Document gaEgNKB1r4KgJBMDbk4pr0p73

Polychlorinated Blphanyla in tha Hudson River (Hudson Felle-Fort Edward, New York State) Royal J. Nadaau and Robart A. Davis United Stotee invlronmentel Protection Agency Edison, HJ. Off17 Polychlorinated bipheryla (FCB'a), at racmtly aa 1966, hava baan recoffrixsd aa m anvlxcnantal contatinint. FCB'a an primarily uaad In Intestacy and an avan warm persistant that DDT. lhasa ceafamds an aaaaneLally nonaltanble by microbial or physlcal-ctndcal activities and an lnosrporabla Into living proCoplama. The bending batman tha chlorlna atom aid tha blphanyl acructun la raslaeait to ahaarlng by natunl degradation processes, therefore FCB'a an not aaally metabolized by anzyma ayataaa presently found In natura (ALEXANDER 1975). Tha atonic *trueCura of FCB'a givaa Cham specific chanleal characteristics vary daalrabla for certain Industrial uaaa, l.e. dielectric fluids In capacitors and txKiaformara, FCB'a not only an lacorporabla Into living blcaaaa In natural acoayaens, tat an transferable within food webs; tha and result being a such higher ceneantntion of thaae compounds occurring In apacific tissues of svmdt carnivores I'MramgriTfl ratim) It has bean aatinetad that 4 to 5 x 10^ tm/yaar of FCB'a an lose Into tha Nation's fraah aid coastal watan (NUK1 4 SASCrm 1972). in Indication of tha widespread ccntadnatlcn of FCB'a In tndqr's society is UluatraCad In tha Bamorary folarsnca Halts (Table 1) sat by tha IDA In certain food prod ucts OOMEMXni 1974). TABU 1 tWgurary Tblaranca T.lmlta of FCB'a 9fgFte- Level (pout) HUk (fat basis) Daisy Products (fat basis) Poultry (fat basis) Collate and flnlahtd anlnal faada Paper food-padtaglng material 2.5 2.5 5.0 .5 .,A2 2.0 5.0 10.0 Dose not anly to psrkaglng material that la aaperatad frail tha food by a barrier lagantedble to PCB tigratlcn **> PMatte ef Eawaieaatal Caaiaaiatina A Tasteelegy. Vet. 14. Ne. * 1*7* bf rwgsr Vceteg Mew Teak lee. HUNS 006518 Thia dcrlbs th* pr~mc* md sane of concanbuclon of wator, dlnnta,'M biota of cfao Hudson Rlw by industrial uh and discharge of FCB a In cha vicinity of Hudaan Falls-Fort ttmrd, Haw Ton Scats. HHHBlttS & >gnfD8 PaacripClon of Sanpliiat Am - Hudson Rlvar (Figure 1) Station 0 la locatad near tha torn of Hudson Falla, Naw York In a hydroelectric lapeuntant araa. Bile station ia i^wtrai particulates bail* carrlad doan frm m upetraan aourca. Sevwral pmar sills and fiber board nmufactunrs an locatad In Glam Falla, 3-5 adlaa igerran from Station 0. In tha taaln chmal araa, tha bottna la hard shala. hi tha shallows vtwra vatar velocity la lasa, largo dapoalta of aadfcamta lntaminad with bark, branchaa, li*ar aim, md cinders an fond. A aadinanc ample was taken by coring into tha aadlnants with a glass ailing jar and capping It mdarwatsr. A subsurface near Mpla was tahm nearby. A sains was uaad to collect fieh near e petch of --ir* vagaitatlon on an opposite bmk fren tha ndtaune deposits (aaat bat)` Tha gastropod (anall) populations aaaori and with tha ngariHnn wan aaqplad slaultmaoualy. Station 1 la locatad at tha juietlon of tha Ft. Edard out fall aid tha fedaen Unr. Than an aowllar Ima dlachargaa batuaon Station 1 md Station 0. At Station 1 tha