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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON. D C. 20460 September 23, 1975 Dr. Robert . Keller Manager, Applied Sciences Monsanto Industrial Chemicals, 800 North Lindbergh Blvd. St. Louis, Mo. 63166 Inc. Dear Dr. Keller: In reference to our Las Vegas conversation, the following are attached: 1. "Environmental Levels of PCB's" 2. PCB data from the Sauget, Illinois area. If possible, I would be Interested in having a copy of the PCB list of references you had compiled. Call if I can be of further help. My phone number is 202-755-6956. Sincerely yours, Vincent J. DeCarlo, Chief, Monitoring and Information Systems Branch Office of Toxic Substances DSW 011849 STLCOPCB4001802 Environmental Polychlorinated Biphenyl Contamination near Sites of Manufacture and Use prepared by Environmental Science and Engineering, Inc. P.0. Box 1354, Gainesville, Florida 32604 for OFFICE OF TOXIC SUBSTANCES ENVIRONMENTAL PROTECTION AGENCY WASHINGTON, D.C. 20460 Contract 68-01-2978 July 1975 DSW 011850 STLCOPCB4001803 INTRODUCTION Polychlorinated biphenyls (PCBs) have a basic chemical structure as follows: From one to ten chlorine atoms may be attached to the structure re sulting in 210 possible isomers. PCB's have certain physical properties; including high heat capacity, chemical stability, and excellent dialectric properties which make them highly desirable for a number of industrial uses. Concern has been expressed in recent years over the widespread dispersion of PCB's in the environment. These compounds are suspected to have significant adverse effects on organisms at the top of the food web, including man. Biomagnification of this contaminant in natural predator-prey food chains has been documented by numerous studies. To complicate the problem, the rate of degradation of PCB's In the environ ment, particularly the higher substituted isomers, is postulated to be extremely slow. This situation allows for the possibly significant accumulation of these persistent chlorinated organic compounds in the environment. A thorough discussion of the problem and of the environ mental data that are available has been presented by Selikoff (1972) and the U.S. Government Interdepartmental Tasks Force (1972). DSW 011851 STLCOPCB4001804 In response to the rising concern over PCB's in the environment, the single domestic manufacturer of these materials (Monsanto Co.) has voluntarily taken two actions to reduce the environmental hazard. The trade name for these domestically-manufactured compounds is Aroclor. Beginning in 1970, the production of Aroclor was voluntarily reduced by the manufacturer and supply was discontinued to those users who could not control release to the environment. Production of the more highly chlorine substituted Aroclor mixtures has since been curtailed or discontinued and a lower-substituted, refined mixture (Aroclor 1016) has been introduced. Some researchers have concluded that the lower substituted PCB isomers do not persist as long in the environment as the higher substituted isomers, and that they may be amenable to bio logical degradation. Aroclors are still employed In electrical capacitors, transformers, vacuum pumps and gas-transmission turbines (Hutzinger, Safe and Zitko, 1974). There are a number of foreign producers of PCB. The major foreign products are listed In Table 1. Some domestic industries, whose supply of Aroclor has been curtailed by the producer, have turned to foreign supplied PCB's. The extent of the use of these foreign products In the U.S. is not know at the present time. The Environmental Protection Agency, Office of Toxic Substances has undertaken an environmental monitoring program to assess the magnitude and potential hazard of PCB contamination of the environment and to assess the effectiveness of voluntary controls on use of these compounds. The first phase of thisjnonitoring program has been completed. The initial effort was directed toward the evaluation of PCB contamination DSW 011852 STLCOPCB4001805 Table 1. THE WORLD'S MAJOR PRODUCERS OF PCB* Producer Monsanto Bayer Prodelec Country U.S.A. and ' Great Britain Germany France Kanegafuchl MitsubishiMonsanto Caffaro Sovol Chemko Japan Japan Italy U.S.S.R. Czechoslovakia Tradename of PCB Aroclor Clophen Phenoclor and Pyralene Kanechlor Santotherm Fenclor after Hutzinger, Safe and Zitko (1974). DSM 011853 STLCOPCB4001806 of soils in the vicinity of potential industrial sources and of waste waters from these sources. Soil samples have been taken in the vicinity of Yates Manufacturing Co. in urban Chicago, Illinois; Valcast, Inc. in Troy, Michigan, a suburb of Detroit; and the Monsanto Co., Krummrlqh Plant in Sauget, Illinois, near East St. Louis. Prior to 1972, the Yates Manufacturing Co. used Aroclors 5460, 6090 and 5442 in the production of wax mold material for the investment casting (lost wax) process. These mixtures contain both PCB and polychlorinated terphenyl (PCT). Subsequent to 1972, this company has been purchasing a PCB of foreign origin. Fenclor DK, a product of Caffero Corporation in Milan, Italy, has been substituted for the unavailable Aroclors. Valcast, Inc. is an investment casting facility. It has been reported that Valcast purchases the necessary wax compounding materials from Yates Manufacturing Co. The Krummrich Plant of Monsanto Co. is the only PCB production facility in the U.S. All domestic Aroclors are produced at this location. DSW 011854 STLCOPCB4001807 EXPERIMENTAL Sampling Methods Surface soil samples were collected at each site from the plant boundary to a distance of approximately one mile at h mile intervals in each direction subject to the physical constraints encountered. At each sample point, five