle, capped tightly, and frozen for shipment and storage. To preserve the integrity with respect to volatiles, handling and transfer must be minimized. 7.2 Purging of Volatiles The apparatus is assembled as depicted in Figure 1, including the Tenax GC cartridges (1.5-cm diameter x 6.0-cm length). A carbon cartridge 1.5-cm diameter x 4.0-cm length is connected to the effluent end of the Tenax cartridge to prevent contamination of the cartridge by laboratory vapors. The milk sample is cooled to ~A°C, shaken vigorously and 100 ml diluted with 350 ml distilled water. The pH of the solution is adjusted to 4.0 with sulfuric acid. A glass-wool plug is inserted into the center neck of the flask just above the level of the solution and, with the flask in a heating mantle, the solution is heated to 70°C while it is stirred with a magnetic stirrer. The sample is purged at 15 ml helium/min and 70°C for 90 minutes. The loaded cartridge is removed and stored in a culture tube containing 1-2 g CaSO, desiccant for 2-12 h. The desiccant is removed from the culture tube and the dry, loaded cartridge stored at -20°C. 7.3 Analysis of Sample Purged on Cartridge The instrumental conditions for the analysis of volatile compounds of (2-9) the sorbent Tenax GC sampling cartridge are shown in Table 1. The thermal desorption chamber and six-port valve are maintained at 270°C and 200°C, respectively. The helium purge gas through the desorption chamber is adjusted to 15-20 mL/min. The nickel capillary trap at the inlet manifold is cooled with liquid nitrogen. In a typical thermal desorption cycle a sampling cartridge is placed in the preheated desorption chamber and helium gas is channeled through the cartridge to purge the vapors into the liquid 109 �nitrogen cooled nickel capillary trap. After desorption the six-port valve is rotated and the temperature on the capillary loop is rapidly raised; the carrier gas then introduces the vapors onto the high resolution GC column. The glass capillary column is temperature programmed from 20°C to 240°C at 4°/min and held at the upper limit for a minimum of 10 minutes. After all of the components have eluted from the capillary column, the analytical column is cooled to ambient temperature and the next sample is processed. 7.4 Quantitation All data are acquired in the full scan mode. Quantitation of the halogenateci compounds of interest is accomplished by utilizing selected ion plots (SIPs), which are plots of the intensity of specific ions (obtained from full t.can data) versus time. Using SIPs of ions characteristic of a given compound in conjunction with retention times permits quantitation of components of overlapping peaks. Two external standards, perfluorobenzene and perfluorotoluene, were added to each Tenax GC cartridge in known quantities just prior to analysis. In order to eliminate the need to construct complete calibration curves for each compound quantitated, the method of relative molar response (RMR) is used. In this method the relationship of the RMR of the unknown to the RMR of the standard is determined as follows: std where A std unk g GMW = = = = = - Auak/m°leSunk "A.td'"lM.td peak response of a selected ion, standard unknown number of grams present, and gram molecular weight. Thus, in the sample analyzed: . tAtok)(OWunk)(l.td) 110 �The value of an RMR is determined from at least three independent analyses of standards of accurately known concentration prepared using a gas permeation system. ' The precision of this method has been determined to be generally ±10 percent when replicate sampling cartridges are examined. 8.0 References 1. Michael, L. C., M. D. Erickson, S. P. Parks, and E. D. Pellizzari, Anal. Chem., 52, 1836-1841 ( 9 0 . 18) 2. Pellizzari, E. D., "Development of Analytical Techniques for Measuring Ambient Atmospheric Carcinogenic Vapors," Publication No. EPA-600/276-076, Contract No. 68-02-1228, 185 (November 1975). 3. Pellizzari, E. D., "Development of Analytical Techniques for Measuring Ambient Atmospheric Carcinogenic Vapors," EPA 600/2-75-075, 187, (November 1975). 4. Pellizzari, E. D., J. E. Bunch, R. E. Berkley and J. McRae, Anal. Chem., 48, 803 (1976). 5. Pellizzari, E. D., J. E. Bunch, B. H. Carpenter and E. Savicki, Environ. Sci. Tech., 9, 552 (1975). 6. Pellizzari, E. D., B. H. Carpenter, J. E. Bunch, and E. Sawicki, Environ. Sci. Tech., 9, 556 (1975). 7. Pellizzari, E. D., Quarterly Report No. 1, EPA Contract No. 68-02-2262, February, 1976. 8. Pellizzari, E. D., J. E. Bunch, R. E. Berkley and J. McRae, Anal. Lett., 9, 45 ( 9 6 . 17) 9. Pellizzari, E. D., Analysis of Organic Air Pollutants by Gas Chromatography and Mass Spectroscopy. EPA-600/2-79-057, 243 pp., March, 1979. Protocol Prepared, June, 1980 111 �APPENDIX C ANALYSIS OF SEMIVOLATILE ORGANIC COMPOUNDS IN MILK 112 �ANALYSIS OF SEMIVOLATILE ORGANIC COMPOUNDS IN MILK 1.0 Principle of the Method Milk samples are collected from nursing mothers and frozen until ready for analysis. An aliquot of the thawed sample is then extracted, cleaned up by Flori.sil column chromatography and analyzed by GC/MS/COMF. The extraction procedure used here is preferable to that used by the AOAC , since both polar and nonpolar compounds are extracted from the milk. Tie AOAC method is designed for pesticide residues and would not efficiently extract polar and/or acidic compounds. Opea column chromatography is a necessary prerequisite to GC/MS/COMF analysis. Although some loss of sample may occur during the extraction and cleanup, these procedures remove proteins and fats from the sample which would otherwise create overwhelming interferences for GC/MS/COMP analysis. Since the compounds of interest in these fractions cover such a broad range of volatilities, the GC/MS/COMF analysis can be rather complex. The higher PBBs of interest in the extracted fraction must be chromatographed on a very short column (45 cm x 0.2-cm i.d., 2 percent OV-101 on Gas-Chrom Q) at high temperatures to elute them as sharp peaks which may be identified and quantitated. These chromatographic conditions are not applicable to more volatile compounds since they are not resolved from the solvent. Thus, the extracted fraction is analyzed a second time using a nonpolar SCOT capillary column (either OV-101 or SE-30 liquid phase) to separate and identify semivolatile constituents (e.g. chlorobenzenes, PCNs, pesticides, etc.). The chromatographic conditions are typically 60°C initially, programmed to 2AO°C (or the column limit) at 6°/min. The: mass spectral data are stored on magnetic tape. The mass spectra of interest: will be printed out by the instrument operator for qualitative analysiii. Quantitation from this data may be achieved by integrating the area of selected ions and comparing them to the area of the external standard. 