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Fish
Fish
Kilts Fillets
Collected From Pool 2 of the Upper Mississippi River
| JColbo1n..NewLasndgte,, WSiellaTa.Kn.WRego en,RGelrnHA.edHm ohnark,E. nlc, I Joh~ L. Newsted~', William K. Reagent, Gary A. Hohenstein[, Mark E. E!!iso.:Elle~'son.:~, Cleston L. Lange:]:, Susan T. Wolt~ and Ryan Holem~"
+Carn ENTRIX,Okc, icin, 4864 ~ Cardno ENTRIX, Okemos, Michigan, 48864 3M Company, Eavionmetal Lars5onPa,l, Mines,UndSts ~ 3M Company, Environmental Laboratory, St. Paul, Minnesota, United States 130 Company Evora& egalsoryAT,5. Pal,Mins UndSts ] 3M Company, Environmental & Regulatory Affairs, St. Paul, Minnesota, United States
Corresponding Author: Corresponding Author: [roe-- * John L. Newsted Cart rin Cardno Entrix 1295OnesRo, Se 101 4295 Okemos Road, Suite 101 Okemo, Mihi 461, USA Okemos, Michigan 48864, USA eral on eveedGnin com Email: john.newsted@cardno.com Phos: SI7IBL134, Fux SI7381-1435 Phone: 517-381-1434, Fax: 517-381-1435 Keywords:
Key words:
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AmsTRACT ABSTRACT 10201sty perso pds PFC)wrcondi fitsls In a 2011 study perfluoroalkyl compounds (PFCs) were analyzed in fish fillet samples taken omPol 2h Ue Misi Rives, 3 ileshoenceof hc. fi~m Pool 2 ofthe Upper biississippi River, a 33 mile stretch ofriver inclusive oft.he MioscspoS.PakMises mops gogagica ar. Appia 00 cachof Minneapolis/St. Paul, Mdnnesota metropolitan geographioa] are~ Approximately 100 each of cgi ih (HGS),rb dr FVD, litbs(SM)a whi us (WE) bluegill sunfish (BGS), freshwate~ drum (FWD), smallmouth bass (SMB) and white bass (WHB) er clifoom 10 panicsampling ches of spesiile figy, Ffhl were collected fi'om 10 separate sarapling reaches ofapproximately 3 miles in length. Fish fillet ome er syd operon cay id (HCAS) C5C12, pertoiied tissue were analyzed for perfluorinated carboxylie acids (PFCAs) (C4-C 12), perfluorinated li i PFA (OC,184 Cspertocinesiarid PFOSA). sulfoni a~ids (PFSAs) (C4, C6, and C8), and perfluorooctane sulfonamide (PFOSA). Peron frat (PROS) as hse wit Grete: ee de prs. Perfluorooctane sulfenate (PFOS) was observed with the greatest frequency and at the greatest concgigo om 2.3c 1760t lgwo:Mes (arPiFOS concentration in fish tissues ranging from 2.3 to 760 ng/g ww. Mean (geometric) PFOS | mea 0S7,501VI er 223 pits concentrations In BGS, FWD, SMB and WHG were 20, 28, 29 and, 58 ng/g ww, respectively. Concenuionsf peter iste(FBS), peisbete(PHsS), RsOSA Concentrations ofperfluorobutane sulfonate (PFBS), perfluorohexane sulfonate (PFHS), PFOSA nh in CC RCA hd cep met ensocrns ttwe and the nine C4-C12 PFCAs had species-specific geometric mean concentntfions that were less nS.Compr of currfh esfmi scodus cote nfs than 5 ng/g ww. Comparison ofthe c::..'.-c= ~ data from this study to data collected in ~00~......
| mee showed significantly lower rca.:c:i:n= ~f perfluorooctane sulfonate (PFOS) fish tissue
cncmaons bvghn Poo.The dct menoPsEOSssnnonfsor concentrations throughout Pool 2. The reduction in mean (geometric) PFOS concentrations from 2009 2011 forBGS,FWD, SMDand WHDwee6%,600556, an 20 spectively. The 2009 to 2011 for BGS, FWD, SMB and WHB were 60%, 60%, 43%, and 30% respectively. The essed diei shprion PEOS cls rhMissi RiverPos 2 gon measured declines in fish population PFOS levels for the Mississippi River Pool 2 r~ion are cist il he 10sstonof matungapotsbd on prborocas consistent with the >10-year cessation of manufacturing ofproducts based on perfluorooctanyl chm ait ogin fosinMist iilcml ses ofPC oh chemistry and with ongoing efforts in Minnesota to effectively control sources ofPFCs to the Missi River. Mississippi River.
(Sm)
2
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INTRODUCTION
INTRODUCTION
The stadofperurivated compounds (PFC) ithe cvicnment hasreseed
The study of perfluorinated compounds (PFCs) in the environment has received
considerablesionsincetentialreports of gol disributon 1 human populatioxnsd considerable attention since the initial reports of global distribution in human populations and ie (1.2),Recentreviewsof PEC: moniaing nbaand manshave bee reported (3.4). wildlife (1,2). Recent reviews of PFC monitoring in biota and humans have been reported (3,4). PCs ave benmesure nsw ndseawater cnvicnments (voterandails) a ats PFCs have been measured in freshwater and seawater environment~ (water and animals) at parts pervilion per trillion levels levels (3, 35,-599))..
Potential sures of exposureofPEC bo hans cle inhalofahtouiseohonld dst,
Potential sources of exposure of PFCs to humans include inhalation of household dust,
contact ithconsumerproducts,drising wateandconsuofmfood (10-1).Of ese contact with consumer products, drinking water and consumption of food (10-12). Of these
ours food consump has been mated 0conusoverS0% fhe ime: sources, food consumption has been estimated to contribute over 913% of the total lifetime exposureoccupationallyexposed hans 13). Generallymeasureable concentrations of exposure to non-occupationally exposed humans (13). Generally mcasureable concentrations of PFCs hav bonobserved in eshte fis ndseafood ndsedis haveshownthatboi can PFCs have been observed in freshwater fish and seafood and studies have shown that both can accoorm>S034ofthe xpos fnham populations Canad,Spain, Plan, Chin,ar account for > 50% of the exposure in human populations in Canada, Spain, Poland, China, and Sweden (12, 1417), However,fhsndseafood eve aobnshown 1 be minesource of Sweden (12, 14-17). However, fish and seafood have also been shown to be a minor source of PEC exposurein pogalations from Norway and the UK indicatingGt regions] ferences a: PFC exposure in populations from Norway and the UK indicating that regional differences are importantwhen valuinghumanexposes(13:20). Over, these iasuppor he nes important when evaluating human exposures (18-20). Overall, these data support the need to lunehumanexposurebased oregionalor specificditht cludes ot ly 1hPFC. evaluate human exposure based on regional or site-specific data that includes not only fish PFC unitlc o regio-o speciic n opueton diffsard corsponding dieay habs concentrations but also region-specific population differences and corresponding dietary habits.
