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Polychlorinated Biphenyls in the Hudson River (Hudson Falls-Fort Edward, New York State) Royal J. Nadeau and Robert A. Davis United States Environmental Protection Agency Edison, N.J. 08817 Polychlorinated biphenyls (PCB's), as recently as 1966, have been recognized as an environmental contaminant. PCB's are primarily used in industry and are even more persistent than DDT. These compounds are essentially nonalterable by microbial or physical-chemical activities and are incorporable into living protoplasm. The bonding between the chlorine atom and the bi phenyl structure is resistant to shearing by natural degradation processes, therefore PCB's are not easily metabolized by enzyme systems presently found in nature (ALEXANDER 1975). The atonic structure of PCB's gives them specific chemical characteristics very desirable for certain industrial uses, i.e. dielectric fluids in capacitors and transformers, PCB's not only are incorporable into living biomass in natural ecosystems, but are transferable within food webs; the end result being a much higher concentration of these compounds occurring in specific tissues of sunnit carnivores (bicmagnification). 3 It has been estimated that 4 to 5 x 10 tons/year of PCB's are lost into the Nation's fresh and coastal waters (N1SBET & SAROFEM 1972). An indication of the widespread contamination of PCB's in today's society is illustrated in the Temporary Tolerance Limits (Table 1) set by the FDA in certain food prod ucts (K3MSBROUGH 1974). TABLE 1 Temporary Tolerance Limits of PCB's Substrate Level (ppm) Milk (fat basis) Dairy Products (fat basis) Poultry (fat basis) Eggs Conplete and finished animal feeds Animal feed conponents Fish and shellfish (edible portion) *Paper food-packaging material 2.5 2.5 5.0 .5 .2 2.0 5.0 10.0 *Does not apply to packaging material that is separated from the food by a barrier impermeable to PCB migration 43b Bulletin of Environmental CoolmlnnUn & Toxicology, Vol. )6, No. 4 1P76 by Springer-Verl*g New York Inc. River late) IS 1966, . PCB's .sis tent than y microbial ' into living nd the bi- ' degradation d by enzyme c chemical '1 uses, i.e. ass in i webs; the e caipounds r of PCB's (NISBET & imination mporary i food prod- 2.5 2.5 5.0 .5 .2 2.0 5.0 0.0 ble This paper describes the presence and extent of contamination of water, sediments, and biota of the Hudson River by industrial use and discharge of PCB's in the vicinity of Hudson Falls-Fort Edward, New York State. MA1ERIALS & MEIHODS . Description of Sampling Area - Hudson River (Figure 1) Station 0 is located near the town of Hudson Falls, New York in a hydroelectric impoundment area. This station is upstream and separated from the Ft. Edward discharge outfall by a hydro electric dam (height - 15m). At sampling time (3:15 pm, August 12, 1974) the water was heavily laden with fibrous particulates being carried down from an upstream source. Several paper mills and fiber board manufacturers are located in Glens Falls, 3-5 miles upstream from Station 0. In the main channel area, the bottom is hard shale. In the shallows where water velocity is less, large deposits of sediments intermixed with bark, branches, lumber slabs, and cinders are found, A sediment sample was taken by coring into the sediments with a glass sampling jar and capping it underwater. A subsurface water sample was taken nearby. ' A seine was used to collect fish near a patch of emergent vegetation on an opposite bank from the sediment deposits (east bank). The gastropod (snail) populations associated with the emergent vegetation were sampled simultaneously. Station 1 is located at the junction of the Ft. Edward out fall and the Hudson River. There are smaller known discharges between Station 1 and Station 0. At Station 1 the liudson River is a roaring, tumultuous river witii a high velocity, high volume streamflcw (4466 cfs)l. The river is heavily laden with heavy suspended loads of fibrous material. Water and sediment samples were taken at this point in the same manner as at Station 0 (9:15 am, August 13, 1974). The sediment sample was taken from a small submerged cinder-gravel spit at the outfall junction. An upstream gastropod population was sampled several meters above the junction. This station is only accessible by boat because the river banks are precipitous shale rock faces, 15m in height. Station 2 is located about 0.25 miles downstream from the outfall junction where water and sediment samples were collected (10:00 am, August 13, 1974). River flew conditions are the same as at Station 1. No macroinvertebrate or piscine populations were observed at this station. The water is laden with the same fibrous suspended materials as evidenced at Station 0. The river bottom is mainly a shale ledge. A sediment sample was collected ^Calculated from N.Y. State Water Resources Data Book, 1971. 