Document q80M57jvGLNaykGOzvzkG9YR

) APPENDIX D Occurrence, Transfer, and Cycling of PCBs in the Environment Table of Contents I. Occurrence in the Environnent II. Behavior in the Environment A. Air B. Water and Sediment III. Exposure and Biological Accumulation 17. Discussion V. Research Needs and Opportunities Tables 1. PCB Manufacturing and Sales Data From Monsanto'Industrial Chemicals Co. 2 . Concentration of PCBs in ffeinicipal Sewage Treatment Plant Outfalls 3. PCB Concentrations in Industrial Effluents Ii. Total Estimated Contribution of PCBs to the Aquatic Environment ?. Concentration of PCBs in Sewage Sludges 6 . A Sampling of Measured Occurrences of PCBs in the Environment 7. Accumulation of PCBs by Various Aquatic Organisms Page 92 99 99 102 103 85-86 J 8*1 1 1 1 90!! 9lj 93-98 100 83 ADM 00122 U TOTAL PRODUCTION (For Domestic Sales)^' DOMESTIC SALES DOMESTIC SALES BY CATEGORY Heat Transfer Hydraulics/Lubricants Mise. Industrial Transformer C a p a d tur PlastLcier Applications^) Petroleum Additives Total DOMESTIC SALES BY P GRADE Aroclor 1221 Aroclor 1232 Aroclor 12l|2 Aroclor 121*8 Aroclor 1251* Aroclor 1260 Aroclor 1262 Arcolor 1268 Total TABLE 1 PCB MANUFACTURING AND SALES DATA FROM MONSANTO INDUSTRIAL CHEMICALS CO. 1957 THROUGH 1971 (Thousands of Pounds) 1957 1958 1959 I960 32299 26061 3I3IO 37919 35211 1612 701 12955 17028 - 32299 _ 15U9 755 5719 11)099 3939 - 26061 2685 1569 5981 161)99 1)573 - 31310 2523 1559 7921 16967 62L 6 - 3521 23 196 18222 1779 ll6l . 7587 31 - 32299 16 113 oiiUt 2559 6691 5982 181 72 2606I 251) 21*0 13598 3381 6751) 6619 359 102 313IO IO3 155 18196 282? 6088 7330 326 189 35211) NOTE: (i) Production amounts prior to I960 are not available. (2) Amounts for plasticizer applications prior to 1958 are not available. 1961 1962 36515 37538 38353 . 3801)3 1)110 2111* 6281 15935 9098 - 37?3 157 3915 1681 7981) 15382 8921) - 3BU 9ii 2l*l . 19827 1)023 6291 65l|0 361 158 37538 11|0 22li 2065I) 31)63 6325 6595 1)32 210 3801,3 <7?t o o o wav estimated that one-third of the PCBs released to the air and one-half of those released to water have now been degraded. The PCBs in dump's probably have undergone less degradation. Given the diversity of uses of PCBs and their chemical stability (greater stability in the higher chlorine species), it is not surprising that residues are now widespread. While satisfying quantitative estimates of the contribution of various pathways into the environment are not possible with existing data, there are enough data to be certain that they do reach the environment at least from the following sources: -- Open burning or incomplete incineration (at usual temperatures) 3 of solid wastes, municipal and industrial. Incineration at 2000 F or above for two seconds will destroy PCBs, but poorly operated incinerators or open burning may result in PCBs being released to the atmosphere unchanged. -- Vaporization from paints, coatings, plastics, etc. (Nisbet and Sarofim, 3) estimate that as much as 20 percent may be vaporized. -- Municipal and some industrial sewers (present in treated as well as untreated wastes). Tables 2 and 3 -- Accidental spills or improper waste disposal practices. -- Formerly, direct application to the environment as ingredients of pesticides or as carriers for pesticides (such uses are now prohibited). -- Dumping of sewage sludge, municipal and industrial solid waste, and dredge spoil at sea. -- Sewage sludges disposed of on land. -- Migration from surface coatings (paints, etc.) and packaging materials into foods and feeds. Probably the largest amounts of PCBs circulating in the environment reach it through industrial and municipal discharges to inland and coastal waters. Tables 2, 3? and k present data on such discharges. Based on Table h, we can estimate 6,000 tons per year may reach these environments. In addition, PCB residues occur in sludge from municipal sewage systems. Table 5 presents results of analyses from several such sludges. Sewage sludge is disposed of by incineration, landfill, spreading on the land, and dumping at sea. Four million tons per year reach the Atlantic Ocean and Gulf of Mexico, which would include only 10 or so tons of PCBs (!j). Analysis of the waste water from the effluent