1 15 1 https://www.nal.usda.gov/exhibits/speccoll/files/original/daa1b6097f5c84f0247a7f1743a72c9a.pdf 82d619d19856d6c1d7978d75e5a2fe97 PDF Text Text 00167 Author Kotchman, G.S., Jr. Non-Explosive Munitions Division, Air Force Armament Laboratory, Air Force Systems Command, United States Air Force, Eglin AFB, Florida Typescript: Flushing Techniques For Defoliant Spray Tanks, June 1970 Journal/Book Titla 0000 (Month/Day D 20 Technical Notes AFATL-TN-70-?; Typescript is followed by handwritten editing notes and reference materials. Included in the typescript is a table describing the military codes, trade names, common names and formulations of agents orange, white, and blue. Friday, January 05, 2001 Page 167 of 194 �AFATL-TN-7G- FLUSHING TECHNIQUES FOR DEFOLIANT SPRAY TANKS by G. S. KOTO-WAR, Jr., 1st Lt, USAF A, L. YOUNG, 1st Lt, N. A. TECHNICAL AFATL-TN-7Q-1 JUNE 1970 NON-EXPLOSIVE MUNITIONS DIVISION AIR FOICE LABORATORY AIR FORCE SYSTEMS UNITED STATES AIR FORCE EGLIN AIR BASE, FLORIDA �ABSTRACT In support of development of the F-4D/PAU-7B (modified TMU-28) defoliant spray tank, flushing techniques were develop'fbr flushing mnd/or washing defoliant agents Orange, White or Blue from spray tanks and/or from aircraft surfaces in the event of contamination. In addition, a solvent technique was developed for dissolving the precipitates formed following the mixing of defoliant agents Orange or White with agent Blue. �GENERAL COMMENTS The use of more than one defoliant agent in Southeast Asia (SEA) has resulted in compatibility problems between the agents. Remaining quantities of the defoliants Orange or White in the spray tank or in other parts of the spray system, if not properly removed, will fern persistent precipitates with agent Blue. The need for a solvent system, applicable for use in the field, which will dissolve these precipitates, is of interest to defoliant operations. In addition the development of the F-4D/PAU-7B (modified TMU-28) defoliant spray tank for use with agents White and/or Blue has generated a requirement for techniques in flushing and/or washing defoliant agents from not only the spray tanks but also from the aircraft surface in the event of contamination. A description of the three agents used in defoliant operations in SEA is given in Table 1. Further data on these agents can be obtained from a technical note by Young and Wolverton ( ) or from a technical report by 5 Darrow, Irish, and Minarik ( ) Orange is readily soluble in fuel oils or 4. &eorganic solvents, but insoluble in water. Agents Blue and White are soluble in water but insoluble in organic solvents and diesel fuel. None of the three agents are compatible with each other, more especially agents Orange and White with agent Blue. The liquid formulation of Blue was introduced to the SEA operations in 1965 ( ) 4. In a technical manual on the use of herbicides (1), dated 22 November 1966, agent White was first described for use in defoliant operations. In a "CAUTION" statenent in this manual the compatibility of Blue �TABLE 1. Descriptions of the three military defoliants used in Southeast Asia with their military code, trade name, common name, and formulation. Military Code Trade Name Common Orange Brush Killer 2,4-D, 2,4,5-T 50-50 mixture of the 80% n-butyl esters of 2,4-D (2,4-dichlorophen.oxyacetic acid), and 2,4,5-T (2,4,5-triehlorophenoxyaeetie acid). White Tordon 101 2,4-D, picloram 10.2% of the triisopropanolamine salt of picloram (4-aminQ-3,5f6-trichloropicolinic acid), 39.6% of the triisopropanolamine salt of 2,4-D, and 50.2% inert ingredients (primarily triisopropanolamine). Blue Phytar 560 G cacodylic acid, sodium cacodylate 4.7% cacodylic acid (dimethylarsinic acid), 26.4i sodium cacodylate (sodium dimethylarsinic acid), 3.4% sufactant, 5.5% sodium chloride, 0.5% antifoatn agent, and 59.5% water. / Formulation �(Phytar 560 G) with White (Tordon 101) was noted: "When Phytar 560 G and Tordon 101 are mixed a precipitate will form that will clog the spray system. Particular care will be exercised to remove residual Phytar by liberally flushing with water prior to filling aircraft