Hudmn Unr la a roaring, andtugua river with a hldi vwloclty, Mah imlim stnmflow (4*66 cfa)l. Iha river la haavlly ladm with heavy suapandad leads of flbcooa wacariel. totter md eadtnanr la^iln wan takan at thla padnt In tha ana law as at Station 0 (9>15 , August 13, 1974). Iha saiHnanr s^la was takan Ann a anall ulmaigad cindar-gravel spit at tha outfall jtactisn. An iwatram gastropod population was a^ilail wnral antars toon tha jmotion. This stataon la only aocaaaibla by beat harauaa tha rlvar backs are precipitous toala reck fans, 13n In bad^ie. Station 2 la located about 0.23 nilaa dramtram firm tha outfill (Am Mtam nl nmilmMK nanltoa mm wnllniittoil (10:00 an, Agat 13, 1974). Uvar flow eenStlans an tha aim an at Station 1. Mb mrrnli martabrata or piscina popular!cm l at this station. Tha vatsr is laden with the asm _ ndad nanriala as avldmcad at Station 0. The dear bottm la aalnly a shall ladga. A serf!want mpla u collected Valciilarsd frm g.T. Sean toiear Data look, 1971, MONS 004519 Vlllog* of HUDSON FALLS nOUB 1 - LaroHan of Sapling Slew In 1 TUla-Vare EAard Arw Rivar In tbtan HONS 006520 fno a rnmait shale flak*, cinder deposit bade abova the Mh wacar mark. All tha collecting sites downstreat from BakarFalls ware submerged until Septmrber 1973. Whan an abaidonad hydrolaceric dan at Fore Eawrd was recovad, tha water level was drasdealiy lowered 3-15 maters. Scadon 3 la located about 0.3 miles downstream frem Station 1, water and sadiaane amplas wtra collected (11:00 am, August 13, 1974). In this area an extensive sludge baric exists at a rasnant of past industrial activity. Tha bade sedimanea consist of gravel, cinders, lidier slabs, and bark from loggii^ activi ties that ceased 40 years ago. The aedlmane staple was collected from a avhmergad deposit near tha sea area where several fish wtra collected by seining. In the shallow area, tha fibrous material, suspended at cne upstraw stations has flocculated onto tha river bottom, coating tha bottom with a "paper wrappii*". Scadon 4 Is located 0.75 mtlas downstream from Station 1. The river Is slightly wider at this point with decreaaad velocity. Fish populations are abisadanc In tha shallow shorelina araas. Thaaa populations ears aaplad by saining. Hater and aadimne stIsa were eoUaetad in tha river, three (3) maters iparrsw from the Inaction of a small strut that flow* In on tha watt shots (1:15 pm, August 13, 1974). Oamdcal Analyala A naaatirad volute of aaacar trie waa extracted with taaaaa. Tha extract was dehydrated, concentrated, and aialysad by ctapucarixed gas chrtmatography/masa spectracetry (QC/M).1 The sedlmant ample was partially dried aad extracted by eolun eludon with a mixture of 1:1 acatona/hnana. The extract was washed with water to remove tha acetone mxi than tha poly chlorinated blphetyls were extracted from tha water with 13 paroant OLfiL, In hernia. This extract waa dm dehydrated, rmrew tracao to i staeaola voiiam, ma aialysad by oonputadaad GC/tB> Tha biota tagla ware blended with anhydrous aodiini sulfate (prawsehad with radladlled ecatcoe) and the htarganafe was at tracted with a mixture of haxmna aod ethyl achar (3:1 v/v). Tha extracts ware placed ot a 20 p florlsil coliaan, eluted with 25 ml *A Mxttflcadcn of madxxls published In WIH0D6 FDR CRGMRC HW n uan An UASIBATER. 