Document ZBGEvK0yp0kroZm5Q77YGkGMV

E Em S EETLE E E TERY Ere ae Ene] } ETE a 3 MMisisssiissssiippppii RRiivveerr PPooooll 22 IInntteennssiivvee SSttuuddyy off PPeerrfflluuoorroocchheemmiiccaallss iin FFiisshh aanndd WWataeterr:: 22000099 March 2010 March 2010 po. @ Minnesota Pollution Control Agency 22556655..00000011 Exhibit ses 33MM_MMNN0033004433007777 MMiinnnnee5ss2oo0ttaaLaPPfooallylleuutttiitooennRCCoooandnttrrNooollrtAAhg~eennccyy SS5aa2ii0nnttLPPaaafuaulyl,,eMMttNNe R555o51a1d5555N--44o11rt99h44 hitp:/ fun pea. state. mn.us http:/twwv.pcaostate, ran.us 665511--229966--66330000 oorr 880000--665577--33886644 ttooltl[ ffrreeee T3-TI-YY 665511--228822--55333322oorr880000--665577--33886644 ttoollll ffrreeee. AAvvaaiillaabbllee iinn aalltteerrnnaattiivvee ffoorrmmaattss Authors and Contributors Bruce Monson Bruce Monson Laura Solem Laura Solem Paul Hoff Paul Hoff Marin Hora Marvin Hora Pot Mccann Pat McCann Mark Briggs Mark Briggs Joel stiras ]oel Stiras Steve Delain Steve DeLain Document numoer Document number XAS-SPLA\oI1\Agoncy_File<\EAO\PFC Data and Reports- Prfiminary\Data\Fsh\2009 ish data\Mississippi XRi:\v\eSr-SPP14o2\Ivnot1oe1n\AsligveencSyt_uFdilye\sM\EiAsiOs\sPiFpCi PDoaotla 2anPdFCRse2p0or0ts9 -FiPnraelliRmeipnoarrty\SDMaItaA\RFLisOhd\o2c00x9 Fish data\Mississippi River Pool 2 Intensive Study\Mississippi Pool 2 PFCs 2009 Final Report 8MAR10.docx 22556655..00000022 33MM_MMNN0033004433007788 T Taba leoofbfCCoonl wt,teene nttss TABLE OF CONTENTS .......................................................................................................................................... 1 LIST OF TABLES csr 2 LIST OF TABLES ................................................................................................................................................... 2 LSTOFFIGURES. - - 2 LIST OF FIGURES ................................................................................................................................................. ABBREVIATIONS GLOSSARY ................................................................................................................................ 3 EXECUTIVE SUMMARY ....................................................................................................................................... 4 INTRODUCTION .................................................................................................................................................. 6 MISSISSIPPI POOL 2 ........................................................................................................................................................ 6 [I ---------- - 5 WHAT ARE PFCs AND WHY ARE TH EY AN ENVlRONM ENTAL CONTAM INANT? .............................................................................. ALENT MOM8PIFC OMFON20N08 nse ern] AMBIENT MONITORING OF PFCs BEFORE 2009 ................................................................................................................... 7 Wns tuo. 5 WHY THIS STUDY? .......................................................................................................................................................... 8 METHODS .......................................................................................................................................................... 8 FONCOUECTON sss sss FISH COLLECTION ........................................................................................................................................................... 8 WATULCOACIrOrN ress soe senses WATE R COLLECTION ....................................................................................................................................................... 9 LABORAIGRSANAS cress ee omens LABORATORY ANALYSIS ................................................................................................................................................... 9 Quan Asunanes 0 QUALITY ASSU RANCE .................................................................................................................................................... 10 REIS ANDRIES mmsmsssmmsssassmsmsasmssmasmsmsmmsssmssmsmmmsmsmsmmossnltl RESULTS AND DISCUSSION ................................................................................................................................11) SUA WATIR ss crn 10 SURFACE WATER .......................................................................................................................................................... 10 fn re - - BY RSH ........................................................................................................................................................................... 11 J Q u ulity Ass urance ............................................................................................................................................... 11 `Sati Distrivtion of FOSby Specs. 1 Spatiol Distrib ution o)~ PFOS by Species ............................................................................................................... 11 TemporalDistiution of FOS Concertrations. - 2 Temporol Distribution o.f PFOS Con centrotions................................................................................................... 12 RelationshipofPFOS eels 0sGender, 0G NAS... svc 5 Relutionship o[ PFOS levels tofish gender, oge, und size.................................................................................... 13 BOACCUMULATION FACTOR io WATchQuay Carin. " ni 1 BIOACCUMULATION FACTORS AND WATER QUALITY CRITERIA .............................................................................................. 13 COM10OPWEXLAOAISCAS ssn 13 COM PARISON I O O I HE R LOCAl IONS ................................................................................................................................ 14 CONCLUSIONS ................................................................................................................................................... 15 REFERENCES ...................................................................................................................................................... 17 TABLES .............................................................................................................................................................. 19 FIGURES ............................................................................................................................................................ 24 RESOURCES ....................................................................................................................................................... 37 AppendiAx Mapoffish colectons in Pool 2 Appendix A Map offish collections in Pool 2 Appendix B ResuoflPtFCss analysis of fish calectedinMisisippi Pool 2n 2009 Appendix B Results of PFCs analysis offish collected in Mississippi Pool 2 in 2009 Mississippi Pool 2 PFCs 2009 + March 2010 Mississippi Pool 2 PFCs 2009 . March 2010 1 Minnesota Pollution Control Agency Minnesota Pollution Control Agency, 33MM_MMNN0033004433007799 22556655..00000033 Liof Tsabltes List Tables Table 1 Ancilry information aboutwatersampling stations (2 uly 2009) 1 Table :Z Ancillary information about water sampling stations (2 July 2009) ............................................. 19 Table 2 PECconcinewatne at12ratiaonsitMIiSSSoIPPInP00s12. 19 Table 2 PFC concentrations in water at 12 stations in Mississippi Pool 2 ................................................. 19 TTaabbllee 33 FFiisshh ccoolllleeccttiioonniinn Msssopi Mississippi PPooooll22 0by MMODNNRR cs 2 .............................................................................. 21 Tabl4eSummary statistic for PEOSconcentrationsby pecies inPoo 2... 22 Table 4 Summary statistics for PFOS concentrations by species in Pool 2 ................................................ 22 Tables Numbofefirsh collected each year byspecs. 2 Table 5 Number of fish collected each year by species ............................................................................. 22 Table Published PROS CORCENIBIONS fish. 23 Table 6 Published PFOS concentrations in fish ........................................................................................... 23 List of Figures List of Figures Figure 1 Location of Mississippi Pool 2. 2 Figure i Location of Mississippi Pool 2 ...................................................................................................... 24 Figur2e Misisipi Pool 2 sections and Water Omple salon. 25 Figure 2 Mississippi Pool 2 sections and water sample stations ............................................................... 25 Figur3e ComparoifsHoVnS (rd,top bar) and 3M blu] resulftos PFOS concentration in water from Figure 3 Comparison of AS (red, top bar) and 3M (blue) results for PFOS concentrations in water from 12 satons in Pool 2 embedded figure showsAXYS versus 3M PROS with 11 ne 2 12 stations in Pool 2; embedded figure shows AXS versus 3M PFOS with 1:1 line .................................. 25 Figur4e CompariofsAXoYnS (red, topbor) and 3M (sue) results forPFOS concentratiforonms same Figure 4 Comparison of AXYS (red, top bar) and 3M (blue) results for PFOS concentrations from same ish homogenates: embedded igre howsAXYS Versus 3M PFOS With 1:06... 27 fish homogenates: ; embedded figure shows AXYS versus 3M PFOS with 1:1 line .................................... 27 Fire's Distributionf POS by species within eachSection(1-4) and alsectionscombined... 23 Figure 5 Distributions of PFOS by species within each Section (1-4) and all sections combined .............. 28 FiFgiguurree 66 PPFOOSSiinnSSpepceiceiess-SSeeccttiioonn Mtr; Matrix; vveerrttiiccaall bbaarrss reare 4400 ppppbb aanndd 220000 ppppbb vv 29 ....................................... 29 Figure 7 Distributioonfs PFOS byyear for each species (al sections. 0 Figure 7 Distributions of PFOS by year for each species (all sections) ....................................................... 30 FFiigguurere8iDsrisbtriubtutoionnssooffPPFFOOSS bbyy yaryear fofor ceaacchhssppeecciieess Hd limited t1o0SSeecctoionn 4& v3 ........................................... 31 Figure FOS concentrations b gender of ech species 2 Figure 9 PFOS concentrations by gender of each species ......................................................................... 32 FFiigguurree 1100 FOS PFOS ccoonnccenetrnattiornabtbyyiaaoggene fofor eeaacchh ssppeecciieess . ............................................................................. 333 Figure 11 PROS concentbyrleangtthifooenacsh species 3 Figure 11 PFOS concentrations by length for each species ....................................................................... 34 Figure12 PROSconcbeypnerctentrpias otreaichsopecines. S-- 3 Figure 12 PFOS concentration by percent lipids for each species ............................................................. 35 Figure 13 Relationship between PFOA (C10) and PROSfrom Pool 2 all species and sections) 3 Figure 13 Relationship between PFDA (C10) and PFOS from Pool 2 (all species and sections) ................. 