sub-samples were collected within a radius of 10 m to a depth.of 2.5 cm over a 100 cm2 area. This mode of sampling, which was designed to collect a homogeneous surface soil sample representative of the chosen sample point, is illustrated in Figure 1. Vegetative matter was removed with forceps and the five sub-samples were composited and thoroughly mixed. Every attempt was made to select sample points where surface vegetation was sparse and where it appeared unlikely wind scour would be a major soil transport factor. Samples were placed in pre-cleaned, wide-mouth glass jars with aluminum foil-lined closures. Water samples were collected from a drainage ditch adjacent to the Valcast plant, of Valcast effluent cooling water and from the sanitary sewer system downstream of Valcast. Wastewater samples were taken from tho influent and effluent of the Sauget, Illinois sewage treatment plant. The Monsanto facility uses this treatment plant for wastewater treatment. These latter water samples were 24-hour composites of the treatment plant influent and effluent; the former were grab samples. All samples were taken in 1 1. glass containers, composited and stored in 4 1. pre-cleaned glass-stoppered reagent bottles. DSW 011655 STLCOPCB4001808 0$w 011856 Figure 1. Diagram showing surface soil sampling method. Not to scale. Five sub-samples are composited to yield a single sample. STLCOPCB4001809 Extraction and Concentration The soil sample is thoroughly mixed and sectioned into quarters. Two of the quarters are rejected and the remaining quarters are again mixed and quartered. This is continued until a representative sample size of about 50 g is obtained. This sample fraction is allowed to air dry at room temperature. PCBs are extracted from the soil using a soxhlet apparatus and 75 ml of 1:1 nanograde hexane/acetone for a 10 g soil sample. The extract is concentrated to 5 ml on a Kuderna-Danish apparatus and dried with sodium sulfate. This concentrate is evapo rated to dryness under dry N2 at room temperature then redissolved In 1 ml of nanograde hexane. This procedure basically follows that described by the EPA (1974). Water samples are triple extracted with 15 percent nanograde ehtyl ether in hexane, dried with sodium sulfate, concentrated on a Kuderna-Danish apparatus, evaporated to dryness under N2 and redissolved In 1 ml nanograde hexane. This method is similar to that recommended by the EPA (1973). Sample Cleanup Both the soil and water extracts are cleaned-up by the use of a silicagel column. The column is eluted with nanograde pentane followed by nanograde benzene. The PCBs present in the extract appear in the pentane fraction; pesticides appear in the benzene fraction. The pen tane fraction is further treated with concentrated H2SO4 to eliminate unstable organic compounds. The silica gel separation procedure is described by Snyder and Reinert (1971). The sulfuric acid cleanup was adapted from Murphy (1972). DSW 011857 STLCOPCB4001810 Analytical Methods All analyses are by gas chromatography. A dual-column Varian 2760 instrument is employed with the following conditions: a) detection and quantifications glass column, 6' length, 1/8 ID 1.5S/1.95* 0V-17/QF-1 liquid base Chrom W-HP, 80/100 mesh support Ng 38 psig inlet pressure, 68 ml/min detector temperature 225 C column temperature 200 C injector temperature 215 C b) confirmation stainless steel column, 5' length, 1/8 ID 1.5%OV-101 liquid phase . Chrom G-HP, 100/120 mesh support N2 30 psig inlet pressure, 43 ml/min detector temperature 225C column temperature 205 C injector temperature 210 C Detection is by electron capture using a tritium detector. Hass spectrographic confirmation has also been obtained on selected samples. The PCBs are quantified in a two-step process. First, the elution . pattern is compared to those of standard mixtures and the closest pat tern match is considered to be the PCB present. The relative peak heights in a mixture are a good indication of a match with a standard, as is the presence or absence of later eluting peaks. Good matches with standard Aroclor mixtures have been obtained. The presence of * decachiorobiphenyl is easy to ascertain since it is a single peak. Once the elution pattern is subjectively matched to a standard PCB pattern, quantification is conducted by electronic integration of peak areas using a Hewlett-Packard Integrator Model 3380A. The total area of all accepted matching peaks in the elution pattern of the sample is compared m DSW 011858 STLCOPCB4001811 with the total area of the same peaks in the standard mixture and a sample concentration is calculated. The Aroclors used for preparation of standards were obtained from the Monsanto Company and the EPA Southeast Environmental Research Laboratory. Fenclor DK was provided by EPA Region V personnel. Sample Replication and Recovery Studies A number of replicate analyses were conducted to determine the repro ducibility of both the analytical method and the sampling method. The results of these replications are tabulated in Tables 2 and 3. All replications conducted to date are of soil samples. Table 2 lists the results of the analysis of two fractions of a single soil sample. Table 3 lists the results of the analysis of replicate samples and, hence, represents both sampling and analytical variability. The results of several PCB recovery studies are tabulated in Table 4. DSM 011859 STLCOPCB4001812 Table 2. . ANALYTICAL REPLICATES OF SOIL SAMPLES Replicate Y-l V-l V-2 V-3 V-4 V-5 V-6 M-l M-2 M-3 M-4 Aroclor 1260 (ppm) 0.86 0.51 mean 0.69 <0.01 0.11 mean 0.06 0.07 <0.01 0.01 mean 0.04 0.13 0.11 mean. 0.12 0.13 0.15 mean 0.14 <0.01 <0.01 <o7oT <0.01 0.03 0.04 mean O? 0,06 0.13 mean OTiU 0.21 0.30 mean 0.26 1.8 0.95 mean 1.4 Decachlorobiphenyl 0.65 0.50 mean 0.58 0.084 0.16 mean (HTr 0.066 0.096 mean OST 0.95 0.84 mean 0.90 0.49 0.67 ' mean 0.58 DSW 011860 STLCOPCB4001813 Table 3. SAMPLE REPLICATES OF SOIL SAMPLES Replicate Y-l M-l M-2 , M-3 Aroclor 1260 (ppm) Decachloroblphenyl (ppm) 0.53 0.40 mean 0.47 . 