1971. Bnrlronaaitsl Ptocacdcn Agency, national bidronmantal Research Cancer, Clndmad, Ohio. 2A modification of methods published In ANALYSIS OF FESnCHS msmns IN HARM AM) nrnknomL SMVUS, I961. Perrins Research Laboratories, Environmental Protection Agaicy. 41* HONS 006521 of hnm, and the volume of the eluata waa adjuatad ao tha final concentration of PCB'a was within tha linaar rang* of tha gaa chromatograph. Tha ample of rock baa* from tha diacharga en quired a SO fold dilution before analysis. Tha presence of PCB'a In all amnia* uaa confirmed by orechlorinating tha samples with SbCl, for four hours at i70c to form Cj^Cl,q. Tha C. yCl.Q waa subsequently analysed by gas ehromagBjrlphy uaing l tfifee-foot column of 3 percent Dexail-300 Subsequently, a QC/HS analysis of tha rode baas extract waa performed along with analysis on Aroclor 1016 and 1262 atwdards. Analysis Results Dstaction of PCB's in wear nd sadtmanta was acccnpliahad by oonparlng camutarlaad OC/MS Spectra of various Aroclor adjctuns including 1016 supplied by the discharger aid EPA with environ mental ample axeraeta. PCB'a Identified as Aroclor 1016 wars found in the water amplaa at detectable ccnemutrationa at all ssnplina locations except Station 0 (control) and Station 4 (furthest downstrama) (Table 2). TABLE 2 Analysis of Hater and Sadlmane Smplas for Aroclor 1016 from the Hudson River in tha Area of Fort Eduard, Naw York Location Contmdnatlcn Laval* Water ug/1 sealant ng/kg tab) tom) Station 0 Station 1 Station 2 Station 3 Station 4 1.0 2800.0 2.2 (3.0)* (3.1) 1.0 6.9 6700.0 340.0 2980.0 6.6 SRaault* of replicate melysls - e quality i At all station* tha aadlaanta contained higher cmcantradona of Aroclor 1016 than tha water colurt bacaua* PCB'a preferentially adsorb onto auapandad or already aattlad matarlala. HONS 006622 Ib* high ccncadnatlen level at Station 1 Indicate* tha a]sorptive capacity and consent exposure of tfaa sediments naaraat tha outfall Co tha Aroclor 1016. Stasa sediaanta vara also heavily laden with noticeable oil and great* which lervts at a eolvene for PCS ecopaixtd*. Ac Station 3, high concentration* (2980 mg/ta) occur In tha edlmanta, reprasntUK acnmilatad level* of PCB'a, 103 fold graatar chat tha outfall concentration, the high laval la a produce of hlatorical pin* praent adaorpticn and dapoaitten of PCS compounds. Tha PCS laval at Station 2 represent! hlatorical deposition mainly. Although PCB'a In tha wacer colum era below dactactabla llades at Station 4, PCS'* occur in alffilflcjnc quantities in tha aadhaanea. Biological Tlaaua Station 0 The saslas collactad above the diacherge contained tha laearaluting PCS'* with retention tdnaa of 84, 98, 104, 112, 125, 148, and 178 relative to pp DDE. Theee are characteristic of Axoclor 1254, another PCS that wa* used eatnsively prior to Axoclor 1016, In aiirUHm. major PCS component* were found at relative retention times of 37, 40, 47, 58, 58, 70, and 78. Tha relative cencanDratlon of the FCB uapenanta fouid In the control station samplas and tha abemire of PCS cuayuiaiita eluting earlier than 28 suggest that die PCB'a in the biota can beat be sstlmetad as a mixture of Aroclor 1258 and Arodor 1288. Using tha latar-elutlng ecqxmanes of Axoclor 1258 and the earlier-eluting eceponanes of Aroclor 1288, die PCS cencantratlane in tha biota unplas were aetimetad and are preairert in TABLE 3. TABLE 3 PCS Concantratiana In Biota Collactad In tha Kidacn River SlslUa O PImIm Nbm8 T*t*l PCS Caltafe4 T.tal Kl !