35 Wisissippi it4ississippi PPooooll 22 PPFFCCss 22000099 +. MMaarrcchh 22001100 2 Winnesota /vlinnesota PPoolllluuttiioonn C Coonnttrrooll AAggeennccyv 33MM_MMNN0033004433008800 22556655..00000044 Abbreviations Glossary GGrroouuppss PECs. perlucrochemicals or periuorinated compounds PPaFsCss-- perluoroaliy surfactants perfluorochemicals or perfluorinated compounds PPrAaSss-=peperfrlfulourooraolckayrlbosruyrifaicctaanctds PEs PFCAs - ppoelryflluuocrroicnaartbeodxayllkicylascuidbstances PFIFOSHAs~-fpluoolyrfoluteolrionmaetredalacolkhyollssubstances FPTOFHA- fl--upoerrfoitueolroamalkeyrlaalcciodhsols PFAAs - perfluoroalkyl acids Individual PFA -perfluorobutanoic PFBA- perfluorobutanoic aacciidd ((CC84 AAcciidd)) PF perfuorobutane sulfonate (C4 Sulfonate) PFPA --perluoropentanoic acd (C5 Acid) PFBS- perfluorobutane sulfonate (C4 Sulfonate) PFPeA - perfluoropentanoic acid (C5 Acid) PFA perfluoronexanoic acid (C6 Add) PPFrHixAs- ~ppeerrflfulouroorhoehxeaanneoiscualfcoidna(tCe6(ACc6idS)ifonate) PFHpA -perfluoroheptanic acid (C7 Acid) PFHxS - perfluorohexane sulfonate (C6 Sulfonate) PFHpA - perfluoroheptanoic acid (C7 Acid) PPFFOOAA - ppeerrfflluuoorrooooccitaannooiicc aacciidd ((CC88 AAcciidd)) P#7F0O5S~-ppeerfrflluuoorrooooccttaannee ssuullffoonnaattee ((CC88 SSuuflfoonnaattee)) PPFFOOSAA --ppeerfrflluuoorrooooccttaannee ssuullffoonnaammiiddee ((CC88 SSuullfoonnaammiiddee,, PPFENNAA -=ppeerrlfluuoorroonnoonnaannooiicc aaccidd ((CC93 AAcciidd)) PPFFDOAA -~ ppeerrfflluuoorrooddeeccaanncoiicc aacciidd ((CC1100 AAcciidd)) PFURA PFUnA -perfiuoroundecanaic - perfluoroundecanoic aacciidd ((CC1l1l AAcccid)) PFDA PFDoA --ppeerrfflluuoorrooddooddeeccaannooiicc aacciidd (CC1122 AAcciidd)) bbrraanncchheedd)) OOtthheerrAAbbFbbFrreEevvi-iaatatiiqoounnessous fire fighting foam AFFCFFF~-elaeqcuteroouchsefmiirecafligfhltuinorginfoataimon FCA~ ECF - FCA - fish consumprion advisory electrochemical fluorination fish consumption advisory MOH - Minnesota DepartofmHeeanltth MDNDRH -MMininnenseosotataDDeeppaarrttmmeenntooffNHateuarltahl Resources WDNWRT-P-MiwnansetseowtaatDereptarretamtemnent tofplNaanttural Resources WWTP - wastewater treatment plant Mississippi Mississippi PPooooll 22 PPFFCCss 22000099 +. MMaarrcchh 22001100 3 M Miinnnneessoottaa PPoolllluuttiioonn C Coonnttrrooll AAggeennccyv 33MM_MMNN0033004433008811 22556655..00000055 EExxeeccuuttiivvee SSuummmmaarryy Perfiuorochemicls (PFCs) emerged as a global pollutant in 2001 when scientist reported perfiuorooctane sulfonate Perfluorochemicals (PFCs) perfluorooctane sulfonate (F05) was emerged as (PFOS) was measured in wildife a global pollutant in measured in wildlife throughout 2001 when throughout the world. Numerous scientists reported the world. Numerous studies studies have demonstrated thal PFOS i the primary form of PC found in is and other biota. 3M Company's ChoatvteadgeemGroonvsetrfaatecidlyth,aitnPtFhOeSsoisutthheeapstriemrnarTywfionrmGiotefsPFMCetfrooupnodliitnafnisAhreaan,dwoatshearmabijootar. m3aMnuCfaocmtpuarnery'sof PCFoOttSagfreoGm rotvhee 1950's facility,0in 2th00e2.soTuhthee3aMsteCronttTawgienGCriotiveesfaMcielttroypdioslictahnarAgeresat,rweaatsead m praojcoersm s waantuefarcatunrder of cPoFoOlSinfgrowmattehreto19P5o0o'sl2toof2t0h0e2.MTishseis3sMippCioRtitvaegr.e Although the Grove facility dfaisccilhtayrgdeissctorentaitneudedprporceosdsuwctaiteornfanPdFOS in 2c0o0o2li,ngthwaftearctoi Pdiosoclh2arogef cthoentMiinsuseisssitppihaRviveerm.eAasltuhroaubglhethPeFOfSacciolintycedntisrcaotinotninsu.ePdooplro2d1uscationneaofr3Plryosmiinle r2e0a0c2h, tohfethfaecMiilistysidsissicphpairRgievecrobnetintuweesentoLohcakve& Dam 1 and measurable LPoFcOkS&coDnacmen2.trTahtioenMse.tProopool l2iitsaan Wastewater nearly 33 mile TreraecahtmoefntthePlManists(isMseitprpoi Rpilvaenr )betthweeaerngeLsotckwa&stDeawmat1erantdreLaotcmke&ntDpalmant2.inThMeinMneestorotap,olaitsaondW isachsaterwgeastetro TPoreolat2m, eanndt alsoPlanth(aMsemteroaspulraanbt)l,ethleevelalsrgoefsPt wOaSsitenwtsateefrfltrueenatt.mWeansttpelwaantt einr Mcainnbneesoastaig,nailfsiocadnistcshoaurrgceesotfo PPFoCosl case these 2, and also has cmheemaiscuarlasblhealveeveblseeonf iPnFcOlSudineditsineaffwluiednet.raWngaesotfewcaotenr scaunmbaeenradsiingdnuisfticraianlt psrooudruccetosf tPhFaCtscbaencaevuesnetuthaellsye bcehedmiiscaplosshoeafdveinbemeunniicnicplauldewdasitneawawtiedre sraysntgeemso.f cThoinssurempeorrt doesnotexamine the and industrial products tlhoaadticnagnfervoemnptousaslilyblbeseoduisrpcoesseodfPoFf CinstmouPnoicoilpa2l,wbuatstreawthaeterrfoscyustseemsso.nThPEisCsreipnfoirsthdoaensdwnaotteerxafm roimne the ilosaidsisnigpfproimRipveorssPiobolel 2, base sourcesoonf PiFnCtsentosivPeoomlo2n,itbourtirnagthceormfpolceutseeds in the summeorf 2009 on PFCs in fish and water from Mississippi River Pool 2, based on intensive monitoring completed in the summer of 2009. Since 2004, the Minnesota Pollution Control Agency (WPCA) and the Department of Natura Resources (MDNR), with participation Since 2004, the Minnesota (MDNR), with participation of the Health Department (MOH), have analyzed ish and Pollution Control Agency (MPCA) and the Department of of the Health Department (MDHt, have analyzed fish and river water for PFCs Natural Resources river water for PFCs rom Pool 2. An intensive study of PFCs in fish and water was completed inthe summer of 2009. Of the f3r6o7mfiPsohoaln2a.lyAznedinfternosmiv2e st0utdoyp0roefsPe4FnCts,297were in fish and cwoallteecrtwedasinc2o0m09p.leitnedadidnitthioen,swuamtmerersaomfples were 2009. Of the c3o6l7leficsthedaanal1y2zesdtaftroiomns2t0h0r4outgohpouretsPeonot,l in297 w20e0r9e. cToollecchtaerdacitner2i0z0et9.heIn sapdadtiitailonc,swtaitbeurtsiamonfplePsFCwseirne Pcooolllec2t,etdheatre1a2cshtwaatiosndsitvhirdoeudgihnoouftoPuorosle2ctiinon2s0,0w9i.tThoScehctairaoncte1aritzeththeemost upstream end spatial distribution aonfdPFSCesctinio&n aPbooovl e2,tthheeHraesatcihngwsaDsadmivi(dLeodci&nktoDfaomur2)s.ecFitigounrse, 2woifththSeemcatioinn1reaptotrhtesmhoowsst uspecsttrieoanmboeunnddaarnidesSaencdtion 4 waabtoevre sthaempHlaesltioncgatsioDnas.m (Lock & Dam 2). Figure 2 of the main report shows section boundaries and water sample locations. Allis and water samples were analyzed for ECSby AXYS Analytical Lt. For quality assurance, water ASallmfpislhesanrdowmaatelr1s2satmaptlieosnws earneda3n0alryazneddofmoiry-PsFlCescbtyedAXfYisSh samples were Analytical Ltd. aFnoarlqyuzaedlitybyas3sMurEannvcier, ownametenrtal Laboratory. The samples from all Laboratory. The high degree 12 stations high degree ofdata and 30 of data correlation between the two labs provides confidence in the quality randomly-selected fish samples were analyzed by 3M Environmental correlation between the two labs provides confidence in the quality ofthe results of the results. The highest water concentraotfiPoFnCsswere found in Section 4, in particular, Staion 11 Perfiuorobutanoic The highest water Perfluorobutanoic acid (F84) was detected at all 12 stations. FOS, perfluorooctanolc acid concentrations of PFCs were found in Section 4, in particular, Station 11. acid (PFBA) was detected at all 12 stations. PFOS, perfluorooctanoic acid ((PFFOORA),), aanndd. ppeerrffliuuoorroohheexxaannooiicc aacciidd (FH) (PFHxA) wweerree ddeetteecctteedd iinn SSeeccttiioonnss 22,, 33,, aanndd 44,, wwiitthhtthhee hhiigghheesstt ccoonncceennttrraattiioonnss iinn SSeeccttiioonn 44.. TThhrreeee ootthheerr PPFFCCss----PPFFPPeeAA,, PPFFBBSS,, aanndd PPFFHHSxS---w-weerree ddeetteecctteedd iinn SSeeccttiioonn 44. PPRrOoSs wwaass ddeetteecctteedd iinn nneeaarrllyyaalll ffiisshh ffrroomm PPooooll 22.. TThhee hhiigghheesstt PPFFOOSSccoonncecnetnrtraattiioonnss iinnffiisshh ccooiinncciiddeedd wwiitthh tthhee hhiigghheesstt wwaatteerr ccoonncceenntrtraattiioonnss iinn SSeeccttioino4n4.. OOtthheerrPPFFCCsswweerree ddeetteecctteeddiinn fiisshh tthhaatt hhaadd hhiigghheerr concentrations ofPFOS.Ofth five targeted fish species in Pool 2--bluegill sunfish carp, freshwater dcorunmc,enstmraatliolnmsouotfhPbFaOssS,. Oanfdthwehifitvee btaarsgse--tferdesfihshwastpeercdiersuimn Phaodol t2h-e-bhliugehegsiltl sPuFnOfSishco,nccaernpt,rafrteisohnsw.atDerrum hdarudmn,otsmbeaellnmsoaumthplbeadssp, arndtiwo 2ho0it0e8r,babsesc-a-furseeshtiwsatneortdcruomnhsaditdhaeethryipgeihcaedlstsPpFoOrSischo.ncBeansterdatoionntsh. eDrum had not been sampled prior to 2009, because it is not considered a typical sport fish. Based on the Mississippi Pool 2 PFCs 2009 + March 2010 Mississippi Pool 2 PFCs 2009 . March 2010 MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00000066 33MM_MMNN0033004433008822 MDNRs observation thatthedrum s a popfisuhhalrvaestred in Pool 2for humanconsumptiftowna,s. iMnDclNuRde'sd oabssaetravragteiotnstpheacitethseind2r0u0m9 is a popular fish harvested in Pool 2 for human consumption, it was included as a target species in 2009. TThhee MMODHH hhaass ddeevveellooppeeddaa rreeffeerreennccee ddoossee ffoorr PPFFOOSS tthhaatt iiss suseedd aass tthhee bbaassiiss oforrffiisshh ccoonnssuummppttiioonn aaddvviiccee.. MMeeaann PPFFOOSS ccoonncceennttrraattiioonnss iinn ffiisshh bboettwweeeenn 4400 aanndd 220000 ppaarrttss pperr bbiillllioionn ((ppppbb)) aarree aassssiiggnneedd mmeeaall aaddvviiccee. ooff oonnccee ppeerr wweeeekk;; tbewtweeeenn220000 aanndd880000 ppppbb,, tthhee aaddvviiccee iiss oonnee mmeeaallppeerrmmonotnhth,, aanndd aabboovvee 880000 ppppbb,, ddoo onott eeaat.t. FFiisshh ccoonnssuummppttiioonn aaddvviissoorriieess wweerree mmaoddififiieedd ffoorr PPooooll 22 bbaasseedd oonn tthhee 22000099 rreessuultltss.. FFrreesshhwwaatteerr ddrruumm hhaadd tthhee hhiigghheesstt PPFFOOSS ccoonncceennttrraattiioonnss aanndd wwaass tthhee oonnlyy fiisshh ssppeceiesciinin PePooosoll 22 aasssigsniedgaanooennede mmeeaall ppeerr mmoonntthh aaddvviissoorryy bbaasseedd oonn aa mmeeaann PPFFOOSS ccoonncceennttrraattiioonn ooff 222299 ppppbb.. SSmmaallllmmoouutthh bbaassss aallssoo hhaadd aa mmeeaann PPRFOOS5ccoonncceenntrattrioanotofif22o00n99 ppppbb wwhheennddaattaa ffrroomm 22000044ttoo 22000099 aarree ccoommbbiinneedd;; hhoowweevveerr,, mmeeaall aaddvviiccee iiss ot givoretins species in Pool 2 because only catch-and release fishing is allowed n(ohtttpgivfenusfosr thheiasltshpesctiaetseinmoP.uoso/ld2ivbee/ceahuysfiesoh)n.ly catch-and-release fishing is allowed (http://www.health.state.mn.us/divs/eh/fish/). NNooddiisscceerrnnaabblleettrreennddss wweerree sseeeenn iinn PPFFOOSSoovveerrttiimmeeffoorr ssppeecciieess tthhaatt hhaadd bbeeeenn ssaammpplleedd ssiinnccee 22000044 oorr 22000055.. PPFFOOSS ccoonncceennttrraattiioonnss iinn ffiisshh mmuusscclleewweerree nnoott ccoorrrreellaatteedd wwiitthh ffiisshh aaggee oorr ssiizzee,, aanndd tthheerree wwaazs nnoo ddiifffeerreennccee bbeettwweeeenn ggeennddeersrs.. BBiiooaaccccuummuulalattiioonn ffaaccttoorrss ((BBAAFFss))wweerree ccaallccuullaatteedd ffoorr PPFFOOSS uussiinngg tthhee wwaatteerr aanndd ffiisshh ddaattaa..BBAAFFssffoorr PPFFOOSS wweerree iinn tthhee rranageonoff4g4000e000 1to0 66000000 LL//KKgg,, wwhhiicchh sisaatt tthhee llooww eenndd ooff tthhee rraannggee ooff hhiigghhllyy bbiiooaaccccuummuulalattiivvee ccoommppoouunnddss.. M Misisssiissssiippppii PPooooll 22 PPFFCCss 22000099 .