`Several uci haveshownthas shallt from nigeions]Pol21athe Upper
Several studies have shown that fish collected from navigational Pool 2 in the Upper
sisiRiverin the MincapolisSt. Pal meiopalian ara ave essreable enviromental
Mississippi River in the Minneapolis/St. Paul metropolitan area have measureable environmental
conceraoftFiCosnwishPFOShavingthegreats costrb0tthiewoinlbodyburden of
concentrations of PFCs with PFOS having the greatest contribution to the total body burden of
{hese ish (21.23). The Minnsoa Pollo ControlAgency(MPA) reeseda2009sy
these fish (21-23). The Minnesota Pollution Control Agency (MPCA) released a 21309 study
ened, "Missspp RivPeor 2 tensiveSud ofPeflrochenicalsin Fish and Water
entitled, "Mississippi River Pool 2 Intensive Study of Perfluoroehemicals in Fish and Water
:
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2009"whichrepored PFOSconccoaonsnletsoffive peesofsh 24).Prtthe
2009" which reported PFOS concentrations in fillets of five species offish (24). Prior to the
2
009
2009
study
study,
oonnlyyllimeitdedssaammpplilinnggwwaassccoonndduuccted
ooffffissh
foorr
thheepprreesseenncceeooffPPFFOOSSiinn
PPooool
2 2
2(253,,
2295.). FFiisshhfforommPPooootl 22wweerree ffiirssttetsestteeddiinn22000044,,aanndd ssppoorraaddiiccssaammplpilningghhdadcoccccuarrreddiinvvrairoionuss
lolcoactaitioonnssiinnsds and/or imme dwnseam immediately downstream fofhtheeppooooliinn22000044,,22000055,,22000066 aandd 22000088;;Bhoowweevne,r, elatielylownumbers ffi wescolle,and hefhspeciesampled varidbetweenyears.
relatively low numbers of fish were collected, and the fish spccivs samplad varivd between years.
102009,MPCAconductedthefsccmprensiveevasionofPRC nfh roughest Pol2, In 2009, MPCA conducted the first comprehensive evaluation of PFCs in fish throughout Pool 2,
which volvedfivefishspeciessampledinfourgeographicsectionssunning hecicofhe
which involved five fish species sampled in four geographic sections spanning the entirety of the
Ppooool.l. DDaatta frroommtthheeMMPPCCAAsastduldyy idnidcicaatteeddtthhaatttthhee reste freshwaterddrruummhhdad thheehighestathe highest arithmetic meanPROSconcern t229 nig 5 (gometicmeanofT0ng). Thestay sso conlodd
mean PFOS concentration at 229 ng g-1 (geometric mean of 70 ng g-l). The study also concluded
htthat nnoo dissccearmniibblleevWeennddsswweerreesoseen1inPPRFOOSS eves levels in isuoverim fish tissue over time foorr pees species hthtathhaadd
censampinle2e00d4. Usingdtfromthe 2009 MPCAsad,theMimestaDeprcntof
bc~n sampled since 2004. Using da~a from the 2009 MPCA study, th Minnesota Department of
Heth(MDH)isu ishconsmpsionadvisoryofone calpcmonthfor heFests
Health (MDH) issued a fish consumption advisory of one meal per month for the fr~wat~r
dmbas drum basedconntthhe verge ~-~o~-agc hms manconcenofPFOS arithmetic mean concentration ofPFOSeexxccoeoeddiinngg220000nngg3gqG(266)).. AAcoserodridinngglly,,PPooooll 22wwaass liisstteed aas imppaaiireddffoorrPPFFOOSS.. Ist hshoouullddbbennootteeddhthtatffishhccoonnssuummgpttiioonn
aaidvvsiseorriiessaannddhtheeiimmpapiairrmmeennttdedteeterrmmininataitioonnwweerreeaallrreeaaddyyin pllaacceebbuasseedd oonnaobtheerrccoornssttiituteenntss,.
AZO11 shstdwasdesignededcodctedwiththe activesofpain hepv 209
A 2011 fish study was designed and condu~l with the objectives of updatlng the previous 2009
MMPPCCAASaStduyd,y,ccoonntrtriibbuuttiinngg ato thheekkmnoowwloleddggeeooffppootteennttiiaallssoouurrcceesstthhrroouugghhoouutt thheeppoololaanndd {avestiguingthetemporalimpactofthe 10-yearcossaton ofmashingofproductsbased
investigating the temporal impact of the > I O-year cessation of manufacturing of products based
oonnppeerrtfilusoorroooccttaannyylcchheemmisitstrryy iin thheerreeggiioonnsannddoonnggooiinnggceffforstsiinnMisofo Minnesota to ceffffescttiivveellyy cone controlssoouurrcceessooffPPFCCs ote to theMissi River. Mississippi River.
MATEARNDIMAETLHOSDS
MATERIALS AND METHODS
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Sy te.Theupperand owe exten of isis RiverPo 2is ied by bo ams ad Study Site. The upper and lower extent ofMisslsslppi R2ver Pool 2 is defined b)' two dams and loko (Fin1. Tosper xisisboundedby FondDem(Lock& Dam #1) od locks (Figure 1). The upper extent is bounded by the Ford Dam (Lock & Dam #1) located tween MicaadliioPchfs ort of conforof oe Misiend. between Minneapolis and Saint Paul, just north ofthe confluence o~'the Mississippi and Vineet Rives,whileteower rtf defndby eHasingsDam(Lock Dar#2) Minnesota Rivers, while the lower extent is defined by the Hastings Dam (Lock & Dam #2) {oct jt pst ofHastings, MN. A alo10spingresches ofsprenis3 mtileys locatedjust upstream ofHastings, MN. A total of 10 sampling reaches of approximately 3 miles inl wer denied i Po 2 Eh 10200 "Ber nes ewe xhof ech. in length were identified in Pool 2 with 100-200 m "buffer zones" between each of the reaches. The 2001 ihSty cud rs ilypngpicalysidsapling of Pon 2h The 2011 Fish Study included a more highly geographically stratified sampling of Pool 2 than the 2009 MPC Sty. Instead of hefussinsof vio ngs aed revo by he MPCA 2009 MPCA Study. Instead ofthe four sections of varying lengths sampled previously by the MPCA 220he020911mneymore rly vided the vossectors five i en recheof in 2009, the 2011 survey more ~'mely divided the various sections ofthe river into tea reaches of ppm x gh ampereScions 1-4vesKesh 410; 1 eedoni approximately equal lengths (compare Sections 1-4 versus Reaches 1-10; Figure 1). B~sed on this porsche dds for vensees (1hsampled pe ee ile) aired by 65. approach, the data density for a given species (fish sampled per river mile) also increased by 67%. Fi Coleco.To fhcollection focus on species hsmybehavedbylcnsod Fish (Tollectton. The fish collection focused on spoeies that may be harvested by licensed `mgs or consumption had ben eff vious Missi Rive PECssn anglers for consumption or had been the focus of previous Mississippi River PFC assessment is. Th spc ltd cadesmalithbs (codepli,ewhesbss studies. The fish species collected included smallmouth bass (Mieropterus dolomieu), white bass trons css, tvsdu pinsgre, xd Boss (zpos 7). The (Morone ehrysops), freshwater drum (Aplodlnotus grunniens), and bluegill (Leporais spp). The Camplin bstive stocolt 10h er ces 1 xchof henspin esses. The sampling objective