Document LoX63m7eMeN5RGNpYV5n8vvV7

--B- P MBES-OOMI-IOn4 m of Inorginic mexury Maria!. Anil. Blochem. lnniolo|ic eviluiiion of Wtrift, Suppleincnlum 4. It: mtltbolic convetilon ikt and cellular dlilrlbule acetale by pea rooti. It of biological maierlal. lobar 5,1972. POLYCHLORINATED BIPHENYLS IN SOLID WASTE AND SOLID-WASTE-RELATED MATERIALS R. A. CARNES. 1. U. DOERGER. and H. L. SPARKS Office of Research and Monitoring U.S. Environmental Protection Agency National Environmental Research Center Solid Watte Research Laboratory Cincinnati, Ohlo4S268 Municipal refuse along with various solid-waste processing samples were analyzed for polychlorinated biphenyls (PCBs). In all cases, the samples required drying, par ticle-size reduction, separation of extraneous material, and extraction with anor ganic solvent. The extracts were cleaned-up by chromatography and analyzed by gas chromatography. The qualitative results obtained indicate that PCBs were prcsont in several of the samples analyzed. These results are consistent with findings, by other investigators, that there is PCB contamination in many parts of the environ ment and they indicate that disposal of solid waste contributes to this contamination. Recently, analysts involved with environmental pollutants have come to realize that polychlorinated biphenyls (PCBs) ate widely distributed in the uiwtonment (Rtsebtougn et /. 1969). These compounds were not discovered in the environment until 1966, in Sweden, and 1967, in the U.S., despite the fact that they have been available commercially for 40 years (Gustafson 1970). Concentrations of PCBs in fish and birds are highest in such industrial outfalls as San Francisco Bay and San Diego Bay, and concentration gradients apparently exist from these areas to more remote regions (Risebrough 1968, Risebrough et ol. 1968). Polychlorinated biphenyls are produced by various manufacturers in a number of countries. Some of them are marketed under the name of Aroclor (a mixture of chlorinated lerphenyli) by Monsanto Chemical Co., St. Louis. They represent "a series of inert, ehemieally-resistant, Ore-retarding plasticizers compatible with a wide variety of resins** and they vary "from mobile, oily liquids to white crystals and hard transparent resins** (/Monsanto Co. 1968). They are used in synthetic resins, synthetic and niturai rubbert,cellulose resins, paint, varnish, wax, asphalt, and in ally! starch. They also find ap plications for dust prevention, moisture prooOng, sealing, impregnation, and vapor sup pression to prolong the residua] life of pesticides (Lichtenstein etal. 1969). The objective of this study was to analyze for PCBs in municipal refuse and in the products of processed refuse. This involved analyzing samples, of varying geograpliic 27 Archive* of Environmental Contamination and Toxicology, Voi. I, Ho. >. 197 J. I 973 by Springer-Varlag New York Inc. MUNS 086590 28 R. A. Carnet et L origin, from a compost plant, raw municipal refuse, incinerator fly ash, incinerator gaseous stack emissions and residue, and leachate from a sanitary landfill. Material and methods Sample preparation. The raw municipal refuse (Saint Bernard, Ohio) was a grab sample from a 10-cubtc yard packer truck which was ground in a large hammermill to approximately I" x 1* in size. Subsequently, the refuse was ground in a Wiley Mill, to pass through a 2-mm screen, and dried in a laboratory oven at I05*C to constant weight. After drying, a portion of the sample was weighed into a pre-extracted extraction thimble. The liquid condensate from incinerator stack and the products trapped in ethylene glycol were obtained from an experimental, high-temperature, low-capacity refuse in* cinerator (located at the Environmental Protection Agency facility at Center Hill). A sample probe was placed in the stack and a portion of the gaseous emissions were diverted through this probe. The diverted emissions were routed through a series of water-cooled condensers