scrubbers of three sludge incinerators showed no detectable residues of PCBs (level of sensitivity 0.1 part per billion), suggesting that most PCBs had been destroyed by incineration. The total amount of PCBs con tained in the sludges would not b efore than * ^ 7 0 tons per year. 87 ADM 000126 V .y TABLE 3. PCB CONCENTRATIONS IN INDUSTRIAL EFFLUENTS Location Kind of Industry Date Aroc lor Compound Detected Concent rat ion in Effluent (ppb) Saukville, Wise* Ohio- Great Chemical Plant Paper Coating Co. 3/70 1/71 1242 1242 & 1248 2.50 27 Miami River S' Florida- Escambia cd River VO Paper Treatment Appliance II Chenical Plant 1/71 1/71 1/71 4/69-10/69 1242 1254 1254 1254 430, 470* 5 18 2.5-275 Source of Data Vieth and Lee, 1970 EPA data- Analytical Quality Control Lab. tt tt n Duke, et al., 1970 "Samples from treatment lagoon AOM cecine J C o l 1e c t i o n S i t e Cali forni a Hyperion (Los Angeles) Bursl o w TA ISLE 5 . ('Of:C ENTRATIOH OK IHJ IS IN GI'WAGE SLUUGES Rate Arce lot' R e t et. r I'd Concentuat ion ( p p b ) _________ Sludge iet* day toiis/day Eat. PCB Coni.tint Day (Ilis-? Source 12/70 7/21/71 1254 1254 85 (78.5-02. 1) 2 0 , 0 0 0 ^ 1400 1.4 3.2 .004 Schmidt., ci. al., (13) EPA Unpublished data Oh io Day tor. (Miami River) Lillie Miami (Cincinnati) ltJI Crudi (Cincinnali) Lebanon (Turtle Creek) Shay 1or Run 1254 1254 1254 1254 1254 105,000 32,000 12,>00 2,500 3,200 47.9 20.2 83.3 l.U * 10.1 1.3 2.2 .005 EPA Unpublished data M It 1 Il II H II II H 1 II 1* Virginia Corion 1254 l ,200 - - II It II Indi ana Indi.nnnpoli.ii 1254 3, S00 126.1 1.03 Il VI II \J Tliis number is based oh outfall discharge and represent.:, a relatively dilute sludge. The estimated P'J'd cunLent in lbs./day is the important figure here. Assumptions: Each million gallons of sewage contains about 1 ton of sludge. The daily output of sluti'C, then is 150,000,000 sewered population x 130 gal. sewage per day = 1fi,500,000,1100 gallons per day and 10,500 tun;; of sludge per day. At 10 ppm of PCIIs (highest level found), the daily output would be 10,500 tons x 2000 lbs. = 3(I million lbs. x . ` ppm -= 39i) lbs. per day, at l ppm, 30 lbs./day. These would b e .respectively 70 and 7 tons/year. ADH Q00130 ! K-S TABLE 6. A SAMPLING OF MEASURED OCCURRENCES OF PCBS IN THE ENVIRONMENT - Loo at ion No. Samples Date A roc lor Compound Detected Concentration (ppb) Source of Data Remarks Air Precipitation United Kingdom 196B N.S. Detected but not quantified Tarrant and Tatton, 1968 Florida 1971 N.5. Below level of quantification USCS- Unpbl. - Sweden 1970 N.S. Present in snow Smithsonian Inst. CFSLP- 1970 Suspended Partigniate Water A U. S. cities 1968-1970 n .s ; ^27-230 ppm on suspended solids EPA- Unpbl. Quantification questionable Great Miami River, Ohio 19 11/70 1242 Ohio River 2 11/70 ND to 15.fi - = 5.7 X ND EPA- Unpbl. M 3 samples above Dayton below level of detec tion. Mean of 16 samples 5.7 Big Suaintco River, Wise. - <0.01 Velth, 1972 PesLigo River t Wise. 11/70 4/71 Summer *71 1254 M II 0.31 0.38 <0.01 M H OconLo River Wise. 11/70 4/71 Sunnier *71 1254 ii it 0.45 0.16 <0.01 M 1 - Mi Iwaukee 10 1970 1242 0.03t 2.07, X 0.29 Veiili and Lee p River 1260 0.02-0.13, X 0.08 1970 ADM 00G132 rS . ; Blot a Marine Plankton Location No. Samples North Atlantic TABLE 6 (Continued) A roc lo r Compound Hate____ De Lee Led Concentration ippb) 1971 N.S- x 200 Zooplankton Irish Sea 7 10/69 N.S. 10-30 Invertebrates Mussels ii M / Oysters it ii Irish Sea Baltic Sea StockhoIm Archipelago (about 200) 10/69 AO 1965-1960 15 II N.S. N.S. Escambia Bay, Pla. H M Florida Georgia S. C. 18 1971 2 1970 2 1969 B 1964-1970 12 1967-1970 3 1965-1969 1254 M It It H Blue Crab Florida Crabs _ -(| 1 Shrimp Norvay Lobster S. C. Escambia Bay, Fla. H Irish Sea 10 33 2-3/70 1969 1969 1969 N.S. 1254 1254 50-500 4300 (1900-8600) 5200 (3400-7000) 650 (100-1400) 840 (710-970) 1050 (1000-1100) 1400-2700 2000 Present but not quant ifled it < 100 1000-7000 1500-2500 10-100 Source of Data Remarks Harvey _in Nesbit & Sarofim, 1972 Holdgate _in Nesbit & Sarofim, 1972 n Jenson, et al., '69 If EPA- Gulf Breeze, Unpbl. M ff M I M tl Duke, et al., '70 II ft HoldgaLe 1970 in Nesbit & Sarofim, 1972 ^ciooo wav vJ Location Biota (continued) Ho. Samples Bi rds - Land Start ings Continental U. S. 124 Woodcock N.S. - Nothern U. S. Bald Eagle 25 states 69 Birds - Water Guillemot Eggs Ilaltlc Sea 9 Wlii t e - t a i l e d Ea^le Stockholm 4 Archipelago Heron 4 Double-crest ed 3ay of Fundy (.omorant (egg: >) Abdominal Iat Herring Gull Bay of Fundy Fat ACH CCC136 TABLE 6 (Continued) Date Aroc lor Compound DeLccted Core entrt ion (pnb) Source of D a m 11-12/70 N.S. Fall 1971 N.S. 1966-03 N.S. 5/68 3/65-6/66 4/67 1971? II II 125/4 1254 1254 X 660 (50-24,300) Bureau of Sport Fi slisries & 1.'iId 1., L'npub 1. 