Document 3NXGYVVrNe0jO7jkVVD5DX5Vy

m. ***'!. wv - -flr-4>" Irx- POLYCHLORINATED BIPHENYL USAGE AND SOURCES OF LOSS TO THE ENVIRONMENT IN MICHIGAN John L. Hesse* '^Polychlorinated biphenyls (PCB's) are used in a ^variety of applications including dielectric fluids in m 'Bfrners and capacitors; plasticizers in paints, inks, lastics. and coatings; hydraulic systems; heat transfer %ms; investment casting waxes; and many more. This fr idescribes industrial uses of PCB's in Michigan and mfmses on those uses which were found to be sources of frorimental contamination. It describes PCB use figf^supplied by several industries and concentrations Wd in industrial and municipal effluents and sludges. nMWr TtT:.* :-'V' . INTRODUCTION 1- H" ' Polychlorinated biphenyls (PCB's) are complex mix tures of chlorine-substituted biphenyl compounds and have beer, produced commercially in the United States sirice 1929. Their properties of nonflammability, stabili- * ; r ty, resistance to acids, alkalis, and other caustic chemi cals, and low volatility under prolonged heating have majde them useful in a wide range of industrial products. Monsanto Chemical Company, the sole U.S. manu facturer of PCB's, recently released production and sales figures through 1974 (ref. 1). These showed that produc tionj)nd sales roughly doubled between 1960 and 1970, \inth .nearly 80 million pounds sold annually in the United States by 1970. "Broadhurst (ref. 2) has summarized many of the uses of PCB's. The five largest uses for PCB's prior to I97O were dielectric fluids in capacitors, plasticizer ^applications, transformer fluids, hydraulic fluids and lubricants, and heat transfer fluids. The list of other uses islengthy. ' Because of the widescale usage of PCB's, they have become distributed throughout the world. Since 1967, reports of PCB residues in fish, birds, water, sediments, and other environmental samples have been common. -They are of concern in the environment because of their Persistence, potential for biological magnification, and chronic toxicity. `Supervisor, Toxic Material Unit, Department of Natural Resources, Lansing, Michigan. By 1971, Monsanto recognized the environmental problems which had developed because of PCB's and initiated a program to phase out sales for all open-ended uses, finally limiting sales to uses in electrical capacitors and transformers. Many officials believed this action would result in rapid reductions in environmental con tamination but little evidence of this has yet been docu mented. Michigan officials have been studying the PCB situa tion since 1969 when excessive PCB residues were de tected in Great Lakes fish. After development of ade quate laboratory capabilities, we instituted a monitoring program for PCB's early in 1971 consisting of a state wide water sampling survey -in -inland waters and tribu taries to the Great Lakes. Supplementary sampling has since been conducted on fish from inland and Great Lakes waters, stream sediments, potable water intakes, sanitary landfill runoff, municipal wastewater treatment plant effluents, and industrial discharges. Limited ques tionnaire surveys of industrial usage have also been con ducted. This paper will report briefly on the industrial uses of PCB's that we have identified in Michigan and focus on those uses which were found to be sources of environmental contamination. Electrical Applications Prior to the 1971 Monsanto limitation of sales to the so-called "closed-system" uses, approximately 60 percent of U.S. sales were for. electrical capacitor and transformer applications. In 1968, annual capacitor and transformer sales totaled approximately 30 and 16.8 mil lion pounds, respectively (ref. 3). While losses from the use of PCB's in these applica tions have been estimated as minimal (ref. 3), incorrect disposal practices and accidental losses from equipment and storage areas do occur and can result in environ mental contamination. In response to an industrial questionnaire sent to a cross section of Michigan industries in 1971, one major power company in Michigan reported an annual use of 562,000 pounds of PCB's (250,000 in precipitator trans formers and 312,000 in capacitors). Company records showed annual losses of approximately 