was to collect 10 fish per species in each ofthe ten sampling reaches. The emary collection hig ws los(hSiiRono,Varsooe, WA, USH), primary fish collection technique was eleetrofishing (Smith-Root, Vancouver, WA, USA), owen ined ok adnspi esl id whe colinwas ek five. however limited hook and line sampling was also used when electrofizhing was not effective. Duet prcpaoncen edi hestof eldfor,wat lia Pol 2 wer gly Due to precipitation events preceding the start of field efforts, water levels in Pool 2 were highly atantd eeie. As esl, colin wes bendsnd es eld olenruns variable and elevated. As a result, eleetrofishing was hampered and three field collection rounds (RoundfmMay tr,201,Bond2 from Aug 121.2011snd Rnd or (Round 1 from May 31-June 9, 2011, Round 2 from August 1-11,2011 and Round 3 from SSeepotmebe.r51121058240.11) wer esr 0cumple shslic romMoy3hwgh September 11-15, 2011) wer~ necessary to complete the fish eolleotion frem ~,~-a3' 3 ! tEreug.~
s
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Upon oleion, fhwere asf toleanconesconsibed cend mmo ton
Upon oolleetioa, fish were Wansferred to clean coolers con~ining bagged ice and lyansportcd to a
ab forproco essing. Fis wrecxaminedfocger bestndover boris,
laboratory for processing. Fish were examined for general health and overt abnormalities,
mewseighued1ndrphoetogap,bed.Oohwere removedfor gedeterminations. Fish were
measured, weighed and photographed. Otoliths were removed for age determinations. Fish were
ict basedonUSEPAgidline2s7.Thefiletypeforallfhspecieswassled andsn
fillvte~l based on USEPA guidelines (27). The fillet type for all fish species was scaled and skin-
onoorbonesremoved)whic i const ford sd hesespiesby on (major bones removed) which is consistent for data that is used for these species by the
MincatsDepartment ofHealth(MDI fo csabish sh consumpicnadvisories. Fillswere
Minnesota Department of Health (MDH) to establish fish consumption advisories. Fillets were
nigh and omogenized na chemically leanedsnesfodprocessor (ReoCoupes, weighed and homogenized in a chemically-cleaned stainless food processor (Robe Coupe@, JckaonMS, USA)sig zefcrmethod. Homogetsncrwadhafoitnlo Jackson MS, USA) using a l~eeze-fracture method. Homogenized fillet tissue was then put into lean olenbag ndkeptfrozenwalnly. A alof396 is werecllecieodr clean polyethylene bags and kept frozen until analysis. A total of396 fish were colleoted for cheney. chemical analysis.
WeerCollection.Toes wate scwerecle romsshsping sch dring he fluter Collection. Three water samples were collected f~om each sampling rem~h during the | ton s,m oso.Sisween meva middle round (August, r~ Round 2) offish collection. Samples were taken from the water columnspray 121024 below he afcad omteminsivercanoeandlor column approximately 12 to 24" below the surface and I~om the main river ~hannel and/or Towcherae fihweoeconllecsted. Alspies wee collected gab spewinglrg locations where fish were collected. All samples were collected as grab samples using large lyinbt sweistbt2e50dm ighdstpy(Dl PF) se pl polyethylene bottles and were distributed to 250 ml high density polyethylene (HDPE) sample es th consid crastandards (155)andsuo covery sanders(SRS. bottles that contained internal standards 0Ss) and surrogate recovery standards (SRSs_).
fee me Experimental-Analytlcal. Standards and Reagents. All target analytes, ISs_, SRSs_, and mass rions(MS/MS 0d) reshown ble 1, Sporting Infomation. Prrcbepansic transitions 0dS/MS mode)are shown in Table S1, Supporting Information. Perfluoroheptanoie acd(FTA)was purchasedfom gmaAldich (Mike,WI,USA) while acid (PFHpA) was purchased from Sigma Aldrich (Milwaukee, WI, USA) while peforaonaoiccd(PFA)perforce acid(PFDA), ndpefsoradodecancc cid perfiaorononanoic acid (PFNA), perfiuorodecanoic acid (PFDA), and perfluorododecanoic acid (PFDoA)wereporchse rom OsovondProducts(WestColm,SC,USA). Predomintly (PFDoA) were purchased from Oak-wood Procluets (West Columbia, SC, USA). Predominately
iar omer sanders ofperloruocaoicsid PFOA),pefsoroboans sone(FHS). linear isomeric standards ofperfluorooctanoic acid (PFOA), perfluorohexane sulfonate (PFHS), pepfeirfolurooroocotcatanneessuullffoonantee((PPFFOOSS)),aanndd hethe foolllloowwiinnggsstaablle cope isotope eld labeled ferencesandr reference standards
.
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weepurchased from WellgionLaboratories (Golp, ON Canada): 12346 "CPFBA, were purchased from Wellington Laboratories (Guelph, ON Canada): [1,2,3,4-13C4]PFBA, [12345 CPFPeA,(1L27GIPFHR1A,2345 CIPFHPA, [1234,5,67,CIPFOA, [1,2,3,4,5-~3Cs]PFPeA, [1,2-13C~]PFHxA, [I,2,3,4,5-~3Cs]PFHpA, [1,2,3,4, 5, 6,7, 8-~3Cs]PFOA,
[123456785 CIPNA, [1,2,3,4,5,6,7,8,9-13Cg]PFNA, [1234.5"CIPFDA, [1,2,3,4,5-13C6]PFDA, [1334567 CPFUIA, [1,2,3,4,5,6,7-13Cz]PFUnA, [12[1,2-
VCIPFDOA, [123-"CPFHS, 1234.5,678CUPFOS, 0d[12343676CIPFOSA. ~C2]PFDoA, [1,2,3-~3C~]PFHS, [1,2,3,4,5,6,7,8-~C8]PFOS, and [1,2,3,4,5,6,7,8-~3Cg]PFOSA. The sabe stop beled standard (10, PFSwaseid rom RT Iernationa (Research The stable isotope labeled standard [~O~] PFBS was acquired from RTI International (Research
TrianglePak,NC) orue as 1 ermalstandard.Th flowingstolelly bedreference Triangle Park, NC) for use as an internal standard. The following isotopieally labeled reference
sandrdswere purchasedfrom WelngionLbocsaris (Guelph, ON Canad)forsea standards were purchased from Wellington Laboratories (Guelph, ON Canada) for use as srgrecovery standart: [1234 C.PFOA, 112,34-C,2JnPd1F2OSC,.JPFUBA surrogate recovery standards: [1,2,3,4-~3C4]PFOA, [1,2,3,4-1~C4JPFOS, and [1,2-~3C~]PFUnA. `Standards contin bh rachodnd nar somers of PROS (potas sal,Lot 217), Standards containing both branched and linear isomers of PFOS (potassium salt, Lot #217),
POA(ammosln,Loit #u33m2),and FOSAwerecbsinedfrom 3M Carp (St.Pa MN, PFOA (ammonium salt, Let # 332), and FOSA were obtained from 3M Company (St. Paul, MN, USA). Alchemicalsand reagentswed xtacionscoursweefom SigeAkich or USA). All chemicals and reagents used in extraction procedures were from Sigma-Aldrich or
VWRScenic (ridscpon,N,USA)whe [PLCgrade methanol sndacti were VWR Scientific (Bridgeport, NJ, USA) while IIPLC grade methanol and acctonitrile were
ppuurrcchhaasseedd
fomfrom
EEMM
SScciieennccee
(Gibbsiown,
(Gibbstown,
NJ,
N J,
USA).