1.0 1.4 mean 1.2 9.8 9.3 mean 9.6 1.3 l.o mean T7T 0.12 0.46 mean 0.29 0.015 0.069 mean 0.042 0.23 <0.01 0.12 0.64 0.58 mean 0.61 DSW 011861 STLCOPCB4001814 Table 4. RESULTS OF RECOVERY STUDIES FOR PCBs PCB Type Aroclor 1242 Aroclor 1260 Aroclor 1260 Percent Recovery 105 85 122 DSW 011862 STLCOPCB4001815 RESULTS AND DISCUSSION PCBs were detected in soils at all three sampling locations. The X---- -------------- -------------------------------------------------------------------------- -------------,------------elution patterns obtained most closely matched Aroclor 1242, Aroclor 1260 and decachlorobiphenyl. Soil concentrations ranged from the detection limit of 0.001 ppm to over 20 ppm. Data from Vicinity of Yates Manufacturing Co., Chicago, IL. Figure 2 illustrates: a) a chromatogram of Fenclor DK, the foreign supplied PCB presently used by Yates Mfg. Co. in the production of investment casting wax compounds; b) a chromatogram of a standard Aroclor 1260 and; c) a typical chromatogram of a soil extract taken in the vicinity of the site. Figure 2a demonstrates that Fenclor DK is nearly pure decachlorobiphenyl. This compound is unusually pure for a technical grade material. One minor peak elutes just before the predominate decachlorobiphenyl peak. The retention time of the minor contaminant peak is such that it may be expected to be an octachlorobiphenyl since it exhibits the same retention time as the latest eluting peak in a standard Aroclor 1260 mixture. It is apparent by comparison of peak retention times with the sample chromatogram. Figure 2c, that decachlorobiphenyl is present in the soil sampled. The measured concentration of decachlorobiphenyl in this particular sample was 1.0 ppm. The presence of decachlorobiphenyl in this sample has been confirmed by mass spectrometry. Figure 3 illustrates a portion of the mass spectrum of the sample and a standard decachlorobiphenyl obtained from a different source. The sample elution pattern also indicates the presence of Aroclor 1260 as can be seen by comparison with the Aroclor 1260 elution pattern. OSW 011863 STLCOPCB4001816 (a) Fenclor DK I Figure 2. Typical chromatograms of standard PCBs and of a soil sample taken in the vicinity of Yates Mfg. Co., Chicago, Illinois. DSW 011864 STLCOPCB4001817 S T LC O P C B 4001818 o (/> o CO O' Figure 3. (a) Portion of nass spectrum of sample taken in vicinity of Yates Mfg. Co. (b) Parent molecule mass cluster of decachlorobiphenyl. The concentration of Aroclor 1260 In this sample is 0.53 ppm. There is no Indication of degradation of the Aroclor 1260 since virtually all peaks in the sample chromatogram are present in the same relative propor tion as in the standard. There are no significant, undefined peaks in the chromatogram following the acid cleanup procedure. Certain of the sample chromatograms indicate the presence of lower weight PCBs, however the quantities present tend to be far less than either Aroclor 1260 or decachlorobiphenyl at this site. Figure 4 depicts the quantity of Aroclor 1260 measured in samples taken In the vicinity of Yates Mfg. Co. There exists no apparent spatial pattern of Aroclor 1260 distribution over the study site. There is little to indicate the source of the Aroclor 1260 contamination is Yates Mfg.Co. Aroclor 1260 has not, in fact, been used by Yates. Prior to 1972 Aroclors 5442, 5460, and 6090 were purchased by this company. Subsequent to 1972, Fenclor DK and Aroclor 5460 have been in use. Aroclors 5442 and 5460 are terphenyl mixtures with 42 percent and 60 percent chlorine by weight, respectively. Aroclor 6090 is 90 percent terphenyl and 10 per cent Aroclor 1221. Aroclor 1221 does not appear in the soils at this site. ' Figure 5 illustrates the distribution of decachlorobiphenyl in soils near the Yates facility. The distribution has some elements of a pattern of higher levels closer to the Yates facility with decreasing concentration with distance. Such a pattern may be expected if Yates were the source of the decachlorobiphenyl (or Fenclor DK) contamination. DSW 011666 STLCOPCB4001819 Figure 4. Concentration of Aroclor 1260 in soil as a function of distance from Yates Mfg. Co. Concentrations are expressed in ppm. DSM 011867 STLCOPCB4001820 Figure 5. Concentration of decachlorobiphenyl in soil as a function of distance from Yates Mfg. Co. Concentrations are expressed in ppm. OSW 011668 STLCOPCB4001821 Data from Vicinity of Valeast Corp., Troy, HI. Valcast Corp. Is an investment casting facility located in a small indus trial park in suburban Detroit, MI. PCBs are a constituent of the wax mold compound used to fashion intricate shapes which are to be cast. Figure 6 is a typical chromatogram of a soil sample extract taken from this location. Aroclor 1260 is present in many of the soil samples. Decachlorobiphenyl is absent in the soils. Figure 7 shows the concen trations of Aroclor 1260 observed in the vicinity of Valcast Corp. Ho distribution pattern is evident. The one observed concentration of 18 ppm Aroclor 1242 appears to be anomalously high, however, replicate analysis yielded values of 16 ppm and 19 ppm, respectively. Aroclor 1242 was not detected in any other soil samples from this area. A small drainage ditch passes adjacent to the north boundary of the Valcast facility. This ditch serves to remove stormwater runoff in the vicinity and receives discharged cooling water from Valcast and other local small industries. Analysis of the Valcast cooling water at the point of discharge