300 pounds of PCB liquids to soils from burst capacitors and 12,000 pounds from salvaged capacitors. This fluid from the capacitors was reportedly disposed of through waste 127 TOWOLDMONOQ46426 haulers. Waste haulers then dispose of these wastes in many ways, including dust control on roads, sale of oils as fuel in low-temperature boilers, and treatment and discharge to municipal sewerage systems. Fluid recover ed from precipitator transformers was returned to Mon santo for incineration. In the same industrial question naire survey, a smaller power company reported that it had been disposing of approximately 700 pounds of PCB's per year by mixing with other waste oils and using the oils for dust control on their driveway and parking lot. In October 1975, a 55-gallon drum of PCB trans former oil on inventory at a Michigan power company developed a leak from a defective seam. Approximately 45 gallons of the fluid soaked into the ground, resulting in more than 100 cubic yards of contaminated soil hav ing to be removed and disposed of in an approved land fill. This situation illustrates the lack of such proper safe guards as diking around storage areas and represents an example of environmental loss from a so-called "closedsystem" use. Most industries other than utility companies using electrical transformers containing PCB's contract either the transformer manufacturer or smaller companies for servicing and do not concern themselves with the prob lem of disposal of the waste fluids. Frequency of servic ing appears to differ between industries, varying any where from every 6 months to 10 years. While water sampling programs in Michigan have failed to identify any electrical applications of PCB's as major point sources of loss to aquatic situations, envi ronmental losses do occur which have the potential of indirectly reaching watercourses through atmospheric fallout or leaching from contaminated soils at spill or disposal sites. Losses directly to water may occur on occasion but would be difficult to detect because of their intermittent nature. Plasticizer Applications Plasticizer applications represent the single largest "open-ended" or dissipative use of PCB's. PCB's are or have been used as plasticizers in most countries in a wide variety of consumer products, including paints, inks, copying paper, adhesives, sealants, plastic products, and textile coatings, many of which are traded internationalIV (ref. 4). Monsanto's U.S. sales figures for 1970 showed a volume of nearly 20 million pounds for plasti cizer applications (ref. 1). Sales for this use were discon tinued in 1971. Environmental losses from past sales will likely continue for a long period of time. Papers used in the thermographic, xerographic, or pressure-sensitive copying processes have had PCB's added as plasticizers either in the ink or paper coatl Recycling of these papers can result in contaminatiojf food packaging materials and other paper products || 3). Effluents from paper recycling or deinking p||J also become contaminated. In Michigan, paper indufg effluents have been found to commonly contain frpf to 10 Mg/I of PCB's. Contamination of fish has identified as high as 110 mg/kg in the Kalamazoo downstream from Kalamazoo, Michigan, where Mji gan's paper industry is primarily centered. Stream'^ ments in the Kalamazoo area contain as much as || mg/kg PCB's; this is believed to be a result of past del ing processes in the area. Lower level contamination dp tinues from processing of recycled paper but most del ing mills have ceased operation over the past 10 years! While Monsanto stopped sales of PCB's for paf applications in 1971, one Michigan paper company! cently reported to the Michigan Department of Natu Resources that several raw products that they pure still contain PCB's. Two coloring compounds reported have 23 and 500 mg/kg PCB's and nearly all of tiff wood pulp contains from 0.5 to 1.0 mg/kg. Burning of waste papers containing PCB's, wh]| occurs every day, undoubtedly results in atmosphef losses. PCB's have been detected in snowfall sampleff Wisconsin (ref. 5). The largest quantities of PCB's in plasticizer applij tions end up in dumps and landfills. Much of the mat al is in sealed containers