USA).
FishTceAnlst.Anaya mecohr ssh suesaspublbiysMahliesd 4. 29)
Fish Tissue Analysis. Analytical methods for fish tissues as published by Malinsky et al. (28)
werefollowed istad. Bit oven lssampleswere horsogenzedfez withdy ice were followed in this study. Briefly, frozen fillet samples were homogenized frozen With dry ice
10schicve finpowdercosine. Afehomogethndisszwaasttaniseorrnd0,2 to achieve a fine powder consistency. After homogenization, the tissue was transferred to a
polelylen bawhich wasstorednscled 20 C1oallowth residualdy ft bln
polyethylene bag which was stored unsealed at -20 C to allow the residual dry ice to sublime.
Approximate0l.y5 graofmexsch sample homogerat was rane centagbees and
Approximately 0.5 grams of each sample homogenate was transferred to centrifuge tubes and
eachsample luo rceveda fxd quan ofsable opeabd1S nd SRSforuein
each sample aliquot received a fixed quantity of stable isotope labeled ISs and SRS for use in
qquuaannttitiattioan,,
aannddffoorreevavluaatiolnoofufaanaailytte rireeccooovveerrn3y",, rreessppetcitivvleyly..
Exacionofcachsample is.
Extraction of each sample was
pertmod by brnageizaion 82.5 mlofscone, flowed by cenifugaion snd analysis
performed by homogenization in 2.5 ml of acetonitrile, followed by centrifugaticn and analysis
bbyyhhiigghh ppeerrffoormmaanncceelliiquuid hchrroommtaotgogrroapphhyyt/taannddeemm mmaassssssppeeccttrroommeettrryy ((HPPLLCCM/SMISM/SM)S.).
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| Sump wrydwin 9Agi 1100HPLC ys wilhine pu PloAT,CA) |
Tm, | cHrPLiCsmyem trrucro wi--th0--ABSl--e (--Fraia--gham--,MA)mAPLt$000mrass--pectr--ometer || BFC werespan ensemecrschromaograpicalywigsOui LB ne |
ndscimolehsesm a ow teof400. issndsn ctinvolumeof |
on
!
|
Wrrt.The scmetsdcetWboty.) werelowes | I WoOerAr~dysis. The analytical methods described by WolfeL al. (29) were followed in this
suty. rityallsamples,calibrationsandr, andascitedqualycontrolsampleswere | ! study. Briefly, all samples, calib~tlon standards, and associated ~luality control samples were extinct in hte pr condiodWater 18 ldphasectnction(SP)cuvide extrace~ using either a preconditioned Waters tC18 sofid pha~e cxtrac'don (SPE) cartridge (PPAPFDA, FUGA, PFDAPS, EIS, PEOS ndFROSA) or procnacicodOnl | | (PFNA, PFDA, PFUnA, PFDoA, PFBS, PFHS, PFOS and PFOSA) or a lm,'-coadidoned Oasis HLRSPBcris(PFBA, RPE,PFA,PPA,sod PRO).Trg sywsere I-ILB SPE ~rtridgv (PFBA, PFPA, PFHxA, PH-IpA, and PFOA). Target analyteS Were
nthmt tc il ih25 nmon hc, Salve | : extracted with methanol into polypropylane vials with a 25x concentration factor. Samples were
hnwld io nAlt 120 se(Plo Al,CAVHPLCye ic ianAD. | ! then analyzed using an Agilent 1200 series (Palo Alto, CA) HPLC system inter~'aced with an AB
Scex (Framingham,MA)AP S500mas specter ppdwithaTubolnin lec S~iex (Framingham, MA) AP15500 mass spectrometer equipped with a Turbolon ionTM electrory tertcnand peed in negative SMSmde.Ansty of he rg snes as | spray interface and operated in negative-ion MS/IVIS mode. Analysis ofthe target analytes was
pete sig BtsTMC18 lyn] conn 2. mn x 100m:Stailsz) held | i pcrfvrmed using a Beta~ilTM C 18 anglytical cohmm (2.1 mm x 100 ram; 51~ particle si~) held at
30 ith20sincevor dmc blehs se The Bove | | 30C with 2 mM ~mmonium a~etate in water and methanol mobile phase system. The flow rate
| a300Li dhe ection volumevasihr Sx 104.
|
Det AnaysSais) sosyss wer permedwilSAS(SAS,Vr9.3 Cary,NC,USA). | | .was 300 pJ., rain"l and the injec'don volume was either 5 or 10.pL.
D~,~budysis. Statistical analyses were performed with SAS (SAS, Vet. 9.3; Cary, NC, USA).
KKolomlmogoogroorovv--SSmmirirpnoovtteesttaannddpprroobbaabibliliittyypplloottsswweerreeuusseeddttooeevvaalluusate~ nnoorrmmalailittyyaannddiiff
|
|
A | necessary, data were log-transformed to approxima~e normality. Variance homogeneity was
vita witLevene' tt. Spainlocation PFCconenration ifrence weeeva | | evaluated with Levene's tesL Species and location PFC concentration differences we~
.