113 �The sensitivity of the determination may be significantly improved for quantitative purposes by using the technique of selected ion monitoring (SIM), also known as multiple ion detection (HID). This technique monitors up to 9 ions at a sensitivity 10-100 greater than the normal operating mode. This technique is used for quantitation of compounds in samples where the increased sensitivity is necessary for detection or accurate determination. 2.0 Range and Sensitivity The detection limit of the GC/MS/COMP system has been determined to be about 5*50 ng/pL for pesticides such as v-BHC, £,£(-DDE, atrazine, trifluralin and heptaculor using a 40 m SE-30 capillary column. When SIM was used, the detection limit was about one order of magnitude less (i.e., 0.5-5 ng/pL). The detection limit for tetrabromobiphenyl is about 1 ng/[.(L in the SIM mode using A5 x 0.2-cm i.d. column packed with 2 percent OV-101 coated on GasChrom Q. For an instrumental detection limit of 1 ng/pL, the overall sensitivity of the method should be about 6 ng/mL (6 ppb) milk assuming a 50 ml milk sample extracted and extract concentrated to 0.3 ml. This detection limit may be improved by using SIM and may be worsened by background interferences. 3.0 Precision and Accuracy When electron capture gas chromatography (GC/ECD) was used, the mean recoveries from cow's milk for seven replicates ranged from 57 to 93 percent for six model compounds. Thus, the results obtained may be as little as half the actual amount in the sample. The relative standard deviations (RSD) for the above replicates ranged from 11 to 33 percent, with the average RSD at 21.7 percent. Thus the precision of the method is about + 20 percent. It is anticipated that accuracy and precision will improve with experience with the method. 4.0 Apparatus 4.1 Gas Chromatograph 3 A Fisher-Victoreen 4400 gas Chromatograph with an H electron capture detector, a 10 AFS electrometer, and a 1.0 mV recorder is used. 4.2 Gas Chromatography Column For most compounds, separation is achieved using « 40 m SCOT glass capillary column coated with 1 percent SE-30 and 0.32 percent Tullanox. For 114 �the compounds of very low volatility (e.g. the higher PBBs) which will not chromatograph'on the capillary column, a 45- x 0.2-cm i.d. glass column packed with 2 percent OV-101 on Gas-Chrom Q is used. 4.3 Liquid Chromatography Column A 24-mm i.d. glass column with a Teflon stopcock is used. 4.4 Gas Chromatography/Mass Spectrometer An LKB 2091 gas chromatograph/mass spectrometer with 2 PDF 11/4 computer is used. The system is equipped with a glass jet separator and is used with either glass capillary or packed glass column. 5.0 Materials Kuderna-Danish evaporators: 5 ml receivers 250 ml KD flasks Snyder columns 500 mL flat-bottom boiling flasks 250 ml separately funnels Clean glass wool Whatman 1 P/S .filter paper Florisil Sodium sulfate (anhydrous) Acetone "Distilled in Glass", redistilled Pentane "Distilled in Glass", redistilled Toluene "Distilled in Glass", redistilled Ethyl ether "Distilled in Glass" 6.0 Procedure 6.1 Extraction (1) Mix 50 mL (or volume available up to 50 ml) of a milk sample with clean glass wool and 150 ml of acetone to precipitate the proteins. (2) Decant and filter the acetone/water layer. (3) Repeat steps 1 and 2 with two 50 ml acetone fractions. (4) Concentrate to about 20 mL using a Kuderna-Danish evaporator. (5) Extract the precipitate with 40 mL of toluene; decant and filter the toluene layer. 115 �(6) (7) (8) (9) (10) Combine the toluene extract and the acetone extract with shaking. Let the layers separate and draw off toluene (top) layer. Repeat Steps 5-7 with 40 ml toluene and then with 10-20 mL toluene. Discard the lower water layer. Dry the organic layer with anhydrous sodium sulfate and concentrate to desired volume using a flat-bottom boiling flask and Snyder column. Quantatively transfer to a vial and concentrate to 5-10 mL under a gentle stream of nitrogen. 6.2 FlqrisrLl Column Chromatography (1) Prepare Florisil by beating to 130°C for at least 5 hours. (2) Prepare a 24-mm i.d. column so that the Florisil is 10 cm high after settling. (3) Place about 1 cm of anhydrous sodium sulfate on top of the Florisil. (4) Rinse column with 40-50 mL pentane, never allowing the solvent to go below the Na.SO, layer, as channeling may result. (5) Add up to 10 mL of sample to column. (6) Elute with 200 mL of 6 percent ethyl ether/pentane solution at <5 mL/min. (7) Collect and concentrate in a Kuderna-Danish evaporator. (8) Evaporate under nitrogen stream to 1 1.5 mL. Quantitatively transfer to a vial, store in a freezer. (9) If sample solidifies after concentration, repeat the Florisil cleanup (Steps 1-8). 6.3 Standards Standards are spiked into the sample following the extraction and workup (d..-pyrene was used at 200 ng/mL). 6.4 Analysis 6.4.1 GC/MS/COMP Analysis for Semivolatiles Inject 0.2 yL onto a 40 n SE-30 SCOT capillary at 60°C initially, program at 6°/min to 240°C, then hold until no more peaks are observed. Collect mass spectral data at 2 sec/scan from m/z 20-500. Compounds amenable to this analysis include organic compounds with volatility lower than that for purgeable compounds. Only the very low volatile compounds (e.g. higher PBBs) will not elute from the capillary. 