or impregnated in plastics arial slowly released to the environment. Nisbet and Sarofm (ref. 6) reported that vaporization directly from pain coatings, and plastics does occur, with losses as greatl 20 percent. Open burning in landfills also releases PCJ| to the atmosphere. Another source is loss to leachag from landfills. Samples of surface runoff water fra nine landfills in Michigan showed five of the nine san pies having PCB concentrations ranging from 0.04|j 0.30 jug/I, while the others contained less than 0.01 jLijjj In 1970, the U.S. Food and Drug Administratjl identified milk contamination in Ohio, Georgia, arj Florida resulting from use of a PCB-containing sealantj silos (ref. 3). In 1975 the Michigan Department of Ag|j culture investigated problems from this usage and four 76 dairy herds in Michigan with PCB's in milk rangira from a trace to 14 mg/I on a fat basis. Scrapings froj silos on these farms contained PCB's up to 10,0013 mg/kg. Eighty additional silos have been identified aj having the PCB sealant and have been removed from use! until a protective coating can be applied to eliminat(j| transfer of PCB's to the cattle feed. Hydraulic Fh ' PCB's hi involving exi tions. Annua uses totaled (ref. 1). In ij industries ha tensively. I documented pounds/year lected and losses of PCI directly to Wastewate pCB-hydraul 7.1 mg/I PC per day. It which show imately 30,1 calculated 1 atmosphere year in abs< lost to soil 5,000 poun mainder inc All indi in hydraulic ucts, mostly PCB residui even with r fluids indici Residues in taminated i tinued low ries and pc processing systems no have been which we ii of PCB flui' In sum usage of PC of envirom contribute degree. Heat Trans. PCB's steam or si building cc explosion have good Monsanto 128 TOWOLDMONOQ46427 Wife Fluids ^C^'s have found wide usage in hydraulic systems f extreme pressure and high-temperature condi- nndal U.S. domestic sales of PCB's for hydraulic Jtlflerj approximately 8 million pounds in 1970 *|Wh Michigan, the automotive and metal finishing gjtpf -have used PCB-containing hydraulic fluids ex Industrial inspections and questionnaires ^mSifed past usage to have been as much as 878,000 fHlyear in individual plants, with most being col- 'and disposed of through waste haulers. Large g||jf PCB's from these plants to municipal sewers or iy to surface waters have also been identified, fe'fi/'ater discharges from identified users of IB-hydraulic fluids have had concentrations as high as ^oig/l"PCB's, indicating losses as great as 30 pounds lafay. In a materials balance study, one industry ich showed in its records that it was replacing approx- 30,000 pounds PCB's/year in hydraulic systems 'Inflated that 10,000 pounds/year were entering the friosphere through vaporization losses, 8,000 pounds/ in absorbents placed in landfills, 6,000 pounds/year to soils and drainage systems on plant property, ,;000 pounds/year going to waste haulers, with the re- inder incinerated. r:AII industries that we have identified as using PCB's /hydraulic systems have converted to substitute prod ucts, mostly phosphate esters. Complete elimination of PCB residues from the systems has proved ineffective seven with repeated flushings. Sampling of replacement Igfluicls indicates PCB contamination as high as 100 mg/I. jgResidues in discharge lines combined with loss of con- ..'rtaminated replacement fluids appear to result in con- /"tiriued low-level discharges. Because of existing invento ries and possible purchase from foreign sources or re processing companies, it is unlikely that all hydraulic systems not included in our surveys or questionnaires have been switched to replacement fluids. One facility Which we investigated had an inventory of 9,000 gallons of PCB fluids in storage. ' . In summary, Michigan's surveys of hydraulic system usage of PCB's suggests that this has been a major source of environmental contamination and may continue to contribute to the problem to a lesser but still significant degree. Heat Transfer Systems PCB's heat transfer fluids have been used in place of steam or superheated water in many industries and large building complexes. They provide advantages of reduced explosion hazards, absence of corrosion problems, and