4000-9000 II Not quant if ied M 250,000 14.000. 000, 3,400,00017.000. 000 9,400,000 17,200 52,000 75,000 Jensen, et al. , 1970 (22) M Junsvii, et al,, ivu9 (19) Z iLl.u, et al., 1972 (20) II M million in some fish and birds near the top of the food chain (1/8 of ar. inch is about one trillionth of the distance to the moon; and a part per million is about 5 steps on a walk from Washington to San Francisco).* Mar., who is also at the top of a food chain, carries residues ranging up to 2 parts per million or occasionally more. II. BEHAVIOR. IN THE ENVIRONMENT A. Air - The relative importance of the atmosphere as a transport mechanism is not known. Hiile PCBs have been identified in air, the residence time, transformations, and movement from air to land or water surfaces through fall out or rainout, or return to the atmosphere are virtually unknown. There are at least two observations that suggest substantial aerial transport; data on residues in fish in Lake Minto in a remote part of northern Quebec (7), and residues in woodcock which feed almost exclusively on earthworms, which in turn pick up residues from the soil. Only by invoking aerial transport can we account for residues in arctic lakes or in more or less wilderness areas of the North where woodcock summer. Nisbet and Sarofim (3) suggest airborne PCBs will have been adsorbed on particles and have a relatively short residence time_ thus most will have been re deposited on the U. S. continent, but some will have reached the oceans. B. Water and Sediment - The water environment is probably the principal sink and transport mechanism for PCBs. Calculations based on measured occurrences in municipal and industrial outfalls, in the receiving waters, and the down stream reaches of the waterways demonstrate transport through the aquatic sys tem. Measured residues in fishes from various environments suggest accumulations at the downstream ends of the drainageways. There are few data on removal, disappearance, and sequestering of the sub stances in soils or bottom sediments of rivers, lakes, estuaries, or the ocean. Table 6 includes some data that indicate presence in bottom sediments, and sug gest that sediments may be a major reservoir of PCB residues. Work by Ninmo and his colleagues at Gulf Breeze (8) has shown that at least pink shrimp and fiddler crabs are able to take up PCB residues from this source. Fiddler crabs and pink shrimp exposed to clean flowing sea water in aquaria containing sar.dy silt with initial residues of 6l parts per million (dry weight basis) of Aroclor 125ij accumulated an average of 80 * 25 parts per million in the whole crab and 2li0 parts per million (or.e pooled sample) in the hepatopancreas of the shrimp. Accumulation was much less, 1 7 + 9 parts per million and 6.1 parts per million, respectively, with silt initially containing 30 parts per million. Some accumu lation took place 3.2 + 0.9 parts per million (in crabs) and 1.1 parts per mil lion (shrimp hepatopancreas) from silt initially containing 2.5 parts per mil lion. The same investigators have shown transfer of residues from sediments to overlying water. Effluent water from the aquarium with 61 parts per million Aroclor in sandy silt contained 3*5 parts per billion; from the aquarium with 30.0 parts per million in silt, effluent water contained 0.5 parts per billion. III. EXPOSURE AND BIOLOGICAL ACCUMULATION \ Experimental Work on biological accumulation by individual species of vertebrates and invertebrates has been conducted by a number of laboratories in the United States and elsewhere. Table 7 presents selected data that demon strate accumulation factors of up to 75*000 in whole organisms, and in the 99 ADM 