tank with'Tordon. Residual Tordon will be removed by the same means prior to filling with Phytar." No mention was made as to how to remove this precipitate if it occurred or of the compatibility of Orange with Blue. Compatibility of Tordon 101 and Phytar 560 G was discussed by Buerge in a research memorandum of the Dow Chemical Company (3)« Buerge noted that a white precipitate formed when the two formulations were mixed in a ratio of 1:19 or 19:1, Tordon 101 to Phytar 560 G, respectively. This precipitate was recognized as the sodium salt of 2,4-D which is only 4-5% soluble in 7 water. Ingredients which were trjLed to prevent this precipitation from 0 **• forming included kerosene, #2 fuel oil, heavy aromatic naphtha, @>lyglycol P-400, (Pblyglyeol P-26-2 and each of the Dowanols. However, none of these chemicals prevented the precipitate from forming. Thus, Buerge concluded that the only way to prevent a precipitate^ from forming and to make the two formulations compatible was to dilute the formulation remaining in the spray tank with Jl5r^ water. In considering the JJinfet A/OlSY-l J|efoliant jlispenser, Buerge stated: O "If a. minimum of 150 gallons of water is added to either formulation remaining $ the tank and then the resulting mixture pumped or drained back down to 50 I in gallons, no precipitate will form when 950 gallons of the other formulation is added. If it is not desirable to pump or drain the mixture of water and *~\ formulation in the tank back down/to 50 gallons, then 150 gallons of water can be added if Phytar 560 G is leftain the tank, and then Tordon 101 can be added (to bring tsfae total volume in the tank) to 1000 gallons. If Tordom 101 is left �in the tank, however, approximately 500 gallons of water would have to be added before the Phytar 560 G is added to 1000 gallons to prevent a precipitate, Even then a little precipitate will form in this mixture after standing overnight." Furthermore, Buerge noted that to prevent the possibility of any precipitate forming in the lines when spraying is started, the remaining formulation in the tank should be diluted with water and pumped through the lines to clean the concentrated formulation out before the tanks are filled with a new formulation. In a Dow Chemical Company research memorandum, Buerge (2) reported on the compatibility of Tordon 101 and Orange. Mixing of these two defoliants did not produce a precipitate. The only problem recognized with the mixing of Tordon 101 and Orange was a separation of the two on standing (with Tordon 101 on top) when the ratio of Orange to Tordon 101 was high and sufficient agitation was not present. The need for solvent systems, applicable for use in the field, that will flush the spray tanks and systems efficiently is obvious. Improper flushing requires a solvent system to remove the formation of any precipitate. The 1 efforts reported in this note were undertaken not to 'clearly identify the precipitates formed from the mixing of the defoliants, but rather to determine solvent systeias and techniques which would meet the above requirements. Considerations were given to chemical availability in normal supply channels and to cost effectiveness. �LABORATORY AND The precipitate formed when White and Blue are mixed has been identified as the sodium salt of 2,4-D,which is only 4-5% soluble in water ( ) The precipitate fonued when Orange and Blue are mixed nay thus be . 3. the sodium salt of the n-butyl ester of 2,4-D or 2,4,5-T or a nixture of the two. The precipitates formed from mixing prange or White with Blue appeared - 6 to be different as indicated by various solubility tests. To find a solvent system which would dissolve these precipitates, many solvents were tried. Solvents which were unsuccessful in dissolving both precipitates included chloroform, hexane, ethanol, keorsene, benzene, petroleum ether, carbon tetrachloride, toluene, butanol, methanol, and dilute hydrochloric acid. The precipitates were partially soluble in acetone^ani mot water with detergent broke up the precipitate fomed from Orange and Blue. solvent system which will dissolve both precipitates