+ MMaarrcchh 22001100 5 MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00000077 33MM_MMNN0033004433008833 Introduction Mississippi Pool 2 MMisisssiissssiippppii RRiivveerr PPooooll 22 ((FFiigguurree 11)) eexxtteennddss ffrroomm LLoocckk && DDaamm ##22 aatt HHaassttiinnggss,, MMiinnnneessoottaa,, uuppssttrreeaamm nneeaarrllyy 333 mmiilleess ttoo LLoocckk&& DDaamm ##11 ((FFoorrdd DDaamm).). TThhee MMiissssiissssiippppii ccoonnfflluueenncceewwiitthhtthhee MMiinnnneessoottaa RRiivveerr sis aatt tthhee upper reach of Pool 2 an the confluence with the St. Croix River ijust below Lock & Dam #2. Within Puopopler2,raevaechraogfePaononlua2lafnldotwhse acboonufltue1n5c,e00w0icthubtihcefSeet.tCpreorixseRcivoenrdis(cjus)s,t bPoeololw21Losackre&ceDivaimng #w2a.tWerithfionr tPhoeolla2r,gaesvterpaugbeliacnanlulya-l oflwonwediswaasbtoeuwta1t5e,r00t0recautbmiecnfteeptlpaerinnseMcionnndes(ocftsa).,Ptohoel M2etisroaproelcietiavninWgW-wTaPt,erwfiotrh tahnealvaerrgaegset pdiusbclihcaarlglye-oowf n18e5d mwilalsitoenwgaatleorntsrepaetrmdeanyt(p2l8a6ntfsin),MainndnetshoetaEa, gthlees MPoeitnrtopWoWlTitaPn, WwiWthTaPn, with average discharge of 4.2 an average discharge of average discharge of 4.2 mgd. The 31 CompanyCottageGrove facity is next to, and downstream 185 million gallons per day (286 cfs), and the Eagles Point WWTP, with an mgd. The 3M Company Cottage Grove facility is next to, and downstream ooff,, tthhee EEaagglleess PPooiinntt WWWWTTPP.. TThhee 33MM ffaacciilliittyy ddiisscchhaarrggeess iinndduussttrriiaal pprroocceessss wwaatteerr aanndd ccoooolliinnggwwataeterr,, wwiitthh aa ccoommbbiinneedd ffllooww ooff 8 mmggdd.. W Wh~aatt aamree PPFFCCss aan~d wwh~yy aa~ree tt~heeyy aa~n eennvv~ireo~nKm~eennttaa~l contaminant? PPeerrfflluuoorroocchheemmiiccaallss ((PPFFCCss))----aallssoo kknnoowwnn aass ppeerrfflluuoorriinnaatteeddccoommppoouunnddss---a-arree ccoommppoosseedd ooff aa ccaarrbboonn cchhaaiinn ssaattuurraatteedd wwiitthh fflluuoorriinnee aattoomrss,, wwiitthh aa ffuunnccttiioonnaall ggrroouupp aatt tthhee eenndd ooff tthhee cchhaaiinn.. TThhee ffuunnccttiioonnaall ggrroouuppss aarree ttypyicapllyiaacssuuallffolonnlaatteey(6(0530))oorr aacacrabrbooxyxlyilicc aaccidd ggrroouupp (--CCOOOOHH))..TThhee ffuunnccttiioonnaallggrroouuppmmakakeess tthhee PPFFCC ssoolublleiuinnbwwalatteeerr ((hhyyddrroopphhililiicc),, wwhheerreeaass tthhee ccaarrbboonn cchhaaiinn mmaalkeess tthhee PPFFCC mmoolleeccuullee ssoolluubbllee iinn lpipiicdss ((llipipoopphhiillicic) aanndd rreessiissttaanntt ttoowwataeterr ((hhyyddrroopphhoobibci)c.). TThhee uunniiqquuee pprrooppeerrttiieess ooff PPFFCCss hhaavvee bbeeeenn eexxppllooiitteedd ffoorr nnuummeerroouuss ccoonnssuummeerr pprroodduuccttss,, mmoosstt nnoottaabbllyyffiirreef-ifgighhttiinngg ffooaamm,, sstaaiinn pprrootteeccttiioonn,, aanndd nnoonns-sttiicckk ssuurrffaacceess.. PFCs "are globally distributed, environmentally persistent, ioaccumulative, and potentially harmful" (Giesy and Kannan, 2002). Although there are naturally occurring fluorinated organic compounds that PFCs "are globally distributed, environmentally persistent, bioaccumulative, and potentially harmful" (Giesy and Kannan, 2002). Although there are naturally occurring fluorinated organic compounds that cconotainnoontneefalfluuoiorriinnnee aattoomm,, aallll PPFCEsiiCnntthshee eennvviirroonnmmeenntt aarree aanntthhrrooppooggeenincic.. ((GGiieessyy aanndd KKaannnnaann,, 22000022)) VaVrairoiouussttooxxiicc eennddppooiinnttss hhaavvee bbeeeenn mmeeaassuurreedd iinnllaabboorraattoorryy ssttuuddiieess ooff PPFFCCss.. AAccccoorrddiinngg ttoo aa 22000077 MMODHH pprreessss rreelleeaassee,, oobbsseerrvveedd eeffffeeccttss ooff llooww ddoosseess ooff PPFFOOSS iinncclluuddee ddeeccrreeaasseedd hhiigghh ddeennssiittyy lliippoopprrootteeiinn cchhoolleesstteerrooll ((HHDDLL)) aanndd cchhaannggeess iinn tthhyyrrooiidd hhoorrmmoonnee lleovveelss iinn ssoommee aanniimmaalsls.. BBiioollooggiiccaall mmeemmbbrraanneess aarree pprriimmaaririllyy ccoommppoosseedd ooff pphhoosspphholoilippiiddss,, wwhhiicchh aarree aammphpihpiphihliliicc mmoolleeccuulleess.. TThhee aammphpihpiphihliliicc pprrooppeertryotofyf PPFFCCssmmigighhtt eennhhaannccee cceellll mmeemmbbrraannee ppeerrmmeaebaibliilittyy ooff ootthheerr ppoolllluuttaannttss,, tthheerreebbyy iinnddiirreeccttllyy iinndduucciinngg aaddvveerrssee eeffffeeccttss ccaauusseedd bbyy ootthheerr cchheemmiiccaallss ((WWaanngg eettall,., 22000099).). Perfluorooctane sulfonate (PF0S) is the predominant PFCfound in mast fish (Houde ct 1 2006). Fish fPreormflucoornotoacmtiannaetseudlfaorneaatsem(aPFyObSe) aisstihgenipfirceadnotmsoinuracnet oPfFCdifeotuanrydPinFOmSoesxtpfoisshur(Heo(uBderegeert aotl 2a0l,062)0.09F)is.hThe ffriorsmt rceoponrttamofiPnRatOeSd aasraealsombaaly bceonatasmiginniafinctanint swoiulrcdeeowfadsieatsatruydPyrfousndeexdposbuyre3 (Giesy and Kannan, (Berger et al., 2009). The 2001). When first report ofPPFFOOSScaosncaegnltorbaatliconosntaarme ihniagnhtininfwisihldtliifsesuwe,aostahesrtuodnygfucnadrebdon-bcyh3aMin (PGFiCess,ysauncdh asKannan, perfiuorodecanoic 2001). When PFOS perfluorodecanoic acid (C10), are often detected. concentrations are high in fish acid (C10), are often detected. Detection limits generally range from2.5 to 5 tissue, other long carbon-chain PFCs, such as Detection limits generally range from2.5 to 5 nanogramsper gram ng/g), or parts per bilion (ppb). Rather than beinglipophilic icemanyother pnearnsoigstraenmtsorpgearngircapmol(lnugta/gn)t,so(rPOpPasr)ts, speevrerbaillliosntud(piepsb)h.aRveathsuegrgtheastnedbetihnagt PFCs are lipophilic plirkoetemiannopyhoitihce(rConder eptearls,ist2e0n0t8)o.rgPaRnOicS pboelhluatvaenstsve(rPyOdiPfsf)e,rseenvtelyrafl rsotumdioetshehravPeOPssu,gghaevsitendg tdhifaftePreFnCcsesareinpinrotrtienisniocpfhacilticors(C, osnucdher aset as surface activity, al., 2008). PFOS surface activity, water solubilty, non-measurable octanolfwater coefficient values, andrelatively low behaves very differently from other POPs, having differences in intrinsic factors, such water solubility, non-measurable octanol/water coefficient values, and relatively low M Misisssiissssiippppii PPooooll 22 PPFFCCss 22000099 .+ MMaarrcchh 22001100 6 MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00000088 33MM_MMNN0033004433008844 bioaccumulation potential. Despitethesedifferences, PFOS biosccumulates in ish tissue and fs. considered a POP (Wang eta, 2009) bioaccumulation potential. Despite these differences, PFOS bioaccumulates in fish tissue and is considered a POP (Wang et al., 2009). Ambient monitoring of PFCs before 2009 TThhee MMPPCCAA ssuummmmaarriizzeedd aammbbiieenntt mmoonnititoorriinngg tthhrroouugghh 22000088 iinn PPEFCCss iinMMininnneesostoata''ssAAmmbibeienntt EEnnvviirroonnmmeentn:t: 22000088 PPrrooggrreessss RReeppoorrtt ((hbttip::!/wJwawn.pecsa.ssttaattee.mmnn..uuss/fppuubblliiccaattiioonnss//cc--ppffcc1l--0022..ppfd).f). IIn aaddediittioonn ttoo ffiisshh, tthhee report covers PEC monitoring inground water, surface wate, wastewater, and a. report covers PFC monitoring in ground water, surface water, wastewater, and air. FFiisshhiinn PPooooll 22 wweerree ffiirrsstt tteesstteedd ffoorr PPFFCss iinn AAuugguusstt 22000044 aanndd fiisshh ccoolllleeccttiioonn ffoorr PPFFCCss hhaass ccoonnttiinnuueedd eevveerryy yVeeaarr eexxcceepptt 22000077.. IInn 22000044,, PPFCCswweerreeddeetteecctteedd iinn tthhee ffiillleettss ooff ttwwoo ssmmaallllmmoouutthh bbaasss (PFOS: (PFOS: 105 105 ng/g ng/g and and 995500 nngg//gg)) aanndd oanneeccoommpopsoistitee ssaammppllee ooff ffoouurr wwhhiittee bbassss ffiilllelettss ((PPFFOOSS:: 113388 gn/gg/)g.). IInn 22000055,, 22000066,, aanndd: 22000088,, aaddidtitoionnaall tteesstteedd ffiisshh ssppeecciieess iinncclluuddeedd wwaalllleeyyee,, ccaarrpp,, cchhaannnneell ccaattffiisshh,, bbllaacckk ccrraappppiiee, ssmmaallllmmoouutthh bbaassss,, wwhhiitteebbaasss,s, ssmmaallllmmoouutthh bbuuffffaalloo,, eemmeerraalldd sshhiinneerr,, aanndd ggiizzzzaarrdd sshhaadd.. Fie Fillet ttiissssuuee ssaammpplleess rraannggeedd f2rr0oo0mm5,ootnnheee tthooigffihfietteseteenPnFfiiOssShh cppoeenrrcsseppneetccriiaeests.i.oAAnnnwcciaillslaariryny wmmheeiatasesuubrraeesmmse,ewnnitttsshiinanccrlluudadeedndollfgeenn8egg4tthhn,,gww/egeiitggohht1t,,8aa6gg0ee,,ngaa/nng.dd ssIenexx.2.00IInn6, smallmouth bass had the highest PFOS concentration was in smallmouth bass, with raofn19ngg/g to 2005, the highest PFOS concentration was in white bass, with a range of 84 ng/g to 1860 ng/g. In 2006, smallmouth bass had the highest PFOS concentration was in smallmouth bass, with a range of 19 ng/g to 5150ng/g. Smallmouth bas had the highest concentration agin in 2008 but th range was c5o1n5s0idnegr/agb.lySmnaarlrlmowoeurththbaanssinha2d00th6e(PhFiOgSh:es4t9cnongc/etngotr3a8ti0onnga)g.ain in 2008, but the range was considerably narrower than in 2006 (PFOS: 49 ng/g to 380 ng/g). IInn 22000066, ffiisshh wweerree tteesstetde orfor PPFFCCss iinntthhee uuppppeerr SSt.t. CCrrooiixx RRiivveerr((aabboovvee tthhee t.St. CCrrooiixxFaFlalllssddaamm)) aanndd LLaakkee. CCaallhhoouunn iinn MMiinnnneeaapoploiliss.. TThhee PPFFOOSS ccoonncceennttrraattiioonnss iinn ffiisshh ffrroomm tthhee SStt.. Cro, Croix, aass eexxppeecctteedd,, wweerree bbeellooww tthhee ddeetteeccttiioonn elevveell.. IInn LLaakkee CCaallhhoouunn,, tthhee bbulueeiglilllss hhaadd PPFFOOSS ccoonncceennttrraattiioonnss ooff 118811ttoo 337733 nngg//gg;; pprroommppltiinngg aaddddiittiioonnaall llaakkee mmoonintitoorriinngg iinn tthhee ffoolllolowwiinngg yyeeaar.r. 1In022000077,, PPFFCC mmoonnititoorriinngg iinn fiisshh ffooccuusseedd oonn 3300 TTwwiinn ites Cities mmeettrroo llaakkeess, lloowweerr SStt.. CCrrooiixx iRviveerr,, aanndd tthhee uuppppeerr MMiissisissssiippppi RRiivveerr nneaarr BBrraaiinneerrdd.. FFiivvee olakkeess--EEllmmao,, GGeerrvvoasis,, Hari, Harriet, JJoohhaannnnaa,, aanndd TTaamnenerrss----hhaadd ffiisshh wwiitthh PPFFOOSScocnocnecnetnrtarattiioonnssggrreeaatteerrtthhaann 220000 nngg//gg.. LLaakkeeEEllmmoo hhaidd tthhee hhiigghheesstt ccoonncceennttrraatitoinosonosff PPFFOOSS,, rraannggiinngg ffrroomm 114499 nngg//gg t1o0771111 nngg//gg..IInntthhee UUppppeerr MMiisssiisssiipoppi RRiivveerr nneeaarr SBarainineerrdd,, PPFFOOSS ccoonncceennttrraattiioonnss iinn ffoouurr ffiisshh ssppeeccieiessrraannggeedd ffrroomm oonnlly6y6 nfng/g tLoo 1188nnegf/g.. IInn aadddciititoinotono tthhee mmeettrroo laakkee ssaammpplleess aannaallyyzceedd bbyy AXAYXYSS AAnnalayltyitcicaall LLttd,, fiisshh hhoommooggeennaatteess ffrroomm 5599 llaakkeess ffrroomm tthhrroouugghhoouutt tthhee sstaattee aanndd sseevveerraall MMiisssiissispipppii RRiivveerr llooccaattiioonnss wweerree sseennttttootthhee UUSSEEPPAA llaabb iinn RReesseeaarrcchh TTrriiaannggllee PPaarrkk,, NNoorrtthh CCaarroolliinnaa ((DDeelliinnsskkyy eett aall.,, 22001100).). UUSSEEPPAA''ss aannaallyysseess llooookkeedd aat bblluueeggililll aanndd ppuummppkkiinnsseeeedd ssuunnffiisshh,, aanndd bbllaacckk ccrraappppieie.. TThhee ssaammpplleess wweerree mmoossttllyy ccoommppoossiitteess ((oonllyy tthrheeroofeftthheee 7700 