116 �6.4.2 GC/MS/COMP Analysis for Low Volatile Compounds 6.4.2.1 Normal Procedure Inject 1.0 pL onto a 45 x 0.2-cm i.d. glass column packed with 2 percent OV-101 on GasChrom Q at 220°C initially, program to 300° at 12°/min and hold until all peaks have eluted. A helium flow rate of 20 mL/min is used. The mass spectrometer is scanned from m/z 20-1000 at 2 sec/scan. 6.4.2.2 Alternate Procedure Using the same chromatographic conditions analyze the sample by SIM. Preselect up to 8 ions characteristic of the compound(s) of interest and one ion characteristic of the standard. Retention times provide qualitative identifications. Peak areas may be used for quantification as discussed below. This alternate procedure has 10-100 times better sensitivity than the full scan mode and provides faster quantitative results. The main disadvantage is that only preselected compounds may be identified. In addition, if specific halogenated compounds are found to be present with little interference in most samples, they may be analyzed by GC/ECD. This procedure improves the sensitivity and reduces the analysis time (since GC/MS/COMP requires an offline data output). If GC/ECD is used, approximately 10 percent of the analyses are verified by GC/MS/COMP. 6.4.3 Qualitative Data Interpretation Spectra are interpreted by visual comparison with standard spectral (2 3) reference collectionsv ' where possible. Where standard spectra are not available, tentative identifications are made based upon interpretation of the mass spectrum. Where possible, the GC retention time is also used to assist in the identification procedure. All identifications and interpretations are checked independently by other experienced chemists or spectroscopists to assure that the interpretations are correct. 6.4.4 Quantitative Analysis In order to eliminate the need to construct complete calibration curves for each compound to be quantified, the method of relative molar response (RMR) is used. Successful use of this method requires information on the exact amount of standard added and the relationship of RMR (unknown) to the RMR (standards). In general, the RMR for a compound is determined for a 117 �characteristic ion (parent or fragment) in its mass spectrum. The integrated ion current may also be used, but is generally less precise. The value of RMR is determined from at least three independent analyses. The method of calculation is as follows: A ./moles unknown/standard " Astd./moles std. . .. A = peak area, determined by integration or triangulation of the total ion current or for a selected mass of each compound . "/U ». A = peak area, as above g = number of grams present GMW = grain molecular weight Thus, in the sample analyzed: 7.0 References 1. Horowitz, W., ed., AOAC Methods of Analysis, 12th ed., Association of Official Analytical Chemists, Washington, DC. (1975). 2. McLafferty, F. W. , £. Stenhagen, and S. Abrahammson, ed., "Registry of Mass Spectral Data," John Wiley and Sons, New York (1974). 3. Eight Peak Index of Mass Spectra. Vol. I (Tables 1 and 2) and II (Table 3), Mass Spectrometry Data Centre, AWRE, Aldennaston, Reading, RG74PR, UK (1970). Protocol Prepared, June, 1980 118 �APPENDIX D VOLATILE COMPOUNDS IDENTIFIED IN SELECTED PURGES OF MOTHER'S MILK 119 �Table D-l. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO. 1081 (Bayonne, KJ) Chromltoiraphlc Faak Mo. Uiitiaa fnp. C'C) CUr o»» tographic PftAk. MOa QMBOUBd riuttoB Taap. CO CnayBUBd 41 150 £-»ct«. 42A 152 421 132 tatracblBroatbylaM CjE16 laoaar (tut.) CgE16 lanMT (MBt.) •llauaa C.E, , iaoaar (MBt.) 8 16 ehlorobman* 1-ehlorohaicaBa (cant.) •thylb.««. STlaaa laoMr r.s carbon dloxlda cblorocriflneroa* chu* propylaa* C^Uomr (•6 C 43 44 154 4 5 6 f,7 C4Bj iaOMt 45 159 V3 acauldabjrda 46 161 74 71 •13 aeatma 47 74 48 49 168 SO 171 3»hapf BTMriiw J II r imrnift SI 52 171 1-haptBBBB* 173 acTTU* .13 93 87 t ri cUoraf luenv* cbw* c.-paBtaoa iaeprapaaol •atbylua cblorida fnoa 113 carbon dlaulfida B-bucaaal cyclopaatam 163 166 89 91 92 94 14 U 1 1 58 (1 2 3 8 9 76 77 10 79 11 .to 12 13 14 IS 16 17 4*10 *"•" S34 531 S3C 173 173 174 C,B,0. iaOMT S3D 174 xylaaa laeatr Mtbyl athyl batBaa 54 173 C CjEjj laoatr 55 56 178 10H22 *«— * £-BOBaBa 179 C 57 181 584 183 184 laopropjlbaacaBa 581 S9 604 188 189 C 601 189 10E16 1"*'r CjEj.O laoMt (taut.) 18 19 95 20 21 96 97 22 99 234 102 102 104 btufluorobcntao* (1st. atd.) D-bauB* ehlarefoi* C?EK IkoMt C£BU ICOMT parfluetotaluana <iot. atd.) MebylcyelepaBcana 1.1.1-criehleroatbaaa 231 156 C E 9 16 lg—r CjEjp iaoMr £-haptaul <t nt > ' - 10E22 lt<mtr S-vatbTl-l-lBdobutaaa C 10E22 t"m'r 11B24 tK»" C 61A 191 baualdahrda 25 26 27 105 CjE^ i»am»r 611 191 B^propjl baaaaaa 108 112 twBMB* 62 193 194 C.-a.lk]tl baasaaa 28A :i3 ttbyl Tiajrl kctoat 195 C9B18 lao«T 281 a4 2-paataDaaa 29 30 31A )13 M6 C.B..O <tact.) B.p.ocu.1 65 66 67 196 197 C 11E24 l>0—r oecaaoBa laoacr 199 C :.i9 CricblBroacbylana 68 69A 200 201 691 70 202 203 204 24 311 32 33 34 35 36 37 38 39 40 119 63 M crelebaua* .L22 C E 7 12 ot C6E8° U-" B_-baptaaa .126 C E L29 134 B 16 *>olnl C E Ue 714 r 7 J4 ~ 1-ehletepaBtaBa 135 72 73A tBlUBBB 145 147 C£E^jO laoaar (Mat.) £-baxaoal C E t t 8 16 «« 205 206 210 731 73C 74 unknown 138 143 711 210 210 211 - CoBtlBIMd - 120 CjEj0 taaavr (tint.) 11E24 lM~r 2-paBt7lf«raB C 11E24 ttol"r g-octanal alleiau C 10E22 t'01"r dieblorobaataBa C 11E2* t'°-r 10E14 1K>-r CjElt ifomtr (cast.) C ant. hydroearboa aat. hydrocarbon �Table D-l (cont'd.) Chreuto- SluKion Tctip. (raphlc P**k No. CO 75 76 77* 77B 78 ' 79A 798 SO 81 82 S3 84 to 212 21.1 21.1 21ft 2111 Co-pound !.. !. ». • t hydrocarbon •. imMt. hydrocarbon •onochlorod*caM (t«nt.) C 2! 1) 22,'L 22:! 224 22'i 22'» 230 9»18° tc*tophnoM •*t. hydrocarbon •at. hydrocarbon 2-000*000* dlMthylatyrm* B-geaaaal n.-undicau Chrouto- Uutloo irapaic T««p. Puk No. CO 86 87 88 89 90 91 92 93 94 93 96 97 121 240 240 240 240 240 240 240 240 240 240 240 240 Compound mat. hydrocarbon • l U l O M naphtha l*n* C H ( 10 20°Uo-r " ' ") £-dod*can* uakaovn unaat. hydrocarbon •lloiana CUH22 laoMr alloun* ankaowa •iloxaa* �M 1 Sf........V.........fc ^Jw^M***-,^^ i i . *........r.....i " i i Figure D-l. Total ion current chromatogram from GC/MS analysis for volatiles in sample no. 1081 (Bayonne, NJ). �Table D-2. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO. 1040 (Bayonne, NJ) Cbrouco- t.utioo •r«p. iraphlc Fuk Me. 1 2 38 3 . 