437 ______________________________________________________ DSW 028831 ' j 1 i 1 ; ' 1 ^ STLCOPCB4012793 FIGURE 1 - location of Sampling Sites in Hudson River in Hudson . Falls-Fort Edward Area 438 DSW 028832 from a water were s electr drasti St 1, wat 13, 19 rennan of graties ~tl fran a were c< materi; the ri' St; The ri^ Fish pc These p samples from tl shore ( Chanica A ir The ext erized The colum < was wasl chlorin, cent QI. trated : The (prewash tracted ' extracts ^A modif RESIDUE Agency, modif RESIDUE Researc frcm a ramant shale flake, cinder deposit bank above the high water mark. All the collecting sites downstream from Baker Falls were submerged until Septenber 1973. When an abandoned hydro electric dam at Fort Edward was removed, the water level was drastically lowered 5-15 meters. Station 3 is located about 0.5 miles downstream frcm Station 1, water and sediment samples were collected (11:00 am, August 13, 1974). In this area an extensive sludge bank exists as a remnant of past industrial activity. The bank sediments consist of gravel, cinders, limber slabs, and bark from logging activi ties that ceased 40 years ago. Ihe sediment sample was collected from a submerged deposit near the same area where several fish were collected by seining. In the shallow area, the fibrous material, suspended at the upstream stations has flocculated onto the river bottom, coating the bottom with a "paper wrapping". Station 4 is located 0.75 miles downstream from Station 1. Ihe river is slightly wider at this point with decreased velocity. Fish populations are abundant in the shallow shoreline areas. These populations were sampled by seining. Water and sediirent samples were collected in the river, three (3) meters upstream frcm the junction of a small stream that flows in on the west shore (1:15 pm, August 13, 1974). Chemical Analysis ' A measured volume of water sample was extracted with hexane. The extract was dehydrated, concentrated, and analyzed by comput erized gas chromatography/mass spectrometry (GC/MS) . 1 The sediment sanple was partially dried and extracted by colimn elution with a mixture of 1:1 acetone/hexane. The extract was washed with water to remove the acetone and then the poly chlorinated biphenyls were extracted from the water with 15 per cent CH2C12 in hexane. This extract was then dehydrated, concen trated to a suitable volume, and analyzed by computerized GC/MS.2 The biota samples were blended with anhydrous sodium sulfate (prewashed with redistilled acetone) and the homogenate was ex tracted with a mixture of hexane and ethyl ether (3:1 v/v). The extracts were placed on a 20 gm florisil column, eluted with 25 ml A modification of methods published in METHODS P0R ORGANIC RESIDUES IN WATER AND WASTEWATER, 1971. Ehvirormental Protection Agency, National Environmental Research Center, Cincinnati, Chio, o A modification of methods published in ANALYSIS OF PESTICIDE RESIDUES IN HIMAN AND ENVIRONMENTAL SAMPLES, 1961. Perrine Research Laboratories, Environmental Protection Agency. 439 STLCOPCB4012795 of hexane, and the volume of the eluate was adjusted so the final concentration of PCB's was within the linear range of the gas chromatograph. The sample of rock bass from the discharge re quired a 50 fold dilution before analysis. The presence of PCB's in all sanples was confirmed byjprechlorinating the samples with SbCl- for four hours at 170C to form C, oCl.q. The C, n wa3 subsequently analyzed by gas chromaFogrSphy using^a three-foot coknri of 3 percent Dexsil-300 at 200 C. Subsequently, a GC/MS analysis of the rock bass extract was performed along with analysis on Aroclor 1016 and 1242 standards. Analysis Results Detection of PCB's in water and sediments was accomplished by comparing computerized GC/MS Spectra of various Aroclor mixtures including 1016 supplied by the discharger and EPA with environ mental sanple extracts. PCB's identified as Aroclor 1016 were found in the water sanples at detectable concentrations at all sarrpling locations except Station 0 (control) and Station 4 (furthest downstream) (Table 2). TABLE 2 Analysis of Water and Sediment Samples for Aroclor 1016 fran the Hudson River in the Area of Fort Edward, New York Location Contamination Levels Water ug/1 Sediment mg/kg (PPb) (PPn) Station 0 Station 1 Station 2 Station 3 Station 4 . 1.0 2800.0 2.2 (3.0)* (3.1) - 1.0 6.9 6700,0 540.0 2980.0 6.6 *Result9 of replicate analysis - a quality assurance procedure. At all stations the sediments contained higher concentrations of Aroclor 1016 than the water colunn because PCB's preferentially adsorb onto suspended or already settled materials. 