ssaammpplleess wweerree ssiinnggllee ills). fillets).TThheeirir hhiigghheesstt rreeppoorrtteedd PPFFOOSS ccoonncceennttrraattiioonnss wweerree iinn bblluueeggililll ffrroomm PPooooll 22 ((22000000 nngg//gg).). UUppssttrreeaamm ooff PPooooll 22, ththe hhiigghheesstt PPFFOOSS ccoonncceenntrtraattiioonn wwaass 2200 nngg//gg.. TThheeiirr rreessuullttss ffoorr llaakkeess rraannggeedd ffrroomm PPFFOOSS lleessss tthhaann ththe mitlimit ooff qquuaanntitittaattiioonn ((L1O0Q0== 1I nngg//gg)) ttoo:ahhiigghh ooff 5522 nnegf/g;; 5522 ooff tthhee 5599 alakkeess ((8888%%)) hhaadd PPFFOOSS ccoonncceennttrraattiioonnss leessss tthhaann 33 ng.ng/g. 1Inn 22000088,, PPFFCC ssaammpplliinngg iinncclluuddeedd 2222 mmeettrroo aarreeaa llaakkeess aand2n2alakdkeess nneeaarr DDuulluutthh,, iinn aaddddiittiioonn ttoo mmoorere: ssaammpplliinngg iinn PPoooollss 22 aanndd 33 ooff tthhee MMiissssissispipppii RRiivveerr.. TThhiirrtteeeennoofftthhee llaakkeess,, nnoott iinncclluuddiinngg CCaallhhoouunn aanndd EElmmoo ((wwhhiicchh aaggaaiinn sshhoowweedd hhiigghh PPFFOOSS ccoonncceentnrtraattiioonnss)),, hhaadd ssppeecciieess-mmeeaann PPFFOOSS ccoonncceenntrtraattiioonnss aabboovvee 4400 nngg//gg.. TThhrreeee llaakkeess----TTwwiinn ((BBrooookkilyynn CCeennttee)r),, HHaarrrriieett,, aanndd LLaakkeeoofftthhee sIsileess----hhaadd ssppeecciieess--mmeeaann PPFFOOSS ccoonncceennttrraattiioonnss aabboovvee 220000 nngg//gg.. IInn PPoooolls2s2 aanndd 33,, oonnee ttoo ffiivvee ffiisshh ppeerrssppeecciieesswweerree aannaallyyzzeedd;; gills bluegills aanndd Mississippi Pool 2 PFCs 2009 + March 2010 Mississippi Pool 2 PFCs 2009 . March 2010 7 -7- MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00000099 33MM_MMNN0033004433008855 smallmouth bass again had maximum PFOS concentrations greaterthan 200 ng/g althoughthespecies. msmeaanllsmoinuPthoobla2sswaegraein17h3adngm/gafxoimrulmucgPiFlOsS acnodnc1e6n2trnagt/iognfsorgrsemaatlelrmtohuatnh2b0a0ssng/g, although the species- means in Pool 2 were 173 ng/g for bluegills and 162 ng/g for smallmouth bass. W Whhyy t~h:~iss ss[t:~u(d~yy?? The MPCA slegalyrequired tls waters as impaired if the fish consumption advisory foakre or river TthheatMsPmCoAreis rleesgtarlilcytirevequthiraendatomeliaslt pweartewreseaks i(mMipnani.re.d ipft.th0e5f0is.h01c5o0n,suumbpp.tio7n). aPdovoisloryhfaosrbaeelankeliostrerdiv3e5r tihmaptaiisremdodreueretostPriRctOivSenthfaisnh asimnceeal20p0e8r,wbeaesked(Moninn.onR.cpet.p7er05m0o.0n1t5h0a, dsusbapr.y7)f.orPobloul e2gihlalsin 2007. been listed as AimddpiatiiroendalduPeECtodaPtFaOwSerinefwisahrrsainnctee2d0g0i8v,ebnatsheed somnalal osnacmeplpeersimzeosnotfhfaisdhviisnoyreyafrosrpbrliuoergtiolls20in0920a0n7d. becauseboth water Additional PFC data because both water and fish PFOSconcentrations are need to were warranted given the small sample sizes and fish PFOS concentrations are needed to establish offish in establish site-specific water quality years prior to 2009 and site-specific water quality rcirtiteerriiae.. MMPPCCAA,, MMODHH,, MMDDNNRR,, aanndd33MMssttaaffff mmeettoonn 1133 MMaayy 22000099 ttoo ddiissccuusss ththe iinntteennssiivvee mmoonintitoorriinngg ssttuuddyy ooff PPooooll 22..33MM ssoolliicciitteedd aa pprrooppoossaall orfor assttuuddyy ffrroommtthhee ccoonnssuullttiinngg ffiirrmm,, EEnnttrriix,, wwhhiicchh wwaass tthhee bbaassiiss ffoorr a ddiissccuussssiioonn.. TThhee MMODNNRR offfeerredettdoo ccoolllleecct ththe ffiisshh aanndd MMPPCCAA wwaanntteedd ttoo oovveerrsseeee tthhee ssttuuddyy;; tthheerreeffoorree,, titwwaass aaggrreeeedd tthhaatt MMODNNRRwwoouulldd coect collect tthhee ffiisshh aanndd MMPPCCAA wwoouulldd ccoooorrddiinnaattee tthhee llaabboorraattoorryy aannaallyyssiiss aanndd aannaallyyzzee tthhee rreessuulsts.. 33MM wwaass pprroovviiddeedd wwiitthh ssppilitt ssaammpplleessooffffiisshh aannddwwataeterrffoorr aannaallyyssiiss iinn 3M 3M's EEnnvviirroonnmmeennttaall LLaabboorraattoorryy ((mmorree deta details uunnddeerr MMeetthhoodds)s.). Methods Fish Collection Forths For this study, study, Pool Pool 2 2 wwaassddiivviiddeedd ninttooffoouurseseccttiioonnss F(Fiigguurree 22)),, bbaasseedd oonn tthhee pprrooffeessssiioonnaall jjuuddggmmeenntt ooff Joel tias, MONA Fisheries; and were agree to by the representatives from MOH, MPCA, and 3M. Joel Stiras, MDNR Fisheries; and were agreed to bythe representatives from MDH, MPCA, and DDeessccrriippttiioonnoofftthheeffoouurr PPooooll 22 SSeeccttiioonnss:: Section 1: 3.6 river miles from Ford Dam toconfluencewith Minnesota fiver. Se~f~o# ~: 3.6 river miles from Ford Dam to confluence with Minnesota River. Section 2: 9.5 iver miles from confluence with Minnesota iver to lower channel to Hog Lake and Pig's SEvee~Loa~ke2,:b9u.t5nroitveirncmluildeisnfgroHmogcaonndfluPeing'ceEvwe litahkeMs;innMeestortoapoRliivteranto(Mloewtreor)cwhaasntneewlatoteHrotgreLaatkmeeanntdplPaingt's aEnyed LHaoklem, abnutFineoltd ianicrlpuodritnagrHe oign tahnids sPecigti'sonE.ye lakes; Metropolitan (Metro) wastewater treatment plant and Holman Field airport are in this section. Section 3: 13.7 river miles include Hog Lake and Pig's Eye Lake as well s River, Baldwin, Moors, and Spring lakes and Lower Grey Cloud Se~$~os S~ 13.7 river miles include Spring lakes and Lower Grey Cloud Slough. Hog Lake Slough. and Pig's Eye Lake as well as River, Baldwin, Mooers, and Section 4: 47 river miles to Lock & Dam 2 in Hastings; Eagles Point wastewater rcatment plant and S3eMCCfoo#tt4a~ge4.G7rorivveerfamciiletsytaoreLoicnkth&isDseacmti#on2. in Hastings; Eagles Point wastewater treatment plant and 3M Cottage Grove facility are in this section. FFiivvee ttaarrggeett ffiisshh ssppeecciieess wweerree aaggrreeeedd uuppoonn:: lbulueeggiilll ssuunnffiisshh ((B86G5S)),, ccoarrpp ((C))., ffrreesshhwwaatteerr ddrruumm ((FFWWDD)),, ssmmaallllmmoouutthh bbaassss S(SMMEB)),, aanndd wwhhiittee bbaasss ((WWHHEB).). FFWWDD hhaadd nnoott bbeeenn ccoolllleecctteedd pprreevviioouussllyy;; ccrreeeell ssuurrvveeyyss and field bservations by the MDNR haveshownfishers catch and eat FWD. and field observations by the MDNR have shown fishers catch and eat FWD. MDNRcollected fish from the 33mile reaofcPoha 2 n late May 2008. oe! Stirs, MONR Fisheries, and. SMtDevNeRDceotallienc,teMdDfNisRh fErcoomlogthiceal~3RemsoiluerrceeaschLoonfgP-oToelrm2 iRneslaotuercMeayMo2n0i0t9o.riJoneglPSrtoirgarsa,mM, DcoNlRleFctisehdefriisehs,inand Steve DeLain, MDNR Ecological Resources Long-Term Resource Monitoring Program, collected fish in Mississippi Mississippi PPooooll 22 PPFFCCss 22000099 . + MMaarrcchh 22001100 "3 MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00001100 33MM_MMNN0033004433008866 three days using electroshocking equipment. The fish collection locations were mapped (Appendix A). tFhisrehewedraeyswursainpgpeedleicntraolsuhmoicnkuinmgfeiqluaipnmd eimnmt.edTihaetfeislhy fcroolzleenc.tioTnhlofcraotzioennsfiwshewreermeaapbpeelde(dAwpiptehnadiuxnAi)q.ue sFaismhpwleerIeD wberafoprpeedshiinppailungmoinveurmnifgohitl atnodthime mlaebodriaattoerlyy.frozen. The frozen fish were labeled with a unique sample ID before shipping overnight to the laboratory. W Waatteerr Collection Watersamples were collected at 12 stations--3 stations per section--corresponcing to areas where fish wW eraetecrausgahmtp.leWsawteerresacmopllelcetsewdearte12coslltaectitoendos-n-3Jusltay2ti,on2s00p8.erMsPeCctAiocn--ocorrlestphlornedeeisnagcmtpoltaerseaaetsewadhcehre fish wsteatreiocnaaungdht3. MWcaotellrescatemdpdleupslwicearteescopllleusctsepdikoensJaumlpyl2e,s2a0t0a9l. M12PtCaAticoonllsecatsedweltlh.reAellssaammpplleessawtereea:ch collected as station and collected as grab samples justbelowthewater surface 3M collected duplicates plus spike samples grab samples just below the water surface usailnargge polyethylene bottle that was at all 12 stations as well. All samples were using a large polyethylene bottle that was uusseedd t1o0 5psplit tthhee wwaatteerr ssaammpplleess aammoonngg 33MM aanndd MMPPCCAA bboottttlleess.. DDeessccririppttiioonn ooff 1122 wwaatteerr ssaammppllee ssttaattiioonnss ((FFiigguurree 22)).: 11.. Section 1; main channel at river mile 847 Section 1; main channel at river mile 847 22.. Section 1; old Minnesota River channel, near river mile 845.4 Section 1; old Minnesota River channel, near river mile 845.4 3. Section 1; main channel upstream of confluence with Minnesota River at ivermile894 3. Section 1; main channel upstream of confluence with Minnesota River at river mile 844 44.. Section 2; main channel near boat launch at river mile 842 Section 2; main channel near boat launch at river mile 842 55.. SSeeccttiioonn 22;; mmaaiinn cchhaannnneell aaddjjaacceenntt ttoo HHoollmmaann FFiieelldd aatt rriivveerr mmiillee 883377 66.. SSeeccttiioonn 22;; bbaayy ssoouutthh ooff PPiiggss EEyyee LLaakkee nneeaarrrriivveerrmmililee 883344 7. 7. SSeeccttiioonn 33;; mmaaiinn cchhaannnneell nneeaarr bbooaatt llaauunncchh aanndd ddoowwnnssttrreeaamm ffrroomm AAsshhllaanndd OOiill rreeffiinneerryy aatt rriivveerr mmiillee882299..5 ((oorriggiinnaallllyy iintnentdeendtdtooebbedenneeaarr14149944 bbrriiddggee,,aatt uuppppeerreennddooff SSeeccttiioonn 33,, bbuutt nnoo ffiisshh were collected in that reach) were collected in that reach) 88.. SSeeccttiioonn 33;; mmaaiinn cchhaannnneell uuppssttrreeaamm ooff lIsalanndd 111122 aatt rriivveerr mmiillee 882277..55 9. 9. SSeeccttiioonn 33;; SSpprriinngg LLaakkee,, nneeaarr irivveerr mmiillee 882211 1100.. SSeeccttiioonn 44;; mmaaiinn cchhaannnneell,, ddoowwnnssttrreeaamm ooff GGrreeyy CClloouudd SSlloouugghh aatt rriivveerrmmiilee 881199 1111.. SSeeccttiioonn 44;; nneeaarr sshhoorreelliinnee,, ddoowwnnssttrreeaamm ooff 33MM CCoottttaaggee GGrroovvee ddiisscchhaarrggee,, nneeaarr riivveerr mmiilee 881177..55 1122.. SSeeccttiioonn 44;; mmaaiinn cchhaannnneell,, uuppssttrreeaammooffLLoocck&k& DDaamm ##22attrriivveerrmmililee 881166. LLaabboorra;~t:oorryy AA~naa~lyyss~iss AAXXYYSSAAnanlaytlyitcicaall SSeerrvviicceess LLttdd aannaallyyzzeedd aalll wwaatteerr aanndd ffiisshh ssaammpplleess ffoorr PPFFCCss..EEmmppttyyccoooolleerrss wweerree sshhiippppeedd bbyy AAXXYYSS ttoo tthhee MMPPCCAA ffoorr ffiisshh ssaammpplleess aanndd ccoooolleerrss wwiitthh bboottttlleess wweerree sshhiippppeedd ffoorr wwaatteerr ssaammpplleess.. TThhee wwhhaolele. ffiisshh sshhiippppeedd ttoo AAXXYYSS wweerree mmeeaassuurreedd ffoorr lleennggtthh aanndd wweeiigghhtt;; aallssoo,, ggeennddeerr aanndd aaggee wweerree rreeccoorrddeedd.. AAXXYYSS hhoommooggeenniizzeedd ffiisshh ffiillleettss wwiitthh ssccaalleess. ooffff aanndd sskkiinn oonn,, wwhhiicchh iisstthhee pprroottooccooll uusseeddffoor ffiisshh ccoonnttaammiinnaanntt aannaallyyssiiss wwhheenn rreessuullttss aarree uusseedd ffoorr ffiisshh ccoonnssuummppttiioonn aaddvviissoorriieess.. M Misisssiissssiippppii PPooooll 22 PPFFCCss 22000099 .