60 4 5A 67 74 59 SB 74 5C 75 SO 73 77 6A 61 78 6C 78 60 6£ 79 79 7 81 8 82 84 9 10 1 1 85 87 12 90 13 14 92 94 13 16 96 97 17 98 18 19 101 104 20A 201 107 106 21 109 22 110 23 11 1 24A 113 24B 25A Covpouad jrtphle P«ak No. Mrbaa dteaida caleratrlfluoroajatbaaa dlMtbyl ataar C.H.0 iWMr laopaatMa trlehlarofluoreajathaa* •eatoaa CjH10 laaaar n-paataaa laepraaa laoprapaaal 23B 26 27A 115 117 28B 121 28A 123 124 127 28B 29 30 31 32 33 130 132 136 138 1*0 COllMO* 35A 141 1-paataael 351 142 imkaown 36 145 37 146 C;H16 laoMr ^phtfMUuil 38 149 ISO 39A 39B 40A 40B 41 42A 42B 42C 131 152 153 153 154 154 154 43 155 44A 44B 137 157 45 161 46A 162 162 46B 47 163 48 165 49 167 30 6«12 "" parfluoroteluaM (lat. >td.) 1,1.1-trlchlemthaaa 3-Mthylbutaaal (tut.) 2-Mthylbutaaal bauaat c«rboa tatraealaxidi cyclobuun* 169 51 52A Uo 173 174 52B 173 53A 113 113 115 Compound 34 Vl2 Uo~r vtnylldlaa eblerida avtbylana cfalorid* ftaoa 113 earboa diaulflda 2-vataylprepanal eyelopaatana unknown Mthyl athyl kacoaa C.tL, laoaar buaflueTobaaiaa* (int. atd.) £-haxaaa calerefoni C Uutloa Taap. fC) 175 176 331 34 177 35 36 179 57 181 182 58A C H 7 1* •tbyl vlayl katoa* 2-p«nt«noo« Tlnyl proplaaaM (taat.) tziebloreatbylaaa 581 S9A 59B 181 183 184 185 60 191 63 66 67A aluam " - Caatlauad - 123 •at. hydrocarbon oaaat. hydrocarbon C>H16 iaeawr CgB14 laoMi ailouaa uaaat. hydrocarbon aat. hydrocarbon oBMt. hydrocarbon aakaewa ebletohtcan* athylb«uaaa *ylaat iaoawr 2-bap canon* •tyt*o* 2-£-bucylfuran (tant.) a^haptaaal sylaaa taoaar C9B18 laoaur CjBjQ laoatar •at. hydrocarbon 1 r Vis "~ 3-*aehyl-l-ladebutaa« C,HI8 l.o~r taeptopylbaaxto* aat. hydrocarbon hydrocarbon 190 63 64 7 12 " W oakaoim C7814 laoa*r CjH14 laoMr dlMtnyl diauldda 1-ealenpaataa* 189 61 62 C H 8^1 & laHMaT unknown C|B1& taoMt CjH18 UoMt tr«n»-*-oet«n« tatraehleTo«thyl«a« 190 192 194 196 196 uaaat. hydrocarbon baasaldabyda £-propylb«nt«n« (tant.) triaathylbrataaa iaoaur laoaayl format* (taat.) aakaevB �Table D-2 (cont'd.) ChroMceiraphlc ptak No. UuCioo T«*p. CO traphle raak to. Covpouad 671 197 aat. hydrocarbon •4 68A 198 681 69 70 " 199 200 CgEjg laoawr C,-«lkyl bkniaoa 85 86 aat. hydrocarbon 2-pantyl furan 67 71 72 201 203 203 204 H •9 Cj-alkjrl bcuttM C 90A 90» H 1C 20 7i 207 •llnuna dlchlorobanaana Cj-alkyl bmaaM (cent.) 76 209 C H 77 76 211 212 •aothaaa (taot.) 79 80 213 216 81 82 216 217 E3 219 73 74 206 91 92 93 94 95 96 97 98 99 100 S 14 A IAC cbylccby HVCOXWM ivoMtr llaoDaoa C1,E,2 iaowtr uaaat. hydrocarbon *at. hydrocarbon •unknown 124 butlra C-pc^ <%' 220 222 223 22} 226 228 230 231 234 239 unknown aeatopbaaona aat. hydrocarbon C 10>22 i " " " 1 diBathylatyran* 240 n-nonanal alloxan* alloxana tatraMthylbauao* (tant.) •llouna •lloxaaa napbtbaluta 240 C 240 240 240 240 240 240 12E26 i"a*t unknown allouna 2-nndaeaaoDa C 13E28 alloxana �I1 I'. Il Figure D-2. I»T-» T • > • i ••• i iTTf • i »T»y«^'i^Tr> ••• rn Total Ion current chromatogram from GC/MS analysis for volatiles In sample no. 1040 (Bayonne, HJ). �Table »-3. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO. 1107 (Jersey City, KJ) ChroBate- Elutiea iraphlc lap. Paak No. CC) Chr ovate- Uutlea graphic tap. Peak Ho. * ^ 113 114 Yloyl proplonat* o-puntanal 116 117 C 221 22C 118 22D 118 23 24 120 1 64 SMM 201 2 65 67 carbon dloxld* fraoa 22 dlchlorodlfluoroMtbua £-propant but«Di laoBtr ja-butana 21 22* 3* 31 4 67 69 54 56 70 SC 72 36 6A 7 73 74 8* 71 75 76 81 8C 78 78 9A 79 91 10* 79 81 10B 83 IOC 85 06 86 26B 125 127 26C 127 C B 27 28 128 129 29 131 8 16 1"°**r dlMtbyl diaulfld* dlhydropyran cblorop«BCaoa 30* 134 tOllMO* 30B 137 31 aeataldahydt butwa l*oMr chlorocthan* tctraMtbjlaUau trichlerof luoroai than* 1-pantao* accent* laopropanol «~p«itan. Mttyrlu* cbloild* Tram 113 7«14 *— « tt 1 chl oro» chjlaoa E-dloian. •tbyl furan (cunt.) B-hnptaot 2.2,4- criM tbyl-l-pcBtaoa lietwuiul CtEloO l.o.r 4-Mcb7l-2~p«Bt«noBa 139 141 25 26* 32* 321 123 124 lor 11* in 86 carbon dKulfldt (me*) •atbyl »tnyl Uton* (tract) Bttbyl propwol nitrowtlkut (teat.) 88 cyclopcs taa« 89 12* 90 35 36 121 91 13* 92 2-Mtbyl putiaa vlajrl aeatata a-butaoal 3-«*cbyl pantant 131 14* 93 94 C B 381 156 38C 39* 156 IOC 101 141 97 14C 98 100 15 164 101 161 102 16C 102 17* 104 171 17C IB* 105 106 181 19* 191 19C 19D 20* 108 109 110 110 11 1 12 1 112 Conpoiart 33* 331 34 143 146 147 148 149 37 38* 6 12 *«»" parfluorobuima (int. ltd.) v-basu* eblorofeiB dibydrofuraa Utrabydrofuran pcrfluororoluaM (1st. ttd.) MCbylcyclopaatana £-»ttbyl acacnld* 1,1.1-trlchlerMtbaB* 3. 3-diB»tbylo»ta» (Mot.) buuaa carbOB tctracblorld* 1-buunol cyclobaian. Cjlj^pO ivowr •tbjl vlnjl kctoM (teat.) 151 154 156 391 158 159 40* 160 401 161 40C 41* 161 411 163 164 42* 421 43 44* 441 44C AS* 451 46 2-p*BUBOB« - Cootlauad - 126 162 165 166 167 168 168 169 170 172 Vie uo-r C6E120 iaoMr £-huanal Vj6 i.*r ji-octana C E 8 16 t>OBtr tatrachloro«tb>l«n« Vl6 i*°**t •lloxaa* inkBCVB CjHjj Ifomn cblorobaaiao* j-bcxaaal (teat.) ehlorabuBJU C B 7 12° U""r •tbyl bm*»« CjEJ8 iMMr 4-hcptaBOBi ryl.n, IMMT BbuylacatylaBt J-hupcanon* 2-hcptnaoB* C^jO (tut.) •tyraw B-hapiaBal xylana I»OB«T •at. byrtroearkoo C.1L| laomr ..-«««« �Table D-3 (cont'd.) Chroaata- (lutlon Ta». iraphic I*C) 47 48 49* 49B 49C 49D SO* SOB SI S2A 52B 32C S3 54 55* S5B 5« 57 58* S8B 59 60* 608 61* 61B 62 63* 63B 63C 63D 64* 64B 64C 64D 64E 65 66* 668 66C 66D 47* 67B 47C 68* «8B 173 174 175 17S 176 176 176 177 178 181 182 182 184 186 187 187 187 188 190 190 192 193 193 194 194 193 196 196 197 198 200 200 201 201 201 202 203 203 204 204 205 206 206 207 207 (raphlc PMk Mo. CoapOUOd •at. hydrocarbon C10iJO laoMr aat. hydrocarbon •thyl aathyl cyclobaaaaa 69* 69B 70 71* 71B 72* 7 IB 73* 73B 73C 74 75* 7SB 76* 76B 77 78* 78B 79* 79B 80 81 82* 82B 83 84* 84B 84C BQk&OWB C7H1()0 laaan laoprepyl baaaana C H 10 221*OB<r CjH140 laoaar (tact.) tzana-2-baptanal a-plaraa busaldohydo nrpropylbauua xylana laoawr aat. hydrocarbon C 10»22 Uo*tr bauonitrlla (tract) •at. hydrocarbon phenol triaatbylbauaaa pantyl turaa £-octaaal baniofuran trfcatthylbaaxaaa laoMra C 10B20t ° t *•lluaaa C,,B_ _fl ^/^±0 o*4ccuM dichl orobtnxnt llutlon Tan. (*C) 208 209 210210 211 211 212 212 212 213 213 214 215 215 216 217 218 219 220 220 221 222 223 224 224 225 226 226 CoBnooad C- l , b . « 4.klu. C ll»22lM-r 11H221 ~ " r C l0 ll»22 < -* phthalld* (tut.) •at. hydrocarbon dacalla (taat.) aat. hydrocarbon C C 11B24Uo—r C^-alkylbauu* laoaar 2-flonanona C 11H22Uo— * C4-alkyl banaana iaowr Mt. hydrocarbon £-ooaaaal C 11822 Uo-« 10»120 »— « n^vadacana allosana C C 11H22i ° r '" r 10B18 «*" C^-alkylbanxaaa laoaar ClJHj6 laosar CUH:4 iaoMr 2-atthyldacalln (tant.) C C 12»26 C.