Dioxins and furans in fisb berow Love canar, New york: concentration reduction forrowiug renedíatio¡.
Lawrence C. Skin¡er New York state Departnent of nnvírãnnental conservation S0 Wolf Road Albany, Ne¡r york L2233
Subnitted i"¡ compretio¡ gf project titled ,Dioxi¡s ôibenzofurans in ca¡ruga _t-be a¡d evaluation crãet fishrî ,L-i.u is o¡e part of an of tue etrectiveness of remedial activlties associated with the Love canal area, r¡i"g.ti-r"iîJ, Nes york.
Augrust 1993 ABSTRACT The cayuga creek drainage.basin ¡¡aters has served.as the receiving for leachates_originating-.arnong-tn" frorn-ihe inactive hazardous waste site known as Love canal. numerous compounds originating frorn che¡nicar 2,3,7,8-tetrachrorodibenzo-p--aioxin'.the site, €nã- mo;t-t;;i; i= the efficacy of remedial wolk õ-;a ,7 ,8, -TCDD) . To examine ¡nonitori!9 or "==o"iàiåà'ritú r,ovã'canar, _young f ish f or dioxin=-ana dibenzofurans hras conducted. of the chemicals examinã¿,-"ùn" ;lã-;;pouna for Love canar *¡as 2,3,2,g-TcDD. lilønostic2'317r8-TCDD concentrations Decrines in averaged zo percent between 1992 and L987, and further decLines ¡etween 46 and 86 percent occurred between L9g7 and 1992-defendeni-or-i"""tiãilanglnf basin. The reductions h'ere consiètent i¡ tt" encapsuration -.rrawiirr õñi;ãïon of of the Love canar site, rater'õiãã"i"g of storm ¡¡ater drainage systems and rernovar oi ttre most hi;ñit contaminated sediments from reduction tribuiaiies--or cayuga creek. Totar of 2,3,7'8-TCDD concentrations h¡ere 84 percent or more.
L :TÀBLE OF CONTENTS
Page ABSTRå,CT i TÀBLE OF CONTENTS ií LIST OF TABLES l].l_ LTST OF FTGT'RES v TNTRODUCTION 1 IIÍETHODS 2 Sanple collection 2 Chemical analysis 3 Data analysis 3
RESULTS 4 Fish collections 4 Dioxins 5 Dibenzofurans 6 2,3,7, 8-TCDD toxiciÈy equivalents 7 DTSCUSSTON 7 2 g_TCDD ,3 ,7 , I Dibenzofurans 9 Other inrpacts 10
coNcLUSroNs L2 ACKNOWLEDGEMENTS 14 LTTERATTIRE CITED 15 TABLES 20 FIGT'RES 47 APPENDTCES ii 49 LTST OF TÀBLES Table Title Paqe
1 Mean concentrations of dioxins containing the 2 ,3, 20 7,8-chloro congener group in Voung_ol_irrã_y"", fish from rhe cavuga-creãk dråin;ée-b";i;,'ñiãg.r" Fal1s, New york.
2 Mean concentrations of arr._dioxin congeners in young- 24 of-the-year fish from the cayuga creeÉ arainãge'ùã=írr, Niagara Fa1ls, New york.
3 The relative contribution of the 2,3,7,g 27 -tetrachroro congener to totar aioiins-ilãh and totar dibenzofurans- in-young-of-the-y"át from the Cayuga Creek basin, t'tiagara faits, wãw--york. 4 Comparison of mean 2,3,Zr8-TCDD concentrations 28 in yogng-of-the-year. cypiiniform-ilsñ--ior arr l_ocations by yeai ot coitecrion, óãvgã=õr;;k basin, Niagara Falls, Neq¡ york 5 Comparison of 2,3,Zr8-TCDD concentrations in 29 y-oung-of-the-year cypriniform fish over tine for the Cayuga Creek dráinage basin aãwnsiream of Love Canal, Niagara FaIIs, Nerrr york. 6 Comparison of mean concentrations tetrachloro of 2,3,7,g_ 30 -- containing heptachrorodiúãñzðaioxins-Uy _i1 ygung-of-the-yg_ar cyfrinir"r.-ii=t y"", in Little River and the Cãyuga Creek basin] Niagara Fa}ls, New yorkl 7 Conparison of mean octachlorodibenzodioxin 31 concentrations in young-of-the-year clprinifor¡n fish {Tor cayuga creek and Berghortz creek ä"ri"g-igelr-'" Niagara Fal1s, New york. I conparison of mean concentrations of octaehrorodi- 32 benzodioxin in young-of-the-year cypriniforn fish in the cayuga creekbasin over tirner- uiãgara Falls New York.. r
9 Mean concentrations of dibenzofurans containing the 33 2 ;3,7, 8-chloro congener group +n young-of_ttre_feãi- fish from the Cayuga creãk alainale básÍn, Niagara Fa1ls, New york.
1tr- labl.e TitIe Paqe
10 Mean concentrations of alr dibenzofuran congeners in 36 young-of-the-year fish from the cayuga creeÉ drainage bãsin, Niagarà falls, New york. 11 con¡rarison of concentrations of dibenzofurans 39 containing the 2,3,7 r g-tetrachloro group. in young-of-the-year. cyprinitãin'iisñ"orrgãrr", ¡V locatíon, cayusa creek-arainå|ã-bã;ñ; ñi"g"rå Fal]s, New york. T2 2,3,7r8-TCDD toxicity equivalents and percent 42 contribution to 2,3,1,e-TcDD toxiciiy ãquivatents by Z13,7rB-TCDD and 2,3,4,2rg-pCDF i; young-of-the-year fish from cayuga creek drainage basin, Niagara Falls, New york. 13 Comparison of 2,3,Zr8-TCDD concentrations in 44 cypriniform fish from the cayuga creek arainage basin by year, Niagara Falls, ñew york 14 Percentage change in Z,3,7r8-TCDD concentrations 45 nrith ti¡ne in cyprinifoim'f ish from the cayuga creek drainage basin, Niagara Falls, New iõiX. 15 Cornparison of 2,1,ZrB-TCDD toxicity eguivalents 46 in cyprinifor¡r fishàs from the cayûga'ðieex drainage basin by year; Niagara Fa1ls, Nehr yõrk.
tv LTST OF FrGT'RES
No. Titl-e Paqe 1 General and specific area of study 47 for assessing dioxins and furans rn young-of-the-year fish from the Cayuga Creek drainage basin. 2 Sanpling siÈes for assessing d.ioxins 48 and furans in young-of-the-year fish from the Cayuga Crèek draináge basin.
v TNTRODUCTION
Love Cana1 is an inactive hazardous waste siÈe 1ocated in Niagara Falls, New York. The site achieved national notoriety in L978, and thereaft'er, due to perceived human health iurpaãtÀ-i,o=-- residents located adjacent to Lt¡e site. The human health irnpacts are believed to be càused by the disposal of chenicãi wastes by the former Hooker chemical óorporatiðn (the ,ror owned by occidentat chenical corp.). The esti¡oãteã-äi,äéo-tons"orp-tty-i= of chenicat wastes disposed iir íove canãi-i;;i;ã";-ñ;;s orhers, chlorinated solventé, oirs, chlorouenãenes, hexachlorocycro_ l-ï11::, polychlorinared biphenyls (pcBt , and rrichlãrophenot (NYsDoH, 1981). Dioxins aré coñta¡nin"nts of trichlorophenol (Firestone, LgTz; Rappe et ar., 197gà)--and dibenzofurans are contaninants of pcB (Èowes et al., tgisa and 1975b) ãnd chlorophenols (Rappe et aI., Lg7gi. Itater and leachate from Love canar entered d_raiTage the cayuga creek basin via storrn drain aiscnãiões to Brack creek" The chemicals trere subsequenlly distribuaãá srrc"e==i.rãry-to dovnstream waters and sediinents Ín.aerjnortz creek, cayuga creek, the Little River and the Niagara nivei] rn preriminary work, crayfish from Berghottz creeÉ irnnediatety doilnstreã¡r of Black creek showed pg/g of 2,3,7, B-tetrachtorodibenzo-p-aioiin (2 8-rcDD)1zg0 (NysDoH, - '3 ,7 ' 1esí) . subseq"""i-il;1t;ï!-or rish demonstrated 213,zr8-TCDD concentratións as greát as pglç, (Kuzia, orKeefe et êr., 113 anatvzed._1995; 19g3). ôiuenzorurans were not rn w!or9 carp from tne íittle Rivei,-ð[ãrii"g ¿iõezl reported 644 pglg totar dioxins of which en pâlg was contributed by.the 2,?,2,8-TCDD congener. Further, ttre cäíþ-coñiained 1019 pglg totar dibenzofurans which hrere principaiii-"ãrpiisea or L r2 r3 I 4,7r8-heïachloro-, !,2,3, 4, 6,7-ra-heplachioror' octachloro - dibenzofurans. ãnd Extensive remedial work has been conducted in the environs surrounding Love canar. The site has been encapsulated, arl known drainage terminated, a leachate collectioi anà treatment system installed, and homes most rikety to be irnpãôiea rrere destroyed. Remediation also included ðleaning-t,ñe-=ùrm water drai_nage syst'em and removing soils and sedir"it=--irãr'trr" cayuga creek basin (Black and Berqhortz creek) where 2,3;7,e-tcpo concentrations exceeded r.õ part per uittion. To evaruate the effectiveness of these rattei actions, a monitoiinj'progr", ,"" instituted which incorporat,ed fish as one cornponent. This latter study and its findings are reported here.
I METHODS Sanple Collection
Young-of-the-year fish v¡ere collected by the NyS Departnent of Environmental conservation's-negion é fisñeries biorogists. cotrections were made ar seven locárions il-Ëñ;-õ;ñ;; creek lla]nage basin in october of the years igez, 1990 and Lsgz. The 1987 cotl.ections r¡ere made prior t,o areaginó õr- Àrãär Bergholtz creeks" The 1990 and "na successiyely 1992 colÍecf.ions srere one year and three years pãst-dreaging. Fish $¡ere collected at the forrowing six slaiiã"-=-i" arr Étriãe sanpling years (see Figure 1 and 2l: Station No. Location 1 Little River upstream of the nouth of Cayuga Creek opposite the southern tip of Cayuga Island 2 Little River downstream of the mouth of Cayuga Creek 3 Cayuga Creek at the Lindberg Avenue Bridge 4 Cayuga Creek at the Cayuga prive bridge 5 egrgþ9llz creek approximátety 100 netérs west of !{illiarns Road 6 Cayuga Creek at the porter Road bridge rn 1987, the seventh station, _cayuga creek upstream--Ë", of Lockport Road (a contror location), did nôt-"ontåin risr¡. 1990, the station ltas moved to the-Ñiagara nivãi-upstream of Little River as a control- rn Lgg2, the étation was leturned to cayuga creek upstrearn of Lockport Road where brook sticiiãËãðx-1cJr"u inconstans) were collected. \-' Due to differing habitat and fish-habitat preferences, the fish species avairable differed between station's in ãny given )r.ear. -.Ii"t.population structure fluctuates from và.i to year thus differing collections.of fish nere expected between years. Further, the dredging activily"p"ði"= modified thä avairable habitat aL severar statioñs útricn resürled in further a].teratÍon of fish species ared popuration_compositigr, rn 1992, young-of- the-year fish hrere not avairable iñ sufficieni for chemical analysis at four rocations. Therefore,"ür¡ãi= order aged fj.sh (norrnarly ageã.r+¡ lrere coLrecred to fitl saurprin!-;;;=. order f i=lr_ may- introduce grearer dara variabiiiat .á"Ë-to potentiarJ.y."ggd longer duration of chemicaJ. exposure " greater nobility of the fish. and to the Fish htere collected-by use of electrofishing gear or seines as appropriate for the site conditions.