+ MMaarrcchh 22001100 e MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00001111 33MM_MMNN0033004433008877 The USEPA hasnotyet approved an analytical metha for PECs; however, al laboratories conducting TPhReC aUnSaElyPsAishaosn neonvt iyreotnampepnrtoavlesdaamnplaensaulysteicaalmmetehthooddoffolriqPuFiCdsc; hhroowmaetvoegrr, aapllhlya-bcolreacttorroiessprcaoyntdaunctdinegm mass spectrometry (LC/MS/MS). Sample homogenization, extraction, and clean-upsteps can PFC analysis on environmental samples use a method of liquid chromatography-electrospray mass spectrometry (LC/MS/MS). Sample homogenization, extraction, and clean-up steps can vary. tandem vary `aammoonngg llaabboorraattoorriieess.. AAXXYYSS ddeessccrriibbeess tthheeiirr mmeetthhoodd aass,, AAXXYYSS MMeetthhoodd MMLLAA--006600:: AAnnaalylyttiiccaall PPrroocceedduurreeffoorr tthhee AAnnaallyyssiiss oof]PPeerfrflluuoorriinnaatteedd OOrrggaanniicc CCoommppoouunnddss iinn AAqquueeoouuss SSaammpplleessbbyy LLCCMMSSIIMMSS.. The reporting level is the limit of quantitation (LOGY, defined as the lowest non-zero calibration standard Thahveinregpaocrctuinrgaclyevoefl 100 430%. is the limit of quantitation (LOQ), defined as the lowest non-zero calibration standard having accuracy of 100 +30%. QQu~aal~iit{yy AAssssu~rraa~nccee IInn aaddddiittiioonnttoo tthhee mmuultltiippllee lleevveell qquuaalliittyyaassssuurraannccee pprroottooccooll aatt AAXXYS5,, WWiillliiaamm SSccrruuttoonn,, QQuuaalliittyy AAssssuurraannccee CCoooorrddiinnaattoorr ffoorr MMPPCCAA''ss EEnnvviirroonnmmeennttaallAAnanlaylyssiiss aanndd OOuuttccoommeess DDiivviissiioonn,, rreevviieewweedd aallll ddaattaa ppaacckkaaggeess ffrroomm AAXXYSS aanndd iiddeennttiiffiieedd aannyy rreessuullttss nneeaeldiinngg ttoo bbee qquuaalliiffiieedd aass aann eessttiimmaattee iiff lalll QQAA rreeqquuiirreemmeennttss wweerree nnoott mmete.t. SSaammpplleess wweerree ssppilitt ffoorr ffiisshh aanndd wwaatteerr wwiitthh 33MM ttoo vveerriffyy AAXXYSS llaabboorraattoorryy rreessuullttss.. SSiixx ffiisshh ooff eeaacchh ooff tthhee. ffiivvee ffiisshh ssppeecciieess wweerree rraannddoommllyy sseelleecctteedd bbeeffoorree bbeeiinngg aannaallyyzzeedd ffoorr PPFFCCss aanndd hhoommooggeennaatteess ffrroomm tthhoossee ffiisshh wweerree sshhiippppeedd bbaacckk ttoo MMPPCCAA aanndd ddeelliivveerreedd ttoo tthhee 33MM EEnnvviirroonnmmeennttaall LLaabboorraattoorryy.. AAss mmeennttiioonneedd aabboovvee,, wwaatteerr ssaammpplleess wweerree ccoolllleecctteedd aatt tthheessaammee ttiimmeebbyyMMPPCCAA aanndd 33MM aatt aallll 1122 ssttaattiioonnss.. TThhee rreessuullttss ffrroomm 33MM aarree ggiivveenn iinn tthhee 33MM EEnnvviirroonnmmeennttaall LLaabboorraattoorryy FFiinnaall AAnnaalylyttiiccaall RReeppoorrttss NNoo.. EE0039--00336655 ((ssuurrffaaccee wwaatteerr)) aanndd NNoo.. E0099.-00337722 ((ffiisshh ffiilllleett hhoommoogegneantaetse)s.). Results and Discussion SSu~rrffaa~cee W Waatteerr Surface water samples were collected on 2 uly 2009 from the 12 water sample stations selected for PSouorlfa2coefwtahteerMissasmispsliepspiwReirveer.coAlldedcitteidonoanl 2inJfuolyrm2a0t0i9onfrcoomlletchteed12towchaaterracstaemripzleeesatacthiosntsesienlcelcuteddedfor temperature, Pool 2 of the temperature, dissolved oxygen, depth, and conductivity (Table Mississippi River. Additional information collected dissolved oxygen, depth, and conductivity (Table 1).to 1). Temperature was characterize each Temperature was relatively constant, site included relatively constant, rreemmaaiinniinngg wwiitthhiinn 2214--2266 CC rraannggee tthhrroouugghhoouutt PPooooll 22.. DDiissssoollvveedd ooxxyyggeennddrrooppppeedd ffrroomm 99..22 mmag//Lk aatt SSttaattiioonn 11tto077..33 mmgg//LL aatt SSttaattiioonn 1122.. W Waatteerr ddeepptthhss rraannggeeddffrroomm 11..22 mm ttoo 66..77 mm.. SSppeecciiffiicc ccoonndduuccttiivviittyy iinnccrreeaasseedd aafftteer tthhee MMiisssiissispipppii ccoonnfflluueenncceewwitithhtthhee MMiinnnneessoottaa RRiivveerr,, bbeettwweeeenn SSttatiaontsi33aoannndds44 ((338822 s/c I~S/cm ttoo 553366 ulaSSf/ccmm)),, aanndd iinnccrreeaasseedd sslliigghhttllyy aaggaaiinn bbeettwweeeenn SSttaattiioonnss 55 aandn66((55d2255 u/c I~S/cm ttoo 558800 Sla/Sn/c)m,),bbuutttthheenn rreemmaaiinneedd sstatblaeffoborrltthheee rreesstt ooff PPooooll 22.. CCoonncceentnrtraattiioonnssffoorraallll PPFFCC aannaallyytteess iinn eeaacchh ttrriippllicicaatteessaammpplleeffrroomm tthhee 1122 wwaatteerr ssaammppllee ssttaattiioonnssaarreeggiivveenn iinn TTaabblele22.. SSaammpplleess aarree iiddeennttiiffiieedd bbyySSecetcitoionns-sttaattiioonn-rreepplliiccaattee.. PPFFOOSScacnocnecnetnrtarattiioonnss oor rreeppoorrttiinngg lleevveellss aarree lliisstteedd iinn tthhee sseeccoonndd ttoo llaasstt ccolumonaalnnddaauvveerraamggeessnffoorr eeaacchh ssttaattiioonn aarree slistteedd iinn tthhee ffiinnaall ccoolluummnn.. W Whheenn the concentratwiaosn below the reporting limit, the reporting level was used to calculate descriptive tshtaetisctoicnsc.entration was below the reporting limit, the reporting level was used to calculate descriptive statistics. Mississippi Mississippi Pool Pool 2 2 PPFFCCss 2009 2009 + . MMaarrcchh 22001100 0- 10- M Miinnnneessoottaa PPoolllluuttiioonn C Coonnttrrooll AAg~eennccyv 22556655..00001122 33MM_MMNN0033004433008888 Variability as indicatedby coefiofcvaerinatiton (CV) among ipicate water samples ws below 10% for PFOaSt Variability, aasllinstdaictiaotnesdebxycecpotesfftiactieionnt o12f,vwahriiactihonha(dCVa%C)VaSmofon2g6t%r.ipTlichaeteavweraatgeerCsVam%pfloers PwasOabtetlSohwe 1f0i%ve fsotartPiFonOsSwahtearllesPtaFtOioSnwsaesxdceepttesctattiaonbwla1es2, 9w.h0i%c.hThhaedCaVCfVo%roPfF2B6A%,.dTeheteavcetraaagbetlaCelVl%12 sfotartPiFoOnsS,awt athse five 1.2% stations where PFOS was detectable was 9.0%. The CV% for PFBA, detectable at all 12 stations, was 13.2%. AcomparoifsFoOnS concentrations rom AXYS an 3Mshor good agreement (Figure 3). Resultsof APFcOoSminpawraistoenr offoPmFO3SMcoEnnvciernotnramteionntss!frLomaAbXYoS arwnedar3eMtgensoehrorawlylgyoohdigahegrretehmnenfto(mFigAuXrYeS3f).orRtehseulstsaomfe sPtFaOtiSoni.n water from 3M Environmental Laboratory were generally higher than from AXYS for the same station. Most ofthe ather PFCs wore ss tha the reporting eve, although ine of the 13 analytes were dMeotsetctoefdthien soathteironPF1C1s wanedre12le.sTshthhiagnhtehsetrecponocretinntgraletvieonl,saolfthlolugdehtencinteedofatnhaelyt1e3sawnearlyeteisn swteatreion 11. PdeFtBeAcWteadsinthseotantliyonosn1e1oafntdh1e21. 3Thmeeahsiguhreesdt FcoCnscethnatrtawtiaosnsmeoaf saullrdeedtenctdeedteacntaalbylteescwonecreenintrsatattiioonants11f.l wPaFtBeArwtaastitohnes.onPlFyOoAnewaosf tdheete1c3temdaeassutreadtiPoFnCss 6t-h12aatnwdaPsFmHCeaAsvurseddeintedcetteedctaatbsletactoionncse7n-t1ra2.tioPnRsOSawt aalsl wdeatteecrtasbtalteionnss.tPatFiOoAnsw5a7s,d8e,te1c1,teadndat1s2t.aTtiohnesav6e-1r2agaenPdRPOFSHcxoAncweanstrdaettieocnteadt sattasttiaotnio1ns17s-123.0PFngO/SLwTahse ndeextetchtiagbhleestinPsFtOaStiocnosnc6e,n7t,r8a,ti1o1n, wanods 1512. nTgh/eLaotveSrtaagteoPnF1O2.S Tchoencoetnhterrattiohrneeatssattaotionns w1i1twhadset9e0ctnagb/lLe. The PnEe0xSt (h6ig,h7e,satnPdFO8)ShcaodncPeFnOtSraativoenrawgaess o15fng7.1/,L1a0t3,Staantidon8:152g. /TLh,e roetshpeecrttihvreelye. The high PROS. stations with detectable cPoFnOcSen(t6r, a7t,iaonndat8)tahtaidoPnF1O1Swaavseraabgoeustoefq7u.a7l, t1ot0.h3,eancodn8c.e5ntnrga/tLi,ornesofpePcFtiOvAely(.54Thnegh)ighanPdFoOnSehlf the concentration concentration concentration ofat of FB at that sation (163 ng). station 11 was about equal to the PFBA at that station (168 ng/L). concentration of PFOA (94 ng/L) and one-half the The (bThe MMPPCCAA hahas etwee p eessttaabblliisshheedd ca state rn ssiittee--ssppeecciiffiicc wwaatteerr qquuaalilittyy ccrriitteerriiaa orfor us/cleanup/pln hm) on for PPPEFFGOOASS saatnnaddtewPPiFFdOOe.AA iiTnnhPPeoooPollO22S criteria7s n(hg/ttLp:T//hwew2w0.0p9cawa.sttearteq.umalni.tuyss/ctaletiaonnuapv/eprfacg/iensdeexxc.hetemd lt) iasndcr~it:oerriPaFaBtAstsattaiteonwsid5,e.7,T8h,e1P,FOaSndcr1i2t.eriNaoimse7 of hnge/LstTathieon2s0e0x9cweeadteerdqtuhaeliPtyFOsAtatcirointeraivaeorafg2e.s7 egx/cLee(d2,th70is0ncgr/itLe)rioaratt hsetaPtFioOnAsc6ri, t7e,ri8a, o1f1,1amngd/L1.2. None of the stations exceeded the PFOA criteria of 2.7 pg/L (2,700 ng/L) or the PFBA criteria of i mg/L Fish QFQiu~sahal~iwtetyyreAAscsossluslre;acat~nec6deeon 2829 May 2009 and 1 June 2009, throught th length of Pol2 (Tae 3. The tFaisrhgewteorre ceoacllehcsteecdtioonn 2of8-1259 iMndaiyvi2d0ua0l9s apnedr L1aJrugnee s200p9,etwhracosugaichhoeiuetvstehdeolernagltlhseocftiPoonosl e2x(cTeapbtlefo3r). The tbsbamlluragueleigltlilltfiohinnreyeSSweaeecccthrtiioeosnanenc11at,,ilowwynhhzeoeerdfree1i5n11d22iinviidninidddvuiiidavvliiudldayuulasatllhspweewerrertareterhgcaceonotllcleseocpctmetepecdodi.es.istDDweeedsas.pspiiatteechssieoovmmeeedoo[fof rtthhaeell bbslleuuceetggioiillnlsls bbeeexiicnneggpeetxxfottrrreemmeellyy small, they were analyzed individually rather than composited. TThhee ninetre-r-llaabb ccoommppaarriissoonn ooff PPRFOOSS ccoonncceennttrraattiioonnss iinn tthhee 3300 ishfish hhoommooggeennaatteess sshhooww ggoooodd aaggrreeeemmeenntt ((FFiigguurree 4)4). IInn ccoonnttre-asstt tootthhee iinntteer-rladbb ccoommppaarriissoonn [foorrPPFFOOSS iinn wwaatteerr,, thheereressuulltts ooff PPFFOOSS iinn fsfish hfroornm 33MM Environmental Laboratory were generally lowes than fom AXYS forthesame fish. Environmental Laboratory were generally lower than from AXYS for the same fish. Spatial DistributionofPFOS by Species TThhee ddisitrsiburtiobnuooftfPPoFFOOnSS ccoonncceennttrraattiioonnss reare sshhoowwnn iinn asseerrieiseoosff bbooxx--wwhhiisskkeerr pplloottss.. IInnddiivviidduuaall ccoonncceennttrraattiioonnss orfor eeaacchhffiisshhaarree sshhoowwnn aas cciirrcclleess.. TThhee bbooxiiss bbouondeudbnbyyhohdroirziezoonntdatall ssiiddeess rreeporreesseennttinngg tthhee 25" aanndd 75"peprecrecnetnitlileess----tthhee bboouundradrieasroofiftethhese iinntteerrqquuaartrtiillee rraannggee I(IQQRR))---w-witithh tthhee mmeeddiiaann lliinnee: v((5a50l0uthe2s5pp.teehTrrchceeenwnthit7ilil5eest])khewwriistthhiisnntthhehethbbooexoxs..pIIrnnweaoattdhhoeerfr wwvoaorlruddesss,,ttthhhaeet bbooxx are sshhoowwss within ththe 1.5 rranagenoofgftthhee x IR above cceennttrraall 5500%% ooff nd below the tthhee actual values. The whiskers show the spread of values that are within 1.5 x IQR above and below the actual Mississippi Pool 2 PFCs 2009 + March 2010 Mississippi Pool 2 PFCs 2009 . March 2010 -11- MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00001133 33MM_MMNN0033004433008899 1QR. Values beyond the whiskers are considered outliers. Concentration is given on a logscale to iIQmRp.roVvaelutehsebseyyomnmdethterownyheistkheerrs sairdeeocfontshideemreeddioauntlii.ers.tCoobnectetenrtraatiponpirs goivxeniaomnnoaartmloeg-sdciaslteritboution). improve the symmetry on either side of the median (i.e., to better approximate a normal distribution). AA ccoommpapraisornioofsfffoiissnhh ssppeecciieess wwiitthhiinn eeaacchh SSeeccttiioonnaannddaallll SSeeccttiioonnss ccoommbbiinneedd sshhoowwss tthhee PPFFOOSS. concentrations were generally below 100 ng/g (ppb) in Sections 1,2, and 3 (Figure 5. Section 4, in ccoonntcraesntt,rahtiaodnshiwgheerrePgFeOnSercaolnlycebnetlroawti1o0n0s ninga/lg s(ppapcbi)eisn eSxeccetpiotnwsh1i,t2e,baansds 3(W(HFBig).ureFr5e).shSweactteiornd4r,uinm (coPnWtDr)ashta, dhiatdhehihgihgehersPtFPOFSOcSocnocnecnetnrtartiaotnisonininaall