have good heat transfer characteristics (ref. 4). In 1970, Monsanto sold approximately 4 million pounds of PCB's for this application but phased out all sales in 1972 (ref. 3). From 1971 through 1973, Michigan identified at least 12 facilities discharging PCB's to surface waters or municipal sewers from this usage. Concentrations in some discharges were as high as 5.2 mg/I. One automotive company in Michigan reported using 34,000 pounds of PCB's per year in heat transfer systems at three of its plants. The waste fluids were reportedly disposed of by industrial waste haulers. Another smaller plant reported loss of 800 pounds in 1972 and that approximately 700 pounds of this total was incinerated, 75 pounds disposed of in dumps, and 25 pounds lost to sewers and drains. In another Michigan survey, a chemical company complex was found to have an effluent concentration of 35 jug/l resulting from heat transfer system losses. Heat transfer losses are not all from industrial facilities. Samp ling of interceptor lines of the Detroit, Michigan, sewer age system resulted in the identification of heat transfer usage from two residential building complexes and one hospital as large sources of PCB input to the system. Miscellaneous Uses In 1971, Michigan officials found a PCB concentra tion of 6.6 jug/l in the waste lagoon of a soap and deter gent company. The source was traced back to the com pany's usage of PCB's as a dedusting agent at 0.7 percent in one of its powdered products. The company had dis continued this usage in June 1970 and the PCB's were apparently leaching from contaminated lagoon sedi ments. The investment casting wax industry has been re cently identified as another user of PCB's (ref. 7). This casting method, which has largely replaced sand casting for production of low-tolerance-quality metal castings, uses formulated waxes as a basic molding mode. The waxes are injected into metallic dies to form the part shape and then coated with ceramic to form a final mold. The wax is removed by insertion of the mold in an autoclave, which melts the wax. Residues of wax are also secondarily removed by insertion of the molds in a fur nace at 1,600 to 1,800 F. During these two proce dures, the bulk of the wax is collected and usually recy cled but a portion is lost to vaporization, cooling water contact, and poor housekeeping practices. The waxes in use are obtained from a few major suppliers, one of whom is a major importer of decachlorobiphenyl from an Italian source. We have found twelve firms in Michigan using this casting process and several firms that reprocess their waxes. Our preliminary investi gations indicate that most of the waxes contain approxi mately 20 percent of PCB's or polychlorinated terphen- 129 TOWOLDMONOQ46428 yls (PCT's); one recent sample indicates the range may extend as high as 60 percent content in the wax. The nature of these casting operations, including both opera tional and storage modes, at many plants indicates strong potential for environmental loss. An effluent sam ple from one of the Michigan companies using invest ment casting wax contained 2.5 jug/l of PCB's. During a telephone survey of 39 industries in Michigan during May 1975, several industries reported use of a toilet hand soap containing 0.05 percent PCB's by weight. Followup on these reports indicated that this product actually contains a chlorinated diphenyl oxide rather than PCB's. Three industries in the telephone survey reported use of a hydrated lime product that contained about 0.5 mg/kg PCB's. This product was being used for water treatment and in production of glass pellets. No explana tion was available on why the lime contained PCB's but it is assumed to be a contaminant rather than an addi tive. Concentrations in Municipal Wastes Because of the diversity of PCB usage, municipal wastewater is likely to receive PCB's from numerous domestic and industrial sources, many of which are list ed above. Buckley (ref. 3) estimated that municipal out falls would likely contribute less than 5 percent (300 tons) of total annual loadings (6,000 tons) to aquatic environments of the North American continent. His esti mate was based on an assumed average PCB concentra tion of 10 ig/l in