/( Nm< (NHbs CeMte SUait) >BMWI (Mllbll) T.O j7 0 IttllBB t Nm (Ak? OMftll) SliltM I AlM--lHi WHttoU (IbImhm) R#h Ibh) JtBllBB 4 (Nwlktr* Cf*BB Sbiacr) 441 HONS 006523 Distinctly difftrant fran the leaples {ran the control area vara cha aaoplae collected In the vicinity of or halow cha dis charge. It La evidant frem a chrcaatograt of tha saiple of baaa balm cha discharge chat than ara no major FCB canxxmcs eluting 'after 78 relative to DOB. Moiauvu, Cha 21, 28, and 32 consonants ara praaanc In higher concentrations ralativa to tha 37 covenant. This Jiggests that Axoelor 1242, Aroclor 1016, or a mixtun of thaaa mo fornulatlona art praaant In cha Hudson Rivar balm cha discharge. DISCUSSIOW Tha rasults illustrate that PCB's an ubiquitous In distribudon within tha Hudson Rivar within a variety of sihatrataa. Nevertheless, highm-thm-backgromd concentration In tha sadlmanes and biota can ba found in tha lmnadiaca vicinity of the PCB discharge. Although tha pattern of accumulation md magnification of PCB'a in tha biota waa ahollar to that reported in tha literature, insufficient Information exists on trmsfer races of PCB's within aovinosnanCal atheCrates, ibe PCB' a balng discharged an in suf ficient qumddae that centnrination of all tvironnsntal substrataa have occurred: water, sadiamne, md biota. Although an axacc aceunilatton and tranafar modal could not ba datandnad far tha tabling ana, a hypothetical praamtatlcn la given balm: BBJIA DISCHASCf =6-AQUtOUl PHAM (Ada* At all station* tha Moca had higher levels of FCB'a dm tha At all stations tha snail populations an laaortanc acrtmilaLora and eonaantraton of FCB'a (ZABLE 4). Tha apedas eollaccad an primarily hsshivosxus pan, living off tha parlpiwtcn oanig an rocks, limhar subs, and benthic surfaces. Tha malls lngast sadtaanbad matarlsis oontalnlnB tdsorbad PCB's along with thair natml food. 442 HONS 006524 TABLE 4 Ccncandratlcn Factors of PCB't in chs Hudson Rivsr .. Location Station 0 Station 1 (Above Outfall) Station 3 Station 4 -, Substrata Snails Cannon Shlnar Yallow Parch Shells Rode Bass Shells Cenaon Shlnar Ccncsntration Factor Tiasua/Wataf >1.9 x 103 >7.0 x 10? >17.0 x 1QJ 3.63 .98 .41 , 45 x 10J 6.52 117 x 103 .12 >27 x 10? >78 x 103 11.82 4.09 Tha adsorbed FCS's main biologically active within tha food wab atnca snails an anal dietary ccnacLeusnts of larger awn Hah. Ms la a posalbla padmy for blcsapilflcatlan. Likewise, tha PCS'a an raasinlng anvlxanwitally acdva and ars jt takan out of circulation by tha gaoLogic samnantatlen process. An Indication of tha sariouanass of tha problsa in tha Madsen Hlvar la that tha PCS laval In tha Pares flwascaM (Tallow Parch) at Station 0 is 66 tins gnatar dun that found in tha saaa aperies froa Labs Erls (KELSO & FRANC 1974). Tha fish malynd In tha Laka Erie study wan avan