ssipnegclieesfieshxcfeilpettw3h,i5te80bansg/sg)(.WTHhBe).PFFrOeSshcwoantceerndtrruamtioinsn W(HFWBD)rehmaaditnheed haibgohuetsttPhFeOsSamcoenicneanlltrraitvioernsienctaiosnins,glienfcishonfilltert o(a3t,s5h8te0 ontgh/egr).sTpheceiePsF;OwShceonncalelnstercattiioonnss in were WHB were combined, WH remained about combined, WHB had the highest species-specific the same in all river sections, in had the highest species-specific PFOS median (75 ng/g). contrast to the other species; PFOS median (75 ng/g). when all sections CCoommbbininiinngg tthhee ddaattaa ffrroomm aalll ffoouurr SSeeccttiioonnss ooff PPooooll 22,, ccaarrpp hhaadd tthhee lloowweesstt aarriitthhmmeettiicc mmeeaann PPFFOOSS concentration, 77 ng/g (Table 4), and FWD had the highest species-mean, 229 ng/g. Theotherthree. scpoenccieesnthraatdiosni,mi7l7arnagv/ger(aTgaebsle(s4p),praonxdimFaWteDlyha1d00thneg/hgi)g.hFeissthscpoencsieusm-pmteiaonn,a2d2v9icnegs/ga. sTshiegnoetdhteorctahcrehe species species species based on the species arithmetic mean PFOS concentration from all sections of Pool had similar averages (approximately 100 ng/g). Fish consumption advice is assigned based on the species-arithmetic mean PFOS concentration from all sections of Pool 2.to 2. MDHeach MDH rreeccoommmmeennddss tthhaatt ccoonnssuummppttiioonn ooffffiishc iets fillets wwiitthh PPFFOOSS ccoonncceennttrraattioinons iinn tthhee rraannggee 4400--220000 nngg//gg bbee limited to one meal per week For fishfilletswith PFOS concentrations in the range 200-800 ng/g, the alidmviiteceditsooonneememaelalpeprermownetehk.. FMoDrHfisahdfviillseetss nwoitthtoPFeOaSicsohnscpeenctireastiothnastinextcheeedranPgFeOS20co0n-8ce0n0trnagt/gio, nthseof 8ad0v0icneg/igs.onMeOmHecaallpcuelramteosnmteha. lMaDdHvicaedvuissiensgnmoutlttoipelaetyfeisahrssopfecdiaetsa,thdaet pexecnededionPngFOtShecotnecmeponrtraaltiotrnesndos.f i8n00thnegc/ogn.taMmDinHancta.lcuFlWatDesarmiethaml eatdivcicmeeuasnindgoemsurltoiptlechyaenagres obef cdaautas,edtehpeeywnedrinegoonnlythceoltelemctpeodrainl t2r0e0n9d.s Tinhethreefocroen,taFmWiDnawnilt.l hFaWvDe athriethmmoerteicremsterainctdivoeesandotvcoihfaocnngeee bmeecaaluspeerthmeoyntwheraenodntlyhecootllheecrtesdpeinci2es00a9l.l within the Therefore, within the one mealperweek advisory. FWD will have the more restrictive one meal per week advisory. advice of one meal per month and the other species fall GGooiinngg ffrroomm SSeeccttiioonn i ttoo SSeeccttiioonn 44,, ccuummuulalattiivvee ddiissttrriibbuuttiioonnss ooff PPFFOOSS bbyy ssppeecciieess sshhooww aa cclleeaar sshhiifftt ffrroomm lloowweerr ttoo hhiigghheerr ccoonncceennttrraattiioonnss iinn ffoouurr ooff tthhee ffiivvee ssppeecciicess,, wwhheerreeaass iinn wwhhiittee bbaassss ((WWHHB)) PPFFOOSS ddiissttrriibbuuttioionnss rreemmaaiinn rreellaattiivveellyy ccoonnssttaanntt F(Fiigguurree 66)).. AAllssoo,, tthhee rraannggeessooff PPFFOOSS ccoonncceennttrraattiioonnss aarree nnaarrrrooww iinn WWHHBBccoommppaarreedd ttoo tthhee ootthheerr ssppeecciieess.. TThhee mmoovveemmeenntt ooff PPFFCCss tthhrroouugghh ffoooodd wweebbss iis nnoott uunnddeerrssttoooodd.. OOnnee. ppoossssiibbllee eexxppllaannaattiioonn ccoonnssiisstteenntt wwiitthh tthheessee rreessuullttss sis tthhaattaalll tthhee fiisshh ssppeecciieess,, eexxcceepptt WWHHB hhaavvee lliimmiitteedd hhoommee rraannggeess.. W Whhiittee bbaassss hhaavvee bbeeeenn ddooccuummeenntteedd ttoo ttrraavveelllloonnggddisisttaanncceess:: 4400 mmiilleess iinn tthhee MMiissssoouurrii RRiivveerr aanndd tthhrroouugghhoouutt tthhee eennttiirreeLLaakkee rEirice bbaassiinn ((MMoorrggaann aanndd HHaarrrreell,, 22000066).). HHoommee rraannggeess iinn bblluuecglilll ssuunnffiisshh hhaavveebbeeeenn rreeppoorrtteedd aatt oonnllyy3300 ssqquuaarree mmeetteerrss ((PPaarrrr,, 22000022)),, aaltthhoouughgaha sstudtyiinnMuMininndneessoyottaa llaakkeess ffoouunndd ssoommee bblluueeggililll aanndd bbllaacckk ccrraapppplieess mmoovvee aammoonng ccoonnnneecctteedd llaakkeess ((PPaarrssoonnss aanndd RReeeedd,, 22000055).). TThheerree sis ssoommee. eevviiddeennccee iinnddiiccaattiinngg tthhee mmaajojorriittyy ooff ccoommmmoonn ccaarrpp rreemmaaiinn wwiitthhiinn 110000 mmeetertsoeofftrthheesiir nneessttiinngg aarreeaa aalltthhoouugghh ssoommee mmaayy ttrraavveell lloonngg ddiissttaanncceess J(Joonneess aanndd SSttuuaarrtt,, 22000088)).. T`Tee~mppoorraal[ DDi~ssttrr~ibbuut~ioorxn ooff PPFFOOSS Concentrations FFiisshh wweerree ccoolllleecctteedd ffoorr PPFFCCss nin 22000044,, 22000055,, 22000066,, 22000088,, aanndd 22000099.. OOnnllyy tthhrreeee ffiisshh wweerree ccoolllleecctteedd iinn 22000044 ((TTaabbllee 55)).. MMoorree ffiisshh wweerree ccoolllleecctteedd iinnsusbusbeseqquueenntt yyeeaarrss,, aalltthhoouugghh tthhee ttoottaallppeerr ssppeecciieess rreemmaainiednleloowdw untilthe sample collection in 2009. Because of the low numbers within mst years, assessing temporal turnetnildtshies sdiafmicpullet.coAlplelcottioonf tinhe20c0o9n.ceBnetcraautsieonodf tihestlorwinbubmuybtsepiresocwineitsshinformcoascthyeyaerasr, suggestas assessing temporal tdroenwdnswaisrddiftfirceunldt.iAn PpFloOtSocfotnhceenctornactieonntsra,teiosnpedcisitarilbilunytiosnmaslblymosuptehciebsasfsor(Feiagcuhreye7)a.rHsouwgegveesrts, aprior to 2d0o0w9nwthaerdfitsrhewnedreincPoFllOeSctceodnocnenytriantSioencst,ioensp4;erceia-lplylointisnmg atlhlme oanunthuabladssis(iFbiguutrieon7s). bHyoswpeevcieer,s pwiritohr otonly Section 4 from 2009 does not show noticeable downward trend in the PFOS concentrations (Figure8). 2009 the fish were collected only in Section 4; re-plotting the annual distributions by species with only Section 4 from 2009 does not show a noticeable downward trend in the PFOS concentrations (Figure 8). Mississippi Pool 2 PFCs 2009 + March 2010 Mississippi Pool 2 PFCs 2009 . March 2010 "- 12- Minnesota Pollution Control Agency Minnesota Pollution Control A~encv 22556655..00001144 33MM_MMNN0033004433009900 appears addition! years re needed tomake proper assesosfmteempnortal endsof PF0S i ish fItraopmpPeoaorls 2.additional years are needed to make a proper assessment of temporal trends of PFOS in fish from Pool 2. Relationship of PFOS levels to ish gender, age, and size PROSconcentrations among females, males, and juveniles dd not show anoticeablediference (Figure 9P)F,Oe$xcceopntcbelnutergaitilojnvseanmiloensgwfeermeaolewse, rmtahleasn, aadnuldtsj.uvTehneilrees wdaids 15 not much ference amg not show a noticeable difference age(Figure a9)s, seexscewpitthbiluneegailclhjsupveecniilees (wFiegruerelo1w0]e.r Tthhaentawdouhltisg.hTeshterPeFwOSascaolnscoenntortatmiuocnhs idniftfheerefnrceeshawmatoenrgdarguem were na 3 year od classes within each sapecn8ieysed(aFrigoulred i1s0h).. TThheestwe oreshuilgthseisntdPiFcaOtSe cPoFnOcSendtoreastiononts biniothacecfurmeuslhawteatweirtdhruamge as wit edroeesinian m3oysetarbiooldacacnudmu8layteiavreocldomfipsoh.unTdhse,sesurecshualtss minedriccuartey aPFnOdSPCdBose.sAnnootthbeioraocbcsuemrvualtaiteonwfitrhomagteheasse ctcitohodnencocfeeernsnetstirrnhaawtmtaiiotooennsrtdddbiirssiotturramiicb,bcuuuwttimihooenunrsslbaebtayiysveaatgghceeeomccwllhapaissotssueiinsbdttashh,seeswwusichidhdoeewasrsraavmnneggereeyrcwwtuilritythehiiannrnadaangggPeeeCccBillnsaa.cssAssoeennsscoeiitnnnhtemmrroaostositbtosssneppsreevmccaiiateieson,,ngeefssrpapoenemccdiiaatlhllleyyse twhiethfirneashgwe altaesrsedsr.um, whereas the white bass shows very little range in concentrations among and within age classes. Also, there was no rlationship between PFOS concentrations and fis length or percent pid (Figures ana 12) Also, there was 11 and 12). no relationship between PFOS concentrations and fish length or percent lipids (Figures BBBii~ooaecaacccuccmuuulmmautuil~oanattf~iacootn~orsFF(aaBccAttFoo)rrfssoraaP~nFddOSW WwearateteercralQQcuu~alaalti~etdtyyorCCreriaitcteehrrsiipaaecie, in each section. Water cBoionaccceunmturlaatitorniofamncttohres t(BhAreFes)sftoartPioFnOSwiwtheirne ecaaclchuslaetcetdofnorweeracehavsepreacgieeds., inInedaicvhidusaelctiioshn.fWleatePrFOS ccoonncceennttrraattiioonnss fwreorme tdhievitdherdebeysttahteioanvsewraigtheinPFeOaScchonsceecntitornatwieorne Th individual ATswere then averaged. Individual fish fillet PFOS ccoonmbceinnterdataiosn2sgweoemreetdriivcidmeedabny (thgeeaovmerea)geoPrFeOaSchcosnpecceinestr.at(iogne.oImheetrinidcivmideuaanliBsAtFhsewaenrieotgheonfthe average of combined average of log-transformed values ) Thefins! BAF i as a geometric mean {geomean) for each log-transformed values.) The final BAF is geomean species. (A a geomean of all speces eomeans. This clclaton geometric mean is the antilog of the of all species geomeans. This calculation haaddbbeeeenn ddoonnee iinn pprreevviioouuss ers, years, uusisngaia mmnuucgchh ssmmaalllleerr ddaattaasseett STS(STS CCoonnsstualtnatnsts,, 22000077).). TThhee rreessuullttiinngg wwaatteerr qquuaalilittyy ritria criteria bbaasseedd oonn ffiisshh ccoonnssuummlpitioonn ((rreeffeerrrreedd tooaassffiisshh ccoonnssuummppttiioonn ccrriitteerriiaa,, CC,fCC, wweerree 66 and wate quality criterion nngg//LL ffoorr PPooooll 33 aannd4d4 nngg//LL ffoorr PPooooll 22.. TThhee 22000099 ssttuuddyy hhaass aalllloowweedd ffoorr aa rroobbuusstt rreeccaallccuullaattiioonnooff tthhee BBAAFFss and water quality criterion. PROS lPeFvOelS iwwacat.eterLreccvooenlnccoefenntQtruraaantttiioiontnasstiiinntohent,heLuOupGp)p.peerFr3o3Sr SweaetccteiotrncisoonoofcfenPPnootosrolal t22iwwoenersreebepplrroeewddootmhmieninraaetpteeolrlyytillenessgss ettvhheaalnn, ttohhneee-rrheeapplofortrttihinnegg. rleevpeolrt(ii.en.g, lLeevvelelwoafsQuuseadn.titAatBioAnF,wLOsQc).alFcourlawtaetdeor rcoonncleynStercattiioonns4,bwehloewrethPeRrOeSpwoarttinegr cleovnecle,notnraet-hioanlfsthe wreeproertailnlgableovveel twhaesruespeodrt. iAngBeAF wvastoecaavlo,ciudlatheadvfionr toonluysSeencotnio-nde4t,ewcthaebrleePcFoOncSenwtaratetirocnos.ncTehnetrasptieocnises wSpeecreifiacllBaAbFosveratnhgeedrefproormti2n,g5l1e9vel,Ktgo faovrocidarhpatvoin7g,t0o10usKe gnofno-rdferteeschtawbatleercodrnucme,ntTrahteiognes.oTmehetrsipcemcieeasn- cf aslpescpieficcieBsAFins Sreacntgieodn is 377 LK. The from 2,519 L/Kg for gceaorpmetotr7i,c01m0eaLn/Kogffoalr fsrpeeschiwesafterromdraulmS. eTchteigoenosm7e.5tr5i4c. mean of all species in Section 4 is 3,877 L/Kg. The geometric mean of all species from all Sections is 7,554. These 8474 can be applied tothe cqufoacaltculaitinog nish consumption criterion (CC). The TehqeusaetiBoAnFss can be applied to the equation for calculating a fish consumption criterion (fCC). The equation is RD +BW +E CwhCere=,RF eRXF DA RwIhDe=rer,eference dose, 0.00008 mg/kg/d BWRfD == body weight, 70k reference dose, 0.00008 mg/kgid BW = body weight, 70 kg Mississippi Pool 2 PFCs 2009 + March 2010 Mississippi Pool 2 PFCs 2009 . March 2010 - 13- Minnesota allution Control Asency Minnesota Pollution Control A~encv 22556655..00001155 33MM_MMNN0033004433009911 K= exposure fraction attributed to waterandfish consumption, 0.2 IWK== exipncoisduernetaflraictniogn eattsoribftuwiatetodernt,o 0w.a01teLr dand fish consumption, 0.2 CR=fish consumption rate, IW = incidental ingestion of CR = fish consumption rate, 0.030 kg/d water, 0.01 0.030 