-2- À11 fish corrected were measured for total length to the nearest nillimeter. Fish rvere placed into compo-ité sanptes species at each rocation. A.coirposii"-r"igñ¿-ãi-;ñt""ii,ãtãry'soby grams was desired for analysis identification but not alwãys o¡tãiñea. À pertinent number was -ãssigned io-each composite sample.""iq"ã AII data v/ere recorded oñ rrishTwildlifã'córiãction Recordrl forms and 'rchain of custodyrr forms (Àfpendix r) rãiã conpreted for each transfer of the sárnpres. È"ii"winj iå"ãrãi"g of data, the sampres were praced on häxane - rinsed ãluninun foir, wrapped, labelled and placed on ice. arr sàmfiã=î"r" frozen at the end of the 9.y" sárnpres stere later transferred in a frozen state to the HaLe creek rieta station, cloversviii;, Ny. At the stati_on, sampres were unwrapped, gro,tåa whore, tãroé"nized, repackaged in sorvent-rinseá-glasã jars and frozen. The processed samples ü/ere shipped_by elpress overnight aeiivery to a contract taboratory (rriansie LaËoralãii"=; ñ;:;--ñesearct¡ Triangle park, worth'caroIína) for ;h;i;i ;;ii=i;: Chenical Analvsis chenical _anarysis for tetrachroro-through octachloro- congeners of dioxins and dibenzofurans v¡ere óonducted by methods described in "Nationar Dioxin study Ànarytic"i p;;;ãures and qgllity Assurance plan for the anaiysiÀ ot 2,3,7,8_tcOD,, (EPA/600 /3-851 o9', but with one modiiication.',itrå-rðãification substituted chlorhydric acid in sampie aigestiã"-tä-prevent decompositÍon of certain dioxin and furan congeners" This nodified method has become known as gpÁ Methoá 8290 (u.s.E.p.A., 1e8s) . Àrt resuÉs were reporred in unirs péiá- 1åquivãrã"C ú" parts per trillion) on a weL weight basis tor"t ãáäñ inaiviauar congener or congener group. Data analysis
The data. produced may have one of severar quarifiers and thus are treated differently. where a concentrátion i"-q"ãiified as an rrEl{Pcrr (estiruated maximum possible concentration) ialue, i¡ was assigned a value of zero sinðe identificatiãn-ði-tit" did not comply with criteria for positive identification. "otgårrãiAll non-detectable concentrations were assigned a value of zero for cal.curation purposes. t{here aLl varues for species are at, ress than detectable quantities," """gã"ãr -tñ;--i.rgest ana detection linit is reported_accornpaníed by a råss inã" i.l sign. rn some instances the carculation of ¡neané where sone sampre results are less than detection would result in a ,"år, concentration that was less than stated detection linits. It r¡as judged that these values hlere reasonable approxinations of likãit true concentrations for the population ueii| evafuaãÀd and do noÉ add substantially to overalr cóncentrations of dioxins and dibenzofurans or to their toxic eguivalent,s.
3- rn some_i_nstances,- particularry the 1992 contamination was noted.- data set, blank frequentry Brank occurred most for ocrachror"aiÈãnä"ãi;;il;"""l"rination arthough in one case heptachlorodibenzodioxin was signiriãaåtrv a associated with contaminul:g -ii" .rráðtãä. For sampres congener uiá"r=, datum for the affêcted was modified. wnårÀ sampre"u^pIe data hrere or equal to-ãiscaraed two times the ress than-[ñã data ï"i" by ;;=ï;fi;n:"$åil"oåÊ"I";åTnt3rí3:"åi: blank contaminltigl.wäs ' genãrarÍy at iãw concentrations where anarytical variability cóurd be ås r"ãt, as approach above was 1ooå, the conservaÈive raken. wlrerg_="rpiË datã ,ãå õ.ã"t", than two tines the corresponding- sampte utani^vãtue, the subtracted frorn Lhe coirespänaint.säôr" brank varue was calculation concentration prior to of statistics. rn tñis tåtter instance, sampre data was normally substantially greater than the btank contanination value. Ttre aforementioneä áata tr"ãir,änts had a negrigibte iurpact on carcurarion oi-toxic and treatment of sample comparisons.d;ñ;î;nts ¿--'--- staristicar since data sets nere for specific locations, species or years often sma1l, standard-param.tiið-i"sts to evaruate statistical changes hrere nol appropii.i". À non-pararnetric the Kruskal-Irrall-is test, was Ëäã-ã;-;-measure test, differences within the á.i. of statisticar Fish eollections À total of nine species The predominanr of fish were corrected and analyzed. specieË was bluntnose-nãàr ;ñ";;-?"Irãinlr..= norarusì taken from seven. ór eigrrt stations. (Ambroprites rupestris) was the secõnd þass (four stations). most- trequeniiy caugtrt fish speci.es largely from the Niagara River - r,ittre River areas. Due to their general absence-riorn cayuga creek, rock are excÌuded from statistical cornpari-óns bass years. The uetween locations and arewife (aroæ_Feug"ñarènqüs) was ,ãprã="r,ted as only one sarnple in rde7. rhê-ãm excluded comparisons since they are beli".ràã-io-ue for statistical Erie. nigiÀ"i=-iio, Lake
changes in. fish popuration structure over ti¡ne were anticipated. cirairges refrect differences success as affected^These by in reproductive coorer, weather and habitat ¡nodiricaiitns. wetter weathei than normal occuirea in ttrã-ãiea auring summer L99z- This may have contributed to srnarrer anticipaÈed nurnbers oi young-of-rhe-yeàr iñu' correct,ion period. tisn-ãüii"õ"tn" year . To óornpensate roi ttre lack of young_of_the_ fish at certain locations, older ajea fish were taken. 9there older fish hrere analyzed, ttre the tables" iniór¡ration is footnoted in
-4 The most significant habitat nrodification was the 1989 dredging of Berghortz creek t.o remove sediments containing- excessive concentrations of dioxins (Division of názåraous l{aste Renediation, 1991) . As a conseguen.ce, the fish pãluiation changed frorn one dominated uy gõtaen åhiners 1l¡oliiràqonus crYsoleucus) to more dj.verse põpulations with'b1t¡ntnose n¡innow and common shiner'(Notropis córñutus) as the most common species. Dioxins Mean concentrations of dioxin congeners containing the 2r3, 7,8-ehloro congener in the young-of-thã-year ristr ¡v-rócationr-' fish species and year of coireci,ion aiã ñoted in taËle r. corresponding mean total dioxin concentrations Èv-ðóng"ner group for these fish are provided in Table 2. ol a species basis, the rock bass, a predatory fish, generalry contains the greatest concenùrations oe tnã lower chlorinated dioxin congèner groups. The 2,317,g-TcDD levers are generally at least two times concentraúions found in ¡ninnow species. I{ith the exception of a white sucker (catostomus çomnersoni) sarnple from the Littte River aownstiãliñ]uga Creek, there is relative consistency of reported concentrations of each dioxin congener group arnongËt rninnäw location and year. =pã"iã=-within
In a comparison of the_suq o! 2,3,Zrg_chloro congener dioxins (Tabre l) with totar dioxins'liaËre z¡, at lãast Bog of the total dioxins found were composed of the 2',3,zre-chroro congener groups in 819 of the 43 comparisons 1iaËre 3). The remaining eight comparisons containeä the 2,3,7,g-chloro congener groups in amounts ranging from 54 to 73 percent of the totaÌ dioxin found. The distribution of-thesã rãttãr eight observations is random. Therefore, distribution fãtÉ"rr,' observed for the 2,3,?rg-chloro congener groups are equally applicable to total dioxins In 1987, prior to sedi¡nent dredging, the greatest concentrations of 2,3,7,8-TCDD hrere iouñå in nãrghortz creek (36.4 Ppt) with progressively lower concentratioñs downstream towards the mouth of cayuga creek (Table 4). subsequent to removal of highty contaminated sedirnents from aerghóItz Creek in l:989,. 2,317,8-TCDD concentrations in Berghortz crãek fish declined to levels statistical).y the sarnã as those ior controt areas_of cayuga creek (Table 4). I{hen age 1+ fish are excluded, significant (p <0.05) decLines in 2,3,7rg-TcDD concentrations have occurred at and downstrea¡n of Love Canal. These declines occurred between rg9z and 19g7, and between LggT and the tt¡o succeeding collection periods (Table 5) "
5 There are^no spatial or temporal differences in the distribution of penlachlorodioxiirs-ãrra- n.*"chlorodioxins. In most cases, these.two groups of compounas are at concentrations near or bel0w their respecLive deteätion linits The heptachrorodioxin_r.evers reported hrere armost sorely composed of the ,2 ,3 , 4 , 6, 7, g_heptacñfãro_congener. Heptachlorodioxin.L concentrations- -ä;iãúr" year r"rä-trighit from year to at locations in the Little ni"Ër-anã downstream cayuga creek. rdo ternporal trend was heptachtorodibènzofurans disc"rrr"¡t". o;-ã basis in tnà-iiiiïã-niver and rhe=pãtiar mosr downstream cayuga creek station concentrations significantry (p_io-¡itiii;õ"rg Àvenue bridge) were at and gieater than in upstream controt locations durini ò'"rr"åiiår, y".== 1.e87 and 1992. There hrere no significant airrerãnãã=-Ï" heptachlorodioxin spatially during t99o (Table 6). levels octachrorodioxin (ocDD) was observed in fish at concentratÍons that were conparable 2,3,7,8-TCDD. to or greater than The greatest èoncentrãiior, *u= rls pg/g (TabLe 1) spatial differences in ocDD levels occùrred " concentrations_increased progressively- in ße:7-änry. ocDD creek lpco. ost downstrea¡¡ in highly!1vuga _(TabJ.e 7) . õcpó revets in the Littre River ¡rere variabie in ari three years sanpled. The ocDD revels significantly (p<0.05) aecrinäa itr itä-aownstream l0cations frðm-Zr.g pilg cayuga creer< in Lg87 to non-detectabre lãvers in 1992 (Table B) " Dibenzofurans
Table 9 provides a summary of mean concentrations of 2,3,7, B-chroro congener contaiiing year fish_by location, ãiuãnzoruran= irr-vorrrg-of-the- fish =p""iér-ãtã-y"u, of correction. The corresponding totar dibenzofuians uy ôãngener group are presented in Table LO. The 213,zrg-tetrachroro congener containing groups make up a substantially smaller part of toial furans than-iñ corresponding comparison of dioxins lraure a¡. iné-ã,3,7,8-tetra chloro groups $¡ere the priurary dibenzofurans9ongener constiiutents of totar il glfY ^a:7 percent of the comparisons. Approximately 46.52 ór tne-comparisons contained lãss than 40t of the 2 r3r7 rB-congener groups. contrary ^ to dioxins, l? single fish species appears t,o preferentially accumurate dibenzófurans. iear to yäar variation in concentration of the various are snalr and non_ significant" _colgequently the data";ù;;;s for cypriniforn fishes for the years L987, 1990 ana rggz $rere conbinéã to examine spatiat differences in distribution containing the 2 q3 7 8-tetrachlor_o. congener"{_tlrg (Tabre "otfãn"r.groups ' ' 11i. rién rion-iire Littre River and Niagara River tend Èo have-tieater concentrations of 6- dibenzofurans than fish in the Cayuga Creek drainage basin. This tendency is statistically signifièant (p <0.05) foi hexachroro- dibenzofurans and octachlorodibenzofurans. For heptachroro- dibenzofurans, a greater variation in concentratioñ was encountered. rn addition, reported concentrat,ions of each congener group tended to increase with increasing degree of chlorination, particularly for sarnples collected in tfre Little RivgT and Niagara River. rt is apþarent that the prirnary sources of dibenzofurans are locations other than the Love- canal. 2.3,7,8-TCDD Toxicitv Ecruivalents Due to the large differences in the toxicity of congeners of dioxins and dibenzofurans, the concentrations of the 2 ,3-,'l ,g- tetrachroro - containing congener groups nere converted to 213, 718-TCDD toxicity equivaJ_ents (Table 12) using the internationar toTicÍty equivarency facÈors iir u.s.É.p.A. (19g9b) The toxicity equivalents range from 0.89 for a control loèation' " in 1992 to 37.6 for Bergholtz creek in L}BT prior to renoval of dioxin contaminated sediments. The doninant compound contributing to the carcul.ated toxicity equivalents is 2,3,7,8-TCDD. Àt the two downstream locations in cayuga creek and in the LggT coLlections from Bergholtz creekt ?,3,7,8-TCDD generalry provided 90 percent or more of the toxicity equivalents. rn upstrean cayugá creek, LÍttle River and in 1990 and 1992 colleätions froin Éergholtå creek, 2,3,7r9 - TCDD contributed about s0 to g0 perceñt of the toxicity equivarents. rn the Niagara River upsträan of cayuga creek, 2,3,7r8-TCDD was a minor constituent còntributing auout 20t of the toxicity equivarents. rn the ratter case, z,z,4r7 rg pentachlorodibenzofuran was a principal contributor that próviaea 40 to 5o percent of the calcurated toxicity equivalents. In 1990, the influence of dioxins fron the Cayuga Creek basin on fish from the Litt1e RÍver is evident wheñ ã conrparison of data for the Niagara River and Litt1e River is made. ioxicity equivalent,s in the Little River doubled those observed in the Niagara River. Further, the relative concentration of 213r7rg- TCDD increased by at least four-fold in the Little River compared to the Niagara River"
DISCUSSTON Based on the foregoing information, it is apparent that 2, 3 r7 n 8-TCDD is the only dioxin or dibenzofuran congener that can be conclusively associat,ed with the inactive hazardous r¡aste site at Love Canal, Niagara Fa11s, New york. Therefore, this discussion will focus priurarily on 2,317r8-TCDD.