is a 501 , ,j /by volume) solution of N,N-dinethyl formanide (DMF) in water, pith l— ~ sufficient amopnts of the solvent system in the tank (with scrubbing if possible), A the precipitate should be removed. If difficulties should still persist, a higher concentration of DMF should be used. Purging the systen with water will remove any remaining DMF. DMF has a boiling point of 153°C. (A*-with the vapor can be harmful; thus, DMF should be kept away from heat and open flame. Contact with skin and clothing should also be minimized. Solvent system recommendations for efficient flushing of individual defoliants (Orange, White, and\Slue, respectively) were basej on a residual content of 1 gallon in the F-4l^PAU-?B defoliant spray tank, application- of the r«€OHieitd»ti0n-s--S'hould--r€aiove-any-precipitatioft->--prcJ!W"eiis. �The recommended flushing agent techniques are as follows: a. To flush Orange from tank prior to the addition of Blue: (1) Add approximately 5 gallons alcohol (methanol, denatured alcohol, s or isopropyl alcohol). Mixy Flush as much as possible from tank. Note: \ flushing twice with alcohol u^ing 3 ^ gallons each time would get better s^ results if flushing can be done^ easily. (2) Add approximately 10 gallons water and mix. Flush milky solution froa tank. Again add 10 gallons water and mix. Flush slightly^ cloudy solution n froii tank. If solution is still milky at this stage, repeat water flush third time. (3) Add 2 gallons alcohol to tank, nix, and flush. Repeat adding 2 gallons alcohol, nix and flush. A check can be made at this stage by saving a snail amount of the solution flushed out and adding to it a small amount of Blue. Mixture should be clear and tank should be ready for adding Blue. b. To flush Blue froa tank prior to the addition of Orange: (1} Add approximately 5 gallons alcohol to tank. Mix and flush immediately so that residue does not settle out. ( ) Repeat adding S gallons alcohol, mix, and flush. 2 ( ) Repeat adding 5 gallons alcohol, mix, and flush. Better 3 cleaning can be obtained by flushing five times with 2 to 3 gallons of alcohol. Save small amount of final flush solution and add small amount of Orange. If the mixture remains clear, the tank is satisfactory for filling with Orange. If solution is cloudy, flush again until aixture of flush solution and Orange remains clear. 7 �a. To flush White froa the tank prior to the addition of Orange or Blue: (1) Flush system with 5 gallons of detergent and water, (2) After flushing thoroughly with water, add approximately 5 gallons of alcohol to tank, mix and flush, (3} Save a snail amount of flush solution and add mint snail amount of Blue. If mixture remains clear, the tank is satisfactory for filling with Orange or Blue. If solution is cloudy, flush again until mixture of flush solution and Orange or Blue remains clear. If a spray tank is only to be used with defoliants White and Blue, then the flushing recommendations would be as follows: a. Assuming 1 gallon of WHITE is in the tank, a Minimum of 10 gallons of water should be added. Flush this from the tank saving a saall amount of the flush solution. To the small amount of the flush solution add a small amount of Blue, the defoliant to be used in the tank. Allow to set several minutes. If no semi-solid particles form, the tank is satisfactory for filling with Blue. If a precipitate forms, add more water to the tank and test a small amount of the flush solution with Blue to insure that the solution remains clear, b. Assuming 1 gallon of Blue is in the tank, a minimum of 10 gallons of water should be added. Flush from the tank and test a small amount of the flush solution by adding a small amount of White. If no precipitate forms after setting for several minutes, the tank is satisfactory for filling with White, If a precipitate forms, repeat the flushing and test the flush solution until the solution shows no precipitate. �For all recommendations, the wash containing the diluted Orange, White, or Blue should, if possible, be diverted into pits or settling basins for incorporation into soil. It should not be directed into a stream or river. �LITERATURE CITED 1. Air Force, AFPS, SAMMA. 