wastes serving a sewered population of 150 million people producing 130 gallons of sewage per person per day. Sampling of 58 municipal wastewater treatment plant (WWTP) effluents throughout Michigan in 1973 showed an average concentration of 0.52 jug/l (table 1). This is considerably lower than Buckley's value of 10 pg/l used in his calculations but still exemplifies wide spread contamination in municipal wastes, and docu ments that they are indeed a source of PCB loss to sur face waters. Much of the PCB's entering municipal waste treat ment facilities are removed and become incorporated into the waste sludge. Table 2 shows PCB concentrations in the sludges from Michigan municipal plants sampled in 1973. Concentrations are much higher than in the effluents from the same plants. The average for all plants was 15.6 mg/kg, with individual values as high as 350 mg/kg. Disposal of these sludges may add to environ mental PCB levels. Sewage sludges are commonly dispos ed of by incineration, spreading on agricultural land, or placing in landfills. Discussion While I have characterized in this report p0JI and proven sources of environment loss of PCb|| Michigan from several applications, I want to ackn<f edge that not all industrial effluents tested in Mich|| contain measureable PCB levels. We have tested over( industrial samples, with approximately 40 percent o|| fluents sampled containing PCB's above our 0.1 ' laboratory sensitivity limit. Twenty-three percent of| industries tested had greater than 0.5 jug/l, 18 perdl greater than 1 pg/\, 6 percent greater than 10 Mg/1, anl percent greater than 100 jug/l. This represents a divert of industries showing contamination and in many cal" the source of effluent contamination could not be de|| mined. Since new industrial sources of loss are continuou| being found, we feel we are far from eliminating the p| inputs to surface waters by searching for point souro and taking corrective measures on a case-by-case bass We are far from understanding the impact or compara tive contribution of atmospheric losses but we feel thef are probably very significant also. In light of considerable environmental damage an| economic impact of PCB contamination, an absence ia any apparent decline in environmental concentraticm with current control methods, the ubiquitous nature ol usage, the general lack of adequate disposal facilities and the indication that atmospheric transport and depdl sition is also significant, the Michigan Department q| Natural Resources urges that a national ban be pursues on all domestic and imported PCB's destined for us other than in transformers and capacitors, and that th| critical or essential use of PCB's in transformers ana capacitors be immediately and critically reviewed in ligrnj of current potential replacement products. Feeling that existing legislation was inadequate tol control PCB's, a group of Michigan legislators introduces a bill on August 14, 1975, to prohibit the manufacture! sale, and use of PCB's in Michigan for all application^ other than for transformers and capacitors. The bill] would provide for labeling, reporting, and disposal re-| quirements and specifies penalties for violations. The bill! calls for a stepwise elimination of PCB's with the salej manufacture, and use of products containing 25 percent! or more PCB's forbidden by January 1, 1976; 10 ppm orj more forbidden after January 1, 1977; and 5 ppm orj more forbidden after January 1, 1978. Public hearings! on the bill are currently being conducted by the Michi-1 gan House Committee on Marine Affairs. [The bill wasjj amended and voted out of committee on December 11, 1975. The amendment changed the maximum allowable | concentration after January 1, 1977, to 1,000 ppm and 100 after January 1,1978.] 130 Cit TOWOLDMONOQ46429 S'&Wr' "' Table 1. Concentrations of PCB's in the final effluent from wastewater treatment plants throughout Michigan, Spring, 1973. Concentrations in micrograms per liter, dry weight. City. Adrian Albion Ann Arbor Jay City Battle Creek Benton Harbor- St. Joseph Brighton 'Cadillac Charlotte Constantine Detroit 'Dexter East Lansing Escanaba Essexville Flint Gladstone Grand Haven Grand Rapids Holland Houghton - Hancock Iron Mountain- Kings ford Ironwcod Jackson Kalamazoo L'Anse Lansing Manistique Marquette . Marshall Menominee Midi and Milford Monroe Mt. Clemens Mt. Pleasant Muskegon Muskegon Heights Niles Norway Owosso Pontiac (Auburn) Pontiac (E. Blvd.) Port Huron Saginaw Sault Ste. Marie St. Ignace Three Rivers Traverse City Trenton Warren Wayne County Wyoming Tpsilanti Ypsilanti Twp If 1 Ypsilanti Twp #2 - Date 3/7/73 2/22/73 3/1/73 3/1/73 . 