440 serf the hea\ so h sedi gref proc PCB depr dect quar Biol Stat elut and 125^ In time tier and that Aroc of P 124E and Stat St at i (Abr Stat St at DSW 028834 the final ie gas ge re- yjF*0 C to gas xsil-300 act was .tandards, dished by mixtures TTvironater ations tream) 1016 ; York ',7kg ntrations 'erentially Ihe high contamination level at Station 1 indicates the ad sorptive capacity and constant exposure of the sedirrents nearest the outfall to the Aroclor 1016. These sediments were also heavily laden with noticeable oil and grease which serves as a solvent for PCB compounds. At Station 3, high concentrations (2980 mg/kg) occur in the sediments, representing accumulated levels of PCB's, KH fold greater than the outfall concentration. The high level is a product of historical plus present adsorption and deposition of PCB compounds. The PCB level at Station 2 represents historical deposition mainly. Although PCB's in the water colum are below dectectable limits at Station 4, PCB's occur in significant quantities in the sediments. Biological Tissue Station 0 ' The saiples collected above the discharge contained the latereluting PCB's with retention times of 84, 98, 104, 112, 125, 146, and 174 relative to pp DDE. These are characteristic of Aroclor 1254, another PCB that was used extensively prior to Aroclor 1016. In addition, major PCB conponents were found at relative retention times of 37, 40, 47, 54, 58, 70, and 78. The relative concentra tion of the PCB components found in the control station samples and the absence of PCB components eluting earlier than 28 suggest that the PCB's in the biota can best be estimated as a mixture of Aroclor 1254 and Aroclor 1248. Using the later-eluting components of Aroclor 1254 and the earlier-eluting components of Aroclor 1248, the PCB concentrations in the biota samples were estimated and are presented in TABLE 3. TABLE 3 PCB Concentrations in Biota Collected in the Hudson River Local ion Station O Piscine N ame Notopia cornutua frontaiia (A faaaiz) (Northern Common Shiner) Tol.l PCB u*/*m wet-wt. C aat r opod Name 7.0 Heliaom* *p Phyaa ap Perea ttaveacena (Mitchell) (Yellow Perch) 17.0 Station t None (Above Outfall) HeJiaom* ap Phyaa ap Station 3 Ambloplelea rupcatria rupeatri* (R (innqur) (Northern Rock B) 350.0 St at ion 4 Notropia cornutua frontaiia (Afaaaix) (Northern Common Shiner) 78.0 Heliaoma ap Phyaa ap Limnacea ap Total PCB u(/ f m wet-wt. 1.9 [0.45] [27.] 441 DSW 0 28835 STLCOPCB4012797 Distinctly different from the samples from the control area were the samples collected in the vicinity of or below die dis charge. It is evident from a chromatogram of the sample of bass belcw the discharge that there are no major PCB components eluting after 78 relative to DDE. Moreover, the 21, 28, and 32 components are present in higher concentrations relative to the 37 component. This suggests that Aroclor 1242, Aroclor 1016, or a mixture of these two formulations are- present in the Hudson River below the discharge. ' DISCUSSION ' The results illustrate that PCB's are ubiquitous in distri bution within the Hudson River within a variety of substrates. ' Nevertheless, higher-than-background concentration in the sedi ments and biota can be found in the imnediate vicinity of the PCB discharge. Although the pattern of accumulation and magnification of PCB's in the biota was similar to that reported in the literature, insufficient information exists on transfer rates of PCB's within environmental substrates. The PCB's being discharged are in suf ficient quantities that contamination of all environmental sub strates have occurred; water, sediment, and biota. Although an exact accumulation and transfer model could not be determined for the sampling area, a hypothetical presentation is given belcw: BIOTA . DISCHARGE ' (Adsorption) (Grazing) AQUEOUS PHASE------------------- -* PLANKTON------------ -- SNAILS | (Ingestion) EPIFAUN AL COMMUNITIES (Adsorption & Sedimentation) (Ingestion) SHINERS, YOUNG PERCH ------ (Ingestion) --ROCK BASS ------------ At all stations the biota had higher levels of PCB's than the background water concentration. At all stations, except Station 3, the biota contain higher levels of PCB's than the sediments. At all stations the snail populations are important accumula tors and concentrators of PCB's (TABLE 4). The species collected are primarily herbivorous grazers, living off the periphyton growing on rocks, lumber slabs, and benthic surfaces. The snails ingest sedimented materials containing adsorbed PCB's along with their natural food. 442 Loca Station Station (Above 1 Station Station The web sine fish. : the PCB out of c An : River i: at Stat; species the Lake lected i nation f fusion a If the p source o mainly p It i PCB's, e perinhyte namely tl ye1lew pc The r level doc U.S. (NI5 PCB cent. Alth< in this ; spread rc populace sues in i DSW 028836 STLCOPCB4012798 n.ir area disf bass eluting lponents mponent. e of .