Document Bv5pLGkea4w2vD4d05VMqaOv8

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 Dm. These compounds are essentially nonalterable by microbial or physical-chardcal 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 atomic 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 bicmass 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 (bioma&uficaticn). 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 (NISBET & SAROFIM 1972). An indication of the widespread contamination of PCB's in today's society is illustrated In the Tenporary Tolerance Limits (Table 1) set by the FDA in certain food prod ucts (K3MSBR0UGH 1974). TABLE 1 Temporary Tolerance Limits of PCB's Substrate Level (ppm) Milk (fat basis) Dairy Products (fat basis) Poultry (fat basis) Eggs Complete and finished animal feeds Animal feed components 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 436 tillrtln at Environments! OntsntiMilnn A TstlrolntrV*l. ). Nu. 4 * l>76 bf 5|in|ff'Vrlt Nn> York Ins. This ; of water, use and d E&ord, 9h MATERIALS Descripdc Static In a hydro and acpara electric d August 12, particular paper mill Falls, 3-5 area, the velocity 1 back, brae sample waa saipling j saspLe was A stir* vegetation bank). flu emergent v Scatiar fall and tt between Sts is a roarir streanflcw suspended 1 were taken (9:15 SB, A a small sifc An upstreoB the junctlo the river b Station outfall jirs> (10:00 < as at Stadi were observi fibrous sue? bottom is mt Calculated Rlvar late) u 1966, . TCS'i alacane chan y microbial Into living nd tha bldegradation d by arueyma c chmlcal 1 uaaa, l.e. .iia In i weba; tha a cempoimda r of PCB's (NISBET & mination nporary i food prod- (PW) 2.5 2.5 5.0 .5 .2 2.0 5,0 0.0 ble This paper describes Che 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. MATERIALS & METHODS . Description of Sampling Area - Hudson River (Figure 1) Station 0 is located near the town of Hudson Falls, New York in a hydroelectric lnpoundnent area. This station is upstream and separated fran the Ft. Edvard discharge outfall by a hydro electric dm (height - 15ro). At sorpling 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 sanple was taken by coring into the sediments with a glass sampling jar and capping it underwater. A subsurface water sanple was taken neieby. 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 witfi die emergent vegetation were sanpled 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 Hudson River is a roaring, tumultuous river with a high velocity, high volume streanflow (4466 cfs)l. The river is heavily laden with heavy suspended loads of fibrous material. Water and sediment sanples were taken at this point in the same manner as at Station 0 (9:15 am, August 13. 1974). The sediment sample was taken frcm a small stfxnerged cinder-gravel spit at the outfall junction, Anupstrean 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 fran the outfall junction where water and sediment samples were collected (10:00 am, August 13, 1974). River flow conditions are the sane 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 sarple was collected ^Calculated fran N.Y. State Water Resources Data Bode, 1971. *37 from a water ir were n. electrl drastic St* 1, wets 13. 197 remnant of gre* ties eh from a were co materia the riv Sta the riv Fish pc| These pi saplea from thi shore (I Chemical A me The extx erizad ; The colum e was wash chlorine cent (Btraced f The ; (prewasb tracted \ extracts FIGURE 1 - Location of Sailing Sites in Hudson River in Hudson . Falls-Fort Edward Area 438 XA modif; RESIDUES Agency, 2A raodifi RESIDUES ltesearct HONS 083800 ge el >N FAUS liver In Hudson frcm a ramant shale flake, cinder deposit bank above the high water mark. All the collecting sites downstream frcm Baker Falls were submerged until Septaifcer 1973. When an abandoned hydro* electric dan at Fort Edward was removed, Che water level was drastically lowered 5-15 meters. Station 3 is located about 0.5 miles downstream frcm Station l, 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 Sank sediments consist of gravel, cinders, luxrber slabs, and bark frcm logging activi ties that ceased 40 years ago. The sediment sanple was collected from a submerged deposit near the sane area where several fish were collected by seining. In Che shallow area, Che fibrous material, suspended at the upstream stations has flocculated cnto the river boctan, coating Che boccccn with a "paper wrapping". Station 4 is located 0.75 miles downstream frcm Station 1. The river is s lightly wider at this point with decreased velocity. Fish populations are abundant in the shallow shoreline areas. These populations were sanpled by seining. Water and sediment samples were collected in the river, three (3) meters vpstrean from 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 sorple was extracted with hexane. The extract was dehydrated, concentrated, and analyzed by comput erized gas chranatogpraphy/masa spectrometry (GC/lti). 