-alfcylba»ana lioacr C^-alkylbonaana iaoaar 396 •Av 86* 86B 86C 86D 86E 86F 86C 87 88 89 90 91 92 93 94 • 5 C 11H22 U<"*r onkaown trl»tthyl baaiaoo iaontar unknovn C^-alkylbantana •at. hydrocarbon C 11H23 * * *" aat. hydrocarbon llaoa*n« CjjHjj iaoa«r •a thyl ityrana Mt. hydrocarbon C H 11 22 * " *• dlathylbutana iaoatr •at. hydrocarbon acatophanona • Coatlnatd - 127 228 228 229 229 229 230 230 MO 230 230 230 230 230 MO 230 230 C 12H24 * " ^ 11H20UOMI(««e') C H 12 24 llo~r C H 10 12° " " " C B 10 18°1>OMI unknovn C C 11H16 Uc~r •llosana •at. hydrocarbon •at. hydrocarbon •at. hydrocarbon aat. hydrocarbon aaphthalana unaat. hydrocarbon jg-dodacana aat. hydrocarbon �Table D-3 (cont'd.) Chrouto§«phic Pt»k No. Chroiatogrmphle Puk Ho. ElUtlOB fc^d Co' Elution Tap. CO CCMBDOUBd unkaovn 105 230 2-CrldKIAOM •it. hydroorbon 106 107 230 230 •»t. hydrocirboo 230 unknovB 108 230 vllouni 230 230 • llOXUM 230 230 phth»l»te •it. hydrocarbon 109 110 unknovn 11 1 230 dil»obutyr«t« itoacr diphuyl tthur 112 230 C 96 97 230 230 •lloun* 98 99 230 100 101 102 230 103 101. 230 230 2-undocuon* Mt. hydrocarbon 128 Ittctoni ivoBtr (tint.) 14R22° 1>OMr �m rt-fr* Figure D-3. (-rrvrr> *-vf--rr*T<-»r-.^f < • • » > ! < • F T I - T T I . £""•* rr^fwr »•• py,,^.....^ ^,....,^,™ Total Ion current chroroatogram from GC/MS analysis for volatiles in sample no. 1107. (Jersey City, NJ). �Table D-4. VOLATILE COMPOUNDS IDENTIFIED IN PITRGE OF SAMPLE NO. 1115 (Jersey City, NJ) ChroM tographic Ptak No. Elutiet CbroMto- Clutlon iraphic . Ta«p. Paak Ha. CO Co^d ro' CiapouBd 1A 62 carbon dioxide 24 120 1 1 63 xanon (traca) 25 122 2 SA' 65 (7 26 27 122 124 31 68 carbonyl aulflda (taat.) chleroBathane unknown 28 126 chlorepantant ORknovn 4A 41 76 trlchlorofluoroMtbkBa acataot 29A 291 128 129 1-paatanol SA 77 131 31 134 4-*etbyl-2-pKntanom s-buinal 6A 78 80 laopaataaa laopropaaal 30 SI •athylaat ehlorlda 32A 61 81 FraoB 113 321 136 137 furaldnhydt (taut.) (tract) 6C 60 62 carbon diaulilda (traca) unknown 33 138 Bj-octant 140 tatrachlorotthyjiant 7 unknown cyclopancaM 34C 140 141 dlchloroproptnt (tract) BA 83 86 34A 341 81 87 avthyl laoprep;? katont BC 89 B-butaaal ISA 331 142 76 82 142 9 90 1-baxana (tant.) 36 143 IDA 92 101 HA 92 94 htxanuorobauBae (int. atd.) Bj-baunt 37A 371 146 147 148 94 chloroform (tract) •ethyl furan 3BA 11 1 381 149 12 13 96 uaaat. hydrocarbon 39 151 98 parfluorotBluana (1st. atd.) 40 14A 99 erotonildahydt (taat.) 41A 411 151 152 141 100 14C 15 16A 100 102 104 161 103 16C 103 17 106 107 18A 181 1 . 1 . 1-triehloroa thant 3-Mtbylbutaul 42A 421 2-BttbylbvtauU (cast.) bansent 42C 43A 431 carbon tatraehlortda (traca) 1-butanol (tant.) unknown 44A 441 1S2 133 153 155 155 156 157 C E 7 J* Uo"*r dlMthyldlaulfidt dlhydropyran toluaoa C.B., iaavar B 10 unknown C H II 5 8 2 CjE^j laimr ailouut 2-haxan«l ehlorobaniant C,E,4 iaoatr 5-Mtbyl-3-hydrofuraD-2-ont (tant.) e-furfuryl alcohol athylba&tant C0Blg iioacr C^MjO (cant.) sylant laomtr phtBylMKCyltnt 5~Mthyl-3-btunoBt 2-b«pttnnM C B 7 12° we athyl vinyl katont 2-ptntanont 158 158 SH20 <trmct) atyrao* b-htpttntl 19 107 JOB vinyl propieaatt 4*0 159 ryltn* Iroacr 20A 201 20C 109 110 11C g-pantanal 45 CjRlg iaomar aat. hydrocarbon ••thylbexaat (tant.) (traca) 46 47 159 160 162 21A 111 11: l-basana 48 163 lodopantant trlehloroathylaaa athylfuraa (taat.) 49 SO 166 unknown 170 trani'2-baptanal 2.5-diMthylfuran arbaptaaa CjBj laoaar unknown S1A 511 171 172 baataldthydi SIC 172 173 17* 211 21C 22A 112 221 22C 23A 231 1* 1 15 1 116 117 11* SID S2A CjEglj (tant.) (tract) -Continute- 130 2-furyl attbyl kttont (tant.) B-nonant S-Mtbyl»2-fnrfura,l onknowB v-propy Ibaniant nylana laovtr �Table D-4 (cont'd.) Chromato- Ilutloa fraphic Tap. Ftak No. CO 52B 175 32C 52D 175 52E 53A 175 176 176 53B 176 53C 176 53D 177 53E 177 177 53F 54 178 55 56 180 57A 181 57B 58 182 182 182 182 59 60 184 184 61 62A 187 188 188 57C 370 62B 62C 63A 63B 63C 180 188 190 190 191 64 192 65A 192 65B 193 66A 66B 194 195 67 196 68 196 197 69 70A 198 70B 198 Chroaa to- Elation graphic lap. Ftak No. CO COBOOUaal 71A banaonUrUa occaoont 711 71C C 10H22 Cj-alkylbtaxtna l-chloro-3-*thylbaiat (tat. ) dibroBodlchloroMtbana (tat.) phenol •at. hydrocarbon 5-«thyl-3-haptaaou (tat.) unknown 6-**thyl-2-btptanoat patyl furan o^oc canal btnzofuran (tract) Cj-alkylbtnaaa 7U> 72 73 199 200 200 200 201 204 74 212 75 76A US 214 76B 77 215 78 US U6 79A 220 79B 80 220 221 81 223 82 Conound 2-nonanona diaithylttyrat (tract) C4-alkylb«nitat (tract) C H 10 16° 1*°-r a-nonanal undacana unaat. hydrocarbon lu 18 n—pantylbtnaana •Uoiant •at. hydrocarbon 2-dtcanont napfathalaat C12H22 Iwmtr n^dacanal n^dodacant •at. hydrocarbon unknown mathyl etanoltat (tut.) (tract) lactont iao*«r (tant.) oxyimatad hydrocarbon phanyl baxaaa Cfyf iao-r •ilosant g-dacana dichlorobtncat 83A 225 226 83B 84 227 228 C H 9 16 ' C^-alkylbaxaa 85 231 86 233 87 237 88 238 89 239 90 240 240 =10=16° 91A 91B 240 allozan* 92 240 93 94 240 93 240 anaat. hydrocarbon •at. hydrocarbon 2.2,4- trlaathylpenta-1, 3-dlol dl-laobutyrata (BKC) aat. hydrocarbon 96 240 C 97 98 240 240 14H30 lB81wr unaat. hydrocarbon aat. hydrocarbon 99 100 240 240 C H 13 32 *— « •at. hydrocarbon C H 10 20 U r llaonant — l.B-clMolt CjgBjj (tract) anaat. hydrocarbon •at. bydrocarboA acatophanoaa »-butylbaiua (tant.) C^BgOj (ttnc.) CUB22 lacnar unknown C 10B18 lgo->r aat. hydrocarbon 131 240 unknown nndacana <M "-) �Figure D-4. Total ion current chromatogram from GC/MS analysis for volatiles in sample no. 1115 (Jersey City, NJ). �Table D-5. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO. 2048 (Pittsburgh, PA) Chroma to- Uutlw graphic tap. •uk No. 1A 1 1 2 3' AA 41 SA SI 6A 61 7A 71 8 9A 91 10 11A 11 1 12A 121 13 14A 141 ISA 1S1 16 17 18A 181 iac 19 20A 201 21 22 23 24A 2*1 25 26 27 28 29 30 31 32 carboa dlodda 58 51 64 66 70 70 71 72 73 74 77 77 79 S3 83 84 87 87 89 89 91 96 96 96 98 102 104 106 107 109 109 112 112 113 119 126 126 127 130 131 133 134 136 138 140 143 Chroma tographic Faak *». Compound 33A 331 34 35 36A 361 37 38 39A 398 39C 390 40 41 42A 421 42C 43A 431 Uo r S«12 trlehlorof luornma thi oa aeatooa X-putaaa laopropuol fraon 113 •athylaaa chlorlda carboa dlaulfida CjHj,, l.o«r ' Vu *-r* CjHjpO iaomar (tut.) macbyl athyl tauoa • C ta 6"l2 "" ha»fluorebaa*ua (int. ltd.) a-baxana chloroform pmfluorocoluaaa (Int. atd.) •atbyHarcloputan. 1.1,1-WlcblaTMChaa* 1-butaaol (tue.) baasaoa eyclebaxaaa C 145 146 147 149 153 154 156 159 161 161 162 162 164 165 166 167 167 168 168 169 170 173 175 177 177 181 182 183 184 184 44 U 6«12 "" CjHjoO 1— r C 6«10 *—" C-pound ?o' 43 46 47 48A 481 49 50A SOI 51A 311 ehlerocrlfluoramathaaa C4H, iaomar C^Hyj laomtr aeataldahyda C UutlOB SIC 52A CjHjj iaomar •nknown 321 S3 54 55 56A 561 57 58 S9 60A 601 61 62A 186 186 187 189 190 190 192 192 19* 19* 195 195 197 198 11 1 C 7»l*° lie"r •lloiaaa Vl2° 1<c-r ohlorobaotaoa (tract) cblotoheiana (traea) athylbanm* •at. bydrocarboo •ylaaa laomtr onkaom C,H20 laa«r 3-baptaoaoa 2-baptanooa atyraaa CjHjj Iaomar (taat.) uc. hydrocarbon pbaptanal xylaaa IIOMT g-aoaaaa C10H,0 Lour CI()HJJ laomar (tant.) laopropylbanitoa C.0ljj laomtr Culj4 laomar C 10*16 1"m" CgHjjO laomar unaat. hydxecarboa busaldabyda !£ • AO* CTl CblOiTOV Cb vl V*M tatrachloroachylaoa CjH16 Iaomar D ' MPf^PT^ JAM S! ** 6«12° *«»k uaaat. bydrocarboa cblerottaacan* •aaat. hydrocarboa (cut.) tolaaaa 1-pmataaol C V, Uo-' Vl2° *— ' pbuanal C,lli taomar t-octaaa 421 133 C H 10 16 *•"" C.-aikyl baaaarc laomtr •at. hydrocarboa oaaat. bydrocarboa C ll"24 U"" U Vl6° t —r 10H22 "*" C ll«24 *— « 2-f«ntylfuraa C11H24 laomar (tut.) C3-a4kylban*«na laomtr 6 C lAfl * " " ' alloxaaa •at. bydrocarboa dleblorobaaiaM �Table D-5 (continued) Chronato- Elutlm iraphic Peak No. «3A 200 63B 6i 200 202 65 66A 66B 206 206 203 67 208 6S 69 209 211 70 212 71 72 213 214 73 74A 74B 215 216 217 75A 218 75E 76 77 220 222 219 ChroHto- Slutlon grapuie FcaV No. CoBpoimd (*o' unaat. hydrocarbon tat. hydrocarbon (teat.) uoaat. hydrocarbon 2-*chyl-l-baxanol 82 B5A 235 ilaonan* C10B180 Un*r •at. hydrocarbon (teat.) •at. hydrocarbon C4-alkylb«nt«n» acatophaooaa •at. hydrocarbon •at. hydrocarbon •at. hydrocarbon C^-alkylbanxnvt KB 236 11B20 1M-r 10B1«° ***» •HezaBii CIOHlgO UOMT 85C 236 C 86 238 240 83 84 87 88A BOA 80S 227 81 229 240 89B 240 C C ic'l4° i*0ftr unaat. hydrocarbon •at. hydrocarbon oapbthalau C1()E220 i.o«r (..«.) 95 96 240 n~t*rpln»ol (tut.) unaat. hydrocarbon .B-dodacMt* ailtntani unaat. hydrocarbon •lloxana 2-undacanonn ailoxan* 240 C 97 240 96 99 240 100 240 101 240 90 240 92 93 94 134 240 91 •at. hydrocarbon 79 240 240 89A C0Ei5° iaoaar dlMthylatyrcna aat. hydrocarbon p-nocaaa.1 223 226 226 233 8BB B-uodtcao. •iloxane C^-al ky Ibanxana C^-alkylbaiuna unknown 78 231 232 ^unaat. hydrocarbon 240 240 240 240 13B28 i"mrT •iloxaot dacanotc acid (tant.) C K » 30 Uol"r unaat. hydrocarbon alloxana �JL i Figure D-5. i I I I I 7 I Total ion current chromatogram from GC/MS analysis for volatlles in sample no, 2048 (Pittsburgh, PA). �Table D-6. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO. 2071 (Pittsburgh, PA) ChroMto- Eluciao traphlc Tap. Peek Da. CC) 1 59 u 60 (1 34 31 4A 63 64 41 65 3 66 68 6 71 7 8A 73 81 73 9A 75 91 9C 10 75 11* 78 11 1 11C 12 79 Chreaate- KlutUn (raphle Tea*. Feak *o. CO CaqxMBd 33 344 348 35 36 37 38 39 carbon diexld* propylen* (tract) dichlorodlfluoreaBtbaae (trace) dla*thjrldlfluor<MllaM leobutane C.E- laoaer b-bucaae (trace) acetaldefajde chlerocchaB* (trace) a* Chanel aeecwe triehloretluoTnaa f h»rie leopropaael a-peatane 40 41 42 43 44 45A 116 18 1 19 1 122 124 126 127 129 133 138 139 141 144 cE 451 CjHjj laoatr •ethylent chlcrUe 2-«etbyl-2-propai>ol Freon 113 46 145 146 147 47* 149 471 149 48 152 81 82 C B 6 » carboa dliulfldt 49 c H 501 14 15A 83 85 86 153 158 159 . a-propanol (cent.) cyclopentane 51A 160 511 160 C H 32A C H 521 162 163 164 13* 131 76 77 80 151 87 16 87 17 88 18 19 89 90 20 91 21 93 22 23* 231 24 95 96 2iA 100 251 26 100 101 27A 271 102 28 29 30A Ml 31 32 j e *"°»»r 504 « e° 6 12 * •" 6 14 U-" vinyl aeetace • £-butaaal kethyl ethyl katoae 53 54 33 56 Ue r 166 167 baxafluenbeuaiie (lac. acd.) 37 169 170 94 b-bCXUM 58A 173 94 •Cbyl acacate chlerofera 581 174 176 177 179 103 106 107 108 108 11 1 13 1 Via ~ 59 (0 IMrfluorocelueee (Int. atd.) ••thrlcyelope&cane t^ijt laoaar 1 ,1 , } -trleblerea thane CjB^ijO laoavr (tent.) Baaiena carbon tecraehlerld* (trace) fbutaaol (cent.) CTclobasaae •ethyl propjrl keton* e-peacaul (1 (2A (21 63* (31 (4 (5 (t (7A (71 MA 136 C-p-d erlchleroethyleui ^-heptane C l r C7"l4 t—I e"i6 '°~ diaechyl dlaulflde taikamn C.BU laoaaT (tent.) toluene dlbrevoehloreMtbaae (trace) a-bexanal C(Elt lecwer £.oetaae tecrachleroetbrUne CgEu Inner (tent.) ttnkwmn uneac. hydrocarbon •lloxane CfBia laoMr echylbenxeo* C.K.. leoewr xylen* iaoavr ph«oyl*eetylen» 2-heptanona etyren* SjrlaB* laevrr B-heptanal C*TI«~' iaapropjrlbeuent 10 22 **°**t C 10E20 tB™*r 180 180 baualdenyde £-prerj.ylben»en« 182 182 184 183 185 C 186 186 187 10B16 *—r 3 . C E 10 22 i90^T heucoBltrUe Mtbylheptanane laoacr a-Mthrlir^raiM trie, thy Ibenien* leoMr �Table D-6 (continued) •ChroMto- Uutloa triphlc Yap. P«ak No. 688 188 698 70A L88 190 708 70C 190 70D 71 191 192 72A 192 728 72C 193 72D 190 193 194 73 74 194 7SA 196 197 196 758 76 78 79A 798 80 205 205 207 81 208 82 210 . C H Uo 211 211 85 86 212 214 87 215 88 216 89 222 90 223 225 227 91 92 93 94A 230 948 232 95 96 235 97 10H16 lM-r <"«•> 10H16 1'°-r Ct-«lkylb*ni«n* UmotMtM unknown Mt. hydrocarbon acatophcnon* 203 Coapomid 84 C 201 Xlutlon 13 C 199 77 iraphic Puk Mo. Mt. hydrocarbon •thyl n^caproac* putylfuraa (e*nt.) baniofuran (dot.) C4-alkylMU«M trlMthylbnum* ia«*r phenol (txae<) •ilouo* C1QH22 laoMr dlchlorob*u«M unknown C1(JHI4 laomr Mt. hydrocarbon 187 691 Compound 240 240 98A 231 239 988 240 99 240 100 240 101 10 16 ~ •at. hydrocarbon unknown 2-nonanoM 240 102 r 240 240 103 104 137 240 dlJMthylacyrm* Mt. hydrocarbon canncn* (ctnt.) •iloxan* •at. hydrocarbon ••thyl eaprylac* alloxan* caaphor C.