and then through a gas-diffusion bubbler containing ethylene glycol. (The ethylene glycol trap was used to extract any organic material that may have been volatilized in the incineration process.) The liquid condensate was collected and utilized as a solid-waste processing sample 8log with the ethylene glycol sample. These samples, along with the sanitary ir.ndflll leachate sample (Walton, K.y.), were extracted using the procedure described by the FWPCA Method for Chlorinated Hydrocarbon Pesticides in Water and Wastewater (U.S. Department of the Interior 1969). The residue-- and fly-ash samples were collected from municipal incinerators, as listed In Table I, and were prepared according to a unpublished procedure of Cohen and Allen (1972). Briefly, this involved various sorting, grinding, quartering, and drying procedures designed to reduce the sample size and still obtain a homogeneous sample. The final treat ment utilized a pulverizer to reduce the size of particles so that they would pass a 60-mesh sieve. The pulverized, sieved material was used as the sample for this study. The compost samples came from the joint U.S. Public Health Service-Tennessee Valley Authority Composting Project at Johnson City, Tennessee. The samples were all from the tame windrow and were initially ground and mixed at the compost plant. Before shipment to this lab. these samples were dried at 100C; on arrival, the large pieces of glass, ceramics, metals, and rocks were removed. The samples were then processed in the same manner as that used to prepare the raw refuse sample for extraction. Table 1 shows the samples used in this study and the quantity of laboratory sample extracted. Analytical methods. All solids were extracted using a soxhlct apparatus and between 200 and 250 ml of hexane-acetone mixture (9:1 by volume) as the extraction solvent. MONS 086591 fly ash, Incinerator tAll. hard, Ohio) was a grab Ik a large hammermill to bund In a Wiley Mill, to B5*C to constant weight, bt-extracted extraction ota trapped in ethylene low-capacity refuse in* befflHy at Center Hill), gaseous emissions were lad throutfi a series of der containing ethylene material that may have date was collected and ne glycol sample. These n, Ky.), were extracted lorlneted Hydrocarbon ar 1969). >) Incinerators, as listed ure of Cohen and Allen , and diylng procedures sample. The final treat* would pais a 60-mesh is study. nrtoe-Tennessee Valley tuples were all from the plint. Before shipment large pieces of glass, n processed in the same lion. Table I shows the extracted. apparatus and between the extraction solvent. Polychlorinated Biphenyls in Waste Material 29 All samples were extracted for at least 12 hours, the solvent evaporated to dryness, and the residue redisioived in 6% ethyl ether. The PCBs were eluted from a 22-mm 1 D, 250-mm long column containing a small layer (one-half inch) of anhydrous granular sodium sulfate followed by a 15--g charge of activated florisil which was then covered with about three-fourths of an inch of granular sodium sulfate. The eluate was collected and evaporated to 1 ml. A portion (usually 100 pi) was applied to a 20- x 20-cm thin-layer chromatography plate, for further separation, along with several standard PCB solutions (hexme). The system employed was that described by Lichtenstein, s/al. (1969). Table I. Samples Analyzed for PCB Content Sample Description Quantity extracted Evidence of PCBa 1 Raw municipal refuse (Saint Bernard, Ohio) 50.9 g 2 Liquid condensate from incinerator 250 ml stack (Saint Bernard, Ohio) 3 Gaseous emissions from incinerator 300 ml* stack (Saint Bernard, Ohio) 4 Incinerator residue fines . (Media,Penna.) . 90.1 g 5 Incinerator residue fines (Greenwood, S. C.) 254.0 g 6 Incinerator fly ash (Media. Penna.) 