1 The sediment sanple was partially dried and extracted by colum 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 CH^Clj 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 colum, eluted with 25 ml modification of methods published in METHCDS FOR ORGANIC RESIDUES IN WATER AND WASTEWATER, 1971. Environmental Protection Agency, National fiivirorfnental Research Center, Cincinnati, Ohio. modification of methods published in ANALYSIS OF PESTICIDE RESIDUES IN HUMAN AND ENVIRONMENTAL SAMPLES, 1961. Perrine Research Laboratories, Ehvironnental Protection Agency. 439 HONS 08380 i r 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 chranatograph. The sample of rock bass from the discharge re quired a 50 fold dilution before analysis. The presence of PCB's in all sozples was confirmed by_pre- chlorinating the soiples with SbClc for four hours at 170C to form Ci^Cl^fT C12C^10 vas 8ubaequently analysed by gas chranatography using1*! tnree-foot cokxm of 3 percent Dexsil-300 at 200 C. Subsequently, a QC/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 ccnputerized GC/MS Spectra of various Aroclor mixtures including 1016 supplied by the discharger and EPA with environ mental saiple extracts. PCB's identified as Aroclor 1016 were found in the water samples at detectable concentrations at all sanpling locations except Station 0 (control) and Station 4 (furthest downatrem) (Table 2). TABLE 2 Analysis of Water and Sediment Sanples for Aroclor 1016 from the Hudson River in the Area of Fort Ecbard, New York Location Station 0 Station 1 Station 2 Station 3 Station 6 Contamination Levels Water ug/1 Sedimoit tng/kg (ppb) (PP"n) 1.0 2800.0 2.2 (3.0)* (3.1) 1.0 6.9 6700.0 560.0 2980.0 6.6 ^Results of replicate analysis - a quality assurance procedure. At all stations the sediments contained higher concentrations of Aroclor 1016 than the water coliim because PCB's preferentially adsorb onto suspended or already settled materials. solv HONS 063002 the final |U IS* raWco 'xail-300 act wu .tandardt. listed by mixture* Ttviron-atar atione >erwn) 1016 >York M ntrmtlon* wntislly The high contamination level at Station 1 indicates the ad sorptive capacity and constant exposure of the sediments nearest die outfall to the Aroclor 1016. these sediments were also heavily laden with noticeable oil and grease which serves as a solvent for FCB coopoinds. At Station 3, high concentrations (2980 mg/kg) occur in the sediments, representing accimulated levels of PCB's, 10^ fold greater than the outfall concentration. The high level is a product of historical plus present adsorption and deposition of FCB ccmpoiaids. 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 samples collected above the discharge contained the latereluting PC3rs with retention times of 84, 98, 104, 112, 125, 146, and 174 relative to pp DIG. These are characteristic of Aroclor 1254, another PCB that was used extensively prior to Aroclor 1016. In addition, major PCB carponents were found at relative retention times of 37 , 40 , 47 , 54, 58 , 70, and 78. The relative concentra tion of the PCB components foind In the control station sanples and the absence of PCB carponents 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 carponents of Aroclor 1254 and the earlier-eluting carponents of Aroclor 1248, the PCB concentrations in the biota sorples were estimated and are presented In TABLE 3. TABLE 3 PCB Concentrations In Blocs Collected in die Hudson River Til PCB Gattrepod L Pitcin* N u/m Name Sliiitn O Nlpi< tortiutoe frontalis Ta *) (Northern Common Shiner) Perce f(accen* (Mitchell) (Yellow Perch) Stotion I Nooe (Above Outfall) Stetien 3 Amblopleter rupcetria tupeetti* {Rainqu) (Northern Reck Bate) Station 4 Notropie cernutwe frantalie (Af ait) (Northern Cemman Shiner) 7.0 17.0 >S0 0 7.0 Phyia ip Helieome p Phyea p Helitoma ip Phy.a ep Limnacea ap Total PCB wotwt. I. [.45] 441 Distinctly different fran the settles from the control area were the earples collected in the vicinity of or below the dis charge, It is evident from a chromatogram of the sanple of bass below the discharge chat there are no major PCB components eluting after 78 relative to DDE. Moreover, the 21, 28, and 32 carponents 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-backgrowd concentration in the sedi ments and biota can be found in the immediate vicinity of the PCB discharge. Although the pattern of accunulation 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 accunulation and transfer model could not be determined for the sampling area, a hypothetical presentation is given below: BIOTA . DISCHARGE^ AQUEOUS PHASEPLANKTON-"""1"** SNAILS | (Inf EPIFAUNAL COMMUNITIES (Ad.rpUn 4 |, Sedimentation) ' ` ~ SHINERS, YOUNG PERCH 1 --.................. 