and of water in the drainage ditch failed to detect PCB levels greater than the detection limit of 0.1 yg/1. Two bottom sediment samples taken from this drainage ditch, however, had concentra tions as follows: Aroclor 1242 2.3 ppm 9.4 ppm Aroclor 1260 6.7 ppm 8.9 ppm Decachlorobiphenyl 0.09 ppm 0.11 ppm Three grab samples of water and bottom sludge were taken from the sanitary sewer system about 1/4 mile down stream of the Valcast facility. DSW 011869 STLCOPCB4001822 i i I (a) iI o CO o CJD o WSJWaAw__/v. Figure 6. Typical chromatograms of soil samples taken in the vicinity of Valcast Corp., Troy, Michigan--(a) <0.01 ppm, (b) 0.014 ppm Aroclor 1260 S T LC O P C B 4001823 I 1242) Figure 7. Concentration of Aroclor 1260 in soil as a function of distance from Valcast fifg. Co. Concentrations are expressed in ppn\ DSW 011671 STLCOPCB4001824 Table 5. ANALYTICAL RESULTS OF SAMPLES TAKEN FROM THE SANITARY SEWER SYSTEM OF TROY, MICHIGAN, AT INTERSECTION OF ELLIOT AND EXECUTIVE DRIVE. Date Time Type Sample 28 Feb 75 1530 water 22 Feb 75 1815 water 23 Feb 75 1145 water 22 Feb 75 bottom sludge Aroclor 1260 <0.1 pg/1 <0.1 pg/1 7.0 pg/1 0.11 ppm Decachlorobiphenyl <0.01 pg/1 <0.01 pg/1 4.1 pg/1 0.034 ppm DSW 011872 STLCOPCB4001825 This sewer system serves numerous small industries in the area. Results of the analysis of these samples are tabulated in Table 5. It appears that some Aroclor 1260 and decachlorobiphenyl are finding their v/ay into the sewer system. Insufficient information is available to identify the source of these PCBs. Data from Vicinity of Monsanto Co., Sauget, IL. Aroclors have been produced by Monsanto Co. at the Sauget, Illinois site since prior to 1957. PCB mixtures ranging from 16 percent chlorine to 68 percent chlorine have been produced over the years. Production of the higher percent chlorine mixtures has been voluntarily reduced since 1970 and lower substituted isomers have been introduced. Polychlorinated terphenyls and chlorinated benzenes have also been produced at this facility. It is reported (Papageorge, 1975) that terphenyl production was suspended in 1971. A typical chromatogram of a soil sample taken in the vicinity of the Monsanto facility is shown in Figure 8 along with the chromatogram of several other PCBs run under the same instrument conditions. This particular soil sample contains 11 ppm Aroclor 1242, 9.3 ppm Aroclor 1260 and 1.0 ppm decachlorobiphenyl. Lighter chlorinated Aroclor mixtures are likely present as well. The instrument conditions employed, however, I do not give adequate separation of these mixtures to permit accurate quantification. The presence of decachlorobiphenyl at the concentrations observed is interesting. Decachlorobiphenyl has been reported as a compo nent of only one Aroclor mixture, Aroclor 1268 (Hutzinger, Safe and Zitko, 1974). Whether it may be a component of any of the terphenyl mixtures or biphenyl/terphenyl mixtures or a by-product is not known. OSW 011873 STLCOPCB4001826 (a) Aroclor 1242 (b) Decachlorobiphenyl Figure 8. Typical chromatograms of standard Aroclors, decachlorobiphenyl and a soil sample taken in the vicinity of Monsanto Co., Sauget, Illinois. STLCOPCB4001827 The measured soil concentration of Aroclor 1242, Aroclor 1260 and decachlorobiphenyl in the vicinity of the Monsanto facility are depicted in Figures 9, 10 and 11, respectively. Figure 12 shows the long-term average wind direction in the area. The distribution of all PCBs analyzed appears to be higher near the plant site and generally decreasing with distance from the site. Furthermore, there is evidence that generally higher concentrations are present in the soils located to the southeast. This corresponds^ to the predominant wind direction and may suggest an airborne transport of the PCBs from the facility. One 15 cm deep core sample was taken 1/2 mile southwest of the Monsanto site. Analysis of the bottom 11 cm of this soil yielded PCB concentrations basically equivalent to the top 4 cm. A 24-hour composite sample from the influent and the effluent of the Sauget village sewage treatment plant taken beginning 0B00 on February 17, 1975, was provided by plant personnel. The Monsanto Co. jointly owns this facility. Analysis of these samples were as follows: Aroclor 1242 Aroclor 1260 Decachlorobiphenyl influent 6.8 pg/1 8.7 pg/1 <0.01 pg/1 effluent 4.5 pg/1 4.7 pg/1 <0.01 pg/1 The treatment plant effects a reduction of 34 percent Aroclor 1242 and 46 percent Aroclor 1260. No decachlorobiphenyl was detected. DSW 011675 STLCOPCB4001828 { Figure 9. Concentration of Aroclor 1242 in soil as a function of distance from Monsanto Mfg. Co. Concentrations are expressed in ppm. DSM 011876 STLCOPCB4001829 r t DSW 01187? STLCOPCB4001830  Figure 11. Concentration of decachlorobiphenyl in soil as a function of distance from Monsanto Mfg. Co. Concentrations are expressed in ppm.' * DSW 011878 STLCOPCB4001831 IM Figure 12. Ten Year Averaged Wind Rose for St. Louis, Missouri, January through March, 1951-1960. Scale: 1" = 5% Calm Winds = 2.0% osw u8" STLCOPCB4001832 REFERENCES Environmental Protection Agency (1973). Method for Polychlorinated Biphenyls (PCB's) in Industrial Effluents. NERC, Cincinnati, OH. Environmental Protection Agency (1974). Analysis of Pesticide Residues in Human and Environmental SampTeT. Pesticides and Toxic Substances Effects Laboratory, Research Triangle Park, N.C. Hutzinger, 0.; Safe, S.; and Zitko, V. (1974). The Chemistry of PCB's. CRC Press, Cleveland, OH. 269 p. Murphy, P.G. (1972). Sulfuric acid for the cleanup of animal tissues for analysis of acid-stable chlorinated hydrocarbon residues. JAOAC 55:6; 1360-1362. Papageorge, W.B. (1975). Personal cormunication. Manager, Product Acceptability, Specialty and Process Chemicals, Monsanto Industrial Chemicals Co., St. Louis, MO. Selikoff, I.J. (1972). ed. PCBs - Environmental Impact. Environ. Res. 5^:3; 249-362. U.S. Government Interdepartmental Task Force on PCBs (1972). PCBs and the Environment. NTIS document COM-72-10419. OSW 011880 STLCOPCB4001833 CONCLUSIONS 1. The distribution of Fenclor DK suggests that this compound may be transported to soils in the vicinity of Yates Mfg. Co. by way of airborne emissions. 