|
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33MM_MMNN0033220055220055
ei mind ods (PROCMIXED) fstspar meas scout fo iplspl zs. with mixed models (PROC MIXED) and least square means to account for unequal sample sizes. Toysts with ieKenn aprximetionve nd1 vate ifnbeen snr Tukcy's test with the Kramer approximation was used to evaluate differences between treatments (Gedsoiosoe)n. Tits it theStevespeoimton weedvl (species and/or location). T-tests with the Satterthwaite approximation were used to evaluate ila beeen groups whi comlaonswer evlstod whe Spa'srkcst. differences between groups while correlations were evaluated with the Spearman's rank test. Unless moet ll PRC onc sic tradfh ilies wes cxprsdse Unless noted., all PFC concentrations in surface water and fish fillet tissues were expressed as a somesmsn and fs anand co,Trnghont is es dieseswih p<OT5wer, geometric mean and its ~aandard error: _~.9~.~..9.u.~...th!~_ 1~_a~_r_ _.di_ff._e_r_e__n.c__e_s___w_i~t_h~ ._<_ ~._0_~._w_~__m_..............[ Common~ lull: s~ .... r~ a,~m conttoteesgisfictan. considered to be si~!~ificant,
QultyAssan. WotrSamples. Ausfrsspc boo er slidfen ac Quali~v Assuranc~ Water Samples. A total ofthree sample bottles were collected from each locaton Gri, pledl, 0d25 ld mt ik (FMS).MsnFMS location (sample, sample duplicate, and 25 ng L-1 field matrix spike (FMS)). Mean FMS recover wiper eliesnrdans) nl evespiesof G-C12 CAS, recoveries (with percent relative standard deviations) in all the fiver samples of C4-C 12 PFCAs, 4.6,md CBPESAS PROSA, ad(123.4- "CIPFOA, (1234 "CPFOS,md 12. C4, C6, and C8 PFSAs, PFOSA, and [1,2,3,4- 13C~]PFOA, [1,2,3,4- ~3Cz]PFOS, and [1,2PFASRSswe 75-162320290).Dead ulycol ests rovt ~3C2]PFUnA SRSs are 87.5-124% (6.8-22%). Detailed quality control results for the water spe erst Tale52,Sporn nformion samples ~ro presented in Table $2, Supporting Information.
uty Asarance. FiSamples. A selswer sly indulce, ns, Quality Assurance. Fish Samples. All fish samples were analyzed in duplicate. In addition, evryenh spl add hid wd sthsl los htwre ried with every tenth sample included a third and fourth sample aliquot that were fortified with
pefointdcabonylic id PFCAS) (C C12),pivotedslisid (PPSAS) C4, perfluorinated carboxylic acids (PFCAs) (C4q212), perfluorinated sulfonie acids (PFSAs) (C4, C6,80d C8) sdpetcooctanesland PFOA)a lowadigh aorsoeymati pk C6, and C8), and perfluorooctane sulfonamide (PFOSA) as low and high laboratory matrix spike spe(LMS. Alsample supe plist LMSwer red ithe ee SRS samples (LMSs). All samples, sample duplicates, and LMSs were fortified with the three SRSs
(1234 PCIPFON [1234-P4C13PFCOPFSUR,A. Mesaevaeodposss [1,2,3,4- ~3C4]PFOA, [1,2,3,4- ~3C4]PFOS, and [1,2J3Cz]PFUnA. Mean reeovefies and percent oiesandr dvions sdserps samples,sie plete nd LESS) > relative standard deviations in all study samples (samples, sample dupiicates, and LMSs) In >
| tot, ss ted ss 970) 970~
the of the
tthhrreeee
SsRss..s[.~1[2~.3:.42.":3C.~I.P4.F-.A.~,.[~.1.~2.43.~4.P".CFI~PAF-O~SI~,-4sn-~d ![!~1F2~-Cs~P-~ud[n~gw~r.e~...............
107% _+ 13% (n=974), 103% _+ 10% (n=974) and 106% _+ 11 ~ (n---971)~ respectively. Mean
22338822..00000099
33MM_MMNN0033220055220066
LS reconsider evesda devon(17)ofall eensand he three LMS recoverie~ and percent relativv standard deviatio~ (nffi47) ofall the analyt~ and the thw~ SRS re 917113% and 320%, espetively SRSs are 91.7-113% and 8-20%, r~3~ively.
fife reelaf 00, 10 snd 00g, ndcacheenice(>22) withC= MeMaeannlalabboorraattoorryyccoonnt~r'oollssaammppllee((LLCCSS))rereccovoevreireiessaanndd 5%RRSSDDss n> 224}incontrol beg ler ~'n~24~_i.n..c..o.n..t.r.o.l..b.l.u..e.g..i.l.l.f.i.l.l.e.t.... fortified at three levels of 1.00, 10.0 and 100 ng/g, and each level in triplicat~ (n > 224) with C4-
[rmmrmmirm------ (CI2PRCAS,C4,C6,andCBPFSAS,PFOSA, ndthetheoSRS [12,34-"GuIPFOA, 1234.(Ferminses _ C12 PFCAs, C4, C6, and C8 PFSA~ PFOSA, an~i the three SRSs [1~,3,4-~._%]_P_~_OA, [1~,~,4-
FE
--
13% ~0~PFH_x~ ~3~6%-~ i0% for PFHpA~ 96.1% ~- 15% for PFOA, 9~2% i~% for PFNA, :,,~,,
02%. 190or EDA, 96756497 ox PUB,909% 4.0%forPEDO,Si 19 fr ommmbims----)
=~ PFS,97.0% & 9.8%for PFHSand 95.8% & 6.9%forPROSA.TheaverageSRS recoveryand.
RRSSDD foroo~L~CSSSwWeerse a~slfoli~oow:si m1~0'9,'. ~4-12i~% fooer P~C-PPE~OORA,, 1i005~%%4 $S.5~% foorr C. PFU and 105%: 8.5 or C,PROS,The LCSelsdemonstinteccs meio
PFU~-and 10~% ~- ~% for ~c~-PFo~ Th~ LCS results d~nons~tt~ ~edlent m~:hod
(Cm -- : ..... | ~resente~ |n tab~ar form? Ma~Im ~ olumns
| where the 1~ ~,luran In PFr..As and the 2'~ column b
ntoraon. accuracy and precision for all target analytes and SRSs (Tables $3, $4, $5 m Supporting
Information).
Quay Assurance.nerlboraey:.To PECays of al 396 fishandlwrod ~dityAssurance. I~terl~bora~ory. The PFC analyses ofall 396 fish and all water study amples wes conductedbytepinaysaltssig bors CM Emam samples were conducted by the primary analytical tes~ng laboratory (3M Environmental Labrsoy).For quality saeconimstryanalysis of 4 sh presi10%. he Laboratory). For quality a,~suranceo confm~atory analysis of41 fish representing ]0% ofthe cts cumber fh ndall 30 veer samples collected mh10 aches insmpling Round 2 total number offish and all 30 water samples collected fi~3m the I0 reaches in sampling l~ound 2
(hugs (August) werweresisalso alyanalyzedbbyy secondsys a second analytic~l sting t~'tinglbosy(AX'YSAsya laboratory (AXYS Analytical
SeSrervviicessLLitdd.))..