Kg/d L/d AAppppllyyiinngg tthhee BBAAFF ffrroomm 22000099,,tthheererseuslutlitinngg CfCCC sis 77nngg//LL uussiinngg aallll PPooooll 22ffiisshh. CCoom~ppaa~ri~ssoon~ ttoo OOtt~hee~r LLooccaattiioonn,ss W Whheerree ppooiinntt ssoouurrcceess hhaavvee nnoott ddiisscchhaarrggeedd PPEFCCss ,oonnee mmiigghhtt rreeaassoonnaabbllyy aassssuummee tthhaatt ccoonncceenntrtraattiioonnss aarree zzeerroo bbeeccaauussee PPFFOOSS iiss tcl strictly aann aanntthhrrooppooggeenniicc ccoommppoouunndd;; hhoowweevveerr,, PPFFOOSShhaassbbeeeenn ffoouunnddiinn wwililddiliffee,, iinncclluuddiinngg ffiisshh,, tUhhroouugghhoouutt tthhee wwoorrlldd ((GGiieessyy aanndd KKaannnnaann 22000011;; HHoouuddee eett aa1l 22000066).). PPFFCCss aarree gglloobbaallllyy ddiisstrbibuutteedd aannddtthhee lleevveellss iinnccrreeaassee wwiitthh pprrooxxiimmiittyy ttoo uurrbbaann aarreeaa ((HHouodeueetdtaalel,., 22000066).). AAccoommpapriasornoioffwswhhoaolnlee ffiisshh ccoommppoossiittees ((oonnee ssmmaallll fiisshh aanndd oonnee llaarrggee ffiisshh ccoommppoossiittee ppeerr ssiittee)) ffrroomm 3300 isitteesswwitithhiinn tthhee MMiissssoouuriri,, OOhhiioo,, aanndd MMiissssiisssiippppii RRiivveerrss ffoouunndd mmeeddiiaann PPFFOOSS ccoonncceennttrraattiioonnss ooff 2244..22 nngg//gg,, 3311.8.8ng0/g,, aanndd 5533..88 nnegf/g,, rreessppeeccttiivveellyy ((YYee eeat lal,., 220000880)a.). AAlltthhoouugghh tUhee MMiissssiissssiippppii hhaass tthhee hhiigghheerr PPFFOOSS lleevveell,, tthhee tteenn ffiisshh ssaammpplleess aabboovvee220000 nngg//gg PPFROOSS wweerree ddiissttrriibbuutteedd tthhrroouugghhoouutt tthhee tthhrreeee irivveerrs,, iinnddiiccaattiinngg tthhee PPFFOOSS ccoonnttaammiinnaattiioonn iis wwiiddeesspprreeaadd.. AAnn EEPPAA ssttuuddyy ooff 7sPFCs iinn ccaarrpp ccoolllelcetcetdieidnn 22000066 ffrroomm tthhee UUppppeerr MMiissssiissssiippppii RRiivveerr,, rreeppoorrtteedd mmeeddiiaann ccoonncceennttrraattiioonnss ooff PPFFOOSS rraannggiinngg ffrroomm 88 nngg//gg uuppssttrreeaamm ooff SS.t. CClloouudd ttoo 2266 nngg//gg aanndd4400 nngg//gg aatt PPiigg''ss EEvyee LLaakkee aanndd ddoowwnnssttrreeaamm aatt SSpprriinngg LLaakkee ((YYee tet aall.,, 22000088bb)) ((TTaabbllee 66)).. TThhee llaatttteerr ttwwoo ssiitetss aarree iinn SSeeccttiioonn 22 aanndd SSeeccttiioonn33ooff PPooooll 22,, rreessppeecctitivveellyy.. NNoo ccaarrpp wweerree ccoollelclteedbcbytytethhdeeMMODNNRoorr MMPPCCAA iinn 22000066 frroomm tthhee MMisisssiissssiippppii RRiivveerr.. MMeeddiiaann ccoonncceennttrraattiioonnss ooff PPFFOOSS iinn ccaarrpp ffrroomm oouurr 22000098 ssttuuddyy wweerree 2288 nngg//gg oforr lalll ooff PPooooll 22,, 1133 nngg//gg ffoorr SSeecticont22aiannodd8n877 nngg//gg ffoorr SSeeccttiioonn a4.. PPRFOOSS lleevveellss iinn wwhhoollee,, ffoouurr yyeeaarr--oolldd llaakkee ttrroouutt ccoolllleecctteedd frroomm tthhee GGrreeaatt LLaakkeess iinn 22000011 ((FFuurrdduuii eettaall.,, 22000077)) wweerreelloowweesstt iinn LLaakkee SSuuppeerrioiro( r4.84.8 nngg//gg)) aanndd hhiigghheesstt iinn LLaakkeeErEiriee ((112211 nngg//gg)).. IInn aa sseeppaarraattee ssttuuddyy ooff PPFFCCss iinn tthhee LLaakkee OOnnttaarriioo ffoooodd wweebb,, mmeeaann PPFFOOSS ccoonncceennttrraattiioonn iin sslliimmyy ssccuullppiinn wwaass 445500 nngg//gg,., wwhhiillee wwhhoollee llaakkee. out trout wweerree 117700 nngg//gg ((MMaartritinn eett a,al., 22000044).). LLaakkee out trout eeaatt aalleewwiiffee ((9900%%)) aanndd ssmmeeltlt ((77--88%%)); ssccuullppiinn eeaatt mmyyssisaanndd DDiippoorreeisia.. BBeeccaauussee tthhee ssccuullppiinn ddiieett iiss bbeenntthhiicc--bbaasseedd rraatthheerr tthhaannpeplealaggiicc,, tthhee aauutthhoorrss ssuuggggeesstteedd tthhee sseeddiimmeenntt wwaass tthhee pprriimmaarryy ssoouurrccee ooff PPFFOOSS.. TThhee rreessuullttss ooff tthhee 22000099 FPooooll 22 ssuuppppoorrtt tthhee sseeddiimmeenntt.ssoouurrccee hhyyppootthheessiiss,, bbeeccaauussee tthhee hhiigghheesstt PPFFOOSS ccoonncceennttrraattiioonnss wweerree iinn ffrreesshhwwaatteerr ddrruumm,, wwhhicihcihs ais a bboottttoomm ffeeeeddeer.r. TThheeyymmoovvee rroocckkss aanndd ssuubbssttrraattee ttoofflluusshh tthheelirr pprreeyy,, wwhichhaarrieepprcirimmarahirillyy aaqquuaattiicc iinnsseeccttss,, ssmmaallll ifisshh,, aanndd mmoolllluusskkss..TThheeyyaarree kknnoowwnn ffoorr aetaitinngg zzeebbrraa mmuusssseellss ((SSlluussss aanndd HHaarrrreell,, 22000066),). RReeppoorrtteedd BBAAFFss ffoorr PPFFOOSS hhaavvee vvaarriieedd ggrreeaattllyy ffrroomm ssttuuddyy ttoo ssttuuddyy aanndd aammoonngg ssppeecciieess wwiitthhiinn ssttuuddiieess.. IInn tthhee LLaakkee OOnnttaarriioo ffoooodd wweebb BBAAFFs rraannggeedd ffrroomm 99,,880900 LL//KKgg ffoorr aalleewwiiffee ttoo 595,,000000 ffoorr ssucluplpiinn;; alakkee ttrroouutt BBAAFF wwaass 1166,,000000 ((HHoouuddee eett a,al., 22000088).). IInn aa ccoommppaarriissoonn ooff 44--yyeeaarr oolldd llaakkee ttrroouutt aammoonnggtthhee GGrreeaatt LLaakkeess,, tthhee BBAAFF rraannggeeds ffrroomm 55,0,000ttoo022000,,000000 L//KKgg ((FuFrduuieerttaaldl,,22u0000i77)); tthhiss ssttuuddyy rreeppoorLretdeada llaakkee ttrroouutt BBAAFF ooff 55000000 Ke.L/Kg. IInn PPooooll 22,, ssppeecciieess ggeeoommetertriicc mmeeaann vvaalluueess rraannggeedd ffrroomm 22550000 ttoo 77000000 LL//KKgg ffoorr SSeeccttiioonn 44 aanndd 44,,440000 ttoo 1111,,550000 ffoorraallsl escetcitioonnss ccoommbbinineedd.. OOnnaann oorrddeerr--ooff--mmaaggrniittuuddee ssccaallee i(i..ee.,, lloogg:-ssccaallee]) tthheessee BBAAFFss llooookk mmoorere. Mississippi Pool 2 PFCs 2009 + March 2010 Mississippi Pool 2 PFCs 2009 . March 2010 - 14- MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00001166 33MM_MMNN0033004433009922 similar; thats, the logBAF s about 4, which can be compared toPCBsandmercurylogBAFs arou6nodr 7(1-10 similar; 7 (1-10 millon that is, million kg). the IogBAF L/Kg). is about 4, which can be compared to PCBs and mercury IogBAFs around 6 or PPFFCCss wwiitthh sseevveenn oorr lleessss fflluuoorriinnaatteedd ccaarrbboonnss aarree nnoott ccoonnssiiddeerreeddbiboioaacccucmuumlualtaitviveeaaccccoorrddiinnggttoo rreegguulalattoorryy. ddeeffiinniittioionnss ((CCoonnddeerr eott aall.,, 22000088)).. TThhee eevviiddeennccee ssuuppppoorrttss tthhaatt ccllaaiimm bbeeccaauussee PPFFCCss lleosss tthhaann CC88 ((PPFFOOAA aanndd PPRFOOSS]) aarree oofftteenn nnoott ddeetteecctteedd nin fiisshh ((PPoowwlleeyy ectt aall.., 22000088)).. OOnn tthheeootthhoerrssiiddee,, CC88--CC1122 PPFFCCss hhaavvee bbeeeenn ddeetetcetecdatatetidinn ffiisshh,, aalltthhoouugghh tthhee nnoonn--PPFFOOSS PPFFCCss oocccuracattmumuucrchh lloowweerr ccoonncceennttrraattiioonnss tthhaann PPFFOOSS.. AA pprreevviioouuss ssttuuddyy rreeppoorrtteedd tthhaatt tthheerree iis assiiggnniiffiiccaanntt ccoorrrreellaattiioonn bbeettwweeeenn PPFFOOSS aanndd tthhee FCA PFCAs ggrreeaatteerr tthhaann CC88((PPoowwlleeyy eett aal.l., 22000088).). TThhiisswwaass rreeppoorrtteedd ffoorr ffiisshh iinn LLaakkee CCaallhhoouunn aanndd MMisisssiissssiippppii RRiivveerrPPoooollss 22.-55a ccoolllleecctteedd iinn 22000066 ((DDeelliinnskkyy oett aaLl.,, 22000099)),, aanndditiitsis ttrruueeffoorr tthhee 22000099 rreessuullttss ffoorr PPooooll 22. IIn tthhee 22000099 PPooool2l2 results when PFOS concentration wasveryhigh the longer carbon-chain PFCs were aso detectable (reFisguultrse, 1w4)h.enPFPDFAOS(Cc1o0)ncweanstrhaitgiohlnywcoarsrveleartyehdigwhi,ththteheloPnFgOeSrccoanrcbeonntr-cahtiaoinnsP.FCTshewePreearaslsoon dcoerterecltaatbiloen c(Foeigfufirecie1n4t)s. bPeFDtwAe(eCn10P)FwOaSsahnidghtlhyeCco9rr(ePlaFtAe)d,wCi1th0 t(hPeFDPAF)O,SancdonCcLeLnt(rPaFtioURnAs.,TahnedPCe1a2rs(oPnFDcOoArr]ewlaetrieo.n 0c.o0e1ff0ic,0ie.n9t4s3,b0e.t7w3e2e,nanPdFO0S.2a8n0d. Tthhee Cco9rr(PelFaNtAio),nCw1i0th(PPFFDOAS)A, awnadsC0.l7l17(P. FUnA), and C12 (PFDoA) were 0.010, 0.943, 0.732, and 0.280. The correlation with PFOSA was 0.717. DDeellinisknyseetktaya.l. ((22000099)) nnootteedd tthhaatt tthhee CC1100--CC1122 ccoonncceennttrraattiioonnss iinn tthhee HHaaww aanndd DDeeeepp rriivveerrss iinn NNoorrtthh CCaraorloilinnaa---w-witithh nnoo ddooccuummeenntteeddssoouurrcceeooff PPFFCCss---w-weerree ssoommee ooff tthhee hhiigghheesstt iinn tthhee lliiteterraattuurree;; LLaakkee CCaallhhoouunn wwaass aallssoo hhiigghh aanndd hhiigghheerr tthhaann ffiisshh ffrroomm PPoooollss 22--55aa (ffrroomm 22000066 ccaollleeccttoionn)t;; tthhee oonnlylyssttuuddyy rreeppoorrtteedd hhiigghheerr CC1100 aanndd CC1l1l lleevveellss wwaass ffrroomm aa ccrreeeckk iinn CCaannaaddaa wwhheerree aaqquueeoouuss ffiirree--ffigighhttiningg ffooaamm hhaadd bbeeeenn rreelleeaasseedd ((MMooooddyyeettaall.,, 22000022).). MMaaxxiimmuumm ccoonncceennttrraattiioonnss ooff CC1100 aanndd CC1122 iinn PPooooll 22ffrroomm 22000099 wweerree 3322..11aanndd2299..88nngg//gg aanndd eexxcceeeeddeedd tthhee mmaaxxiimmaa rrepeorptedofoforrrttthheeettwwdoo NNoorrtthh CCaarroolliinnaa rriivveerrss.. CC1l1l mmaaxxiimmaa ffrroomm tthhee ttwwoo rriivveerrss wweerree mmuucchh hhiigghheerr tthhaann iinn PPooooll 22 ((4422..22 aanndd 550.05.5 nngg//gg., ccoommppaarreedd ttoo 1111..88 nngg//gg iinn PPooooll 2). Inthe 2009, Pool2results, all PFCs other than PFOS had median concentrations ator below the LOG, but2). but nearly all of In the 2009, nearly all of them had adetectable concentration at some point. Pool 2 results, all PFCs other than PFOS had median concentrations them had a detectable concentration at some point. at or below the LOQ, OOnneeffiinnaall ppooiinnttttooaaddddrreessss iisstthhee bbiioommaagaginfifiiccaattiioonn ooffPPFFOOSSaanndd tthhee aappppaarreenntt ddiissccrreeppaannccyy bboettwweeeenn lliiteterraattuurree rreessuullttss aanndd tthhiiss ssttuuddyy.. NNuummeerroouussststuuddiieess hhaavvee rreeppoorrtteedd PPFFOOSS lleevveellss iinnccrreeaassee wwiitthh ttrroopphhiicc lleevveell iinn ffrreesshhwwaatteerr aannddmmarairinneeffooooddwweebbss ((KKaannnnaanneettaall.., 22000055)),, ssoommeettiimmeess bbyy aass mmuucchhaassafa faactocrooffttthhrroeeee. between trophic levels. This was not seen for PFOS concentrations in ish from Mississippi River Pool 2. Tbheetwwiedeenatrnodphoivcerlelvaeplpsi. nTghirsawngaessnooftPsFeOeSn cfoonrcPeFnOtrSactoionncsenwitrtahtiinonasndinafimsohnfrgosmpeMciiesssisinsiPpopoilR2ivmerayPohoilde2.. the possible diferences among trophic levels, ComparoifsPFoOnS concentrations in largemouth bass The wide and overlapping ranges of PFOS concentrations within and among species in Pool 2 may hide the possible differences among trophic levels. Comparison of PFOS concentrations in largemouth bass aannddbblluueeggilill ssuunnffiisshh ffrroomm tthhee ssaammee llaakkeess iinn MMiinnnneessoottaa ssuuggggeesstt tthheerree mmaayy bbee ttrroopphhiicc mmaagnginfifiiccaattiioonn ooff PPRFOOSS ((ddaattaa nnoott pprreesseenntteedd iinntthhiiss rreeppoorrtt).. TTheffhiisshhfferroomm PPooooll 22 ccaannnnoott bbee ppaaiirreedd bbyy llooccaattiioonn.. FFuurrtthheerrmmoorree,, tthheeyy aarree aallll ccaarrnniivvoorreess,,alablbeeitit aatt ssoommeewwhhaatt ddiifffefrreenntt lleevveellss.. Conclusions AAllll ffiisshh aanndd wwaatteerr ssaammpplleess wweerree aannaallyyzzeedd ffoorr PPEFCCss bbyy AAXXYYSS AAnnaalylyttiiccaall LLttdd.. AAllll wwaatteerr ssaammpplleess aanndd 