22 November 1966. Herbicides. T.O. 42C-1-17. Technical Manual-Use of 2. Buerge, T. £., 30 June 1966. Compatibility of Tordon 101 and Orange. Research Memorandum, Dow Chemical Company, Midland, Michigan. 3. Buerge, T. E., 1 July 1966. Compatibility of Tordon 101 and Phytar 560 G. Research Memorandum, Dow Chemical Company, Midland, Michigan. 4. Darrow, R. A., K. E. Irish, and C. E. Minarik. 1969. Herbicides used in Southeast Asia. Technical Report SAOQ-TR-69-11078, Plant Sciences Laboratories, Fort Detrick, Frederick, Maryland. 5. Young, A. L., and B, C. Wolverton. 1970. Military Herbicides and Insecticides, Technical Notes AFATL-TN-70-1, Air Force Armament Laboratory, Eglin Air Force Base, Florida. "O �f&l A / ' // /? ^u£d OQJU. /. J &i£>£tt*nfy ^ /ILM^^L^L W M t*&tL "^ J r ^ . JB A^ i ^ ^ ™ H ^ /I !_/• VU. ^J^tl^^' 1 ^"j^* f*Fr VXV^y^^*^^ fi J-~ &5' t jf / I / G^ * �Lr ~£a*Jc-, - r/)-4 Afefcs u J) ,, T-~ 1 Mi^i^ / e ^ / ��&JL t4/5V\4 2 - <A n 1 O » , t | o �1. Description of Defoliants i BLUE Is the code designation for a neutralized^ liquid formulation _-4»ntaIniag--cacodylic acid ^diraethylarsinic-acid) arid its sodium salt. The BLUE currently in use is a liquid formulation produced by Ansul Company and is designated Phytar 560G, It contains';a minimum of 21% sodium cacodylate with additional free cacodylic acid for a total clime thy larslnic acid equivalent of not less than 26%; or 2.48 Ib/gal. Phytar 560G contains 5% by volume of a surfactant plus 0.5% of an antifoaia agent. ' \ WHITE is the code-designation -for Tordon 101, a liquid formulation containing picloram (4-amino-3,5,6-trichloropicolinic acid) and 2,4-D in the form of triisopropanolamine salts. The composition of MUTE, based on weight of salt, is: picloram, 10.2%; 2,4-D, 39.6%. Based on .weight of-active-ingredient or acid, the composition is: picloram, 5.7% or 0,54 lu/gal; 2,4-D, 21.2% or 2.0 Ib/gal. The remainder consists of water, wetting agent'j and other inert ingredients. Picloram or Tordon is a proprietary item produced by Dow Chemical Company, 2. Physical, Chemical, and Biological Properties a. Physical State ; BLUE (Phytar 560G) is a liquid formulation of cacodylic acid and its sodium salt. It is a reddish or brownish, free-flowing liquid. WHITE (Tordon 101) is a dark brown, somewhat viscous liquid. b. Solubility BLUE is readily soluble in water and alcohol but insoluble in diesel fuel and oils. .~ * WHITE is misclble in water but insoluble in diesel fuel and other oils. "The" triisopropanolamine forms of 2,4-D and picloram in WHITE are both readily soluble in water. c. Volatility BLUE is nonvolatile. low vapor pressures. Cacodylic acid and its salt have extremely �WHITE is considered nonvolatile. Picloram has a vapor pressure of 6.16 x 10~7 mm of Ilg at 35 C. WHITE, because of.the low volatility of its active ingredients, has been suggested as a substitute for ORANGE for defoliation in areas adjacent to rubber plantations and sensitive broad-leaved crops. However, because of the high activity of the picloram component, extremely small amounts can damage sensitive species. WHITE is stable and moderately resistant to ultraviolet radiation. Despite its water base, the formulation WHITE is flammable with a flash point of 35 C. d. Corrosive Action Corrosion tests with undiluted BLUE showed little or no effect on brass, copper, aluminum, and tin after an explsure of 1 month. Steel showed a rapid initial reaction and moderate corrosion with BLUE. Zinc was the least resistant metal, exhibiting a galvanic reaction in the cacodylate solution. NHITE is noncorrosive on common metals and materials used in spray equipment. e. Biological Properties BLUE is a desiccant or contact herbicide and causes rapid browning of foliage. It shows relatively little translocation or movement within the plant. Foliage of broad-leaved vegetation affected by BLUE may abscise or shrivel and remain on the plant. Grasses may show rapid browning and death of top growth but regrowth of resistant perennial species may occur within 1 to 2 months. Defoliation of woody vegetation