-fl, .0 (tract) (tent.) 1U 10 •lloxana trlchlorob*niw< (tract) •thyl caprylat* naphthaline £-dod«can* wait, hydrocarbon (ttnt.) •Uouat 2-und*caoon« Mt. hydrocarbon •at. hydrocarbon ••thyl dccanoac* illoxan* C, /.H,n (ttnc.) 14 30 •thyl dacanoat* uoMt. hydrocarbon �H 00 101 J|_A_A_jA_JL_JV It 1 k 1 k i Figure D-6. Total Ion current chromatogram from CC/MS analysis for volatiles in sample no. 2071 (Pittsburgh, PA). �Table D-7. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO. 3053 (Baton Rouge, LA) ChroMte- Elucloo iriphle T«p. f«*k No. ("0 u 11 37 2. 3 Cbrom«Cotripble Ho. 62 enrben dioxlda chlototrlfluoroMthaaa cbloroMthaM 63 e 38 4 68 SA 71 JC 72 6 74 76 81 77 9 10 79 80 11 12 86 144 C 8«16 £-oct«n« 38 145 C 8 39 85 141 37 73 7 SA 139 36 4«10 * * * " dlMthyldlfluoroillM* 136 33 70 31 X£L 34 147 •nto furaa 40 149 41 150 42A 153 |,-propanol ••thylaM chlorlda frwn 113 urbon dlaulfld* (traca) CjHjO 421 153 43A 153 431 156 44 158 6 10° fuMldibydc Vu v« C H 6 10° 8 14 C H 6 10° nknowi C H 14A 43C U 459 161 C 46 164 C 47 6 14 °iMxafluorobauaaa (Int. ltd.) 2-aathylfutaa 161 45E r 160 165 Vl6 166 481 88 159 48A 87 13B 139 451 13A 43A ybutu*l •tchyl *thyl katona (tut.) C 8 166 UA 90 90 90 92 151 93 48C 94 49* 169 491 170 171 97 30 172 18 19 20 98 8»18 167 16 17A ((•at.) a-furfuryl alcohol 141 14C 21 22A 97 100 parfluorotoliMo* (Int. ltd.) C4HjO laoMT . 1.1,1-trlehloroathan* 5U 106 JOS C 173 32 104 175 53 6»12 •tbyi 176 34 kateo* tMMT 173 311 7«a4( 178 221 108 33 180 23 109 36 181 24 110 ppaatvul 37* 182 25A 113 £ B 371 182 251 1.13 trlenlorocthylcn* 38 184 ••tbylfurcldchyd* l*e»er 2SC M4 C 39* 26A 391 187 C 261 ,U6 117 39C 188 C 27 120 60 189 28 122 m 29 30 31 32 33 .123 126 133 134 InOHAlT 0 6>8 •eitle «cid 2-rlnylf (tut.) (tint.) MCb7lfur«ld«07da IWMT 10820 10B22 61 191 621 191 C 63* 192 C 631 193 64 dlbydropfMB (tut.) tola 190 62* 194 coatlowtd - 139 ll»22 U«24 (int.) �Table D-7 (continued) Chrouto- Elutiou Ta«p. fraphtc Fiak No. CC) 65A 194 651 66 67A 194 671 68 69 70 71 72A 196 197 198 199 201 202 204 204 204 72E 73A 207 73E 74A 207 208 74B 209 75 210 211 76 77A 77E 77C 77D 78A 78£ 79 80 81 82 83 84 212 212 213 213 214 215 217 Chroaato- Klutlon (raphic T«q>Faak Mo. (C *) CoBpound 871 C.-alkyl bwutM l«e*ar unknown ailoxatw £-d*can* 88A 888 89 10E10°2("Bt-> 91 237 C H 0 r 9 16 U " C^-alkylbcn»Dt (trat.) 92A 238 921 B 6°21 ~ r '' li»on*n« 93A 239 240 unut. bydroearbon C H 931 240 aat. hydrocarbon 94A 948 240 C H 12 22i"MT £-d*eaoal un»at. hydrocarbon c E i r 95 96 n 24 — aat. hydrocarbon acitophanoni C -alkylbancua C B 1 97 98A 981 r 11 24 ' " °11E24i ° ' 'unMt. hydrocarbon aat. hydrocarbon C5Hg02 i«-r 99 C 100 H U < C 240 240 C 240 240 240 240 105 106 C naphthalant (tract) 240 240 103 104 r 12E26 Uo"er 12E26 1W~r C E 1C 20°l«"*r C C 102 C/E0 * I»OB*T (t*nt.) .., D C C 240 240 101 •at. hydrocarbon 240 240 240 240 12E24 ilol*r n.-dodaeaD« 13E28 ilHmI •at. hydrocarbon 13E26 itn*T 11E20°i"»er C E 13 28 Uo~r C 13H28itml C 13E28 lBO"r C B 1 1 °Uo-« 0 6 C K 13 24 tM~r C £-undacanal n-crldceaoi C E Uoi r IO I«° - 107 240 108 240 240 •iloxa&c unaat. hydrocarbon unaat. bydroearbon 240 240 n.-tttrad»cant 109 110 C o r 12E26 U " 228 229 C •at. hydrocarbon 90 226 227 87* 12E24 t§0"tr •lloxan* dlchlerobanxana unaat. hydrocarbon 221 222 224 85 86 234 C 235 236 11 24 ~ 10E16°UC~r n-Donanal B-uadtcan* unaat. hydrocarbon aat. hydrocarbon 218 231 234 COBDOIud 111 112 C 12H261 r •lloxaiw— 113 140 240 240 B.-dod»caaal unaat. hydrocarbon n.-p*otad*cana �*» \iil uJj*K v Figure D-7. I fc'T k' r k fc ' '1 i1 uuu 1"" fcill Total Ion current chroraatogram from GC/MS analysis for volatlles In sample no. 3053 (Baton Rouge, LA). �Table D-8. VOLATILE COMPOUNDS IDENTIFIED IN PURGE OF SAMPLE NO. 3111 (Baton Rouge, LA) Chrocato- Elucioo iraphle Ta»p. Faak No. CC) 1 2 3*. 31 4 5* 51 6* 61 6C 7* 71 8 9 10* 101 11 12* 121 13 14 15 16* 161 17* 171 16 19 20 21 22 23 24 25 26 27 26 29 30 3U 311 32 33* 59 61 65 65 71 7J 74 76 76 77 80 81 82 84 87 88 89 91 92 94 95 96 101 101 104 104 106 108 109 110 11 1 112 114 117 120 123 126 128 135 142 144 146 148 Chrovato- tlution Ta-p. CO COBpOUBd tapond raak *>. carbon dioxlda dlchloredlfluoroMthana •ulfur aioilda C^H, laoMT 331 34 35 36* 361 37 38* 381 39* 391 C}KIO i(o>ar trichaoroflueroaatbana acatona liopropanol £-panta&* CjEg iacwr •athylua chloriM rraen 113 carbon dlaulfida 2,-buuul cyclopaotana C6H14 laoa»r CjEJflO t«».r to 41 42 43* 431 44 43 C H 3 10° 1—" CjE12 Uowr haxafluorebauau (int. atd.) 46 B-btSUI 49 chloroform parfluoretoluMMi (int. atd.) •aihjrl.eyclopan.tana 1.1,1-trichloroathana CjE100 taomar (tut.) 30 47 48 51 52 53 54* 541 55* 551 56 57 58 59 60 61* 611 62 63 64 65 66 67 »6 C E 6 12° i>0—r ' ban* ana carbon tatrachlorida 1 r '."12 «~ CCE120 iaeawt (tut.) C£EI20 laoatr (tut.) £-paBt»al trichloroathylan. ft-bapcana C{EU iMwr C E 7 14 U-" dlaatbyl diaulflda teluaaa 5-ba«anal C E 8 16 *—T D-octana tatrachloroa thylnna 142 148 150 152 155 155 161 163 164 168 168 169 170 173 177 177 178 179 181 183 186 189 18S 191 192 193 194 193 196 197 198 202 204 206 208 212 213 214 217 221 233 240 240 240 uoaat. hydrocarbon C.B.. laoa*r (taut.) •iloxana CyEjg IMMT C$B20 iaoawr (tut.) •thylbaasaaa xylan* iaeaar C E 9 20 lM™r atyrana C E 9 20 U<mtr xylao* laomr C9E2Q iaoa*r CjBjp Umur Ht. hydrocarbon C,-alkyl bauana (t«nt.) C 10E22 i§c*tr 1CH22 UoMr •at. hydrocarbon •llouna baualdahydt ueknovn C c iAt 1>OI*r Cj-alkyl bauan* C 11E24 1>on" 11E24 U—r C E 11 24 1*OI*r C,-alkyl baniana ailosaaa C C 11E2* 1>cmr dicblorobauana Cj-alkyl banian* linoiiaaa aat.. hydrocarbon Ht. hydrocarbon •eatepbanoDa Ht. hydrocarbon •at. hydrocarbon aat. hydrocarbon B-imdacaoa •lleuoa c-dodacant anaat. hydrocarbon •tlesaaa �Figure D-8. Total Ion current chroroatogram from GC/MS analysis for volatiles In sample no. 3111 (Baton Rouge, LA). �APPENDIX E SEMIVOLATILE COMPOUNDS IDENTIFIED IN SELECTED EXTRACTS OF MOTHER'S MILK 144 �Table E-l. SEMIVOLATILE COMPOUNDS IDENTIFIED