-7 2 ' 3,7,8-trCDD rn a review of remedial activities conducted in associat,ion with Love canal, the Division or Hãzãrão.= (1991) waste Rernediation noted that, encapsuration of the Love canal site was completed during L97g and 1980. These activitiÀÀ incruaed instalration of a leachate collect,ion and treatment systen. sanitary and storm- se$¡ers, includi"õ--ttr""e and aisðnãrõi"g to Brack Bergholtz creeks, $/ere cl,eaned ír, igeo and 1997. These sehrers contained as much as sediments. 600 nglg 2r3,7rg-TcDD in the point Brack. and Berghortz cíäe*s were dredged fron the of interception of Ãtorn r¿ater arainãgã-ãiðr-ti.e Love canat area downstream to the junction with cãyuga The creek auring-rõeõ.---- linear distance _dredged was .ppi""iinaÍ,e1y 3oo0 ,ãt".= (NYsDEc, 1990). sediment concentrãtions Berghortz ot 2,3,7r8-TCDD in creek, and itrs tributary erãcr creek, averaged 380 P,glg with areas in excess r ppti -rtr. main creek downstream 9r =å"n ãi c.yrrg. of Bergholtz ciäek .""t.i"ã a á ,i-,2 ,ã-rcpp concentrations averaging 3o0 pglg. nxðlucring ãiãú.úãa dioxir¡ concentrations at the rnouths i¡ã'étorn se$rer creek conÈained outfalrs, cayuga 213 pglg i,317,g-TcDDt in sediments (calculated from"!_av_erage Slack, isae¡. ' rn a comparison of 2,3,7rg-TcDD concentrat,ions in Qpriniforrn fish (Tabre rå1, åubstantial aecrines TCDD in z ,3,7,8 levels have occurred àuring t'tð pãrioas, i.ã.-igaz to 1982 and 1987 to L992. The declines-"*riA"ñi- in eårgtrðitz'creek fish and fish frorn downstrearn portion? ãi-ôãv"ga creek correspond remedial activities associated with initial period, with r,õ"å canat. During the Bergholtz creek experienced 2 13,7rB-TSDD dectines of approxinately 68 percent. an aäaitional eå ieicent decline occurred between l-997 and subsequent.years. coirãspänaing-- - decrines in cayuga creek qrgrg approxiínatery 22 and 46 percent,, respectiv-ely. overalL, 2,3,2,g--icDD in young-of-the-year fro¡n Bergtroltz creek has decrined fish year a¡oui 96 percent in the ten tiure frame between rggz and Lgg2. Deciines in-ôayuga creek h¡ere 84 percent (Table 14). I{hen all the dioxin and dibenzofuran data is converted to 2, l'Zr9:TcDD equivalel!,s (Tabre 15), the decrines noteã tor 2,307, 8-TcDD are essentiarly unchanged.' This is àue t;-añ; general predominance of ln the computatiorr-ãt- à,t toxicity equivalents-2,3,7-,8-TCDD (Tables 3 and L2r. rzr8-TCDD The New l?rr state Departrnent of Health (NysDoH) uses a criterion of ro pglg 2,3,7-,g-TcDD or its equiialeñi='." guideline for protection oi hunan consumers of fish. I{hire" young-of-the-year fish are not normalry consumed by humans, it is evident that 2,3,2,8-TCDD values in tiSn from the downstrean portion_ of_cayuga creek.approximate the NysDoH criterion. older age fish of edibl9 specieé-tnat reside in the lower reaches of ca1ruga creek coul.d be expected to contain greater revels ot z rs, -8 ?r8-TcDD due to their greater duration of exposure. Based on this liketihood, and tñe existence of erevatèd dioxin concentrations in sediments prior to and during 1986, the posting of Black and Bergholtz creeks against, public aña angier access was warranted (Division of Hazardous Wàste Remediat,Lon, 1991) Further, the NysDoH health advisory against eating fish fron " Ca¡ruga Creek, (Horn and SkinleF, 1985; NVSOOH, Lg62) is appropriate until data on edibte fish of edibieTregår sizes is obtained that wouÌd dernonstrate a different concluãion. A study to examine dioxins in older aged fish for human health purposes is recommended as a follow-up effort" Newell et aI (1992) developed criteria for chemical contaminants in fish for the protection of fish-eating wildlife. The criterion for 2,3,7,8-TcDb is 2.3 pglg. young-oflthe-year fish are commonly foraged upo! by spec-iãi-suctr as-rnink, neiring guLls, herons, cormorants, and oÈtrel fish. Based on the criterion of Newell et ar (1982), young-of-the-year fÍsh from the lower portions of cayuga creek and-froñ Bergholiz creek continue to represent a threat to the health of piscívorous wirdlife However, the threat in tggz is substantialry reduced when compared to 2,3,7 r8-TCDD values observed in-earrier years. The fact that in 1992 fish from the lower reaches of Calruga Creek continued to contain elevated dioxin concentrations anâ t!"!.older aged fish are tikely to contain greater concentrations of dioxins suggests that furthár re¡uedial wórX may be necessary. However, the last renedial activity directly irnpaèting the sträa¡n occurred in 1989 and declines in dioxins aré documentãd between 1990 and L992 (Tabres 13, L4 and 15). rt is suggestive that reductions in dioxins in fish may continue and tñat dioxin levels may reach acceptable levels from a human hearth perspective at some time in the future. verification of this süppoãition snðutd be conducted in the future, perhaps 1995. Àt thiä-tine, it ,""iã appear to be inappropriate tó conáuct additional rernãaiåf work with Cayuga Creek sediments in the absence of data which would negate the hypothesis that further declines in dioxins Iikely. are Dibenzofurans No criteria exist for acceptable levels of dibenzofurans in fish for-the protection of fish - consuming wildrife" The substantial concentrations of dibenzofurané observed in fish from the Niagara River and LittLe River in this study (Tabres 9 and 10) and by suns et ar (1985) (i:e. up to 3L79 pg/g total furans) are suggestive that further evaluation of dibeñãofuran toxicity to wildlife and development of criteria protective of nrÍIdlife- are necessary. Since Suns et al (1995) áia not find a correlation between dibenzofurans and PCB (dibenzofurans are contaminants of PCB as well as other courpounds) in fish fron the Niagara River, it can not be assumed thal critäria for pCB will -9 subsume dibenzofurans. The use of an arternative (213,7rg-TcDD åîiå;å:i";silriiiË!!l ":ii recommended a criterion!s'ii,ll*i:"ï"i:îi;!: of 2.3 ?Íåifí¿î;ö"' acceptable rever for piscivorou!-i+írarire.-lgjg ãã'rcoo in fish as an rs accept'ed as ü üG concentration toxicity equivaJ.eni;;-ü"n fish tiã, the Niagara River and Littre nivãi'"ãrit"ir, concenrrarions dibenzofurans for fisñ ããnsuning";;;å=i;e of toward source ,irãiir". Further efforts idenrifi"uiiott ;;ã ;;;tiål appear warranred. Other impacts The criteria of Newell. et.al (1987)"ãår.i'ogènesis for protection wirdrife is based äõ"iå toxiði.t1),, of chronic irnoacts potentiÀiiy"" and/or dioxins präsent irazaras-t;'"iIäîiä."{nåt".,r=ãá'úv-Iish consumption. However, christian are not iistr consumers. (le83) observ"ã reduced expectancy of voles in crose=iõ"i;i;;"tü proxinity density and rife compared to control group to Love canal when deveroped fatty3. aegeneiãiio'ofoñe urile åruy. The same vores glycogen the livers, severery reduced (a rnajor én"r!y-=o,rr"" in aii anirnarsl-rã.rår= reduced weighté ot sevãiai viiãr-ãrõåi= in rivers, controls, and proportionatery r¡hen compared ro than nare voleË. -pioiir,-ãorr."rrtrationsrot"-ñãrãr" vores äyir,q pr"*aturery measured, hovrever, qualitativ" Ín the ,oiã==r"re not hatosenared hvdr"ð"f¡ð"=;-i;;i"äi;;'ìå;seãn"i;;Ë found ,iãã array of hexachrorocvcloh.*.néÃ--1íi"a""ã-;;_ã";;i suanriries" or latter compäund= rãrð-aìJio="a compounds) . These quantity ii r,oie-canat in rhè J.argesr and were found iir_so_ir,;;t;;, reachate vicinitv of Love. canar l'isoon,'rðõiil' pioxin-r"=-'}=oand air in the in soil, sediment, watei ãna reactraiåÀ re¡rorred inpact on the voles thus may arso exert an with regard to fisheries, the dioxin beÌieved to Ée one of the najór-;;"I;ititor=source at Love canar is concentrations in Lake ontarío to observed dioxin of young-of-the-yer-r ri=ü.--ir-",rrr" 1981 to 1983 corrections spottaii-=ñi;;;=, et (198s) demonstrated tne ðayuga ar of 2,3,7 !!"1 creek aråinage was the najor source '8-scDD in the Hiàiar" nivei-Ëã=-t". priraary source of 2,3,7,'-T.DD to Lake oni,ario i=-"iã-the Niagara-The number of investigators (orKeefe River. À 1984; et ãi. ] rser, snith et aJ.., Stalling e! âI. , rdeg; DeVault et.'â1. 1989; zacharewski have denonstrated, and 2,3,7,s-TcDD"l-ul:,_1989) in an array of fish-;Ë;i;;, the presence of concentrations present wirh grearesÈ species. in rake troüt-;;ã four other salmonid rn Lake ontario iare ti"ùi,-öyr"rg et ar (19e0) siuronin (1ee0) documentãa Ët.r" aísãåse inciaãncè-i' and eggs r¡hich resulted in nearry so=ac per;;t'urortarity hatching sac fry- This is consistent with of rake trout "u=ãrv"a reproductive