2. Aroclor 1260 is present in urban Chicago soils. There is no evidence Yates Mfg. Co. is the source of this soil contamination. 3. Detectable, but lower levels, of Aroclor 1260 are present In soils in Troy, Michigan. There is no evidence Valcast Corp. is the source of the soil contamination. No decachlorobiphenyl (or Fenclor DK) was detected in soils in the area. 4. Significant quantities of Aroclor 1242 (18 ppm) were observed in a single soil sample taken in a residential area near Valcast Corp. The importance of this single data point should not be over-emphasized. However, Aroclor 1242, Aroclor 1260 and decachlorobiphenyl were also detected in drainage ditch sediments at much higher concentrations than the observed PCB levels for soils in the area. 5. The drainage ditch sediments near Valcast Corp. contained detectable levels of decachlorobiphenyl. Its source is unknown. A number of small industries are located in the immediate vicinity, ar\y of which could be the source as well as intermittent discharge, leakage or runoff from the Valcast site or facility. 6. One of three grab samples taken over a period of time from the sani tary sewer system near Valcast Corp. contained detectable levels of Aroclor 1260 (7.0 yg/1 and decachlorobiphenyl (4.1 yg/1). The other two samples were below detection limits of 0.01 yg/1 and 0.001 yg/1, respectively. Sewer sludge contained both Aroclor 1260 and decachlorobiphenyl. These STLCOPCB4001834 DSW 0 1 1 8 8 1 materials are apparently discharged to the sewer system on an inter mittent basis. The source is unknown. 7. Decachlorobiphenyl is relatively abundant compared to the other PCBs in soils in the vicinity of the Monsanto facility. Decachlorobiphenyl is not reported to be a major component of any of the Aroclor mixtures. It may be a by-product associated with Aroclor production which is eliminated or greatly reduced in the commercial preparations by refine ment at the Monsanto facility and may, therefore, find its way into the environment at this location. 8. Aroclors 1242 and 1260 were also present in soils near the Monsanto plant. There appears to be a tendency for higher PCB levels close to the plant with decreasing concentration with distance. There is some evidence that higher soil concentrations exist along the northwest to southeast axis which corresponds to the dominate wind direction at this location. This suggests airborne transport of the PCBs from the plant with subsequent deposition, of at least the heavier isomers of PCB, on nearby soils. 9. PCBs are present in Sauget, Illinois wastewaters. The sewage treatment plant removes less than 50 percent of the Aroclor 1242 and Aroclor 1260. Decachlorobiphenyl is not present in these v/astewaters. 10. Aroclor 1260 was found to be present in the soils of all three sites sampled. This product is currently used in electrical transformer fluids and has been used in the past in hydraulic fluids, plasticizers and dedusting agents (Hutzinger, Safe and Zitko, 1974). Aroclor 1242 DSW 011882 STLCOPCB4001835 was found in comparable concentration near the Monsanto facility and in drainage ditch sediments near Valcast. This product has consistently been the most heavily produced by Monsanto of all the PCB mixtures. 11. Decachlorobiphenyl may be more widely spread than would be anti cipated by projection from Monsanto production figures for Aroclors. DSW 011883 STLCOPCB4001836 SUGGESTIONS FOR CONTINUED STUDY OF PCBs 1. Conduct total PCB analysis employing the perchlorination technique of selected samples on hand. Determine what fraction of the total PCB present has been quantified as Aroclors 1242 and 1260 and decachlorobiphenyl. 2. Conduct polychlorinated terphenyl (PCT) analysis of selected samples on hand. 3. Assess PCB and PCT levels in various urban and non-urban soils and stream sediments. 4. Conduct analysis of airborne and precipitation-borne PCB and PCT in the vicinity of known users. 5. Evaluate PCB and PCT levels in and near dumps and landfills in the air, water, soil and groundwaters. 6. Investigate the potential for chlorination of biphenyl at normal wastewater and drinking water treatment levels. 7. Investigate the possibility of chlorinated dibenzofuran, dioxin and naphthalene contamination of various foreign and domestic PCB products. 8. Evaluate the rate of degradation of PCBs in the environment. DSW 011884 STLCOPCB4001837 ENVIRONMENTAL LEVELS OK PCB's Doris J. Huopp Vincent J. Dc-Corlo U.S. Environncntnl Protection Agency Washington, b.C. 20460 ABSTRACT Since . the 1966 discovery In Sweden that chlorinated biphenyls were widely dispersed In the envl ronment their environmental levels have been the subject. ' ol many studies with the results indicating that TCB's can have adverse ecological and toxicological effects. However, a well planned national approach to environmental sampling has not been attempted thus hindering making a national assessment of the l'CB problem This paper reviews the levels that arc currently being found in. the environment. . lt.'TKOnUCTION Since the 1966 discovery In Sweden that chloilnotid biphenyls verc widely dispersed In the environment, their levels have been the subject of winy studies both abroad and in the United States. Extensive Inbortitory and environmental measurements indicate that PC.B's con have adverse ecological and toxicological effects, are very resistant to environmental degradation and ore being discharged by many different, sources. This paper will focus on the current PCB data base In sn effort to assess the TCB levels in the environment on a national basis. ' EKVI HOHMFKTAl, TCB SOURCES Before the TCB data Lose is examined, It would be of interest to review how those chemicals get into the environment. The major sourcos contributing to the environmental levels of PCB'g are Industrial effluents, manufacturing processes, consumer nnd Industrial waste materials, 6ewage treatment facilities and accidental spills. Lacking extensive lr and soil data from these sources, available water data are shown in Table 1. Ihe 5 major l'CB spills in- 1923*15.