Withth crepionof ane pitsapsys,thdia rsh se plsves n good With the exception ofone split ~ample analy.~is, the data for fish tissue samples was in good semen been he boris with he verge relative percent flrs(RPD)fr ! 8greement between the laboratories with the average relative percent differences (RPD) for | rAS aPC ty25. ES a rpn wr Dt PFASs and PFCAs generally 25% or less. PFBS was t~e lone exception with an average RPD of
[ apeoimatly 0%; owes,th significance of his fence i ficultto viegv hat approximately ~0%; however, the significance ofthis difference is di/~cuIt to evaluate given that
0~0
22338822..00001100
33MM_MMNN0033220055220077
twasbas on nly 2samplesapproximantaiynsg metho iitofiain. The slit it was based on only 2 samples approximating analytical method limits of quantitation. The split ith speressbenethe SM EnviranodAnXYsS laboraditstovreriygeoosd fish sample results between the 3M Environmental and AXYS laboratories indicate very good sgrcment.ThePROS essforAXYSwre ypclly Higherta for hecomspending 3M agreement. The PFOS results for AXYS were typically higher than for the corresponding 3M slitsample,Th averagerelativepretdiffrencewas 16%for he2011dataset.
split sample. The average relative percent difference was 16% for the 2011 data set.
tersbrsorysls beenth smetwolswees alyzedfrthe2009 ishsamples, Interlaboratory splits between the same two labs were also analyzed for the 2009 fish samples, ith 8 average relativepresdiffcence of bout 14%(VPCA2009).Tnbothsie,thse with an average relative percent difference of about 14% (MPCA 2009). In both studies, these (8frrewiothicnscestasbl nerlborsicy variation (30,31). differences are within acceptable interiaboratory variation (30, 31).
An dion!poststady QCnersbcomoparrisoknfocPHyOS in ia ese wascomplete An additional post-study QC interlabomtory comparison for PFOS in fish tissue was completed atboththe 3MEnvironmental andAXYSIboratricswi theanalysis of blindeddplcae at both the 3M Environmental and AXYS laboratories with the analysis ofblinded duplicate `sand reecematerial is sues (ton eitofSadar nd ecologysda standard reference material fish tissues (National Institute of Standards and TechnoIogy standard | csmel OTSRA be ot LsStir GR 154 mdLk reference material (NIST SRM)) for lake trout tissue from Lake Superior (SRM 1946) and Lake icin (SRM 1947) nd pitsof prevolyalyzed arcivedPoo! 2 fsdy Michigan (SRM 1947) and splits ofpreviously analyzed amhived Pool 2 fish tissue study sample. Ress from thisQC dyshowed ood grecmentbetweenPFOS concerrion samples. Results from this QC study showed good agreement between PFOS concentration messed i orginalanalysisof te2011 sh suesample scondebybot labors measured in original analysis of the 2011 fish tissue samples as conducted by both laboratories. ndion, PROSconcentrations messedby bot Ioriforth SRMsapsfl witha In addition, PFOS concentrations measured by both laboratories for the SRM samples fell within he acsreangperpaorebdbylNIeST.BasedonaveragePROSconahenla,ve the acceptable range reported by NIST. Based on average PFOS concentrations, the relative perc iffrencsbetwenthereport NIST SRMconsctationsd hose csr by 3Med percent difference between the reported NIST SRM concentration and those measureA by 3M and AXYS ab ws tan 105 es nictin cccscurcy bybhaor. AXYS labs was less them 10%, thus iadicating excellent accuracy by both labormories.
Theiteraborstrycompanbasedon waterPEC conccrcatonswas lime doe ote lrg The interlaboratory comparison based on water PFC concentrations was limited due to the large umberof on-detect reportedby both aortas,Using doafonached samples with
number of non-detects reported by both laboratories. Using data from matched samples with
measured concentrations byboth sboraaies,ie RPDrangedfrom1.60 135% withanoverall measured concentrations by both laboratories, the RPD ranged from 1.6 to 135% with an overall merc average and median of 36% and 3%, especie. Fo PROS, hcRPDrandfom arithmetic average and median o~" 36% and 33%, respective]y. For PFOS, the RPD ranged from
|1710 5635 withansthmesicaverageof 35%. 17 to 56% with an arithmetic average of 35%.
1
22338822..00001111
33MM_MMNN0033220055220088
I
|
[r------ RESULTS AND DISCUSSION
|
|
PRC Concenpien oresr A comic stasisls ral corhs | ] PFC OTmm~raZ~s in Water. A complete set ofwater samples for all ten re~hes was
suclollelecctteedddduurriinnggtthheesseeccoonndd ruounnddooffffiisshhccoolllleacttiioonn((AAuugsuusstt))..RReessuullttssffoorr tthheessees~a.mmplvel~sacs:
i
ConcorsoPFDA,PU.PFD snd PROS inal hiny spewer thanth. | pprreesseenntteeddiinnTTaabbllee 11..OOff.wwo~l'e.~rsa~m.mplpe!sc-~cccalli[ecc~t.ae.d~ffoarr i~lI~r~e.a~cchhe~s..i"n~RPo.cu~n.d~22(~A*u.g.u.s.t.).
|
_e~oncentrations ofPFDA. PFUnA, PFDoA and PFOSA in all thirty samples were less than their
LOOQ~~.F~a..b~l'~e1-^H)1).. SSimimilialarrllyy,,wwitithhtthheeeexxcecpetpitioonnooffaonneessaammpplleeffrroommRReeaacchh 1100,, allll rreessuullttssffoorr
|
FPS,Pip nd FPAwre sthOQ, ConPFOvAwaecrdiyi | PFHS, PFHpA and PFNA were also less than their LOQ. Conve~ely, PFOA was detected in all
ty hen PA inf ee I R1-e 4, alye RCH wilh ten study reaches and PFBA in nine ofthe ten reaches. In Reaches 1-4, the only PFCs with
mesnrabl lvlwrePFOAand BA withscenruions gin rm 21.161d<0 | measoreable levels were PFOA and PFBA with concentrations ranging fi'om <2 - 3.16 and <10 -
121.2.88nrgig/L/L,,rreessppeecctitivveellyy..FFoorrPPFFOOSS,,wwaatteerrccoonncecnetnrtraattiioonnssrraannggeeddffrroommtthheeLLOOQQuuppttoo 113366nngg LL"*l
|
`wwiitthhaapppprrooxxiimmaatteellyy7700%%oofftthheesssammpplleessbbeeiinngglleesss tthheeLLOOQQooff22 nggLL"-.].TThheeg8rreeaatteesstt PPFFCC
|
|
cnnwoe sarda Rech 0 lowed cscs ete Rech. To | toner.air,ions wc~ measured in Reach 10 followed by concentrations repoz~ in Reach 5. The
PCnnn os bthof hi ston iy osbinsby it | | PFC conccnlrations obs=ved atboth ofth~so locations may have been influenced by point
eemSgooee ssd tch,aDebevreenpreofins tiseceas || source mixing zones and as such, may not be representative ofa-tbe river cross section ~f
tthheesseeppooiisnttssoouurrcceessaannddPPFFCCccoonncecnetnrtraattiioonnssiinnssaammpplleessccoolllleecctteeddfforommllooccaattiioonnssoonntthheef~ ar
|
oJ s ekoboil rc i 0,Sel-- on-- BEG || op~site bank ~.&ese-fmffa~ less
bo ound (Supplemenschmeters)Overs diffrencebeeensampling roundsfor
|
CJ ompan mapl ye POSbor 209d21 sil || Comparison ofwater sample analyses for PFOS between 2009 and 2011 indicate a similar enforceable emts prsaf be, wihihr decals | pattern ofnon-detectable results in most parts ofthe river, with higher detectable levels in the
ctdorm, S120,Rs 1. hh emf | most downriver area ofPool 2, (Section 4 in 2009, Reach 10 in 2011). The high frequency of
22338822..00001122
33MM_MMNN0033220055220099
sn-cublewi srpis ohyers ily ss pondcangs.Te non-detectable water samples in both years limits the ability to assess temporal changes. The acon iifo PROS in 01 apes 2g i ee nthe ii 2109 detection limit for PFOS in 2011 (approximately 2 ng L1) is lower than the limit in 2009
((aappppmroxximimaatteelyl$y5 nngg LL"%).