IN EXTRACT OF SAMPLE 1032 (Bayonne, NJ) Chrouto- Uucioa •raphlc Taap. Puk Ho. CC) U IS 2 3" 4 S 6 7 8 9 10 lit 11B 12 13 14 13 16 17 18 19 20 21 22 23 24 Chrouta- Uutlon graphic TBBD. Peak Mo. CC) Compound telum* 01*aa laoMr Ciaifniiiwl 23 26 27 28 29 30 •lloun* •lloun* •lloun* •lloun* •lloua* •lloua* •lloua* dlaatbylblpbuyl (teat.) unknown • t *nd un**t. •. unknown •lloun* •llexaa* ) d10-pyr*n* (ltd . hydrocarbon* 31 •lloun* DOE •lua loa 32 33 34A 341 unknown •lloun* 31 unknown unknown 36 37 38 39 40 41 42 43 44 41 46 47 48 •at. and unaac. •lloua* •at. hydrocarbon •lloun* •lloua* •at. hydrocarbon •at. and onaat. hydrocarbon* •ilffun-t •llosana •lloua* •at. hydrocarbon pathalac* (cant.) •lloua* •at. and uoaat. hydrocarbon* 145 unknown •llnua* hydrocarbon* •lloua* •at. aad uuat. hydrocarbon* Mt. and imut. hydrocarbon* •lloua* •lloun* •lloun* •lloun* •lloun* •lloun* lyeop*ra*a* ehol*at*ryl acatat* •lloun* �8 B S "I" wu - I, n ri K. Figure E-l. Total ion current chrotnatogram from GC/MS analysis for Semlvolatiles in sample 1032 (Bayonne, NJ). �Table E-2. Chroaato- Cluclon graphic Tamp. raak No. CO 1 2 3 4 s 6 7 t 9 10 11 12 13 14 IS 16 17 18 19 20 21 22 23 24 25 26 27 SEMIVOLATILE COMPOUNDS IDENTIFIED IN EXTRACT OF SAMPLE 2121 (Pittsburgh, PA) Chrouto- Uutlon graphic tap. raak Mo. CO Coopouad taluaaa alloxaaa alloxana allouaa allouaa 2 ,6-dl-tir c-buty 1-4-M chylphanol •athyl dodacaaoata athyl butyrata (tant.) alloxana Mt. hydrocarbon •lloxana alloxaoa MC. hydrocarbon •iloxana alloxana alloxana MC. and unaat. hydrocarbona oat. hydrocarbon unknown alloxana aat. and uaaat. hydrocarbona nnkaovn unknown alloxaoa alloxana d10-pyrana (Int. acd.) alloxana 147 28 29A 29B 30 31 32 33 34 33 36 37 38 39 40 41* 41B 42 43 44 4S 46 47 48 49 30 SI Cua^inimil uaaat. hydrocarbon taaat. hydrocarbon »E MC. and uaaat. hydroearbona alloxana paacacbloroblpbanyl aat. and unaat. hydrocarbona alloxana •at. and unaat. hydrocarbona haxachlorobiphanyl •lloxana •at. hydrocarbon alloxana aat. and unaat. hydrocarbon* •at* and uaaat. hydrocarbooa haptaohloroblphanyl alloxana Mt. aad unaac. hydrocarbona alloxaaa •lloxana •lloxana alloxana •lloxana lycoparaana alloxaaa ebolaacaryl acatata �8 Figure E-2. Total ion current chromatogram from GC/MS analysis for Bemivolatiles in sample 2121 (Pittsburgh, PA)- �Table E-3. SEMIVOLATILE COMPOUNDS IDENTIFIED IN EXTRACT OF SAMPLE 3095 (Baton Rouge, LA) Chroma CO- ilucioa (raphlc tap. F«ak Mo. (*C) 1 t 3 4 " 3 6 7 J 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27A 271 28 29 30 31 Chrouce- ilucioa iraphle Top. P**k Mo. (*C) Cnapoumi 32 33* 333 34 35 36* 361 37A 37> 38 39 40 41 42 43 44 45 46A 46B 47 48 49 50A 5C1 51 52 53A 533 54 55 56 57 Mtbylcn* chlorid* tolwn* •llcxan* •ac. hydrocarbon •ac. hydrocarbon (tanc.) illoxua aac. hydrocarbon (cane.) . •lloxan* •ac. hydrocarbon (cane.) •iloxaa* •ac. hydrocarbon •at. hydrocarbon unknown unknown MC. hydrocarbon •lloxan* MC. hydrocarbon •Iloxaa* •ilexint MC. hydrocarbon aac. hydrocarbon•lloxan* •lloxan* •lloxan* MC. hydrocarbon •llosan* •ac. hydrocarbon unaac. hydrocarbon unknown unknown •iloxaa* •lloxan* 149 ConpiiuDd «10-W«« •ac. hydrocarbon un*ac. hydrocarbon alloxan* DDE unknown unaac. hydrocarbon •llexan* unknown MC. hydrocarbon (cane.) •lloxan* uaaac. hydrocarbon (cane.) alloxan* •ac. hydrocarbon (cane.) •lloxaea •ac. hydrocarbon MC. hydrocarbon •ac. hydrocarbon •lloxan* •lloxan* •ac. hydrocarbon •Iloxaa* (ttnt.) •Iloxaa* •ac. hydrocarbon •ac. hydrocarbon lycop*ra«n* •lloxan* chol**csryl acccac* •lloxaA* •at. hydrocarbon ODJuown •iloxan* �Figure E-3. Total Ion current chromatogram from GC/MS analyaJs for semlvolatilea in sample 3095 (Baton Rouge, LA). �Table E:-4. SEMIVOLATILE COMPOUNDS IDENTIFIED IN EXTRACT OF SAMPLE 4093 (Charleston, WV) Chroaato- Clutlon (raphle Ta»p. Paak Mo. CO 1 2 3 4A41 5 6 7 8 9A 9B 10 11 12 13 14 15 16 17 IB 19 20 21 22 23A 23B 24 26 27 28 29 Co^-d Chroaato- Uutloa graphic Tamp. Faak Ho. CO tolaaoa •iloxana •llooa* •lloua* •at. hydrocarbon •lloxaoa •lloxana 30 31 32 33 3* 35 36 37A 371 38 39 40 41 42A 421 43 44 43 46 47 48 •9 50 SI 52 butyric arhydrlda (tut.) •at. hydrocarbon CjHju laoaar onknovn •Uoxana •at. hydrocarbon •at. hydrocarbon •lloxana •lloxana Mt. hydrocarbon Mt. hydrocarbon Mt. hydrocarbon •at. hydrocarbon unknown •lloua* Mt. hydrocarbon •at. and unaat. hydrocarbon •lloxana Mt. and mwat. hydrocarbon* •lloxana S3 54 56 57 58 59 MkBonn Mt. and unaat. hydrocarbon* •at. and iBaat. hydrocarbon* 151 Coapoood •lloua* •iloxana d1Q-pyrana (Int. ltd.) Mt. and unaat. hydrocarbon* •iloun* Mt. and unaat. hydrocarbon* Mt. and uuac. hydrocarbon* Mt. and uuat. hydrocarbon* DDE Mt. and unaac. hydrocarbon* •lloxana •lloxana •at. and uaMt. hydrocarbon* •lloxan* Mthyl d*hydtoabl*tata (tant.) •lloxaoa Mt. hydrocarbon •lloxan* ut. and unaac. hydrocarbon* •lloua* •hthalata •Uoxana •nkaowa •lloxana •Uoxana •Uoxan* lyeoparMna •lloxana cbolaataryl acatact Mt. and unaat. hydrocarbona •llouna tt-tacopb*rol (rltaxdn) �59 s tn NJ s 10 u. • _ * g - & o I' u o Figure E-4. Total ion current chromatogram from GC/MS analysis .for semlvolatiles in sample A093 (Charleston, WV). �UNITED STATES DEPARTMENT OF COMMERCE National Taohnloal Information Sarvloa 5285 Port Royal Road Springfield, Virginia 221 61 OFFICE OF THE DIRECTOR £>' *^s . . Doar ProfosTsional: I wish I could tell you how much time and money the NTIS Abstract. Newsletters could save you. But, I can't. 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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. 033 Folder The folder containing the original item. 0631 Series The series number of the original item. Series III 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. Benjamin S. H. Harris III Edo D. Pellizzari Kenneth B. Tomer Richard D. Waddell Donald A. Whitaker Description An account of the resource <strong>Corporate Author: </strong>Research Triangle Institute, Research Triangle Park, NC Date A point or period of time associated with an event in the lifecycle of the resource 1980-12-01 Title A name given to the resource Acquisition and Chemical Analysis of Mother's Milk for Selected Toxic Substances ao_seriesIII