115.7 g 7 Incinerator fly ash (New Orleans, La.) 87.8 g 8 0-Day compost (Johnson City, Tenn.) 50.1 g 9 IS-Day compost (Johnson City, Tenn.) 63.0 g 10 30-Day compost (Johnson City, Tenn.) 71.7 , n 42-Day compost (Johnson City, Tenn.) 69.3 g 12 Finished, screened compost (Johnson City, Tenn.) 76.6 g 13 Sanitary landfill leachate (Walton, Ky.) 1000 ml No No No Yes Yes Yes Yes No Yes Yes Yes (Trace) No `Approximately 19 standard cubic feet of gaseous emissions were passed through this amount of ethylene glycol. MONS 08659,; 30 R. A. Carnes el il. This system utilized a 250-jj aluminum oxide coating and a heptane-acetone mixture (99:1 by volume). After development, the area of standard PCB spots was sprayed with a solution of Rhodamine B (0.1 mg/ml in ethanol), covering the extract portion so that it was not contaminated by the spray. Fig. 1 shows the chromatographic position of the PCBs on the chromatographic plate of TLC system employed. The standard spots were marked and the area of sample with the same Rf value as the standard spots was re* moved and extracted three times with 10-ml portions of hexane. The extract was Fig. 1. Thin layer chromatogram of PCB and pesticide chemical standards showing area eluted from chromatographic plate for PCB analysis. Solvent: acetone-heptane mixture (1 99 by volume) MONS 036593 uw-Kttoiw mixture I (pole wet tprayad he exlrect portion 10 loprephie poeition of . The itenderd ipoti dandard ipoti wai reim. The extract wu WiKni Front M'-ODD ndftrdi showing area tM-heptane mixture *1 Polychlorinated Biphenyls in Waste Material 31 evaporated to 1 ml and retained for final analysis by electron-capture gas chromatog raphy (GC). A Barber-Coleman Series 5000 Bench Model Gas Chromatograph1, with (JH)-electron-capture detector was used. A coiled glass column (4 ft. x 4-mm ID), packed with one percent by weight of SE-30 on 60/80 mesh Gas Chrom 0, was employed. The GC conditions were: column temperature - 188C; injection-block temperature 185C;detector temperature - 210ftC; gas-regulator pressure - 8 psi;gas - nitrogen, pre purified. All solvents used in the course of this work were of a pesticidal quality suitable for pesticide analysis and the glassware was cleaned with chromic acid befote use. AU thimbles used in the soxhlet extraction were pre-extracted, using the solvent system em ployed to extract the samples. Results and discussion The results of the electron--capture gas chromatography indicate the presence of several PCBs in at least three of the samples extracted, with most other samples showing only traces. The data for the compost samples indicate the presence of PCBs; this finding is not surprising because the compost originated from a municipal refuse source that, no doubt, contained plastics which are associated with PCBs. PCBs are indicated in the chromatograms from incinerator residue and fly ash, pointing up the heat-resistant characteristics of PCBs. The presence of PCBs in the fly ash can also lead to the existence of PCBs in gaseous emissions from incinerators; however, they are not detected in gaseous emissions from the incinerator available during this study. PCBs in the incinerator residue fines indicate the need for careful disposal of these materials to avoid further contamina tion of soil or ground-water supplies. Fig. 2 to Fig. 4 show gas chromatograms obtained from Aroclor standards while Fig. 5 to Fig. 7 show the similar chromatograms obtained from sample extracts. The PCBs in the samples are tentatively identified as Aroclor 1254 in the incinerator residue fines (sample 4), Aroclor 1254 and 1262 in the incinerator fly ash (sample 7), and Aroclor 1248 and 1254 on the 42-day compost (sample ll). Table U lists the retention time for the various peaks of the three Aroclor standards and the retention time (in mm of chart travel) of various peaks from the samples and shows the similarity in retention times. No attempts at quantitation were made due to the difficulty of determining the amount of PCBs present without the use of a mass spectrometer. The results reported in this paper indicate that disposal of municipal solid waste is one way in which PCBs enter the environment. 