201 PECConcentratiinFoinshs.
2011 PFC Concentrations in
`Messi PCconsstionswes ord nal soscolt omPoot2 (ble Measurable PFC concentrations were reported in all fish species collected from Pool 2 (Table 2). |Hee cmon FDA Fi Pg, EON FS 47S However, t~_eported concentrations of PFBA, PFPeA, PFHxA, PFHpA, PFOA, PFBS and PFHS ni ts colt ornPoot 2were indy oneectswhee he renof in fish fillets collected from Pool 2 were dominated by non-detects where the total frequency of donfor ssPEC wry 6, 12,15, 14,25, 5 29 rcv. sth hin deteetion for these PFCs were only 16, 12, 15, 14, 25, 5 and 32%, respectively. As the chain enh RCsns the Bucyof destinof he PRC fn fhaor Us he length ofPFCs increased, the ~equency of detection ofthe PFC in fish also increased. Using the tonic vids name he ns ofdion wf25%fr ROAwh35% carboxylic acids as an example, the frequency of detection went from 25% for PFOA withto 55%
fofo_r~r PPFENNAA n1andd01000%b3ci~h,g deeteictedni=g5~%-+ifdtrheee-:saamtmppileees: -"cw:,'hSi!tlecffooorr PPdFFDD-AA,, PnPFFUU-rR_AA5,,PPF5FDDoo%AA,,
PROS andPROweSr 0A98.WithteexceptionofPES sePEC cession 5 PFOS and PFOSA it ":,'~ 100%. With the exception ofPFOS, tissue PFC concentrations
~-~
enn cd ot ncend gv i fhcols his dy, heightmon PRC 4 generally did not exceed 5 ng g-t ww in fish collected in this study. The highest mean PFC ~ -
76 concentrations were consistently observed in the WHB while the lowest mean eeneentrationsy" ~~'~ =/~
all utPNAweresen ntheBGS; (SMBhadthe lowest PFAlevels). For PFOS,# pool Wh 6
ia AmB
Bowedat
idecmtmea concenatonfora ishwaysfo Po 2was3g wowwie SMB B Sa wide geometric mean concentration for all fish analyzed from Pool 2~g g~ ww while
ssmeicmeanconocnrutons forBGS, FWD, SMBendWHBpele 20,28, Bana ssogg' WBC ? ~eometric mean concentrations for BGS, FWD, SMB and WHB.~e 20, 28, 29 and 58 ng g'~
on, social Tile 2) AsslSpin eos in PROS scncenaton (0.09ws oly observed bowenbls ndwhi bass. Evaluationofanysconection ww, respectively (Table 2). A statistically significant diffe~ces in PFOS concentration ./ (P<0.05) was only observed between bluegill and white bass. Evaluation of analyte concentration
pts i fh Ge hove ttsposmicy 975 he PEC clswere patterns in fish tissue showed that approximately 97% of the total PFC tissue levels were
acefob PROS(6), PFDA (3%), PFA 275%),PDA 24%)ard ROSA accounted for by PFOS (86o~), PFDA (4.8o~), PFUnA (2.70~), PFDoA (2.4%) a~d PFOSA
(0290. Ancamino din PC patil es nit, wibBmcxption of feo (0.8%). An examination ofindividual PFC spatial tren~ indicated that, with the exoeption of
,.{ comment [-~: ~ ~*~tlw 0~ r~o~,st~s
108olcaminopdr as ids pogoCue, | ESR ns PFOS, no clear concentration gradient was observed across the sampling reaches (Table ~:__F_9_r____/" | saaae~ml~mylng drafttl~t~a. ~lm m:~ error~ln
[ PFOS ~evels for SMB, r~aches 3-10 (same as FWD).
22338822..00001133
33MM_MMNN0033220055221100
PFOS, ter was cls ireeonalshi nthe cumlative isbnPROS concerirnions PFOS, there was a clear ~lirectional shift in the cumulative distribution ~t...P..F..O..S....cp_.n.c.~_ti.o.~.....~ .....{ ~.~ittllt~tt [i18]-. Notl....hatthl..... or all hefhspecies with he greatest concenraion beingobserved nsampling reaches 5,6, for all the fish species with the greatest concentrations being observed in sampling reaches 5, 6, | 9,40410. These represent ras wit known dh oi sours of PECs 1 ool 2. 9, and I0. These represent areas with known nearby point sources of PFCs to Pool 2.
TTeemmppoorrawllTTrreennddss nin FFiisshhPPFFOOS$CCoonncce~nnttrraadaoonn:: TTooddiatce,oonnllyytthhe22000099MMPPCCAAssttuddyypprroovviiddeess ulficientdttocvltthenprs changesonPEOS infi tiesforthe ntirety of Pol2.
sufficient data to evaluate the temlmrai changes on PFOS in fish tissues for the entirety of Pool 2.
The2001 resultsindiaovers lowerPFOS ev infishtuefothefourspeciessampledin
The 2011 r~lts indicate overall lower PFOS levels in fish tissue for the four species sampled in
| rt:comet 20 whossmcmscis hgh ie Pool 2, compared to the 2009 study where geometric mean concentrations in bluegill, freshwater drm,salmaadwhitebsswere 51 74 89:12,51.466, 404832.49, drum, smallmouth bass and white bass were 51 ~TA~..8_.9.~._l.2_~__5_l_.~.6_:_6,__.a~._d_.8..3_.~_._4.:.9~.................i.....t Comment [~]: respectively. Funhemor, here as satisticlly significant (9 0.0001 reduction of respectively. Furthermore, there was a statistically signifie~ant (p <0.0001) reduction of -
aapppprrooxxiimmaatteellyy6600%/,~
6600%%,
433%%,,8a5nd03300%%
iinn
hethe
pol videgometcmean pool-wide geometric mean
POSPFOS
fish
fish
conceiraionsin2011whencompared 0.200in boc freshwaterdrm,spall bass
concentrations in 2011 when compared to 2009 in bluegill, freshwater drum~ smallmouth bass
andwhitebas,espocively. Theoverallgeographicptmoffs ss concentrationsin2011
and white bass, respectively. The overall geographic pattern of fish tissue concentrations in 2611
wassila 1209, thate ihestconcernsfr cach pele occurinthe southern. was similar to 2009, in that the highest concentrations for ~ach species occur in the southern- ~
most secoof Pok 2 followed by amiddlesecon deniedas Resches 0d i he 2011 most section of Pool 2 followed by a middle section identified as Reaches 5 and 6 in the 2011.