000130 hepatopancreas of pink shrimp. The data reported in the preceding section demonstrate that pink shrimp are able to accumulate PCB residues- from "environ mental levels as low as 0-5 parts per billion; and Table 7 shows accumulation by fish from levels as low as 1 part per billion. Fvidence from environmental samples (Table 6) suggests uptake of PCB residues from exceedingly low environmental concentrations. Thus the plankton samples from the North Atlantic contain something like 200 parts per billion, yet PCB levels in marine waters are believed to be exceedingly low-- certainly less than 0.01 parts per billion. PCBs, like many of the organic insecticides, are fat soluble, and are stored in the lipids of animals. Like the insecticides, they resist metabolic changes, and tend to be concentrated (at least to some extent) at succeedingly higher levels as they pass through various steps in the food chain. The data presented in Table 6 suggest that there are two components of movement through the biota. One is the familiar pattern of food chain accumu lations. The other involves direct uptake from the environment by various trophic levels; e.g., soil to earthworms; water to phytoplankton, zooplankton, larger invertebrates, and fish, lhe fish and plankton data from the North Atlantic reported by Nisbet and Sarofim (3) are consistent with the hypothesis, in that plankton residue levels are higher than fish levels, suggesting direct accumulation rather than food chain transfers. So, too, is the evidence from feeding studies -reported by Stalling and Mayer (9) that suggest accumulations of no more than a factor of 2 over dietary intake levels in fish. It seems reasonable.that food chain transfers are the principal route of accumulation in warm blooded vertebrates, and possibly in the highest levels of carnivorous fish. Conversely, direct envirormental uptake is probably the most important for aquatic invertebrates and fish. That humans are exposed to PCBs is evident from the data in Table 6. There are a number of possible routes: air, water, food. Fish and shellfish through uptake from water would be expected to provide the principal continuing source in the diet. Sampling of fish to keep those containing more than the FDA interim action level from the market is carried out by PDA and the various States where fish are known to have substantial PCB contamination. Other foods have been found to contain PCB residues, but these residues are for the most part traceable to accidents; e.g., residues in eggs and poultry whose diet in cluded fishmeal contaminated by leakage of PCBs from processing equipment (Monsanto reports they no longer sell PCBs for this purpose); residues in milk traceable to silage stored in silos painted with PCB-containing paints; residues in dry food packaged in PCB-contaminated packaging materials. Aside from the occurrences traceable to incidents such as the above, residues have been found in only Ij79 of 15*000 food samples by FDA during November 1969-June 1971 (200 of the Ii79 were followups on samples found to contain PCBs). In the FDA diet studies during FT 70 and 71, only 22 of 720 composite samples contained PCB residues. It is clear that only a small fraction of the U. S. food supply contains detect able levels of PCBs. 101 ACM CCC14C The effluents from such installations should be regulated and closely moni tored to assure that no more than 0,01 parts per billion results .in the re ceiving water. {So, too, should the manufacturing and disposal facilities of Monsanto.) Good housekeeping should.permit this level to be achieved. Ar. educational campaign'aimed at users to assure proper disposal will also be necessary-- so long as the materials are referred to as transformer oils, cutting oils, hydraulic oils or fluids, etc., care in disposal will beh a r d to assure. After all, oils in moderate quantities aren't regarded as trouble some substances. V. RESEARCH NEEDS AND OPPORTUNITIES 1 . Data provided by Kuratsune and Masuda (11) suggest that PCB-contain ing carbonless copy paper may have been an important source of PCB residues in man. An epidemiological study, involving a group of regular users of such copy paper (airline ticket salesmen; clerical workers; etc.), would shed much light on this question. 