10 inpairnent in Lake ontario (Marsden et ar. 1988). BLue sac disease has also been reporÈed in take trout from the upper creat, Lakes (Mac et al, 1985) as have reproductive impairment (Jude et 3l: r 1981r' Nestor ?nd-poe, 1994) . walker and päterson (iggo) believe chrorinated dioxins, furans and biphànyrs-á;;--ótn"t sitniiícant contributors to the incidence of blue sac ãiseäse. causes that have been associated with the disease include cvtoÞþaqa psvchrophilê the bacterium ($Iarren, 19g1, slnaula et ar. r--1990), a'¡'uonia from metaboric wastes and imiroþer egg incuú.àion ternperatures (vtorf , L9s7) . However ,- 2,1r7,g-TcDD has been definitely linked_ with production oi uiuå sac dise"=" ir, ãarty Iife stages of lake trout in l-aboratory experi¡oãntãiion (I{alker and Peterson, r99o; warker et.ar., 1991; sþitzuergen et ár., 1991). The lowest concentration of 2,3'rzrã-tcoo-ír--"gg= that produced blue sac disease was approximaÈ,eiy 40 pglg. rn the absence of a known relationship-between 2,3,7re-úôóO concentrations in adurt rake tiout and rake-tiout eggs produced by the same fish, one could assume a 1:1 ratio. rn-i,tri!-;;;r- lake_trout ggg: examined by syrnula (1991) and si¡nonin (1990) could contain 213,z,g-TcDD coñcentrátioni in excess of 'ao pglg, and potentialLy in excess of roo pglg for some sanpres from fish with_highly erevated dioxin levels. since symula et al (1991) and simonin. (1990) did not examine 2,3,7,8-TðDD in lake trout eggs in their studies conducted fron LgTg through 1984, and since +FaPÞêga psvchrophiLa was detected in only the 1984 samples from Lake Ontario used_by Symula et aI" (1991) ãnd lastIy because adurt lake trout from Lake ontario have the greatesl 2,317,g-TcDD concentrations of any of the Great Lakes (Devault et ai., igeg; zacharewski et al", 1989) the role of zrziz,g-TcDD in proauctiån of brue sac disease in progeny from Lake òni,ario lake trout cannot be ruled out. rndeed, it appears that 2,3,zrg-TcDD may be a significant contributor to reproäüctive inpaiimånå in lake trout from Lake Ontario" - For 2,3,7r8-TCDD toxicity, rake trout are the most sensitive fÍsh examined-to date (vÍarker et ar., 1991). However, sinirar reproductive impacts at highet 2,3,7r8-TCDD concentraúions in fish eggs have been observed in laboratory experimentation with rainbow trout (Helder, 1981) and northern-pikä (Herder, 19go) The role 2,3,7rB-TcDD may piay in reproduclion òr otrrer fish " species and other fish species from Lake ontario is currently unknown. Two characteristics of blue sac disease, i.e" subcutaneous edema of the.yolk sac and subcutaneous hernorrhage, are arso characteristics of chick ederna disease in herriñg-gulIs from Lake ontario (cilbertson, r9g2) and chickens exposed f,o-dioxin via food contamination (Firestone, L973; Flick-et ar., Lg7zl. Although the herring gulls $rere exposed to other cheuricäl contaminants at erevated levels, notably pcB and DDE, none of the 11 other gonpounds have produced the syrnptornology edema observed in chick disease. rndeeã, there t/as no èorreration beÈween concentrations of pcB, DDE or other disease incidence- girv compounds exa¡nined and significant correlation ?,2,2.ã-rõpõ-äpp".r= to present a since v¡itrr'.úi.i-ãã"ru disease incidence. herring.gulls ge opportunistic ieeders that will consume rarge quant'ities of fish i¡rren ready avaiJ.abJ-ã, incruding young fista, a route of . ex¡rosure to chemical the Lake ontario ánd Niagara Rivei-"ðãäv=tems."or,å.rirã"i=--í='provided in indeed rf z'3,7,8-T.DD i: significant or rnajor cause of reproductive failure in lake trout" ãioã¡."a in its presence has been r,aià"óntario, then lake mãjor-i*pãaiiãit t" re-estabtishnent of trout populations-" these eitoiiÀ to re-estabrish lake trout have been conducted by the New york state Environmental conservãtion_(Eckert, Department of Natural iõõ¿) anä ontaiio Ministry of Resources since tgzz and aie on-going. The few signs returning reproductive success (Marsden of encouraginE" et aJ.., 19gg) are
^ I_astry, Hickey et ar. (1990) reported that brown burrhead from the LiËre River-9"ygsa creek viciniry ;ñ;r;ã-ä" significantrv reduced inåiáencã-;f pãrã=iç.= to eB percenr in conrrol (25 percenr compared incidence risrri-."ã ãis"iriðã"Èlt î.1J".="a of chronic infrãnnaåiãn-"r-ãïir=, kidney and river. The latter changes hrere not parasitã áãsociated consistent with-exposure but are to ãnvironn""iår contaminants" The specific causative- agents were not identifi.d. Hl;ilãy (personar connunication) indicãred rhar retarded brown buri;;ã-år"rËñ^fpp".r= ro be and the population age structure is altered when compared to control' fish from an uncontarninatàã-=ãùi""" on the tatesr findings is in prepi;;¿i;;" A report
coNeLUSTONS The irnportant findings of this study are: 1' of the dioxins and dibenzofurans examined, 2,3,7rg-TcDD concentrations in fish from the cayuga creek basin .rã-th" only diagnostic measure of succe=='of remedial activities associated with Love canar. No other dioxin ãoñg"rr", o, dibenzoruran were reliable indicarã;; ;;-;;;"ãi;i errJ.cacy. 2- 2-13,zr8-TCDD concentrations in young-of-the-year fish have dectined ll_lyo stages. The fiist stage decrine (between L982 and 1982) 9r approxinatery z0 percent is associ-ated with securing the Lóve canaL rãnariir of stormwater site ana-iã creaning drainage sysrems containinj-z,i;r]ã_rcoo. The second decr.ine (between rgBT and 1992) oi "n åaåitional 46
L2 to 86 percent is dependent on location and is due to removal of higtrly contaminated sediments from Brack and Bergholtz creeks. The total reduction in 2,3,7,g-TcDD concentrations in young-of-the-year fish between Lggz and L992 ranges from 84 to 96 percent.
3 Despite the reduction in 2 ,.3,7 r8-TCDD concentrations, young fish continue to possess dioxin levers in excess of recommended for the protectj-on of pi-cirrotou= wirdlife,"ritería i,e. in excess ot. 2,.3 pg/g. Àt downstrèam rocations, ;;;ã fish sarnples exceed the New york state Departnent of Health recommendation of to pg/g 2,3,7,8-TcbD for human consumption of fish. However, the concentrations observed in Lggz are dramatically improved when conpared to varues in excess of 50 pglg observed in t982. These latter varues occurred in some species from downstream locations, most notably Berghortz creek inmediately downstream of Love canai and Cayuga Creek at Lindberg Avenue.
4" Declines in heptachloro and octachroro-dioxin congeners and in- hexa _-, hepta -, and octachloro congeners of dibenzofurans are documented 5 The principal sources of dibenzofurans in fish from the cayuga creek drainage basin appears to be frorn upstrean sources in the.Niagara River. À specific source locality was not determined or sought. 6. 2,3 8-TCDD ,7 r is_ the principal component of 2,3 ,Z r 8-TCDD toxicity equivalents carculated for fish from ö.yuga creek and its tributary, Bergholtz creek. rn contrast-, á,314,7rg- pentachlorodibenzofuran is the major component oi 2',3',7 ,B- TCDD toxicity equivalents in fish-from tñe uiagara irií"r. +s a.consequence, the increased proportion of á13,4rzrg-pcDF in Little River fish is primariry düe to sources fron the Niagara River and dioxin concentlations in the Littre River are reduced due to dilution with waters from the Niagara River
13 ACKNOWLEDGEUENTS
The author wåshes to acknowredge with appreciation ef f orts of : -'r¡-- the o the_DEc.Region 9 Bureau of Fisheries staff for colr.ection of samples, particurariy-sG;ñ;" Mooradian, Michaer r{iJ-kinson, paur-McKeown, Anthony veno, Joseph Evans, Emirio Rende, John Druqos, scott corneåt, a.^oiy o Hohmann, and James Spinel1i. the analytical servióes staff at the Hale creek Fietd st,ation for preparation of samples ror ãnaiysis, norablv samuel Jackling, Eric ùirrei-ã"ã--õãrge Kinber; o and the analytical staff of Tríangle Laboratories rnc. for chemicar anarvses associarea úitn-iñi;-;;;ject. Helpful cornments on the manuscript were provided by Ronard sroan and Gerald Rider, Jr. . rù?rg ptã""==ing- by assistancå ,"= pr".rided Larraine cavin, Ruth oearici, cãirãäñ eraaley and Frances Beeler. Their efforts are grateåuriv-ãðünorsreaged. I..9irg for this _project was provided by the Federar superfund- adninistered loóaÌIy uv õnði=-oi.ri=ion tlaste Remediation. of Hazardous
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Firestone, D. L972. Deter¡nination of polychlorodibenzo-p-dÍoxins and related compounds in commercial cntoioptrenols. J. Ássoc. off. Analyt. Chem. 55:85-92. Firestone, D. L973. Etiology of chick ede¡na disease. Environ" Health Perspect. 5:59-66. Frick, D.F., D. Firestone, and G.R. Higginbotharn. Lg72. studies of the chick edema disease: nespóñse of chicks fed or aùninistered synthetic ederna-producing-9. cornpounds. poutt.=i"giy- sci. 5tz2O26-2034. GiJ-bertson, M. L982. Etiology of chick ede¡na disease in herring gulls in the lower Great Lakes. can. Tech. Rep. Fish. aquaú" Sci. 1120; Fisheries and Oceans Canada, ottawa-. t4 p.
15 Hickey, J.T., R.o. Bennett, R. Reimschuessel, and c. Merker. Biological indicators of environnentar 1990. Niagara River: Histological-ãvâiùationcontaminants in the bullheads ãr-ii==,r"= fro¡n brown at the Love cãnar --rôã"a_street Dunp site compared to the Black creek reference si.te. u.s. F,ish Cortland, New york. L24 p. "rr¿'-wilali¡e--s;;.ri"", Horn, E-G., and L.c. skinner. statement. 19g5. Finar environmentar inpact for policy on contaminant,s in fish. New york Depart'nent of Envirónnental conseivatiãnl-Ãïù""i, state 150 p New york. Jude, D'J', s.-1. Kl-inger, and, M.D. Enk. 19g1. Evidence reproduction by planted lake trout of naturar Lakes Res. zziz_ç:-. in iãi" ¡tiãtrìg.". J. Great Kuzia, E' 1985- cayuga creek dioxin sampling NYS Departrnent-oi of fish and sediment. Environm""Cãi õãn!"..'ãtionl-Ãiu.r,y, Ny. 8 p. Mac, I{.J., c.c- Edsarr, and J.-G: seerye. 19gs. survivar of rake trout eg9-s and fry reared in wãiår frorn the upper J. Great Lakes Reã. 11:520_529. creat Lakes. Marsden, J-8., c.c._ Krueger, natural and c.p. schneider. 19gg. Evidence of reproductioñ by stoci"á-rãi." trout in Lake J. Great Lakes Res. 14:3_9. ontario. McDougal' I{'J' R'4. Ft¡sco, ' and R.P. otBrien. 19g0. contaminants and t'reatment of the Love canar ranaritr reachate. porl.ut. Control Fed. 52(2) 229L4_2g24. J. I{ater Nester, R.T., and T.p. poe. Lgg|. First evidence of successful natural reproduction of plant"a- iãr" trout in Lake J. Fish. Manage. 4iLz6_128. Huron. N" Àn. Newell, 4.J., p.w: Johnson, and L.K. BioÈa conta¡nination - ÀIren. 19g2. Niagara River wirdlife. niojecti ii=ñ-rlesh criterïa for piscivorous _. rech. Rep. e1-s (BEp), oivisi";-;;-ii!n ana r{irdlife, New York state Depaltment oË nníirãn¡nental Nev¡ york. 182 p. conservation, Albany, NYsDEc- 1990. update - study and crean up progra¡n Landfill, rssue 15, october yori Love canar Environmental 1990. ¡¡ei¡ siate Department of conservation, oivision of Hazardous waste Remediation, Albany, Ny. ö p. -- "Esslsvs- NYSDOH- 1981. Love canal. A special Report to the Governor LegislaÈure. New vork statä oepãrlrnãnt and 7o p. of Health, Àrbany, Ny.