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 acemula tors and concentrators of PCB' s (TABLE 4). The species collected are primarily herbivorous grazers, living off the periphyton growing on rocks, lurber slabs, and benthic surfaces. The snails ingest sedimented materials containing adsorbed PCB's along with Chair natural food. 442 Loce Station Station (Abovi ( Station Station The web sint fish. T the PCB' out of c An i River is at StaCi species the Lake lected i nation f fusion a< If the p source o. mainly p. It it PCB's, c* periphyte ruraely ti yellow p The I level doc U.S. (NIS PCB contt Alchc in this s spread re populace sues in t MQNS Q83801* dUf bass eluting porants 'ponent. ft of :M the itri-.edtcha PCB of erature, within in suf- db- 'I not be ion la han the cation a, cunuladlacted on snails g with *a TABLE 4 Concentration Factors of PCB's In the Hudson River Location Station 0 Substrate Snails Cannon Shiner Yellow Perch Concentration Factor Tissue/Water Tissue/Sedunent >1.9 x 103 >7.0 x I0i >17.0 x 10J 3.63 .98 .91 Station 1 (Above Outfall) Station 3 Station 4 ' Snails Rock Bass Snails Cannon Shiner .. 45 x 10J 117 x 103 >27 x 103 >78 x 10J 6.52 .12 11.82 4.09 Ihe 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 bicmagnification. 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 (Yellow Perch) at Station 0 is 68 times greater that that found in the sane species fran Lake Erie (KELSO & FRANC 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 contanlnaticn 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 die snails, however, small perch are mainly plankton and epifauna considers (THARRATT 1969). It is significant that the shiners and snails both contained PCB's, especially since these species are important grazers upon periphyton connunities and serve as food for large consumers, namely the gone fish; i.e., pike, pickerel, bass, and larger yellow perch. Ihe PCB level in the rock bass is greater than the maxinun level documented for fish taken from any industrial river of the U.S. (NISBET & SAROFIM 1972). this represents a new record for PCB cocitaninatlan of fresh water fish. Although the game fish species are not cormercially utilized in this sdretch of the Hudson, sport fishing is a carmen wide spread recreational activity. Ingestion of these fish by the populace wculd certainly lead to contanination of specific tis sues in their bodies. Occurrence of PCB's in hunan tissues has MQNS 083805 I Mh docunented in the literature, especially in people who are con stantly exposed to PCB's through their occupation or life styles. Even though these compounds have a cooperatively low acute toxicicy for mtmnals, the long term effects may be much more insiduous and devastating. A nutter of investigators have shown that PCB's induce production of liver microsanal 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 IQtANT, et al. 1971).' PCB's have been detected in hunan adipose tissue in such widespread occurrence chat 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 organism of Che contaminated ecosystem. Information on transfer rates and modes is necessary before a plan of action can be reccnmended for ranoving the contaminated substrates from the Hudson Falls-Fort Edward area. ACKNOWLEDGMENTS We gracefully acknowledge and thank Dr. Bernard Dudenbostel and Mr. David Speis for the determination of PCB's in water and sediment ssnples, and Dr. Gilman Velth of the National Water Quality Laboratory at Duluth, Minn, for determining PCB levels in biological specimens. REFERENCE SECTION ALEXANDER, M.: Microbial Ecol. 2, 17 (1975). CECIL, H. L., S. J. HARRIS, J. BnMAN, and J. F. FRIES: Bull, Env. Cant. Toxicol. 9. 179 (1973). OtANT. D. L., D. C. VHLENEUVE, K. A. MC CULLY, and E. J. PHUJ.TPS: Env. Physiol. 1, 61 (1971). HANSEN, D. J., P. R. PARRISH, and J. FORESTER: Gulf Breeze Env. Res. Laboratory Cont. 172 (1973). KELSO, J. R.. and R. FRANK: Ttteis. Alter. Fish. Soc. 103, 577 (1973). KIMBROUGH, R. D.: Critical Reviews in Toxicology 2 , 455 (1974). NISBET, I. C. T.. and A. F. SARQFIM: Env. Health Perspectives, Experimental Issue 1 (1972). PRICE, H. A. and R. L. WELCH: Env. Health Perspectives, Experimental Issue 1 (1972). THARRACT, R. C.: Trans. Amer. Fish. Soc. 8 (1959). TROUT, P. E.: Env. Health Perspectives, Experimental Issue 1 (1972). ~ Eft* Eu> certain e) 1 ANDERSON . t al., I1 exparloont mallards ECBERT, V ; (LONCCORS (HAEGELI < 1974; STIC aparvarlua acraach on (Straptooo machaniaao inhibition PRAKALL. 1 gland; ine at al.. 19 hapatle alt Tha ol with a ap Japantao qi long parlor rasaabla ot uacaptifela reaulta of blphanyl, 4 tha aaehodo ^Praaant ad Protactloo 21.1.1-erla 31.1- dichl `1.2.3.4,1a 14-ando-ot