by BLUE shows shortterm effect, with ~ maximum effect at 2 to 6 weeks after treatment. . « WHITE is a mixture of two systemic herbicides, picloram and 2,4-D, It is partially selective in its defoliant and herbicidal action on an array of plant species and is effective, principally, on woody and certain broad-leaved herbaceous plants. Both the picloram and 2,4-D components are relatively ineffective on grasses, bamboos, and other monocotyledonous plants. Forest areas defoliated with WHITE often show an immediate increase in these resistant plants. Both picloram and 2,4-D are readily absorbed by the foliage. Picloram, apparently, is more easily absorbed by the root system than are 2,4-D and other phenoxy herbicides. �The picloram component of WHITE is more persistent in soils as compared with other chemicals such as ORANGE and BLUE. Microbial decomposition of picloram is limited and losses from soils occur principally by leaching and some photodecompositioii. At rates used for defoliation it may persist in some soils for 1 year\or more. i 3. Storage \ Herbicides are delivered in 55-gallon steel drums marked with an identifying color band. Drums may be stored in either a horizontal or vertical position. Under prolonged storage, stockpiles should be checked • periodically to determine the condition of the "containers and remove leakers or damage drums. BLUE and WHITE are stable chemicals with a storage life of several years. The chemicals may outlast the life of the metal containers under prolonged storage exposure to tropical heat, rain, and humidity. 4. Handling \ BLUE may be handled safely with ordinary sanitary precautions in avoiding prolonged contact with skin or clothing. Cacodylic acid is readily absorbed through the skin; prolonged absorption may lead to a distinct garlic odor in the breath. Spillage should be avoided and =removed by liberal flushing and rinsing with clear water. , Only ordinary precautions are recommended for handling WHITE, as for any common agricultural chemical. It may be mildly irritating to skin and eyes on prolonged contact. Contaminated clothing should be washed before reuse. Spillage on the skin should be rinsed with clear water. BLUE should not be used in a spray system either following or preceding WHITE, without thoroughly flushing the tank and system with water. A mixture of these two agents results in a precipitate consisting of the sodium salt*of 2,4-D (a component of WHITE}. If a change in agents is to be made, the tanks or spray system should be filled at least half full with clear water and the system exhausted of liquid before the new agent (BLUE or WHITE) is added. 5. Methods of Disposal Loading and storage areas subject to chemical spillage may be partially decontaminated by repeated washing with ammonia water and flushing with clear water. Runoff water from such flushing operations should be diverted to settling basins or restricted areas not subject to overflow on cropland. Picloram in WHITE is persistent in spray equipment and containers or in soil, thus full decontamination of equipment or areas subject to spillage is extremely difficult. A vigorous regimen of soap �I and water, ammonia water, and clear water rinses and flushings is necessary. Equipment used for WHITE should not be used for other purposes such as fertilizing or applying insecticides. i Equipment used for application of BLUE should b'e thoroughly cleaned prior to storage or disuse. Several flushings of soapy or detergent water to which ammonia has been added may be used, followed by a clear rinse. For roost spray systems a final rinse with diesel fuel may serve to prevent : rust or sediment accumulation. ; Excess spillage of BLUE in loading or storage areas should be removed by thorough washing with clear water and/or dilute ammonia. Runoff or wash water containing diluted BLUE should, if possible, be diverted into pits or settling basins for incorporation into soil. The chemical is rapidly adsorbed by soil and deactivated. Used containers and residual chemical should be disposed of by burial whenever possible. \ \ 6. Toxicology Cacodylic acid or