Document mq7Oe1La4mgDgODBBkVEEoV2J

POLYCHLORINATED BIPHENYLS IN SOLID WASTE AND SOLID-WASTE-RELATED MATERIALS R. A. Carnes, j. u. doerger. and h. l. sparks Office of Research and Monitoring . V.S. Environmental Protection Agency National Environmental Research Center Solid Waste Research Laboratory Cincinnati, Ohio 4.1268 n Municipal refuse along with various solid-waste processing samples were analyzed / for polychlorinated biphenyls (PCBs). In all rases, the samples required drying, par/ licle-size reduction, separation of extraneous material, and extraction with an or/ ganic solvent. The extiacts were clcaned-up by chromatography and analyzed by I gas chromatography. The qualitative results obtained indicate that PCBs were present in several of the samples analyzed. These results are consistent with findings, by other investigators, that there is PCB con lamina fTon~m man VThmrpfTfre~msTronmein and they indicate that disposal of solid waste contributes to this contamination. Recently, analysts involved with environmental pollutants have come to realize that polychlorided b:;!'.:nyl: (PCBs) ate d,,',y dishilutcu in Ihe eiiviiomnent (Riscurougii et al. 1969). These compounds were not discovered in the environment until 1966, in Sweden,and 1967,in the U.S., despite the fact that they hove been available commeicially for 40 years (Gustafson 1970). Concentrations of PCBs in fish and birds arc 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 al. 1968). Polychlorinated biphenyls are produced by vaiious manufacturers in a number of countries. Some of them are marketed under the name of Aroclor (a mixture of chlorinated terphenvls) by Monsanto Chemical Co.. St. Louis. They represent "a series of inert, chemically-resistant, fire--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 natural rubbers,cellulose resins, paint, varnish, wax, asphalt, and in allyl starch. They also fmd ap plications for dust prevention, moisture proofing, scaling, impregnation, and vapor supptession to prolong the residual life ol pesticides (Lichtenstein et at. 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 geographic 27 AfchKei of Fnvitonmrtilal Contamination and Toxicology, Vt>J. 1. No, 1, J973. <D 1973 by Springer-Verlag Nrw York Inc. OSW 026504 STLCOPCB4010465 28 R. A. Carnes cl al. origin, from a compost plant, raw municipal refuse, incinerator fly asli, incinerator gaseous stack emissions and residue, and leachate from a sanitary landfill. Malerial and methods Sample preparation. The raw municipal refuse (Saint Bernard, Ohio) was a grab tamplc front a 10- cubic yard packer truck which was ground in a large hamrncnnill to approximately 1" x 1" in size. Subsequently, the refuse, was piotind in a Wiley Mill, to pass through a 2-nim screen, and dried in a laboratory oven at I05*C to constant weight. After drying, a portion of tire sample was weighed into a pre- extracted extraction thimble. The liquid condensate front incinerator stack and (lie products trapped in ethylene glycol were obtained front an experimental, high- temperature, low-capacity refuse incincratoi (located al the Environmental I'lolcction Agency facility at Center Hill). A tamplc 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 (hen 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 along with the ethylene glycol sample. These samples, along --id- the sanitary landfill leachate sample (V.'.-.lton, Ky.),\vcrc extracted using the procedure described by the FWl'CA Method for Chlorinated Hydrocarbon Pesticides in Water and Wastewater (US. 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 lo 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. Tire final treat ment utilized a pulverizer to reduce the si/c 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- T ennessee Valley Authority Composting 1'iojcct at Johnson City, Tennessee. The samples were all from the Same windrow and were initially ground and mixed at the compost plant. Before shipment to this tab, these samples were dried al lOCTC: 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 tire raw refuse sample for extraction. Table 1 shows the Samples used in this study ami tire quantity of laboratory sample extracted. Analytical methods. All solids were extracted using a soxhlet apparatus and between 200 and 250 ml of hexane-acetone mixture (9:1 by volume) as tire extraction solvent. DSVf 026505 STLCOPCB4010466 Polychlorinated Biphenyls in Waste Material 29 All samples were extracted for at least 12 hours, the solvent evaporated to dryness, and the residue redissolved 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 sodiunt sulfate. The elualc was collected and evaporated to 1 ml. A portion (usually 100 /at) was applied to a 20- x 20-cm thin-laver chromatography plate, for further separation, along with several standard PCB solutions (hexane).Thesystein employed was that described by Lichtenstein, et at. (1969). Table I. Samples Analyzed for PCB Content Sample Description Quantity extracted Evidence of PCBs 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 iVpp* ) 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 15-Day compost (Johnson City, Tcnn.) 63.0 g 10 30-Day compost (Johnson City, Tcnn.) 71.7 g 11 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. DSM 026506 STLCOPCB4010467 I.U.. 30 R. A. Carnes