ud. To allowfordivesnccomperisans, ishsamples om2011 rom the 10 esches' study. To allow for direct statistical comparisons, fish samples from 2011 from the 10 reaches' `wer signedto hespeopristesection 1-4)from2009 basedan colectinlocaton were assigned to the appropriate section (1-4) from 2009 based on collection location SE RR aia coordinates in 2011. Scatterbox pr~entations of these data sets are provided in (:Figure 2~. Noablylowerconcentrationsaeatsrved for the2011deatfo al species andal arcs the. Notably lower concenlrations axe observed for the 2011 dataset for all species and all arras in the ivr, However,themageof teredcton a FOSconcentrations rom 2009 02011 river. However, the magnitude ofthe reductions in PFOS concentrations from 2009 to 2011
ullowedasimilargeographicpairobservedthish sueconceiratonwithte ast
followed a similar geographic pattgm observcaJ the fish tissue concentratien with the least
reduction cccuminginSecon 1and2whi therastreductionwereobserved nemost
reduction ooctaring in Sections 1 and 2 while the greatest reduction were observed in the most
dovnivrses,Seton 31nd 4.Thegreatschange inPFOSconcenationswasobservedin
downfiver areas, Sections 3 and 4. The greatest change in PFOS concentrations was observed in
Section4wherestitial significant(p<0.05) ecuionsofapproximately 8%,68% nd
Section 4 where statistically significant (p <0.05) reductions of approximately 88%, 68% and
22338822..00001144
33MM_MMNN0033220055221111
70 wer chdi r,Holv nd slia t be, s pet, nr, 70% were observed in freshwater drum, bluegill and smallmouth bass, respectively. In contrast, |e 708am smhi mo ret st the reduction of PFOS concentrations in white bass was much more consistent throughout Pool 2 FEaveraging 26% in Sections 1 to 3 and 36% in Section 4.
Poot21 compby flloecsin hesestt ave bee lodsie2004 awl IA~amaallyysseessoofftthhee lloonngg--tteerrmm tteemmppoorraall trreeanddssooffiflsshh PPFFOOSSccoonnccenetnrtraattiioonnsswwitithhiinn tthh~eenntitirreettyyooff Pool 2 is complicated by differences in the species that have been collected since 2004 as well
| aasslloowwssamaplem sisizzp eess((2l233-2-e25)5.). HHoowweveevre,r,iinnaallllssttuuddiieessccoonndduucctteeddpprriioorrttoo22000099~,mmoossttffiisshhccoolllleecctteedd
Pot2 rc om sos Scion gre 3 InScion, 708 rion from Pool 2 were from locations within Section 4 (Figure 3). In Section 4, PFOS coa~entrations hel, lot dios ow sn si end il concrions in bluegill, smallmouth bass and white bass follow the same basic trend with concentrations eng ei 2003 nd eres i i wi egressdresscurio being elevated in 2005 and then decreasing with time with the greatest decreases occurring ee 290d 01. Th, x wie ns oi ec si schsm between 2009 and 2011. Thus, even with the limitations that are inherent L~'~ in such small i,ee edsheed Fo 2 ris i os snd frss datase~_, the general ~xends observed in Pool 2 are consistent with that observed in other systems eben cmdderedPOS ion is 200k des ks okform fm that have observed decreased PFOS concentrations since 2000 that includes lake trout ~o..'~m from LateOne (32) nterin cs mt emi rt aks 5) pps Lake Ontario (32) and herring gull eggs from the Laurentian Great Lakes (33) that appear to be itdvi ds af PROS eep vires.Th ms dios associated with decreased inputs of PFOS to those environments. The measured declines in fish omit PEOS els ho curentsyfor MisisiptRive Fol 2sinwe population PFOS levels in the current study for the Mississippi River Pool 2 region are also ons i 10-yaser d pd ec consistent with the >10-yenr eessatinn of manufacturing ofproducts based on perfluorooetar~yl
cchheemmisitsrtryyaannddwwitithhoonnggooiinnggeeffffoorrttss iinn MMininnneessoottaattooeffffeecottiivveellyyccoonntrtroollssoouurrcceessooffPPFFCCssttoetthhee.
&
si Riv. Homers, oorqido si nd grinds fh Mississippi River. However, ~o more quantitatively define the rate and magnitude ofthese
ges tin i ei eee EE) changes additional fish data arc necded~ ..................................................................................[ :omm~t [~aol." n~a to ,~....
Adnoiegemets Acknowledgements
Wei anvils om eM Deptsof er Roses or We wish to thank individuals from the Minnesota Department ofNatural Resources for the tomatoe red comin i,eon, vecrv. information they shared concerning fish habitat, populations, movements, etc thin proved mel able sofcb hecho npn cvs. The . extremely valuable in terms of enabling the achievement of our sampling objectives. The
22338822..00001155
33MM_MMNN0033220055221122
7]
bordecree lowing comping all ker:MsHobs,Ms,WollMe, | || Elion snd Drs.LangeandReng ar cpl ofthe 3MCompany hathsmanufactur | authors declare the following competing lb~aneta] interest(s): Mr. I-Iohe~tein, Ms._ Wolt~ Mr~
Ellfson and Drs. Lang ~nd Rcagcn ~ employees of the 3M Company tha~ has manufi~m,cd
PFC.Inakon, is indy vas iddby SM. | || PFCs. In addition, this study was funded by 3M.
ASSOCIATED CONTENT | || ASSOCIATED CONTEN'r
Soprtog tormatn ! | Suplmrtln__gInformation
Ad elo do sniG ve td ty | Additional details are provided including statistical calculations, QC recovery results, and study
ining This ea li ofcharg via ho emt tpbascr. | findinss~ This material is available fre~ ofcharge via the lntemet at http://pubs.acs.org.
" | ||{| Tables
ible1.Oeome mean concnofpoisedcompres6h gs wo) fom | | Table 1. Geometric mean concentrations ofper~uorin~*_~ compounds in ~ (ng/g ww) from
oktteMiiKv 201 | Pool 2 ofthe l~/fississippi Rive~ in 2011.
Fob Semmes ofPFOSconcertosmead n (meFo Pool? |. (Emm)
FE,Sptcoinofprinted pounds PFC)nhcolleo c e Po. mari)
20f theUpperMissi Rive.
2 of the Upper Mississippi River.
Fewrs
|
|
= | | Figure1,Areasof fishandwater sample collection182009842011...
Fie, Comptonof ROS bessn 2000md2011by pic
L EE
mdre._| mr
section (24),
|
|
|
22338822..00001166
33MM_MMNN0033220055221133
ge ---------------- Figure 3. Femporal t~'ends oF PI:,'()S concentrations (geometric mee.n a: standard error)in fish
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Reerences
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,19
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:
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