dimethylarsinic acid, the active component of BLUE, contains arsenic in the innocuous pentavalent state rather than the toxic ;trivalent form. The acute oral toxicity (LDgg) of cacodylic acid in rats i is 1,400 mg/kg for males and 1,280 mg/kg for females. For the formulation Phytar 560G or BLUE containing the acid and its sodium salt, the acute » oral toxicity (UDgo) for rats is 2,600 mg/kg, a toxicity level lower than that of aspirin (1,750 mg/kg). Cattle fed 24.5 mg/kg of cacodylic acid daily in a 60-day feeding test showed no arsenic in the milk and no storage of arsenic in the animal body on a cumulative basis. In tests with fish, Gambusia, shiner, and largemouth black bass were able to withstand concentrations of cacodylic acid of at least 100 ppm for 72 hours, a rate equivalent to 270 Ib.of a chemical per acre-foot of water. It may, thus, be considered nontoxic to fish and animals. When BLUE or cacodylic acid is applied directly to soil, the chemical is rapidly adsorbed and deactivated by the soil colloids so that new crops can be planted during the same growing season. Toxicity data have been collected for the components 2,4-D and picloram and for the mixture WHITE. Picloram is extremely low in toxicity; the LD50 for acute oral toxicity in rats is 8,200 mg/kg; for sheep and cattle it is 488 to 650 mg/kg. For Tordon 101, or WHITE, the acute oral LD5Q for rats has been reported as 3,080 mg/kg; for sheep 2,000; and for cattle 3,163. �In a feeding test on cattle, 97.7% of the administered picloram was recovered unchanged in the urine; no picloram was detected in milk. Median tolerance limits of fish to Tordon 101 ranged from 64 ppm for fathead minnow to 240 ppm for brook trout. Toxicological studies conducted by Cdgewood Arsenal and Dow Chemical Company indicate that a single direct exposure to a spray of WHITE, at prescribed rates, would not constitute \a. hazard to the skin or a systemic hazard by inhalation. The chemical, picloram, is considered nontoxic and not hazardous to humans, animals, and fish. � Dublin Core The Dublin Core metadata element set is common to all Omeka records, including items, files, and collections. For more information see, http://dublincore.org/documents/dces/. Title A name given to the resource Alvin L. Young Collection on Agent Orange Description An account of the resource <p style="margin-top: -1em; line-height: 1.2em;">The Alvin L. Young Collection on Agent Orange comprises 120 linear feet and spans the late 1800s to 2005; however, the bulk of the coverage is from the 1960s to the 1980s and there are many undated items. The collection was donated to Special Collections of the National Agricultural Library in 1985 by Dr. Alvin L. Young (1942- ). Dr. Young developed the collection as he conducted extensive research on the military defoliant Agent Orange. The collection is in good condition and includes letters, memoranda, books, reports, press releases, journal and newspaper clippings, field logs and notebooks, newsletters, maps, booklets and pamphlets, photographs, memorabilia, and audiotapes of an interview with Dr. Young.</p> <p>For more about this collection, <a href="/exhibits/speccoll/exhibits/show/alvin-l--young-collection-on-a">view the Agent Orange Exhibit.</a></p> Text A resource consisting primarily of words for reading. Examples include books, letters, dissertations, poems, newspapers, articles, archives of mailing lists. Note that facsimiles or images of texts are still of the genre Text. Box The box containing the original item. 016 Folder The folder containing the original item. 0167 Series The series number of the original item. Series II 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 Kotchman, G.S., Jr. A. L. Young N. A. Hamme Description An account of the resource <strong>Corporate Author: </strong>Non-Explosive Munitions Division, Air Force Armament Laboratory, Air Force Systems Command, United States Air Force, Eglin AFB, Florida Title A name given to the resource Typescript: Flushing Techniques For Defoliant Spray Tanks, June 1970 Subject The topic of the resource spray equipment herbicide properties Ranch Hand