2/28/73 2/28/73 3/1/73 3/28/73 S/1/73 2/28/73 2/28/73 3/1/73 5/2/73 3/28/73 3/1/73 2/22/73 3/28/73 2/21/73 2/21/73 2/21/73 3/27/73 3/28/73 3/27/73 2/22/73 2/29/73 3/27/73 4/18/73 3/28/73 3/27/73 2/22/73 2/28/73 3/1/73 3/8/73 5/4/73 3/8/73 3/28/73 2/28/73 2/28/73 2/20/73 3/28/73 2/21/73 3/12/73 3/12/73 3/8/73 3/1/73 3/28/73 3/28/73 2/21/73 3/7/73 2/28/73 2/27/73 2/28/73 2/21/73 2/28/73 3/1/73 3/1/73 1242 ' ' PC8`S 1254 0.34 0.25 3.20 <0.10 0.20 0.53 0.34 0.46 2.15 0.23 0.18 0.10 <0.10 0.44 <0.10 1.05 <0.10 0.18 0.69 <0.1 0.22 0.63 0.29 0.15 0.57 <0.10 <0.10 0.29 0.88 0.18 0.48 <0.10 0.12 0.73 0.31 <0.10 <0.10 <0.10 <0.10 0.40 0.22 <0.10 <0.10 1242:1254 0.26 0.33 0.28 0.29 1.12 0.31 2.20 2.90 0.60 0.54 1.80 0.77 0.31 aConcentrations based on best fit of three standards: Aroclor 1242, Aroclor 1254, or a mixture of Aroclor 1242 and 1254 in a 1:1 ratio. '' 131 TOWOLDMON0046430 Table 2. Concentrations of PCB's in the sludge from fifty-seven municipal wastewater treatment plants in Michigan, Spring 19737 Concen trations in milligrams per kilogram, dry weight. CltiL Adrian Albion Ann Arbor Bay'City Battle Creek Benton Harbor- St. Joseph Brighton Cadillac Charlotte Constantine Detroit Dexter E. Lansing Escanaba 1 Essexville Flint Gladstone Grand Haven Grand Rapids Holland Howell Houghton- Hancock Iron Mountain- Kingsford Ironwood Jackson Kalamazoo L'Anse Lansing Manistique Marquette Marshall Menominee Midland Milford Monroe Mt. Clemens Mt. Pleasant Muskegon Muskegon Heights Niles Norway Owosso Pontiac (Auburn) Pontiac (E. Blvd.) Port Huron Saginaw Sault Ste. Marie St. Ignace Three Rivers Traverse City Trenton Warren Wayne County Wyoming Ypsilantl Ypsilanti Twp #1 Ypsllanti Twp Z Date 3/7/73 2/22/73 3/1/73 3/1/73 2/28/73 2/28/73 3/1/73 3/28/73 5/1/73 2/28/73 2/28/73 3/1/73 5/2/73 3/28/73 3/1/73 2/22/73 3/28/73 2/21/73 2/21/73 2/21/73 4/26/73 3/27/73 3/28/73 3/27/73 2/22/73 2/29/73 3/27/73 4/18/73 3/28/73 3/27/73 2/22/73 2/28/73 3/1/73 3/8/73 5/4/73 3/8/73 3/28/73 2/28/73 2/28/73 2/20/73 3/28/73 2/21/73 3/12/73 3/12/73 3/8/73 3/1/73 3/28/73 3/28/73 2/21/73 3/7/73 3/28/73 2/27/73 2/28/73 2/21/73 2/28/73 3/1/73 3/1/73 1242 352.0 32.1 23.3 175.0 2.0 1254 1.5 1.1 2.8 13.8 <0.1 <0.1 6.8 2.1 3.2 4.6 5.9 3.9 6.3 4.1 4.1 11.8 0.8 15.0 5.5 9.5 5.2 3.0 4.4 5.3 1.5 2.8 3.9 4.2 2.9 3.3 6.5 12.7 11.0 7.8 <0.1 2.0 5.0 2.4 1.5 4.1 1.8 <0.1 <0.1 0.58 2.0 <0.1 <0.1 1242:1254 24.0 50.5 12.1 9.2 9.2 Concentration based on best fit of three standards: Aroclor 1242, Aroclor 1254, or a mixture of Aroclor 1242 and 1254 in a 1:1 ratio. 132 TOWOLDMON0046431 REFERENCES William PaPa9eor9e' "PCB Manufacture and Sales, Monsanto Industrial Chemicals Company, 1957 111111 through 1974," handout to Governor's Great Lakes sip/phonal Pesticide Council, Chicago, Illinois, Janu Ir ary 30, 1975. Martin G. Broadhurst, "Use and Replaceability of Polychlorinated Biphenyls," Environmental Health Perspectives, Exp. Issue No. 1 (April 1972), pp. 81-102. ' Interdepartmental Task Force on PCB's, "Polychlor inated Biphenyls and the Environment," National Technical Information Service, Springfield, Virginia, HCOM-72-10419, May, 1972. Organization for Economic Co-Operation and Devel- opment, "Polychlorinated Biphenyls -- Their Use and Control," Paris, November, 1973. 5. Stanton Kleinert, "Statement Before the DNR Rule making Hearings to Consider Effluent Standards for PCB's," Room 421, South Capital, Madison, Wis consin, August 28, 1975. 6. I. C. T. Nisbet, and A. F. Sarofim, "Rates and Routes of Transport of PCB's in the Environment," presented at International Scientific Meeting on PCB's, RougemOnt, North Carolina, December 20-21, 1971. 7. Vincent J. DeCarlo, EPA Monitoring and Informa tion Systems Branch, memo to James M. Conlon, EPA Air and Hazardous Materials Division, Washing ton, D.C., May 12, 1975. 133 TOWOLDMONOQ46432