16 NYsDoH. L992. Health advisory: chemicar contaminants in sportfish and wildrife L992-\993. New york state Department of Hea1th, Àlbany, NY. OrKeefe, P., C. Meyer, D. Hilkei, K. ÀIdous, B. Je1us-Tyror, K. Dillon, R. Donnelty, E. Horn, and R. sloan. 19g3. Anarysis of 2,3,7r8-tetrachlorodibenzo-p-dioxin in Great Lakes fish.- Chemosphere L2 (3) t32S-332. Rappe, C., .H:R. Buser, and H.P. Bosshardt. 1978a. Identification-ana and guantification of polychlorinated dibenzo-p-dioxins (ecOOs) dibenzofurans (PCDFs) in 2,4,S-T-ester forirulations åna Hei¡icide Orange. Chemosphere 7 (S) :431-438. Rappe, c., A. cara, and H.R. Buser. 19z8b. rdentification of polychlorinated dibenzofurans (PcDFs) in commercial chlorophenol formulations. Chemosphere 12:981-991. Rappe, C., !f. Nygren, H.R. Buser, and T. Kauppinen. Lggz. occupational exposure to polychlorinateá-aioxins and dibenzofurans. Pp. 495-513. rn chlorinated Dioxins and nelated Compounds, O. Hutzinger, R.I{. Fre:, E. lteri (eds.), Pergamon press Simonin, H. 1990. Summary of reproductive studies in Lake ontario salmonids. rn: Roundtable on contaminant-caused reproductive problems in salmonids. International Joint cornmissiõn, Ontario. winãsor, Slack, J.L. 1986. Memorandum to J. Hawtey, New York State Departnent of Health dated Novernber 3, 1996 S1oan, R. L982. Toxic Substances in Fish and Wildlife: November 1, 1981 to April 30, LgBz, Volume 5, Number 1. Tech. Rep. g2-2 (BEP), Division of Fish and Wildlife, New York State bepartment of Environmental Conservation, Albany, Ny 25 p. Snith, L.M., L.l{. Stalling, and J.L. Johnson. 1984. Determination of part-per-trillion levels of polychlorinated dibenzorurans and dioxins in environmental sarnpleé. Ànalyt. Chem. 56:183O-L842" snith, R.Iìí., P.w. o¡Keefe, K.M. ÀIdous, D.R. Hilker, and J.E. orBrien. L982. 2,3 ,7 r 8-tetrachlorodibenzo-p-dioxin in sedi¡nent, sarnples from Love Canal storm sehrers and creeks. Environ" Sci. feênnol. 17 (1) :6-10 spitsbergen, J.M., M.K. walker, J.R. olson, and R.E. peterson. 1991" Pathorogic arterations in earry life stages of lake trout, Sêlvelinus namAvçush, exposed t,o 2,3,7,8-tetrachtorodiUenäo-p- dioxin as fertilized eggs. Àquat. Toxico1" L9z4t-72 Stalling, D.L. L982" Letter to L. Skinner dated January 19, 1992. 17 Stalling, D.L., L.M. Snith, J:g:_petty,.J.t{. Hogan, J.L. Johnson, Rappe, and H.R- Buser. 1e83. nãsiá";; ;;';äíycnrorinated C. dibenzo-p-dioxins and ai¡enãår"r""= in ¿aurärr[i.r, creat Lakes fish. p. 221-240. rn a RIE:-;iãii"r, À.L. youngr, (ed') Human and envF""rà"tår-iirr='ot and À.p, cray related' compounds. ðnrãrinatea dioxins and ptenñ p;;=;]-"", york, Ny. suns' K" G'E'.crawford, D-D-.Russelr, and R.E. clement. Temporal trends and spaciar ¿is[íiu,rtion 1gg5. mercury residues in Giear ot-ãröanochlorine and ontario Minisrry Lakes ;ñir;ii ãiiiäi! (1e?s_1e83). of rhe n"viiãnrããt, nexaãlã,--õntario. 43 p" s¡mula, J" J. Meade, J.c. skea, L. cunmings, H.J. Dean, and J. J.R. colquhoun, Miccori. iggõ.-" Blue_sac disease in Lake ontario rake rrour. J. Grear r,ares ñã=.--ieiiiì¿r_ur" u's'E'p'4. 1e8ea. Derer*11:!i:l of porychl0rinared dibenzo-p-dioxins and polychrorinated dibenzofuranä ¡v high chromatogfaply/ltigh resolution iã="iution gas 8290. u-s. Environnental pr"t"ðiiànmass spectrometry. EpA Method Agency, wãshington, D.c" U.S.E.p.A. 1999b. fnteri¡n procedures wirh exposures ro nixruies for estimating risks associated dibenzorurans (cDDs ánd cpril"i-ãrrr"ii;";;å'äil#;"_p_dioxins ãnã-igeg and u-s. Environmentar protecti"i upaatã.---eea¡e 2s .3-Bs loL6, Àö""åv, waËhington, Dc. 21 p. vos' J'G', J'H' Koeman, H.L. vander R'H' Maas, M.c. ten oever de Brauw, and vos' L97o' rdentitiðãiior-ã"a toxicotogicat evatuation chrorinated dibenzofuran and of commercial porychlorinated chlorinated naphthal.enes in two 8: 625-633. uiptrã;ti". Food cosmet. Toxicol.. warker, lf and R- peterson. 'K' , E. 1990 . 2 13 r z g-tetrachlorodibenzo-p- dioxin produces a brue-sac syndrome duringr deveropment of rake trout earry life stage Roundtable on contarninant-èãGEproductive1såi"éiî""= narnavcush). rn: salnonids' problens in rnternational,¡ãi"i-cãinission, t{iñdsor, ontario. I{alker, M.K., spitzbergeD, 2,3,7,8-TetrachlorodÍbãnzó-p-aioxin_J.-M. J.R. orson, and R.E. peterson. 199r. l,iCOO¡ to*i.ity during life stage deveropment of rãre trout_ (sarvelinus early Can. J. Fish. Àquat. Sci. 48:eis_ãe¡" @êvcush) . Warren, J.W. 1991. Wild1ife . U.S. rish and Servicê, Fort Snel1ing, TrJ Cities, Minnesota. I{olf' K' L957' Blue-sac disease investigations: nicrobiology and raboratory Índuction. prog. rish. cur.t. 19:14-18.
18 zacharewski, T., L. safe, s. safe, B. chittarn, and D. Devault. 19gg. Çonparative anaÌysis of .polychlorinated dibenzo-p-dioxin anã dibenzofuran congeners iir cieat Lakes fish extraäts by gas chromatography - mass spectrometry and in vitro ínãuction activities. Environ. sci., rechnôI . 23z73o-73s."n"yrå
LCSl. DOC/LC8. H
19 Table 1 Hean concentr¿rtlons of dioxins containing the 2,3r?,8-chloro congen." grorrp in young-of-the-yeàr fish fron the cayuga Creek drainage basin, Niagara Falls, ì¡ew York
No of No. of I.enoth lrnmì Fliavin ncfener oroun lnolo t $reídhl'ìl Loc species Year SahÞles Fish Ì¡ean Ìtin-ltax 2,3.7 ,A SCl 6C1 7C1 8Cl Sun Little River trpstrean of creek cayuga Àl"ewif e 198 7 1 56 NAb ¡¡À t.2 Bluntnose rninnow 1990 2 85 49 32-69 7.5 0.4 2,I 8.7 51.5 70 2 L992 1 90 36 26- 15 1.9 r.7 6.4 8.8 49 .5 68 3 Rock bass 198 7 3 180 NÀ NÀ 20 .I L.7 12.3 19 1 37 .4 90.6 199 0 1 27 13 36-57 t6.2 1.3 4.7 7 6 75 ,2 45.o 1992 3 94 13 26-54 5.3 1.1 2.7 9 5 167 .8 186.4 Spottaiì shiner l.9a7 1 31 NÀ NÀ 2.1 <0. 3 <0. 3 3 6,7 12. 1 l.lhite sucker ]-9a7 1 25 tfÀ NA LO .2 <1.5d 13.8 17 9 106,2 178 . 1 Little River downstrean of cayuge Creek Bluntnose rninno!, 19 87 1 151 NÀ I'rÀ 6.9 <0. 3 3.1 74 .2 47 0 7 r.2 199 0 1 89 4L 26-57 6.7 <0. gd o.4 <6. ld 2t 4 28 .5 L992 1 100 37 26-50 7.4 1.6 4.7 22 .2 175 5 211.8 GoLclen shiner 7947 1 72 NÀ NÀ 5.9 P.ock bass 19 87 2 67 NÀ NA 17.2 1.5 3.9 3.1 7.5 33 .2 199 0 1 24 4ç 36-61 11.2 1.5 1.5 <2.9d 8.1 22.3 1992 I 18 13 31-53 15.2 1.8 2.9 2.1 e 22 .3 LSr . TBL/C825 20 Table 1: (contlnued) No. of No. of f,êncrth lhnl Dioxin r qrouÞ f /q wet wei qhtlt Locatl-on Soeci es Year Samples Fish Mean Min-Max 2.3 .7 ,A 5C1 6C1 - 7CL gC1 Sun Cayuga Creek at Lindberg Àvenue brldge BLuntnose minnow t987 3 300 NA NA 26.7 0.5 1.3 LL.2 56.8 96.5 1990 2 L52 40 25-62 L2.9 <1.3 <2.L 1.5 16. 1 1992 30.5 1 166 32 2L-42 10. 6 0.6 5.6 4.3 e 2L.T 2 76 52 4 1-60 2A .l o.5 3.O 3.4 e 35.0 Golden shiner 1990 t 22 47 30-64 L6.7 <1.8 <2.4 <3.8 8.o 24.7 Cayuga Creek at Cayuga DrÍve bridge Bluntnose ¡ninnow L987 ,NÀ 3 237 NA 17. O o.2 1.4 3.4 25..8 47.8 1990 3 153 47 32-6I 13.3 0.3 1.3 6.6 L7.2 38.7 L992 18 90 37 2L-50 10. 5 LS1 . TBIJ/CB2 5 2l Table 1: (contlnued) No. of No of Dioxin conoener o fl¡q/c¡ . wet ueloht ì' --¡,e¡d!--(nt¡I- 2,3.7 ,A 5C1 6Cl 7Cr 8C1 Sum r.ncat I on snecies Year Samples Fish Mean Ìlin-Hax above Cayuga Creek 65 42 30-54 0.6 o.5 o.7 5.O 10. 4 common shiner 19 90 2 a2 57 45-7 0 3.7 o.5 L992 ztt 24 a4 7 0-97 9.7 1.6 2.5 2.9 e 16.7 36. 4 <1.7 0.5 5.0 42.3 Golden shiner ]-9a7 3 107 llÀ NÀ o.¿, 3 1.1 0.5 0.3 1.7 L1.4 15. O tliagara River'uPåtrear,r of Bluntnose minnow 199 0 1 5? 49 1-68 Litt1e River' 0.4 22 a Ànalyzed as vhole fish cornposites. Values less than detecbion and EuPc values (see footnote d) are given a value of zero in .cornputation of means and sum of dioxins b NÀ = Not avallabler' only conposite weight (S) is available' c Less than (<) values represent detection limits unless . "¿t' footnote appears. The largest detection limit*is reported where more than one sample is below detection. d Estimated maximun possible concehtration (EltPc) value. This is a tenlative iclentification which did not neet alI requirenents for posltive identification. e BLank contamination invalidates reported concentration' f À9e r+ fish. g Èlixturê of fish with agês o+ and 1+ h ltlxture of fish vith ages 1+ and 2+ i Ì¡o fish were present during the 1987 sanpling effort. This stat,ion lräs not samplecl in 1990 J this station was not sarnpled in.1987 and 1992. Lsr . TBL/cB2 s 23 Table 2! dloxin coneeners Ln iï:äJ:";:ii::ti:i"r3f*ltt vouns-or-the-vear rr.sh rron rhe carrusa creek drainase Þasin, No. of No. of Lcnqth (mnll l¡celir¡n Specic Ye¡r Sampler Firh Mean Àlin-Àlax .lCl t 6Cl ?Ct 8Cl Tot¡l Littl¿ Rivcr upsrrdrn of Cryugr Cræk Alcwifc t987 I 56 NAb NA 1.2 <0.1c 1.0 4.1 10.0 t 6.3 Blunlnosc minnow 1990 2 ss 49 32-69 9.7 0.7 5.6 1992 t 9.6 5r.J 17. I I 90 36 2ó45 t.