2. The detection of high levels of PCBs in house dust by Price (10) suggests that inhalation may be an important source of PCB levels in man. Both the question of occurrence in dust and of respiratory uptake from such dust should be explored. 3. Residues of PCBs have not been determined in soils, though by infer ence they must be present. A set of samples from the program of pesticides monitoring in soils should be analyzed for PCBs; the set should be drawn with care to illuminate distribution patterns in, near, and remote from industrial areas. L. Data on pesticides in air are unsatisfactory. A few samples, in cluding both vapor and particulates, should be collected from industrial areas and analyzed. If the methodology proves satisfactory, a small-scale survey should be undertaken to determine the importance of the atmosphere as a trans port mechanism. 5. The presumption that PCBs do not move to ground water should be tested. The volume of water in this reservoir, coupled with its relatively long residence time, suggests that even very low levels of contamination may be significant. 6 . Dumps And landfills are thought to be the principal reservoir of PCBs, but there are virtually no data on behavior of PCBs in these locations. Smallscale sampling should be undertaken to determine the concentrations brought to dumps, the fate of PCBs from open burning, and into leachate and gases from sanitary landfills. Degradation in place should also be investigated. 7. The presumption that submerged sediments contain a large amount of PCBs should be examined. Such questions as vertical distribution, degradation, movement, transfer of water, should be explored as well as the current distri bution of residues beneath inland and inshore marine waters. \ 8 . The reported finding of PCB residues on the order of 0.2 parts per million in marine plankton of the mid-North Atlantic requires elaboration. 103 ADM 000142 FOOTNOTES 1. Jensen, Soren. 1966. Report of a-new chemical hazard. New Scientist, 32:612. 2. Isono, N, 1970. Jishu Koza, 1 (l):60, 1 (Li):58 (in Japanese). 3. Nisbet, Ian and Adel Sarofim. 1972. Rates and routes of transport of PCBs in the Environment. Environmental Health in Perspective. 1, (in press). b. C.E.Q. (Council on Environmental Quality). 1970. Ocean dumping: A national policy. Washington, D. C. 5* Lidgett, R. A1, and H. A. Vodden. 1970. PCB -- the* enviroriental problem pp 88-96 in PCB Conference, Wenner-Gren Center, September 29, 1970. Stockholm: National Swedish Envirorsnent Protection Board. 6. Acker, L. and E. Schulte. 1971. Vorkommen von chlorieten biphenylen und hexachlorobenzol neben chlorierten insekti2iden in human milch and menschlicher. fettgewebe. Naturwiss, 57:1:97. 7. Risebrough, Robert W., and Brock de Lappe. 1972. Accumulation of poly chlorinated biphenyls in ecosystems. Environmental Health in Perspective. 1, (in press). 8. Nimmo, D. R., P. D. Wilson, R. R. Blakman,* and A. J. ^.lson. 1971. Polychlorinated biphenyl absorbed from sediments by fiddler crabs and pink shrimp. Nature, 231:50-52. 9. Stalling, Ifeivid and Foster L. Mayer, Jr. 1972. Toxicities of PCBs to fish and environmental residues in fish. Environmental Health in Perspective. 1, (in press). 10. Price, Harold A. 1972. Occurrence of polycnlorinated biphenyls in humans. Enviromental Health in Perspective. 1, (in press). 11. Kuratsune, Masanori and Toshito Masuda. 1972. Polychlorinated biphenyls in non-carbon copying papers. Environmental Health in Perspective. 1, (in press). 12. Veith, G. D. and G. F. Lee. 1970. A review of chlorinated biphenyl con tamination in natural waters. Water Research, h:265-269. 13. Schmidt, T. T., R. W. Risebrough, and F. Gress. 1971. Input of poly chlorinated biphenyls into California coastal waters from urban sewage outfalls. Bull. Erivir. Contam. & Toxicol., 6(3)*235--21*3 l2i. Duke, T. W . , J. I. Lowe, and A. J. Wilson, Jr. 1970. A polychlorinated bipheryl (Aroclor 125L) in the water, sediment, and biota of Escambia Bay, Florida. Bull. Environ. Contamin. Toxicol., 5:171-180. 15. Tarrant, K. R. and J. O 'G. Tatton. 1968. Organochlorine pesticides in rainwater in the British Isles. Nature, 219:725-727. IG5 a d m C0014^