__all involved transformers. Til 4 6f those Incidents^ tV.e PCfi's ware splllMiUn" soil while in the fifth the transformer was dropped on a pier And tho contents were spilled into the water. In the Inner Incident, 283 gallons were Bpllled and it was estimated that only 70-90 gallons were recovered. In all cases tho material that could be recovered va6 drummed up end entombed at a cost approaching (2.3 million. . REVIEW OF THE TCB BATA BASE To assess the scope and extent of PCB's in the environment, all national surveys nnd national data bases maintained by the U.S. Environmental Protection Agency (EPA) verc examined, including STORF.T, the national water quality storage and retrieval system, the National Soils Monitoring Program for Pesticide Residues and the Hunan Monitoring 'Program. In addition, data from special data bases maintained by the United Stales Geological Survey nnd the open literature were also examined along with available unpublished reports. Using these data, waps were constructed showing the concenlrntIons of PCB'a In urban soils and the aquatic environment. The data from the national surveys show that a great drnl of effort has been expended sr.d continues to he expended but that tlie data arc very limited. On examination, all Stoles are believed to show some level of VCB contamination. In Table 2 Stales which had significant levels In at least one medium are listed with their reported TCP. levels for surface and ground water, bottom sediments and fish. In Table 3, a number of localised studies are listed Along with the reported environmental dato. In all these 6tudles the most extensive measurements have been In fish. - TABLE 1 ENVIRONMENTAL SOURCES OF PCB's SOURCE EFFLUENT WATER CON CENIRATIONS' (Pub) PAPER MILLS , Wisconsin1 WASTE PAPER MILLS Wisconsin INDUSTRIAL EFFLUENTS 2 California Wisconsin2 Ohio2 " Michigan MUNICIPAL WASTE,WATER TREATMENT PUNTS . Michigan j Wisconsin Ohio2 2 California CAPACITOR AND TRANSFORMER FACILITIES . . New York j Massac. Iiur.cttn 0.1 - 18.5 18.5 0- .04 0- .1 - 76 0.25 17 7000 0.5 .05 - 10 0.16 - 17.0 17 76 2600 42.5 PCB MANUFACTURING F^CILITV East St. Louis SPILLS .t7 Variable 1. Klelnm l, S. JEnvironmental Status of PCB in Wisconsin, liny 8, 1975, Wisconsin Department of Natural Resources. 2. TCB's and the Environncntnl, Report of the Interdepartmental. Tank Torce on PCB's, National Technical Information Service, 1972. 3. Statement of Concerns of the Lake Michigan Toxic Substances Committee Related to Poly chlorinated Biphenyls, June 1975. Prepared by Karl P. Rreiner, USEPA, Chicago, 111. A. Unpublished Data - Royal J. Nadeau and Robert P. Dnvis, Investigation of Polychlorinated Biphenyls in the Hudson River, Hudson FallsVt. Edward Area, August 1974. 5. Field Sampling and Analysis of Toxic Pollutanba Interim Report, Battelle, Pacific Northwest Laboratories, August 1974. DSW 011885 STLCOPCB4001838 HATER On the basis of the national aquatic tiwlconwcnlttl date collected in 1971-1972 nnd in 1974, a continuing widespread accumulation of PCB16 In water, sediment and fish appears to be occurring. However, no trend analysis la possible with the available measurements. For example, whole water measurements have been taken throughout most of the country but- those states reporting non zero readings are few In relation to the number of states showing zero concentrations. This Is due both to the low solubility ol PCb'n and to the usual analytical procedure that limits detectability to the 0.1 ppb level. More meaningful water concentrations were_ obtained In the Lake Ontario* and Orange County, California^ studies where concentrations In water at the ppt (ng/1) level were measured. At these lcvclB, changes In PCB concentrations could be found with distance and time and could be related to other mensurable parameters such os PCB concentrations in sediment, flora and fauna. - SEDIMENTS Since FCB'6 arc relatively Insoluble, It Is not surprising that bottom deposits have shown significant concentrations. Although 30 states collected tanplor. in the 1974 study, IS had less than 4 stations reporting and showed zero readings. Of the rcnialnir.g 15, with at least 4 reporting stations, 13 shoved detectable concentrations. Since the 13 states Involved were not neecssarlly the same In both studies, only a very broad comparison may be made, l.r., five states had lower concentrations, four states were higher and four did not sample again.3 Vc may conclude, then, that in there elutes with any monitoring effort in the 1977, study, PCB's arc present In bottom deposits and the levels nc not any lover than In the 1971-7? study. Considering the peroltilence of PCB'n, a significant proportion of the nation's waters are now affected and will continue to be. SOILS The National foil 6 Monitoring Program la a small sampling effort studying only 5 urban areas each year. However, PCB's wore deterred in three of the five c1l1cs sampled In each of the years for which data ore available, 1971-73. Of the 22 