¿l 4.8 l5.z t 7.6 49.5 95.5 Rock basr I 987 3 t80 NA NA 20.2 1.7 t 7.8 25.8 1990 I 27 37.4 I02.9 4t 3É57 t6.1 t.3 4.8 1992 I t.0 15.2 .49.0 3 9{ 43 2&54 8.3 t.9 7.5 22.O t 67.8 207.5 Spottail shincr I 987 I 3t NA NA 2.1 < 0.3 <3.7¿ 4.8 6.7 l].6 White ¡uckcr t987 t ?5 NA NA to.2 < 6.1,1 30.9 67.9 læ.2 2t5.2 Littlc River downstram of Cryuga Crcck Bluntnosc minnow 1987 ¡5r NA NA 6.9 1.0 9.6 ¡990 21.2 17.O 88.7 89 4t 25-57 6.7 <8.2¿ t992 1.6 4.4 21.4 34. I 100 37 2650 il.5 3.3 t 8.9 52.1 t 75.5 26t.3 Goldcn ¡hincr t 987 72 NA NA 5.9 <0.8d <3.4d 1990 2.O 5.0 t2.9 t6 5t 42-7t 5.9 0.9 t992 <23n < 1.5,1 5.t I t.9 44 49 42-57 t 0.5 1.3 4.8 7.6 k 21.2 Rock brs¡ t987 2 67 NA NA 17.3 t.5 4.2 1990 1.1 7.5 xt.6 I 24 ¡16 36{t 12.2 t.5 t99Z 1.5 < 4.3d 8.t 23.1 t t8 4t 3t-53 16.5 2.O 4.5 3.5 k 26.5 Cryuga Cræk at Lindbcrg Avcnuc bridgc Bluntnosc minnow t987 3 300 NA NA 28.4 t.9 6.6 1990 r 8.7 56.8 t12.1 2 t52 40 2542 t?.9 I 0.8 5.0 r6.t 34.E 1992 I t66- 32 2142 I t.8 1.2 t5.3 7.1 k 2 76 <1 ¿ll{o 38.6 28.9 t.4 7.3 5.7 k 13.t Goldcn shincr t990 22 17 30{4 16.7 <1.y' <1.2¿ < 3.8 t.0 24.7 24- lable 2: (contlnued) No. of l¡ncth lmml l¡c¡tion No. of ¡ Specicr Year Samples Fi¡h Me¡n Min-Mex lct sct ócl ?Ct 8Cl Tor¡l Cayuga Cræk ¡t C¡yugâ Drivc bridgc Bluntnotc minnow l9t7 t 2i7 NA NA t7.t 0.5 3.0 5.2 25.t 5r.t I 990 t t53 17 324t 11.4 0.3 2.2 r 1.3 17.2 15.1 1992 I I 90 37 2t-50 I 1.4 <22.5d l.¡l 3.5 k 2 C t6.3 64 57 13{.5 t2.7 o.6 2.O 4.2 k t 9.5 I 65 6l-7t Rock bass 1992 22.3 0.9 1.0 k k 24.2 Ceyugr Crcck bclow Portcr Road Bluntnosc minnow t990 9 s1 34{6 4.0 0.t 1.7 C 1.0 8.t t1.9 t992 23 6l 56{3 2.0 < 3.Od t.3 4.6 k 7,9 Common shincr t987 3 tt3 NA NA t.9 <0.8 <0.4 <0.7 3.3 5.2 t990 t 68 44 29-65 4.4 0.9 1.2 t.3 I t.4 19.2 1992 I 124 35 2246 0.3 0.5 0.3 2.9 k ¡f.0 Cræk chub t990 32 49 38-68 t.9 1.0 2 2.7 l2.o I t.8 t992 t0 4t 32-5t < t.l ¡l 1.2 2 9.2 50.0 6t.6 Whitc ¡uckcr 1990 I 5 68 62-75 0.8 0.4 0.3 2.3 t2.7 t 6.5 Crcck rbovc l,ockport Road b B¡ook ¡ticklcback 1992 I 65 12 30-51 0.6 d <0.8 0.5 2.3 k 3.4 Bcrgholtz C¡cck tOO mctcrs rvcat of Mlliams Road Bluntnosc minnow 1990 I 3t 50 32-f6 8.4 0.6 t.t 6.3 2t.7 38. I t992 I t9 6t 32-t4 5.5 0.7 t.l k k 7.3 Common 2 ¡hinc¡ t990 82 57 4S-70 4.4 0.6 0.7 o.7 5.0 I t.4 t992 2 24 84 70-97 I 1.3 t.6 3.0 3.9 k t9.t Goldcn chiner t987 t t07 NA NA 36.4 0.4 < 1.7 0.5 5.0 12.3 Nirgara Rivcr upstrcåm of Litttc Rivc¡ J Bluntnosc minnow 1990 I 57 49 3t{8 3.9 0.8 2.t 3.3 I t.,l 21.5 Rock b¡s¡ t990 2t 5t ts& 2.0 1.2 0.¿l < 0.4 2.O 5.6 I Anelyzcd ¡¡ wholc lish comporitcs' v¡lucs lcsr lhrn dclcclion and EMPC vrlucr (scc t footnolc 'd') rrc givcn ¡ v¡luc of zcm in computation of man¡ ¡nd sum¡ of dioxin¡. NA = Not ¡vrilablc. Only composirc wcight (t) ir rveilablc, d Ectimarcd m¡ximum posriblc conccntration, Th¡r ir . tcntativc idcntifiätion which did not med rll rcquiremcnr.s for poririvc idcntificarion, 3 Agc l+ lìsh. 25 lable 2: (contlnued) f E¡timated mrlimum m¡¡ible-conccntr¡tion¡ of 6.7 pglg nd 92.9 pglg werercporrcrt, scr foohotc d for funhcr nobtionr. r Àlixturc of rges 0+ ind I + fish. ! No fish wcrc Prcscnt in cevug-r cræk ¡bovc Lockport Road I during rhc 1987 rampling cfÍorr. Thi¡ ¡rrtion wer not samplcd Mixturcof rgcs l+ ¡nd 2+ fish, in 1990. , r Tlrh rt¡tion wat not trmptcd in lgtl ¡nd t992. Bhnk ænhmination invrlidares rcportcd conccntmtion, LCS4.TBL/LC8.lt 26 Table 3: The distribution of relative percentage contributions of the 2r3,7tB tetrachloro - conçtener to total dioxiñs and total dibenzofurans concentrations in young-of-the-year fish from the cayuga creek basin, Ñi"gãiu-rãii=, New york. Compounds t80 60-79.9 40-59.9 20-39.9 Total Dioxins 81.4 16. 3 2.3 o Total Dibenzofurans 4.7 48.8 37.2 9.3 a lr= 43 comparisons Ls291. tbl/rd30 -27'- lable 4: :;'.::ii::lr3f,^Ëåi"ål'¿l¿3*'S33r;:";îl;:i:t;lïr:: cyprrnirorm il:;'i;;f:rhe-year rish ror arr rocarions by year Locatlon N Mean 958 Confídence 1987 fnterval Group Conoarisonsb Cayuga Cr. below porÈer Rd.r Llttle 3 1.9 2.4 6.2 Rlver 4 - - Cayuga Creek at Cayuga 6.3 o .92-LI .7 Dr. 3 t7.O cayuga Creek at f,tñdberg Ave. 14.0 -19.8 lr Bergholtz Cr. 3 26.7 24.8 -28.6 3 36.4 26.8 -46.0 l 1990 l Niagara Rlver upstreamr - 1 1.1 cayuga cr. belo!, porter Rd.r Bergholtz Cr. 4 2.4 0.21- 4.6 Little 3 5.2 l RLver 4 -1.9 -12.5 Cayuga Cr. at Cayuga Dr. 6.6 4.5 - 8.7 Cayuga Cr. at Lindberg 3 13.3 10.7 -15.9 lrl Ave. 2 2L.2â L6.7 -25.7¿ Cayuga 1992 Cr. below porter Rd.r 3 Bergholtz L.2" 3. o Creek 1 -0.50 - Little .5. 0c ê River 3 Cayuga Cr. at Cayuga Dr. 5.9 -2.6 -L4 .4 Cayuga Cr. at Llndberg 3 LL.7. 6.6 -L6.7 111 Ave. 3 22 .2ê -3.6 -48. 1 a npg g sret s¡e b Based e on Kruskal-Í{all is test paired cornparisons c fnsufflcient data for calcula tion where p -28- Table 5: Comparison of 2,3,7r8-TCDD concentrations in young-of-the-year Cypriniform fish over time for the cayuga Creek drainage basin dowñstrearn oi Love canat, wiagarã Falls, New York. 2,3.7.8 - TCDD fno/crlr croup Year N Mean 958 Confidence fnterval Comparisonsb Cavucra Creek belovr Porter Road lcontroll L992 3 L.26 -0.51 3.0 L987 3 1.9 -o.92 1 L.7 1990 4 2.4 o. 21 4.6 ll Lgg2" 1 LO.7 _f Cavuqa Creek drainaoe at and downst-raam of Love Canalc L992 3 8.7 o.73 L6.7 1990 9 10.9 4.7 17. O L987 9 26.7 20. o 33.4 l Lgg2c 3 96.7 5.2 198 ,l a All concentrations are in pElg wet weight whore fish basis. b Group comparisons using the Kruskal-Wallis test pair comparisons where p <0.05. c Data from Kuzia (1985). d Ag9 1+ fish are included for the control locat,ion only. e This comparison includes data from Bergholtz Creek aná cayuga Creek at, Cayuga Drive and Lindberg Avenue bridges. f The 95t confidence limit can not be calculated. Lsze3 . tbl/rd30 -29- Table 6: comparison of mean concentrations of 2,3 heptachlorodibenzodioxins in young-or-åne-Ie?r17rg-tetrachloro-containing River and cyprinirorm fish by year in the the cayuga creek ¡aåin,--¡li;g;;" Farrs, New york Little Locat on Group N Mean Conparisonsb L987 Cayuga Cr. at porter Road" 3 Bergholtz Creek ND' _ó 3 0.50 -1. 63 2 .63 Cayuga Cr. at Cayuga Drive 3 Cgyuga 3.39 -4.28 11. 1 cr. at Lindberg Avenue 3 LL.2 ll Littte River 3.47 19. O 4 16.8 -L7.27 50.9 1990 Cayuga Cr. at Lindberg Avenue Cayuga porter 1 1. 00 -3.2 95 .30 Cr. at Road" 3 1. 05 Bergholtz Creek o.o 7-2 .18 3 t.g2 -2.8 8-6 .52 Little River 3 4.35 Cayuga Cr. at Cayuga -9 .491 8.2 Drive 3 6. 63 4.3 4-8 .92 Bergholtz L992 Creek 1 ND" _d Cayuga Cr. at Cayuga Drive Cayuga porter 3 2 .19 1.4 7-2 .91 Cr. at Road" 3 3 .20 Clyu9a Cr. at Lindberg Àvenue -1. 5 2-7 .92 I Litt1e River 3 3 .72 L.7 55 .69 3 11 .8 -11. 53 5.1 ll a ana yz ona we o e sh b Group comparisons s s. using the Kruska l--Wallis test pair comparisons c ND below the detection Iirnit. where p <0.05. d The 95t confidence intervar can not be carcurated. e Control location. LS2 . TBL/ CBzs -30- Table 7: Comparison of mean octachlorodibenzodioxin concentrat,ions.in young-of-Èhe-year Cypriniform fish from cayuga creek and Bergholtz Creek during t'ggT; Niagaia fátts, New york Octachlorodibenzodioxin (pq/cr) " Group Location N Mean 95t Confidence fnterval Comparisonb Cayuga Cr. at Porter Road 3 4.82 3.95 5. 69 Bergholtz Creek 3 4.98 -6.20 L6.2 l Cayuga Cr. at Cayuga Drive 3 25.8 9.54 - 42.2 ,l Cayuga Cr. at Lindberg Avenue 3 56.8 -4.98 119 a Fish analyzed on a wet weight whole body basis. b Group comparisons using the Kruskal-lfallis test pair conparisons where p <0.05. LS3 . TBLI CB25 - 3l - Table 8: conparison of mean concentrations cvpriniforrn of octachlorodibenzodioxin-õv;;-;l;;; in young-of-the-year rish in the cayusa creek uasin ñi;e;;"-i;"ii; New york Octachl odibenz inf /ol a Group Year N Mean Comoa risonsb Uostrean I ti onsc L987 6 4.90 1.89 7 .90 1990 'tl 7 lI¡V ^ 5.80 16.3 I L992 4 L2.5f -27.3 - 52.3 J Dot¡nstr ï-ocat ionsd L992 6 NDC ,,, 1990 6 L7 .4 3.4L 31.5 L987 6 41.3 16.6 66.1 a Fish analyzed on a wet we ight, whole body basis. b Group comp arisons using the Krusha l-Wallis test pair comparisons where p <0.05. c Bergholtz Creek and Cayuga Creek at Port,er Road. d Cayuga Creek at Lindberg Àvenue and Cayuga Drive. e ND below detection limits. The 9St confidence interval can f Three of four values were not be calculated. below the detection limit. The remaining value was SO pglg. I_,S4 . TBL/ CB25 -32- Table g: No f ,or:¡t i nn of ÐiÞ-enzçrfuran conqengf crrouÞ lpqlg lret vrelqhtl. Snecl es Year Sanpl-es 2.3 .7 .8 scl 6c1 7cL _CS¡_ _Ég¡L Llttle River upstrean of Cayuga Creek ÀIewife 1987 1 1 7 1. 