*? the stri fes, 'edirhe PCB of orature, within in suf- sub- '1 not be ion is han the -tation enta, cumulallected on snails >g with iWlWrarrmri *mt*m* TABLE 4 Concentration Factors of PCB's in the Hudson River Location Station 0 Substrate Snails Common Shiner Yellcw Perch Concentration Factor Tissue/Water Tissue/Sediment >1.9 x 103 >7.0 x 103 >17.0 x 10J 3.63 .98 .41 Station 1 (Above Outfall) Station 3 Station 4 Snails Rock Bass Snails Common Shiner 45 x 103 117 x 103 >27 x 103 >78 x nr 6.52 .12 11.82 4.09 The adsorbed PCB's remain biologically active within the food web since snails are normal dietary constituents of larger game fish. This is a possible pathway for biomagnification. Likewise, the PCB's are remaining environmentally active and are not taken out of circulation by the geologic sedimentation process. An indication of the seriousness of the problem in the Hudson River is that the PCB level in the Perea flavescens (Yellcw Perch) at Station 0 is 68 times greater than that found in the same species from Lake Erie (KELSO & FRANK 1974). The fish analyzed in the Lake Erie study were even older and larger than those col lected in the Hudson River, The most probable route of contami nation for fish is through the dietary pathway and direct dif fusion across exposed gill, intestinal, and integument surfaces. If the perch collected at Station 0 were older and larger, their source of PCB's might be the snails, however, small perch are mainly plankton and epifauna consumers (THARRATT 1969). It is significant that the shiners and snails both contained PCB's, especially since these species are important grazers upon periphyton communities and serve as food for large consumers, namely the game fish; i.e., pike, pickerel, bass, and larger yellow perch. The PCB level in the rock bass is greater than the maximum level documented for fish taken from any industrial river of the U.S. (NISBET & SAROFIM 1972). This represents a new record for PCB contamination of fresh water fish. Although the game fish species are not commercially utilized in this stretch of the Hudson, sport fishing is a common wide spread recreational activity. Ingestion of these fish by the populace would certainly lead to contamination of specific tis sues in their bodies. Occurrence of PCB's in human tissues has 443 DSW 028837 STLCOPCB4012799  Ti documented in the literature, especially in people who are con stantly exposed to PCB's tluough their occupation or life styles. Even though these conpounds have a comparatively low acute toxic ity for marrmals, the long term effects may be much more insiduous and devastating. A nuriber of investigators have shown that PCB's induce production of liver microsomal enzymes. Others have shown that PCB's can decrease Vitamin A content in the liver (CECIL, et al. 1973). Transplacental passage of PCB's has also been shown "(CPANT, et al. 1971).' PCB's have been detected in human adipose tissue in such widespread occurrence that 41-45 percent of the U.S. population contains 1 ppm or more (PRICE & WELCH 1972). Little is known concerning the specific mode of entry of PCB's into the organisms of the contaminated ecosystem. Information on transfer rates and modes is necessary before a plan of action can be reccmnended for removing the contaminated substrates from the Hudson Falls-Fort Edward area. ACKNCWLEDGMENIS We gratefully acknowledge and thank Dr. Bernard Dudenbostel and Mr. David Speis for the determination of PCB's in water and sediment samples, and Dr. Gilman Veith of the National Water Quality Laboratory at Duluth, Mirm. for determining PCB levels in biological specimens. REFERENCE SECTION ALEXANDER, M.: Microbial Ecol. 2, 17 (1975). CECIL, H. L., S. J. HARRIS, J. BITMAN, and J. F. FRIES: Bull, Env. Cant. Toxicol. 9_, 179 (1973). GRANT, D. L., D. C. VTXLENEUVE, K. A. MC CULLY, and E. J. PHILLIPS: Env. Physiol. 1, 61 (1971). HANSEN, D. J., P. R. PARRISH, and J. FORESTER: Gulf Breeze Env, Res. Laboratory Cent. 172 (1973). KELSO, J. R., and R. FRANK: Trans. Amer. Fish. Soc. 103, 577 (1973). KIMBROUGH, R. D.: Critical Reviews in Toxicology 2, 455 (1974). N1SBET, I. C. T., and A. F. SARQFIM: Env. Health Perspectives, Experimental Issue 1^ (1972). PRICE, H. A. and R. L. WELCH: Ehv. Health Perspectives, Experimental Issue 1 (1972). THAKRATT, R. C.: Trans. Amer. Fish. Soc. 88 (1959). TROUT, P. E.: Env. Health Perspectives, Experimental Issue 1 (1972). ~ 444 Eff< Egg! certain c ANDERSON et al., ] experimer mallards EGBERT, 1 (LONGCORE (HAECELE 1974; STI sparveriu screech o (Streptop mechanism inhibitio: PEAKALL, gland; in et al., 1; hepatic ml The c with a spe Japanese q long perio resemble o susceptibl results of biphenyl, the method-. ^Present ad Protection 21.1.1-tric 31.1- dichlo 41.2,3.4,1C 1,4-endo-e P til If 1 in n( F.nvironn Yol. it, No. 4 J97t ^S838 STLCOPCB4012800