positive readings 17 of them were below 1 ppm. Of the cities sampled In 1973, Pittsfield, Mass., was of particiillrTnlcrest bCNmotr 1 t-tuwa- inrgr--mmHTOTncr and'cendennor plant vsjTSl; TSTgc quantities Of' roll's. Six'- dflTvfctil aomplfug r.lltk WlTTTTn--one tulle- of the-- jtlanr ~--drtprtahlc PCB1' TPnldues. In IcontTasT] thc_ soli surrounding another facTTiflf Ttr `11Ugo.lusltvfi IPCB7tt"ln the manufacture of Invcstment costing waxes wa6 recently measured Tov~TCB content. SBtrpTfrT "Cifkcn In on 'prca bnc-"q'li57'Cr tulle tudlus around the plant rnngcd In value from 0.77-5.2 ppm. The PCB'r. Identified were mixtures of Aroelor 1260 and deenchlorohiphenyl. Levels up to 1.8 ppm Aroelor 1260 were found at 1-1/4 miles from the plant. Samples were collected ,from thlo facility aa part of a study being conducted for the Office of Toxic Substances at sites . suspected to have PCB concent rations. Other sites sampled in March of 1975 were in the vicinity ol an investment casting company in Michigan nijd the PCB manufacturer in Illinois. Surface coll samples were collected at each site up to a distance of approximately one mile from the plant boundary*- at 1/4 tnllc Intervals In all directions. PCIt's were detected in aoils at both sampling locations. Concentrations ranged from the detection limit of 0.001 ppm to over 20 ppm. n.c distribution of all ITT.'s analyzed appears higher near the plant site and generally decreases with distance from the site.4 Details of the sampling sites and the concentration levels measured are shown In Figure 1. TABLE 2 SELECTED STATE DATA ON ENVIRONMENTAL LEVELS OF PCB'a State Surface and Ground Hater1 Hg/1 Bottom Sediment1 PB/kS Fish3 ppm AL AA CA CO CT PL GA IL . TA ' HD MA Ml MN MS NB NJ KY Oil OK PA PR SC TX UT VA W. HI 0.1 0.3 0.1-0.2 0.1-2.1 0.1 0.2 0.1-0.3 0.1 0.1-4.0 0.2 0.1 0.1-3.0 0.1 20-2,400 20-190 5-3502 5-3,200 10-1,300 10-1,200 1.53-5.48 1.69-3.88 2.16-5.34 0.10-1.25 0.52-1.18 1.21-11.3 0.35-1.41 0.56-1.31 50-170 3-8002 3-13.0002 1-5-140 6-7002 t 30-200 7.9-290 5-80 10 4.00-11.7 0.44-1.09 0.47-4.58 0.10-4.00 2.68-9.50 1.73-8.07 0.71-3.62 1.94-2.48 0.10-7.3 0.10- .22 0.15-2.14 0.31 1.20 1.24-14.8 1. All data In this column taken from Hans J. ' Crump-Wiesner, Herman R. Foltz and Marvin L. Yates, A Study of tlic Distribution of Toly- chlurlnnted Biphenyls in the Aquatic F.nviron- ment. Jour, Research U.S. Ccol. Survey 1_, ' 603 (1972, unlcsp otherwise noted. 2. USCS Sediment data, 1974. 3. All data in this column taken from Croswcll Henderson, Anthony lnglls and Kt'hdcll L. Johnson, Organochlorlno Insecticide Residues in -Fish Fall 1969 National Pesticide Monitoring Program, Pesticide Monitoring Journal _5, 1(1971). O DSW 011886 2 STLCOPCB4001839 LAKES A.i nrio1*' * . I i ln* ^ .v. :-.ntirior5 ,N,i llvton ,y. Michigan*# 9 .>** l '-,:c10 ,, ,VJ si . Clair*" rivers TABLE 3 SELECTED PCB STUDIES Fi fell (ppm) .0.14 - 9.17 0.2 - 7.8 0.3 - 5.6 0.16 - 11.0 0.1 - 165.3 3.4 - 9.7. tr - 3.8 Vetr (ur./l) 0.035 - 0.097 0.1 - 0.2 Sediment 43 - 245 3.72 - 636 Plankton (PPm) 3.4 11.6 \, .ihislppi River-*! ;(\.m 5va*c*n River 12 0.9 - 5.5 a.i* , v*vt`' Rivet44 \t!W VoVt S\tJun 13 Mchipan Ltplnnv River"*!' Kalamazoo River* ** rortage Creek* 7 - 350 6.9 - 165.3 (0.01 - 164.56 vixconsin Milwaukee 8 MASIJSn m'lROMtFNT :1 antic Ocean**# 18 Joy of Fundy1 Julf of Mcxico/Cnribbenn Sea** ** fouthern California** . . 0.038 - 0.190 0.07 - 1.54 0.032 - 0.059 0.04 - 6_._6______ .lJrencc~L. Haile, Oilman Vollh, C. Fred Lee nnd ViIlian C. Boyle, Chlorinated Hydrocarbons in the Lake Ontario Ecosystem, EPA-660/3-75-002, .'one 1975, U.S. E.P.A., Corvallis, Oregon. '-'.j'is L. Kaiser, KItcx, An I'nrrcopnired Contami nant of Fishes from Lake Ontario, Science 18, 523 (1974). i: chard L. Carr, Charles E. Flnstcrvaldcr and Micbacl J. Schlbl, Pesticides Monitoring Jour nal 6:23 (1972). ohn R. M. Kelso and Richard Frank, OrganochlorIne residues. Mercury, Copper and Cadmium in Yellow ?erch, White Bass and Snallnouth Bass, Long Point Bay, Lake Erie, Trans. Aner. Pish. Soc., 153:577 (1974). ''"viblltihcd data. Gilman J>. Vcitb and C. E. Class, PiB'e and DDT in Fish from Western Lake Superior, J.S. E.P.A., Duluth, Minnesota. ''v.jl.lishcd Data - John L. Hesse, Bureau of Water Management, Michigan Department of Natural Re- wjrcen, June 1973. . 'published data - State of Michigan Water Rc- inurccs Commission, Polycblorinated Biphenyl Sur rey of the Kalamazoo River and Portage Creok In 'he Vicinity of the City of Kalamazoo, 1972. . lean D, Vcith and Fred G. Lee, Chloroblphenyls in the Milwaukee River, Water Research, 1971, -y'>>) lulled data -^Schacht 1974, F.PA 600/3-74-002. "I A. Bnclie, James W. Serum, William D. Youngs *ud Hnnnld J. Litik, Polychlorinated Biphenyl . Much: Accumulation in CAynga J.nke Trout '1th Ago, Science 177:1191 (1972). 'iren C. Johnson and Robert L. Morris, Chlorin ated Insecticide, Residues in the Eggs of Some J'te'dn/rttor Fish, Bulletin of Environmental Con ' "in I nut ion and Toxicology 11:503 (1974). '"'n A, Schulze, Douglas B. Maul gold and Freeman L. Amirova, Pesticides in Selected Western 'I i,man 1968-157.1, Pesticides Monitoring Jour nal 7s73 (1973). 0.1 -- 0.5 0.1 1.0 - 2800 0.1 0.1 0.1 - 0.21 - 0.45 - 0.48 .02 - 2.17 0.0009 - 0.0036 6.6 - 6,700,000 100 - 560 10 - 475,400 * 0.0015 - 0.019 0.157 - 1.055 13. Unpublished data - Royal J. Nadeau and Robert P. Davis, Investigation of Polychlorinated Bi phenyls in the Hudson River (Hudson Foils - Ft. Edward Area, August 1974. 14. Unpublished data - John J.. Hesse, Monitoring for Polychlorinated Biphenyls in the Aquatic Envi ronment, May 197 3. 15. Unpubl 1 sited dots - Michigan Water Resources Com mission, Evaluation of the Aquatic Environment, of the Kalamazoo River Watershed, Kay 1972. 