el al. This system utilized a 250-u aluminum oxide coating and a heptane-acetone mixture (99:1 by volume). After development, the area of standard PCD spots was spayed with a solution of Rhodaminc li (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 PCHs on tlie chromatographic plate of Tl.C system employed. The standard spots were masked and the area of sample with the same Rf value as the standard spots was re moved and extracted three times with 10-nil portions of hexane. The extract was r L. Area Eluted Solvent From ~i Aroclor 1254 .J ft p.p'-DDT r, '. Dicldiin A f p.p'- DDD Sample Extract Fig. 1. Thin layer chromatogram of PC I! and pesticide chemical standards showing area eluted from chrumatogiaphie plate for PC 1! analysis. Solvent: acetone- heptane mixture (1:99 by volume) QSW 026507 STLCOPCB4010468 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 (3H)-e)cctron-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 Q, w-as employed. The GC conditions were: column lempcratuie - IS8C; injection-block tcmpeiature 185C;delector temperature - 210C; gas-regulator pressure - 8 psi; gas - nitrogen, prepurifted. All solvents used in the course of this work were of a pesticidal quality suitable for pesticide analysis and the glasswate was cleaned with chromic acid before use All thimbles used in the soxhiet extraction were pre-extracted, using the solvent system em ployed to extract the samples. Results nnd discussion The Tfsults of tile 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 ud the heat-resistant characteristics of PCBs. The presence of PCBs in the fly aslt 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 1o 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 arc 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 11). Table 11 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 lo the difficulty of determining the amount of PCBs present without the use of a mass spectrometer. I The results reported in this paper indicate that disposal of municipal solid waste is one way in which PCBs enter the environment. !Mcnrion of commercial products does not imply endorsement by the U.S. Environmental Pre lection Agency. QSW 026508 STLCOPCB4010469 32 K. A. Carnes el al. Fig. 2. Gas chromatogram of 50 ng of Arochloi 1248 Fig. 3. Gas chromalogram of 40 ng of Arochloi 1254 Fig. 4. Gas chromatogram of 50 ng of Aroclilor 1 2b2 DSW 026509 STLCOPCB4010470 Rwpo Polychlorinated Biphenyls in Waste Material 33 Retention time (mm chert travel) Fig. 5. Gas chromatogram of a IO-jjI aliquot of extract (1 ml) obtained from incinerator residue fines (sample 4 in Tabic 1) Fig. 7. Gas chromatogram of a 10-pl aliquot of extract (1 mi) obtained front 42-day compost (sample IlinT able 1) Fig. 6. Gas chromatogram of a 10- p! aliquot of extract (1 ml) obtained from incinerator fly ash (sample 7 in Table 1) OSW 026510 STLCOPCB4010471 34 R. A. Carnes c! al. Table II. Comparison of Retention Times Obtained for Arocltlor Standaid Solutions and Extracts of Various Waste Samples'1 Sample designation Arochlor 1 248 Arochlor 1254 Arochlor 1262 Sample 4, cxlracl Sample 7, extract Sample ) J, cxti3Ct Sample 1 3, extract Retention times (mm chart travel) 16, 18, 21,25, 28, 32.5, 36,44, 5 1, 58, 68. 78, 105 ,28,38,44,51,61,69,81,93, 111, 126, 148 172 37.5,43, 51,60, 70, 75, 8! . 92.5, 105.5, 127, 140, 167, 201,235, 307 23, 27.5, 31, 37,43, 50, 60, 69, 81, 93, 106. 128 21, 23, 28, 37, 4 3, 49, 00, 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, 1 12, 128, 152, 1 70, 207, 240 Sample numbers arc those given in Table I. Retention times arc 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 limes were measured on the original chromatogram. Tig. 4 and f ig. 6 have been reduced; therefore, the peaks in these two figures do not occur at the respective retention times given in this (able. Acknowledgments We thank Dr. D. F. Render and Mr. II. Johnson of this Office for their helpful sug gestions during the course of this project. We also wish lo acknowledge Mr. I. R. Cohen, for his meticulousprcpataliott 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, I. R. and R. L. Allen: Sampling and Sample preparation of solid refuse and incincratot residues. Unpublished report (1972). Gustafson, C. G.: PCDs- prevalent and persistent. Environ. Sci. and Tech. 4,8 14 (1970). ' Lichtenstein. E. P., K. R. Schultz, T. W. Fulircmann. and T. T. Liang: biological inicraclion between plasticizers and insecticides. Jour. Economic Entomology 4, 761 (1969). Monsanto Co., St.l.ouis,Mo.,U.S.A.: 1968 Arochloi plasticizers. Tech. Dull. O/PL- 306. (1968). DSW 026511 )Polychlorinated Biphenyls in Waste Material 35 iRisebrough, R. W.: Chlorinated hydrocarbons in marine ecosystems. In M. W. Miller and G. G. Berg (cds.): Chemical fallout, current research on persistent pesticides, Chapt. I, pp. 5- 23. Springfield, Illinois: Charles C. Thomas (1968). Risebrough, R, W., P. Rciche, and H. S. Olcott: Current progress in the determination of the polychlorinated biphenyls. Bull. Environ. Cont. Toxicol. 4, 192 (1969). Risebrough, R. W., P. Ricche, D. B. Peakall. S. G. Herman, and M. N. Kirvcn: Poly chlorinated biphenyls in the global ecosystem. Nature 220, 1098 (1968). 'll. .5, 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, 197.2; accepted September 29, 1972. i QSW 026512 STLCOPCB4010473