9 7.7 1. O Rock bass 1987 2 9.2 L0. o 8.8 3.3 1.8 33. 1 199 0 1 _6. 5 ?.5 5.2 2.7 3.8 25.7 1992 L 6.1 11.9 Lt.2 4.5 4.9 38. 6 Lss. TBL/C825 33 Table 9: (continued) No- of Dlbenzofuran conqener qroup r ti on lpqlo wet weiqhtì. SnecÍes Year Sarnþles 2.3,7 .8 5C1 6C1 'tcL 8C1 SuÌr Cayuga Creek at Lindberg Àvehue brldge Bluntnose mihnor.t t9a7 3 8.3 2.6 2.8 3.2 5.2 22.t 1990 2 2.3 1.9 o.7 <2.2 <5 .4 4.9 t992 1 2.4 2 .1. 2.3 1.O 1.4 9.2 2ô 3.2 2.4 2.t o.9 1.6 10. 2 Golden shiner 1990 1 3.5 <1.0 <2.O <2.3 <6.6 3.5 Cayuga Creek at Cayuga Drive bridge Bluntnose minnow a9a7 3 1.2 .6 3.2 3.4 1.5 Rock bass 1992 1d 1- .7 1.8 0. 6 o.2 o.4 4 7 cayuga Creek at Porter Road Bluntnose minnow 1990 1 4.9 3.8 1.5 o.6 1.0 11.8 ].992 1d t.7 o.7 1.O o.5 1.O 4.9 common shiner 1987 3 5.o 1.1 0.8 <0 6 <1. O 6.9 1990 1 4.3 2.O o.6 o 3 o.8 8.O 1992 1 <1 .2c o.6 o.2 o 2 <0.3 1.O Creek chub 1990 1 3.2 1.4 0.3 0 4 1.1 6.4 ].992 t 1.. 6 <0. 3 0.9 <0 6 <1. 0 2.5 I{hite sucker 1990 1 1.3 o.7 0.4 0 4 1.2 4.0 LS5 . TBL/ CB2 5 Table 9: (continued) No. of Dibenzofuran conqener groun fpq/q wet weiqhtln tocation Snecies Year sampLes 2.3.7 .A sCl 6cl 7c1 8C1 Sum cayuga Creek above Lockport Roadr Brook stickleback A992 1 <1. 3c o.5 o.3 0.6 1.1 2.5 Bergholtz Creek 1o0 meters west of Williams Road Bluntnose minnow 1990 1 4.8 2.3 o.2 conìmon shiner 1990 2 3.5 2.L o.9 o.3 o.2 7.O 7992 2t 9.9 9.2 4.5 o.6 o.4 24 ,6 Golden shiner 1987 3 6.5 <1. 1 3.0 <1.4 <2.7 9.5 Niagara River upstream of Little Riverh BÌuntnose minnow 1990 1 4.r 4.9 A.2 16.4 36. t 69.7 Rock bass igso 1 5.1 10.3 6.7 20.5 23.6 66.2 a Àna yz äs s compos Va ues ess n ect a va ues see ec are I ven a va ue zeto n cornputati on of tneans and sum of dibenzofurans. b Less than (<) values represent detection li¡nits unless a rrcrr footnote appears. The largest detection limit is reported where ¡nore than one sample is below detection c Estimated maximurn-possibJ.e concentration (E¡'lpC) value". This is a tentative identification which did for positive identification. not ¡neet aLl requirements d À9e 1+ fish. e Hixture of fish of ages 0+ and 1+. f l,tixture of fish of ages 1+ and.2+, g ìto.fLsh were present during the 1997 sarnpling effort. This sÈation was not sanpled in 1992 h This station was not sampled in 1997 and 199ã. Ls5 . TBL/ cB2 5 35 ,- ?rablc 10s UeaD concentratl.ons of all dlbenzof uraD congenera Ln young-of-tba-year basl.n, Nl. ra FaltB, New york. fl.sh fron tho Calzuga Creek dral.nage No l-oc¡tion of Dibc¡rzofuran QTOUN wet weiphtì r Species Year Samples 4Ct scr 6cl 7Ct ECr Total Little Rivcr upslream of Ceyuga Creek Alcwife 1987 I 2.0 2.6 2.O < o,2b 7.1 Bluntnose minnow t990 2 9.5 9.4 l2.o t0.9 t9.5 6t.3 t992 I t4. ! 25.t 21.6 26.6 38.3 t25.9 R¡æk bsss 1987 3 12.8 t4.2 20.1 5.8 2.7 75.6 t990 I 7.7 tl.2 tl.2 2.5 2.7 35.3 1992 3 14.6 29.4 t9.6 8.7 lo.2 82.5 Spotùail shiner 1987 4.r 3.3 5.9 1.7 <0.4 t5.0 White sucker 1987 t 5.5 43.1 36.2 t6.0 l4.l I t4.9 Little River downstreåm of Cayuga Creek Bluntnosc minnow t987 2t.o t5.4 2t.9 30.7 39.4 r 30.4 1990 6.t t0.8 9.7 l4.t 26.1 67.O 1992 9.7 15. r 15.7 t5.0 19.5 ?5.0 Golden shiner 1987 10.9 ,.7 2.8 2.3 l.'l 2t.4 1990 5.6 4:7 t.8 <3.',tc 4.t 16.2 1992 9.9 t0.9 4.7 4.7 6.4 36.6 Rock bass I 987 2 tt.7 t?.0 t2.2 5. I 1.8 47.8 t990 I 9.t 13.6 6.8 4.2 3.8 37.5 1992 t 8.9 19.2 t2.8 5.4 4.9 5t.2 Cayuge Creek at Lindberg Avenuc bridgo Bluntnosc minnow t9E7 3 16.5 I 1.0 8.0 6.1 5.2 46.8 1990 2 4.6 4.9 0.8 36- Table l0: (contlnued) No of f)ihenznhrmn rônoênpr lnp/e wet wciohll . Location Specjes Yar Samples 4Cl scl 6Cl 7Cl tCr Toht Cayuga Creek et Csyuga Drive bridgc Bluntaose minnow t987 3 14.0 t 8.8 8.5 t0.6 <0.8 5 t.9 1990 3 8.6 5.8 1.9 4.2 5.t 27.6 1992 ¡d 2.2 6.0 1.5 <5.9h t.5 ll.2 2c 4.6 3.6 1.4 0.9 t.5 l2.o Rock bass 1992 lc 2.6 2.8 0.8 o.2 0.4 6.8 Cayuga Creck below Porter Road Bluntnosc minnow t990 I r t.4 8.0 2.3 t.4 t.0 24.1 l9v2 lc 3.9 3.9 t.l o.6 1.0 t0.5 Common shiner t987 3 7.O 3.7 0.9 1.2 < 1.0 12.8 t990 I 6.5 4.2 t.l 0.4 0.8 t3.0 t992 I 0.3 1.4 o.2 0.4 <0.3 2.t Cre¿k chub t990 t 4.5 2.9 0.6 0.5 t.l 1.6 1992 I 3.6 o.7 0.9 < 0.8h < t.0 5.2 White sucker t990 2.1 1.5 o.6 0.9 1.2 6.' Cayuga Creek above lnckport Roadc Brook stickleback 1992 I o.2 t.3 0.5 0.7 l.¡ 3.8 tffilliems Bergholtz Creek lü) meters wesl of Road Bluntnose minnow t990 t 12.2 6.7 0.9 <2.4Q < l.5c 19.8 1992 ¡d It.2 5.9 2.O 0.3 0.5 2t.9 Common shine¡ r990 2 6.6 4.7 1.3 o.'l o.2 r3.5 1992 2r t 8.9 21.3 5.3 o.8 0.4 46.7 Golden shiner t987 t 13.3 t0.3 5.6 3.2 <2.',| 12.4 Niegen Rivcr upslream of Litltc iliver t Bluntnose minnow t990 I 13.2 14.0 15.6 22.3 36. r 10t.2 Rock bass t990 t 8.2 16.4 9.6 25.4 23.6 83.2 37- Table l0: (contlnued) ¡ Analyzed as whole ñsh composites' values tess than detection and EMPC values (ser footnote h) are given ¡ value of ze ro in computetion of mes¡s end the sum of dibenzofunns. b l¿ss th¡¡ ( < values ) repre'senr derection limits. l{here nrore then one semple was less than the delection limit, the largest detection limit is reported. c Agc l+ fish. d Mirtut of agas 0+ etrd l+ fish. c No were present fish in cayuga creek above Lockport Road during the sampling effo¡t in 19g7, This station wes not sampled in 1990, f Mirtu¡e of ages l+ and 2+ fish. 8 This stetion was not sampled in l9B7 and 1g92. h E.timated maximum possible concentralion (EMpC) value. This is tentalive ¡ identificetion which did not me€t all requirements for positive identification. LCS2.TBL/LC8.H 38- Table 113 ConparLson of concentratlons of dlbenzofurans contal.nl.ng the 21317r8-tetrachloro congener group Ln young-of-the-year cy¡rrlniforn flsh by locatf.on, cayuga creek dralnage basl.n, Nr.agara Falfa] xeir york. eoncêntFrt-{an fncla wa} ohtl n Group l,aar ? { an N Hean 95t confl.dence f.nterval conÞarl.sonb 2 , 3, 7, 8-tetrachlorodLbenzofuran Little R. upstrean 52 3 0. 58 5.2 Cayuga Cr. at Porter Rd. 103 2 1.8 4.7 Niagara R. upstream L4 1 c Cayuga Cr. at Cayuga Dr. 94 2 1 6 6.8 Cayuga Cr. at Llndberg Ave. 94 6 2 ¿ 7.O Bergholtz Cr. 75 5 3 9 7.O Llttle R. downstrea¡n 65 6 2 I 8.3 2, 3. l 7, 8-pentachlorodibenzofuran d Cayuga Cr. at Porter Rd. 10 t.0 o.34 - 1.8 Bergholtz Cr. 7. L.2 0.14 - 2.2 cayuga Cr. at, Lindberg Av. 9 1.9 1.1 2.6 Cayuga Cr. at Cayuga Dr. 9 1.9 1.1 2.7 Little R- downstrea¡n 6 2.3 o.98 - 3.6 Niagara R. upstream I 4.1 Llttle R. upstream 5 4.7 o.94 - 8.5 39 Table ll (contfnued) concentratlon foqlg net welqhtl a crouE IrOCãt N tlean 95t confl.dence interval conoarLson b Eexachlorodl.benzöfurans c Cayuga Cr. at porter Rd. 10 o.72 0.19 - 1.3 Bergholtz Cr. 7 1.8 -0.41 - 4.O Cayuga Cr. at Cayuga Dr. 9 L.9 o.52 - 3 Cayuga Cr. at Lindberg Àve. 9 1.8 0.84 - 2.A Little R. downstream 1,, 6 6.6 1.1 - 12.1 Niagara R. upstrearn 1 8.2 -c Llttle R. upstrean 5 11.8 L.5 . - 22.L f BergholÈz Cr. 7 0.14 -o. 05 - 0.33 Cayuga Cr. at porter Rd. 10 o.23 0. 07 - o.39 Cayuga Cr. at Lindberg Av . 9 1.4 o.27 - 2.5 Cayuga Cr. at Cayuga Dr. g 1.5 o. 68 - 2.2 Llttle R. downstream 6 g.o -1. 6 - 19.5 Llttle R. upstrean 5 9.3 -o"67 - 79.2 Nlagara R. upstrean 1 16.4 _c -40- ConcentratLon (pcrlcr eret, neLqhtl ¡ Group Locatlon lifean 95t confLdence lnterval comÞarLson b octach lorod Lbenzof uran Bergholtz Cr. 7 0. 11 -0. 07 o.29 Cayuga porter Cr. at, Rd. 10 0. 50 o. 11 0. 89 Cayuga Cayuga cr. at .Dr. 9 2.2 -o. 67 5.1 cayuga Cr. at Llndberg Àv. 9 2.3 o.44 4.1 downstream Llttle R. 6 L6.2 o .62 31.8 upstream Little R. 5 18. 3 1.1 35.4 Niagara R. 1 36. 1 c a Whole flsh conposites. Comblned data for 1987' !