oldar and larger dun thosa collactad In tha Hudson River. Tha seat probable routs of ccntadnaden fer fish la through tha dietary padsiay mi diract dif- fuaion across snatnaart gill, intestinal, and intagutant surfaoas. If tha parch cnllartad at Staticn 0 wan oldar and larger, thair source of PCB's adriit ba tha snails, however, snail parch an nairtly plankton na eplfawa censunars (THARRAIT 1969). It la slntlftcane that tha shlnars snd snails both ccneainad fa's, especially alnoa thaaa spaclaa an laportssit granra tpen periphyton enndas and sens as food for large ccnausan, nwaly tha tana fish; l.a., pika, pldtaral, bass, aid largar yallow pan. Tha pa lasal In tha rode bass la gnatar dun tha aastsan laval dunnanrad for flab takan froa any lnduatrlal rlwsr of thu O.S. (ROD i MCTM 197. This npnsnsea a nau record for Pa concnslnation of fvash water fish. -- Alftnugh tha gana flah spaclaa an not cowan:tally urfHaeri In this anacdi or tha Madsen, sport fishing la a cannon wide spread racnatlcnal activity. Ingasden of thaaa Hah by tha populace would certainly lead to ccnearinaelm of specific da- euas In thair bodias. Occurrarm of PCB's in hunan danaa has HONS 006525 docuaantad In tha literature, eapeclally In paopla who ara ocnaeanely amoaed co PGB'a through thalx occupation or llfa atylaa. Eyan trough thaaa cconoinda have a ccaparativaly low acuta tadc- ltjr for mmmala, tha lens tana affacea nay ba nuch mora inalduoua and devaetatlng. A rasher of lnvaatlgatora hava ahem that FCB'a Induce production of liver adcroaaral enzynaa. Othara hava ahown that FCB'a cm dacraaaa Vltmin A ccntmt In tha llvar (CECIL, at al. 1973). Trmeplacmtal paaaaga of FCB'a haa alao bean ahown 7ANT, at al. 1971). FCB'a hava bam datactad In hunai adlpoaa tlaaua In au3i wideepread occucranca that 41-43 paremt of tha U.S. popular!tin contalna 1 ppn or nora (PRICE & WELCH 1972). Little la known concerning the apedflc node of entry of FCB'a Into tha orient ana of tha ccntaalnatad acoayitam. Information on tranefar rataa and nodaa la nacaaaary before a plm of action cm ba rerremanted fear rmovlng tha eontaadnatad athatrataa from tha Hudacn Falla-Fort Edward area. AOMPmEocrcs He gratefully acknowledge and thmk Dr. Barnard Dudanboetal and Mr. David Spate far tha dotarodnaticn of FCB'a in water md aaillllaiH amplaw, md Dr. Oilman Veith of tha Rational Water Quality laboratory at IUluth, (to. for datondnlng PCS Lavala in biological epaclaane. UJESEKE SECTICM ALEXMUR, M.: Microbial Ecol. 2, 17 (1973). OBCCL. H. L., S. J. HMKS, J. BHMM, md J. F. FRIES: Bull, tav. Cant. Ikadeol. 9, 179 (1973). OtART. D. L.. D. C. TOUNEUVE, K. A. MC CULLY, md E. J FHHUFS: Cm. Ihyalol. 1, 61 0971). HANSEN. D. J.. F. R. PARRISH, md J. 5WESIER: Oulf Snare Ehv. Bm. Laboratory Gant. 172 (1973). KELSO, J. R., and R. IRAK: Trma. Anar. Flah. Soc. 103, 377 (1973). -- KMR0U8, R. D.: Critical Ravlawa In Tkadcology 2, 433 (1974). RISK, I. C. T., and A. F. SUDF1M: Cm. Raalth Fanpactivna, Ihpmiaanra! Iaaua 1 (1972). FRICK, H. A. md R. L. HUB: Be. Health Fanpacdvae, fipariaantal Iaaua 1 (1972). TSARMIT. R. C.: Time. Anar. Flah. Soc. 88 a939). TROUT, P. E.: ta. Health Parapacdvea, Experimental Iaaua 1 (19*2). ~ 444 MONS 006526