16. Michigan Department of Agriculture, Bureau of Consumer Protection, 1973 Great Lakes Environ mental Contaminants Study. 17 T. F. Bidlcnen and C. E. Olrcy, Chlorinated Hyrdocarbonr. in the Sargasso So^ Atmosphere and Sur face Water, Science 143:526, 1973. 18 George K. Harvey, Helen P. Klklas, Vaughan T. Bowen and William G. Steinliauer, Observations on the Distribution of Chlorinated Hydrocarbons in Atlantic Ocean Organisms, Journal of Karine Re search 32:103 (1973). 19. V. Zltko, 0. Httzingcr nnd P.M.K. Choi, Contamin ation of the Bny ot Fundy - Gulf of Maine Area with Polychlorinated Biphenyls, Polychlorinated Tcrphcnyln, Chlorinated Dibcnzodloxins and Dibenzofurans, Environmental Health Perspectives, 1:47 (1972). 20. C. S. Clan, A. R. Hanks, R. L. Richardson, U. M.Sockctt nnd M. K. Wong, DDT, DDE, and Polychlor inated Biphenyls in Biota from the Gulf of Mex ico and Caribbean Sea - 1971. Pesticides Moni . toring Journal 6:139 (1972). 21 C. S. Claw, M. K. Wong, A. R. Hanks, W. M. Sackc.tt, and R. L. Richardson, Chlorinated Hydrocarbons in Plankton from the Gulf of Mexico and Northern California, Bulletin of Environmental Contam . ination and Toxicology 9:376 (1973). 22 llie Ecology of the Southern California Bight: Implications for Water Quality Management, Southern California Coastal Water Research Pro ject, 1500 East Imperial Highway, El Scguudo, 1973. DSW 011887 STLCOPCB4001840 Figure I Concentration of FCC'b in Soil with Distance (ppm) T* Aroclor 1260 Investment Casting Company Aroclor 1260 Investment Casting Vax Manufacturer 4 DSW 0118 STLCOPCB4001841 AIR TABU 4 TCB measurement* ' In *lr . along with the related transport studies are practically nonexistent. Harvey and Stclnhauer^ have reported levels renging from 3.9 - 5.3 ng/m3. Air measurements by Bidlemnn and Olney for Rhode Island ranged from 2.1-9.4 ng/m3 and from 0.21 - 0.65 ng/m3 at Bermuda.^ Snow melt water data from Wisconsin ranged from zero to 0.24 ppb. The suggestion has been made that atmospheric fallout may be the most significant source of PCB dlccharge to the waters of the state of Wlsconoin. ^ LAKE ONTARIO ECOSYSTEM1 nsH, pR/g Alcwlfe Smelt Slimy Sculpln WATER, ng/1 .14 - 4.36 1.40 - 3.49 1.58 - 9.17 38 ' - 97 SEDIMENT, ng/g 43 - 245 NET PLANKTON, pg/g 3.4 - 11.8 FISH FI sit hove been studied on a nationwide basis by the Department of the Interior since 1967. In the 1969 Study, TCB levels were identified In fish from 35 sleten. 8 Data from the nationwide sampling programs, 1970-1973, are currently being prepared but vere not available for this report. Consequently, nationwide fish data are not available any more currently than 1969, with the exception of the icolnted studies listed in Table 3. The 1969 notional study showed l'CB levels generally vlthln the Fl!A 5 ppm guideline. 7n the Crest Lakes area, FOB levels in fish from lake Michigan were so high, 7.6-10.9 ppm, that FDA seized shipments of coho salmon in May 1975.9 Although tranoport mechanisms are not veil known and would vary through different ecosystems, it is interesting to consider the Lake Ontario Ecosystem St oily sucj-nrlziil in Table 4. From this study an estimate of bior..npni f icat ion is possible giving a Erdlr.tcnl to fish ratio of 1:17.0. The FDA guideline of 5 ppm in the edible portion of fish corresponds to a sediment concentration of 41 ppb - e figure exceeded In all 13 states reporting through . USCS in 1974. 1. Haile, C. L., Velth, G. D., Lee, C. F., Boyle, W, C., Chlorinated Hydrocarbons In the Lake Ontario Ecosystem (IFYCL) June, 1975. REFERENCES 1. Haile, C.L., Velth, C.D., Lee, G.F., Boyle, W.C., Chlorinated Hydrocarbons In the Lake Ontario Ecosystem (IEYGL), June 1975. 2. McDermott, D.J., and Hnnsen, T.C., Inputs of DDT, PCB and Trace Metals from llorborr, Coastal Water Research Project Annuel Report, 1975. 3. U.S. Geological Survey. 4. Environmental Polychlorinated Biphenyl Contamination near Sites of Manufacture end Use, Environmental Science and Engineering, Inc., 1975. HUMANS With Pen's ac widespread acroes various media as they ere, it Is expected that levels would be identified in humann as well. The Human Monitoring Program, in 1172, found tliot 3035 out of 4102 samples from 31 Staten showed levels ranging from less than 1 ppm to more than 3 ppm. In 1973, 964 out of 1277 samples from 28 State* agnln (showed levels in the same rongc. In both years approximately 75Z of the adipose tissue analyzed contained some polychlorinated biphenyls. Unfortunately we do not know age, occupation or residential histories of the eases involved so It is difficult to trace the levels back to the potential sources. conclusions Although thero are many national and state groupc collecting environmental TCB data, limitations in the current data base prevent one from making a uniform national assessment of PCB environmental levels. It appears that if a veil planned national approach to sampling vere attempted, the data base could be improved in very abort period of time. 5. llorvey, C.R. and Stelnhnucr, V.C., Atmospheric Transport of Polychlorinated Biphenyls to the North Atlantic, Almocphcrlt Environment, Vol. 8, 1974. 6. Bidlemnn, T.F., and Olney, C.F., Chlorinated Hydro carbons in the Sargasso Sea Atmosphere end Sur face Water, Science, Vol. 163, February 1974. 7. Klclnert, S.J., Environmental Status of PCB'o in Wisconsin, May 6, 1975, Wisconsin Department of Natural Resources. 8. Henderson, C., Jnglls, A., Johnson, W.L., Orgnnochlorlr.c Insecticide Residues in Fish - Fall 1969 National Pesticide Monitoring Program, Pesticides Monitoring Journal, Vol. 5, No. 1, June 1971. 9. Bremer, Karl E., Draft copy of "Statement of Con cerns of the Lake Michigan Toxic Substances Com mittee related to l'CB's," June 1975. DSW 011889 5 STLCOPCB4001842