-99o inslgnlflcant. and 1992 slnce year to year variatlons were statisticalty b Group conparJ-sons calculated uslng the Kruskal-wallls test pafr conparLsonsI where p <0.05. c rnsufflcient data to d calculate the 95t confldence Lnterval. The 2,3t4,?,8-pentachlorodibenzofuran ls the predornLnant congener rnaking up congener contaLning pentachlorofurans in excess of 95t of the 2,3,7,8- e The only detected 2r3'7 r8-congener containlng hexachlorodibenzofurans detected were the 1,2,3,4,7,8- hexachloro L I and r2,3, 6,7 r9-hexachloro-congeners. The ¡,2t3t416,7,8-heptachlorodibenzofuran is the only 2,3r7rB-congener detected. containing heptafuran LCS3. TBL/LC8. H -4I Table fZ: 2¡'7'&TCDD toxic¡ty equivalents a¡rd percent contribution II2J,7,E-TCDD tox¡c¡ty equivalmts by 2,317,&TCGD and 2J,4:7,$-rcDF in young-or-oeyear f¡sh from the Cayuga Crcek drainage basin, Niagara fdb, Nerr yo'rk. 2r3r7rg- % contributed bv: TCDD toxicity 2,3r7rt- 2r3r4r7rg- Location Species Year equivalents TCDD PCI}F Little R. Alewife 1987 2.6 6 36 upstrÊam of Cayuga Cr. minnoly Bluntnose 1990 11. I 68 t1 t992 8.0 24 29 Rock bass r987 30.7 65 20 r990 22.3 73 r5 1992 13.5 38 36 Spottail shiner 1987 3.6 58 23 ÌVhite sl¡cker 1987 19.8 52 25 Little R. Blunhose ninnow 1987 10.0 69 dorvnstream l5 1990 9.1 73 l3 ofCayuga Cr 1992 t2.8 6t l3 Golden shiner r987 8.5 70 17 1990 6.6 7t t4 t992 ll.4 70 r5 h¡ss Rock t987 24.0 72 l5 1990 15.8 7t l5 t992 22.9 66 l8 Cayrga Cr. at Blr¡ntnose minnow 1987 29.6 90 4.2 Lindberg 1990 14.l 47 Ave. bridge u 1992c 24.4 90 4.2 Golden shiner 1990 t7.t 98 NDC Ca¡rga Cr. at Blr¡nhose ninnow 1987 20.3 84 6.9 Cayuga Drive 1990 t5.2 87 6.8 bridge 1992c t0.7 98 ND 1,.9gzb r3.6 9t 4.2 Rock bess ßgzb 23.6 94 t.7 -42- Table 12. (continued) 23,7,t' % contributed bv; TCDD toxicity 23,7,8- 23,4,7,* Location Species Year equivalents TCDD FCDF Ce¡rga Cr. Bluntnos€ minnow 1990 5.2 54 31 below Porter ßg2b 2.6 73 t4 Roed Comnon shiner 1987 3.0 63 l8 1990 5.8 7l t2 1992 0.92 56 20 Creek chub 1990 3.3 57 t4 1992 1.6 74 ND \ilhiæ sucker 1990 1.6 54 t7 Bergholtz Cr. Bluntnose mi¡now 1990 to.2 82 9.3 lfi) mete¡s t992c 7.5 67 l6 west of lVilli¡m¡ Rd. Common shiner 1990 5.4 68 It L992e 16.5 59 26 Golden shiner 1987 37.6 97 ND Cayuge Cr. Brook sticklebsck t992 0.89 64 2Íi ebove I-ockport i¿.d Niagare R. up Bluntnose minnow 1990 4.9 22 42 stream of Little R.f Rock b¡ss 1990 7.7 t9 53 : Br""d on toxicity equivalency facûors published in U.S.E.P.A., 1989. b Age 1+ fish : Mixture of fish of ages 0+ end I +. d No ñsh were preseirt during the 1987 senpling effort. This stetion u¡as not sampled in f990. lUixnreof fishof ages 1+ and2+. t This stetion was not sarnpled in f98? and 1992. I ND : Not detected. lcsTbl.12 ft4.h -43- Table 13: comparison or 23r7,8-TcDD concentrations in cypriniform fish f,rom the Cayuga Creek drainage basin by year, Niagara fãûs, Ny. 2.3_7.8- fnoloì in Location 19g2a t9E7 1990 t992 Little River 7.3 6.3 6.6 4.9 C-a¡rga Creek - Lindberg Ave. 127 26.7 14.8 ro.6b - Cayuga Drtve 50 t7.o 13.3 1r.4b - below Porter Rd. to.7 1.9 2.4 L2b - ebove Lockport Rd. 2.O c d 0.6e Bergholtz Creek l13 36.4 6.1 5.0b Niagara River d d 1.3 d a Source: Kr¡zia, 1985. b Includes soure age l+ fish c No fish wefe pres€,nt. d No collections were atûempted. e Brook stickleback, a non€¡priniform fish species, was the onry species collected. lcsTbl.13 fM.h -44- Table 1l: Perce¡tage change in 2r3r?rg-TcDD coucentrations uiÈb tir? tn eypri¡iforr¡ fisb from the Ca¡ruga Creek Araiaige basin, Itiagara Falls, tfÏ. t chanae in 2-?- . a-IFCDD concentration betwee¡ Irocatio¡ L982-L987 198?-1992 1982-1992 Little River 14 22 33 Cayuga Creek Àve. -79 60 -92 - Cayuga Drive 66 33 -77 below Porter Rd. -82 37 -83 - above Lockport Rd" a a -70 Bergholtz Creek -68 -86 -96 a No collections hrere made in 1982 lcsTbl. 14 fb4.h -45- Table 15: Comparison o12r3,7,t'TCDD toxicity equivalents in Cypriniform fishes from the Caygga Cr€ek drainage basin by year; Niagan Falls, Nor yorl 2.3.7.t-TCDn ecuivalenfs in Year Location lgg2r t9E7 1990 1992 Li$le River 12.5 r0.5 9.5 10.r Cayuga Creek -Lindberg Ave. 140 29.6 t5.7 r2"8b 4ayuge Drive 55.6 20.3 15.2 10.7b -below Porter Rd. t7.o 3.0 4.0 L7b -ebove Lockport Rd. 3.1 c d 0.gge Bergholtz Creek 15l 37.6 7.8 7.5b Niagara River d d 6.3 d 8 Estim¡ted Ûoxicity equivalents es derived from 2,3,7,8,TCDD concentration reported by Kuzia (19g5) divided by the sverage percent 2,3,7,$'T9DD in toxicity equivalents for C¡priniform ñshes atLch locetion i*ng the b current sûrdv. Io"ludo ** l+ fish. c No fish wefe prese,nt."g" d No collections were e attempted. Brook stickleback, a noni¡priniform fish species, was the only species collected. lcsTbl.15 ft4.h -46- Cayuga Creek NEW YORK L Grand lsland ONTARIO Buffalo River Figure l: General and specific area of study for assessing dioxins and furans in young-.of-the-year fish from the Cayuga Creek draÍnage basin. -47- LOCK LOCKPORT 7 NIAGARA FALLS 265 AIR FORCE BASE o 0 ò< rt? G 6 t82 NIAGARA FALLS INTERNATIONAL AIRPORT ROAD Cted< I 5 æ 62 62 I 5 Black 62 @ 3 Love E Canal LEGEND o STATION SITE 9 STATION NUMBER lsland 1 T STATE ROUTE 384 ü US ROUTE ü INTERSTATE Figure 2: sampllng sftes for assesslng dfoxlns and furans 1n young-of-the-year fish from the Cayuga Creek ãralnage basin. Appendix I -49- æ4e?Btt NATÚ YORK STATE DEPARTMENT OF ENVIRONMENTAL CONSEFVATION å CHAIN OF CUSTODY IE of - (ttlnt Nùno) have (Pdnt Addrêrs) collected the on in the vicinity of Town of County Items: said sample(s) were in rny possession and handled according to to standard procedures provided to me pr¡or collection. The sample(s) were placed in the custody of a representative of the New York State Depart- ment of Environmental Conservation on 198_. Signature Date l' have received , the above mentioned samples on the date specified and have assigned identification numberlsì I have recorded perrinent data ror tr,Ë iãä'Jí. my custody untll subsequently transferred, pióareà J,?,li?"_#,îiå,ìf ãr sir¡ppeo at times and ãates as attested to below. Signature Date SECOND RECTPENT (prlnt Namo) TIME AND DATE PURPOSE OF TRANSFÊR SIGNATURE UNIT THIRD RECTPENT (prtnt Neme) TIME AND DATE PRUFOSE OF TRANSFER SIGNATURE UNIT FOURTH RECIPENT (prtnt Nsme) TIME AND DATE PURPOSE OF TRANSFER SIGNATURE UNlT RECEIVED lN LABORATORY By (prtnr Nsme) TIME AND DATE SIGNATURE UNIT LOGGED tN BY (prtnt Name) TIME AND DATE ACCESSION NUMBERS: SIGNATURE UNlT SEE REI'ERSE SIDE -50- NOTICE OF WARRANTY By signatuie to the chaln of custocty (reverse), the signator warrants that the information provided is truthful and accurate to the best of his/her aUlllty. The signator affirms that he/she is willing to testify to those facts provided and the circumstances sùrrounding same. Nothing in this warranty or chain of custody negates responslbility nor liability of the õignators for thõ truthfulness and accuracy of the statements provided. Handllng lnstructlons On day of collection, collector(s) name(s), address(es), date, geographic location of capture (attach alopy of topographic map or navlgation chart), specles, number kept oi each species, anå description of capture vlcinlty (proper noun, lf posslble) along wlth the name of iown and County must be indicated on the reverse slde. Retaln organlsms ln manlla tagged plastlc bags to avold mlxlng capture locatlons. Note appropriate lnformatlon on each bag tag. Keep samples as coolas posslble. Put on lce lf flsh cannot be frozen wlthin 12 hours. lf flsh are held more than 24 hours wlthout freezlng, they wlll not be retalned or anal¡zed. . lnltlal reclpent (elther DEC or deslgnated agent) of samples from cottector(s) is responsibte for obtalnlng and recordlng lnformatlon on the colleCtlon record forms whlch wl¡ accompany the chaln of custody. Thls person wlll seal the contalner uslng packlng tape and wrltlng hls slgnatúre, ilme and date across the tape onto the contalner wlth lndellble marker. Any tlme theled lJ broken, for whatever purpose' the lncident must be recorded on the Ghaln of Gustody (reason, time and Oate¡ ín the purpose of transfer block contalner, then resealed uslng new tape and iewrlting signature, wlth ¡me and date. -5r- NEW YoRK sr^'frì Diir,,\rìÎ.ffirfr or'--õ"rrino¡q¡.r¡¡[u coNSERVATror,l I)tVISTON OF FIS}I AND IIILDLIFE FROI.Í REGION FO TOXIC SUI}SIANCE MONITORING BY CoLLECToR(S) PROGRA}I US ING CottEcTIoN SPECNIENS lfEltroD. PRESERVDD T}Y MBTI{OD FILL IN APPROPRT.I\TE BIjNI(s As coI,fPLETELY AS POSSIBLE. r0R IrtB I]SE OM,Y COLLECTION SBX I;\B ENTRY &/0R OR DATII NO TAC NO RBPROD. LBNCTH SP CI TA I{BIGIIf REr'ütR1Cs TIO Er DIT - 5? -