'Mention of commercial products doe* not imply endorsement by the U.S. Environmental Pro tection Agency. MONS 066594 1 R. A. Carnes et al. 5 ArocMo! |h2r4gn,,,0,r,m of 50 n` 3. G. chromatogram of 40 ng of Arochlor HONS 086595 Polychlorinated Biphenyls in Waste Material 33 HO 1M hmm chart travel) of40ng of Aroehlor Fig. 5. Gas chromatogram of a 10-jil aliquot of extract (I ml) obtained from incinerator residue fines (sample 4 in Table 1) Fig. 7. Gas chromatogram of a 10-pi aliquot of extract (1 ml) obtained from 42-day compost (sample 11 in Table I) TTTTjn 300 2 086596 34 R. A. Carnes et al. Table II. Comparison ofRetention Times Obtained for Arochlor Standard Solutions and Extracts of Various Waste Samplesa Sample designation Arochlor J248 Arochlor 1254 Arochlor 1262 Sample 4, extract Sample 7, extract Sample 1], extract Sample 13, extract Retention times (mm chart travel) 16. 18,21,25, 28,32.5,36,44, 51,58.68, 78,105 28, 38,44, 51, 61,69, 81,93, II I, 126, 148, 172 37.5,43, 51.60, 70, 75, 81,92.5, 105.5, 127,149, 167, 201,235, 307 23, 27.5, 31,37,43, 50, 60,69, 81, 93, 106, 128 21,23,28, 37,43,49,60,70, 74,80,91, 105, 126, 148, 166,199,233, 303 18, 23,28, 37, 43, 50,60, 69.5,81, 93, 128, 171 18. 24, 28, 31. 37, 43, 50, 60, 70, 82, 93, 106,112,128, 152, 170,207,240 * Sample numbers are those given in Table 1. Retention times are measured from the in* jection point with a chart speed of 2.54 mm/min. The injection point corresponds to the coordinate marked "Responses", in the figures. All retention times were measured on the original chromatogram. Fig. 4 and Fig. 6 have been reduced; therefore, the peaks in these two figures do not occur at the respective retention times given in this table. Acknowledgments We thank Dr. D. F. Bender and Mr. H. Johnson of this Office for their helpful sug gestions during the course of this project. We also wish to acknowledge Mr. I. R. Cohen, for his meticulous preparation of the incinerator residue- and fly-ash samples, and Mr. C. C. Wiles, for his assistance in the collection and preparation of the compost samples. References Cohen, 1. R and R. L. Allen: Sampling and Sample preparation of solid refuse and in cinerator residues. Unpublished report (1972). Gustafson, C. G.: PCBs--prevalent and persistent. Environ. Sci, and Tech. 4,814 (1970). Lichtenstein, E. P., K. R. Schultz, T. W. Fuhrcmann, and T. T. Liang: Biological inter action between plasticizers and insecticides. Jour. Economic Entomology 4, 761 (1969). Monsanto Co., St. Louis, Mo., U.S.A.: 1968 Arochlor plasticizers. Tech. Bull. 0/PL-306. (1968). MONS 08659 7 Indard Solutions chart travel) 6,44,St, 58,68, 93,111, 136,148, 1,93.5,105.5, Ml? 0,69,81,93,106, ,70,74,80,91. 233,303 .69.5,11,93,128, ,60,70,82,93, 307,240 isand from the in* corresponds to (he ra manured on the rfore, the peaks in in this table. f Ibalr helpful eugge Mr. I. R. Cohen, lamptei, and Mr. C. poet samples. solid reftrie and in- *.4,814(1970). ig: Biological intertatomology 4, 761 h. Bull. O/PL-306. Polychlorinated Biphenyls in Waste Material 35 Risebrough, R. W.: Chlorinated hydrocarbons in marine ecosystems. In M. W. Miller and G. G. Berg (eds.): Chemical fallout, current research on persistent pesticides, Chapt. 1, pp. 5-23. Springfield, Illinois: Charles C. Thomas (1968). Risebrough, R. W., P. Reiche, and H. S. Olcott: Current progress in the determination of the polychlorinated biphenyls. Bull. Environ. Corn. Toxicol. 4,192 (1969). Risebrough, R. W., P. Rjeche, D. B. Peakall, S. G. Herman, and M. N. Kirven: Poly chlorinated biphenyls in the global ecosystem. Nature 220,1098 (1968). U. S. Department of the Interior (Cincinnati, Ohio), Analytical Quality Control Labora tory, Division of Water Quality Research, Federal Water Pollution Control Ad ministration: FWPCA method for chlorinated hydrocarbon pesticides in water and wastewater (1969). Manuscript received August 17, 1972; accepted September 29,1972. MGNS 086598