3300 ffiisshh Ssaammpplleess wweerree aalssoo aannaallyyzzeedd bbyy 33MM EEnnvviirroonnmmeennttasl LLaabboorraattoorryy ffoorr qquuaalilittyy aassssuurraannccee.. TThhee mmaattcchh bbeettwweeeenn rreessuullttss ooff pitsplit ssaammpplleess ffrroomm tthhee ttwwoo aslabs wwaass vveerryy ggoooodd ffoorr bbootthh wwaatteerr aanndd ffisshh,, wwhhiicchh rreeiinnffoorrcceedd confidence inthe quality of the results, confidence in the quality of the results. Mississippi Pool 2 PFCs 2009 + March 2010 Mississippi Pool 2 PFCs 2009 . March 2010 is- 15- MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00001177 33MM_MMNN0033004433009933 Waterconcentrations of PFCs were highest in Section 4 and in particular, tation 11. Pefluorabutancic W aciadte(rFc8oAn)cewanstradtieotnesctoefdPaFtCaslwsetarteiohnisg.hePsFtOSin, Speercftilounor4oaonctdainnaipcaartcicidul(aPr,FOSAt)a,tiaonnd11p.erPfelurfolurcohroexbauntoalncoic aacciidde(P(FPBPAHA)Aw)awsedreetedcetteedctaetdalnl sSteactitoinosn.s P2F,O3,S,anpder4f,luwoirtohoctthaenhoiigchaecsitdco(PncFeOnAt)r,aatnidonpseirnfluSoercothieox4na.nToricee: oatchideers(P--FPHFxPAe) ,wePrFeBSd,eatencdtFedHinSS--ewcetiornes d2e, t3e,catnedd n4, Section 4. with the highest concentrations in Section 4. Three others--PFPeA, PFBS, and PFHxS--were detected in Section 4. PPRFOOSSwwaass ddeetteeccttaabbllee iinnnneaeralrylyaallll ffiisshh ffrroomm PPooooll 22,, wwiitthh tthhee hhiigghheesstt ccoonncceennttrraattiioonnss iinn ffiisshh aanndd wwaatteerr iinn SSeeccttiioonn 44,, tthhee mmoosstt ddoowwnnssttrreeaamm sseeccttiioonn ooff PPooooll 22.. Moosstt ootthheerr PPFFCCss wweerree nneeaarroor bbeellooww tthhee rreeppoorrttiinngg lleevve,l, talhthoouugghh lloonnggeerr ccaarrbboonn--cchhaaiinn PPFFCCsswweerree ddeetteeccttaabblleewwhheenn PPFFOOSS ccoonncceennttrraattiioonnss wweerree hhiigghh..OOff tthhee ffiivvee ttaarrggeetteedd ffiisshh ssppeecciieess iinn PPooooll 22--b-blulueegiglilll ssuunnffiisshh,, ccaarrpp,, ffrreesshhwwaatteerr ddrruumm,, ssmmaallllmmoouutthh bbaassss,, aanndd wwhhiittee absass--sf--rfreesshhwwaatteerr ddrruumm hhaaddtthhee hhiigghheesstt PPFFOOSS ccoonncceentnrtaratitioonnss.. DDrruumm hhaaddnnoottbbeeeenn ssaammpplleedd pprirortitoo2o2000r009 because itisnotconsidered atypical port ish, but was included as a targeted species because of the DbeNcAasusoebsiteirsvnatoitocnotnhsaidtetresdaaptyoppiuclaal sfpisohkrtefpisthf,obruht uitmwaans cinocnlsuudmepdtaisona atanrdgehtaesdbsepeenciheasrbveesctaeudsebyof the cDoNmRm'esrocbisaelrvfiasthioinngtohpaetraittiisonasp.opular fish kept for human consumption and has been harvested by commercial fishing operations. NNooddiisscceerrnnaabblleettrreennddsswwoerreesseeeenn iinn PPFFOOSSoovveerrttiimmeeffoorr ssppeecciieess tthhaatt hhaadd bbeeeenn ssaammpplleedd ssiinnccee 22000044 oorr 22000055.. PPFFOOSS ccoonncceennttrraattiioonnss iinn ffiisshh mmuusscclleewweerree nnoott ccoorrrreellaatteedd wwiitthh ffiisshh aaggee oorr ssiizzee,, aanndd tthheerree wwaass nnoo ddiifffeerreennccee bbeettwweeeenn ggeennddeersrs.. BBiiooaaccccuummuulalattiioonn ffaaccttoorrss ((BBAAFsF) wweerree ccaallccuullaatteedd ffoorr PPFFOOSS uussiinngg tthheewwataeterr aanndd ffiisshh ddaattaa..BBAAFFssffoorr PPFFOOSS wweerree iinn tthhee rranageonoff4g4000e000 ttoo 66000000 LL//KKgg,, wwhhiicchh sisaatt tthhee llooww eenndd ooff tthhee rraannggee of highly bioaccumulative compounds. of highly bioaccumulative compounds. Mississippi Pool 2 PFCs 2009 + March 2010 Mississippi Pool 2 PFCs 2009 . March 2010 1- 16- MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00001188 33MM_MMNN0033004433009944 References BBeerrggeerr UU25,..,3 GGllsyyonnunnrAcAe,.,oHHfoohllummmssattrrnoomemxKKpo.LEs..,urBBeeertrggollupunenrddflMMu,.o,rAAinnnakktaaerrdbbeaelrrkggylEEHs.H,u.b,TsTotoarrnnnckkeuvsiisistnAtAS..w((e22d00e00n99))- FFAinissahhlyccsooinnsssouufmmeppdtitiiboolnne faissha fsrooumrcLeaokef hVuatmtaenrneaxnpdostuhreeBtoaltpcerSfeluaorCinhaetmeodspahlkeyrl esu7b6s:t7a9n9c-e8s04i.n SDwOIe:den - Analysis of edible 10.1016/j chemosphere.2009.04.044. fish from Lake Vattern and the Baltic Sea. 10.1016/j.chemosphere.2009.04.044. Chemosphere 76:799-804. DOI: CCoonnddeerrJr.e1MvM.,i,eHHwooakkneed RRc..oAAm.,,pDDareeiW Wsooolnlfwf iWWt..,h, rRReuugssusselelalltl oMMryH.H,l.i,pBBopuuhccikkliRRc..CCc..om((2p200o00u88n)d) sAA.rree EPPnFFvCCiAArSosnbbmiieoonaatccaccluumSmuculilaaettinivvcee&e?? 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March 2010 i"- 17- MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00001199 33MM_MMNN0033004433009955 SSTTSS CCoonnssuPloultltlaaunntttisso..n((C22o00n00t77r))olSSuAugrrfeaanccceey.W Waatteerr QQuualailtityyCCrirtiteerriioonnffoorrPPerefrflluuoorrooooccttaannee SSuuflfooniicc AAcciidd MMiinnnneessoottaa W Waanngg TT.,,PPeWWoralaflunlntguigoonYrYo.WWCoc,o.t,naLLtnriioeaalooSAuCClgY.fYe,o.n,nCcaCysta.eiYYi.n.0Qt.s.,,JtJihiaaennSggtGGo.8c.B.k.h((o22l00m005C9)o)nPPveeerrnsstppeiecoctntiivvoeenPsseoornnsitthshteeeInInntccOllurugssiaioonnnicooffPollutants. YeX., StrPEEynnevnvrifialrruoroonnrmMmoeoJenc,ntttaaaNlnlaeSSkccSiaieueynnlfccaoeenmaS&&atFTeT.eeiVncctahhonrntohonleoJlsgo,Sygto4Hyec3lk:f54h3a~o:n5l7tm1]7-L15-C,511oL77n5a5.vz.eoDDnOrtOIico:I:nh1]Ja0o0k.n.~1L0P0i2e7n~r1ds//seisetstrs9eo90nm0t00AO4466rg44aaa(n.2ic00P83o)llutants. Ye X.B., SPWPeiterrsyrfifnllsuauioorprrMipinni.aJat.tR,eiedNvdeacrcksoo,ammyUpapSomoAu.uannEdSdns.sFv.iii,nnrVowwanhrhmnooeslnleeJt.a,ffilisHshhPeolhhflaoolnummttooigLog.en,enL1na5aat6zte:eo1srsc2fhf2ra7ro-kom1mJ2.,tt3hh2Lee.inOOdDhsOhiItioro:o,,mMMiAisss.sBoou.ur(ir2i,,0a0a8nndad)UUppppeerr Ye XB, SM11c00ih.s.11os0e0is1n1s6f6i/pu/jspj.seiennRHvviLvppe,oorlsl.J.,2a20Uh00nS0s88A...N00.E33D..n0.0v11iDr44oe.nlimnesknytaAl.PDo,llSuttrioynnar15M6J:1,22V7ar-1n2s312,. DOI: Nakayama SF, Hefant L, Ye X.B., tSLLhiicnenhddoUssepttnrprofeoummrssAAM.H.iBB.s.L.i.((,s22Ji00ao00hp88nibbs))iPNvPee.rDref..r,lfluuEDonoervrliiiinnnrsaaokttenyemddAce.cnoDotm.m,pISpnototureuyrnnnndadastrsiMoiinnn.aJccl.,oo3Vmm4a:mmr9noo3s2nn.J9c.c,3aaN8rr.ppak((DaCCyyOyapprmriinanuuSss.Fcc.aa, rrHppieiolo)faffinilllteetLts.s,ffrroomm 10.1016/j envint 2008.02.003 the Upper Mississippi River. Environment 10.1016/j.envint.2008.02.003. International 34:932-938. DOI: Mississippi Pool 2 PFCs 2009 + March 2010 Mississippi Pool 2 PFCs 2009 . March 2010 1- 18- MMiinnnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AA~geennccyv 22556655..00002200 33MM_MMNN0033004433009966 Tables sS Tualne1 Anca formation shooterTseS l stiatgiono ns0Tge5e0) coTw. en00d Station B" utucoonoses patton") __(0 unm oat ID nwoen TwiTdTe onest aa emraweaeam ;;;;2;;; aC cG teewre amwsaer amesmemesse 4 UTM Coordinates ;~;8~8~ ;; ;;; ~;9~;;~;~;;; 0489737 49739~0 Time Water Depth Temp Sp. Cond. D.O. ~;S 5;~ ;; 13:17 ;; 6.7 ;; 2;~ ;;;; ;; ; ~;89; 24.21 535 ~ 28;;; 8.67 g 0496075 4975366 6 0497900 4971442 T 3mA m S ema3~8~ EE 10 0505348 4958622 Wo sees eww I~ 0508545 4958789 12:47 R1m2T:e3e0L wx9:5g 10:24 4.0 25.52 525 9.46 ar 2 an 7mo6 1e 1.2 25.03 24~ 580 8 8.72 ~82 12 nm 3.7 23.87 1.2 23.86 @ @ 579 566 7.41 7.92 12 0510018 4956960 10:47 5.2 24.28 574 7.26 Ce eo Sample = or ID~ UNITS PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFBS PFHxS PFOSA PFOS Mean PFOS~ otTToeaiu:stsTTTwwWnhh Haa asen ao<alsei aaaskno aaGaasnm aaaeup aaa amS0 oaauodGompu ocoiassok dcsoewmadaasewe aSaaesnndwsew 18 1-02-1 waa wn ae as as as as as as an os on ap os an 1-02-2 os Wh sm Gm aw am an an an an au ae ae an ae 1-02-3 ng/L ~g/L ~g/L 4.4 4.16 5.~8 < 2.54 < 2.55 < 2.51 < 2.5~< 2.55 < 2.51 < 2.54 < 2.55 < 2.51 < 2.54 < 2.55 < 2.51 < 2.54 < 2.55 < 2.5~ < 2.54 < 2.55 < 2.5~ < 2.54 < 2.55 < 2.51 < 2.54. < 2.55 < 2.51 < 5.08 < 5.10 < 5.02 < 5.08 < 5.10 < 5.02 < 2.54 < 2.55 < 2.51 < 5.08 < 5.10 < 5.02 2.53 oTiomns:d Mwih sGmm ahme Calihuk Talanas Claebne hahewu Totaese oCemT moeons oeaswiws eaoipes ocsonsse oedntses ~gt~ Wisostppt Poot 2 cs 2009 March 010 Mississippi Pool 2 PFCs 2009 . March 2010 inesota olution control Asency Minnesota Pollution Control A~ency - 19- 33MM_MMNN0033004433008977 22556655..00002211 le craT Cnc T et 2s es Sample ri 3 IDa UNITS PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFBS PFHxS PFOSA PFOS Mean PFOSb TTiot WMWA mHah SaGm cGannoGimn aGS nuonmaeE n ammoeE ooemaemS dcne aomm 2-05-1 Im Wim a aw ae aw aw am aw ie on on ow om 2-05-2 Im Win am ok am a du is ik am aw aw sm 2-05-~ n~/L ng/L n~/L 4.87 5.25 5.23 < 2.54 < 2.56 < 2.46 < 2.54 < 2.56 < 2.46 < 2.54 < 2.56 < 2.46 < 2.54 < 2.56 2.51 < 2.54 < 2.56 < 2.46 < 2.54 < 2.56 < 2.46 < 2.54 < 2.56 < 2.46 < 2.54 < 2.56 < 2.46 < 5.07 < 5.11 < 4.93 < 5.07 < 5.11 < 4.93 < 2.54 < 2.56 < 2.46 < 5.07 < 5.15 < 4.9~ 2.52 Ghp P eamcsk i Mra sea nibt Gab mreaCnmrCadb oaa arCwebsCarmaCehsiose oGwhadmw aaetrema e a 3-07-2 Soi WA wy Gm iw Gm se Gm Go Ge Ge an aw ae ow 3-07-Z os Wom dain G8 5 G8 G8 U8 U8 U0 US Gn ~-07-3 a~/L nz/L n~/L 20.6 10.7 9.82 < 2.53 < 2.49 < 2.53 3.00 3.58 2.57 < 2.53 < 2.49 < 2.53 4.48 5.01 4.75 < 2.53 < 2.49 < 2.5S < 2.53 < 2.49 < 2,53 < 2.53 < 2.49 < 2.53 < 2.53 < 2.49 < 2.53 < 5.06 < 4.98 < 5,07 < 5.06 < 4.98 < 5.07 < 2.53 < 2.49 < 2.53 20.5 ~0.5 9.9~ 20.30 pSpeieoAwMmsam daBG seeidraaE icnbaseR esa rasS eaberrS ai SI be ame E eibGsohane 3-09-~ Imi WA ms Gu aw om a ow an an an an a on ae 3-09-2 Ss Ja ms lm ii Gm a lw Gm Gm aw ap aw om an ~-09-~ n~/L ns/L ns/L ~3.2 13.3 1~.9 < 2.52 < 2.52 < 2.59 3.~6 2.76 3.~2 < 2.52 < 2.52 < 2.59 4.22 4.63 5.03 < 2.52 < 2.52 < 2.59 < 2.52 < 2.52 < 2.59 < 2.52 < 2.52 < 2.59 < 2.52 < 2.52 < 2.59 < 5.05 < 5.04 < 5.17 < 5.~5 < 5.04 < 5.17 < 2.52 < 2.52 < 2.5 < 5.05 < 5.04 < 5.17 2.54 R Tm ee l mWa n B E wSGwRe iA nLySGe ORT mREGRGa dSe e Om S H Am SRSR ASWme EeENe AS. e 4-11-1 Li Wom am ome imo ms Gn am am am wom an om 4-11-2 na Woon Woe WoGa G0 G0 GD WoW oGn 4-11-3 ~g/L 16~ ~4,7 ~6,7 5.77 88,~ < 2,54 < 2,54 < 2,54 < 2,54 40,2 2&8 < 2,54 84,4 n~/L 155 15.3 17.9 5.83 95.8 < 2.59 < 2.59 < 2.59 < 2.59 41.7 27.7 < 2.5 91.3 n~/L 189 16.9 18 6.05 98.4 < 2.48 < 2.48 < 2.48 < 2.48 41. 27.9 < 2.48 94.5 90,07 GR mUse aaGe ESRECEO GAeR seAwee ae a. sam~l~ I~: 5e~ion-Station-~e~licate NT tein otmattata b. ~/2 d~t~ction limit used [or c~lcul~ting m~n [rp ---- Mississippi Pool 2 PFCs 2009 . March 2010 Somncrots Fotution Control sere Minnesota Pollution Control A~ency - 20 - 3MM_MNM0N300304433009988 22556655..00002222 =Secinserts tion River Mile JE 1 swsens 1 846.5-847.5 11 wsruerness 1 844.3-847.5 211searsesno 2 840.5-841.0 23 sswesenoe 2 836.4-842.6 220; sswsseisne 2 840.5-842.6 3317 mEiTmbSsamnademsraiee 11 3 834 833,5 and Ho~ Lake 35 11m83a5e3m5sdmoagnree111 3 834-833,5 and Hog Lake s3 wwaarenn: 3 829.7-82?.2 aoi assaesssy Zl 819.8-81.5.2 4aa iammasssaas ~1 819.8-815.2 Carty _cioleted cTeeed County ey S28 GOMROED Ramsey RRaaeed SSosno0 Oo01Oam Ramsey Neeyy 5S2900008 O0RB0O0A1D0D0 Ramsey PRameey sa59n5 LOBoOmLBoD Ramsey Reery 5S2990008 OOR01O Ramsey fvieer SSR9SR0. MWOONUO Ramsey Gwvie 5520808W00G0 Ramsey ODoito 1060900800100 Dakota DDouleos G{6/4009. |MMB0O0. Dakota ODDaivotiuo 1u6/p09 MTw7wI0e Dakota Date Collected 5/28/09 5/28/09 5/29/09 5/29/09 5/29/09 5/29/09 5/29/09 6/~ 6/1/09 6/1./09 6/1/09 Time Collected 0900-1400 0900-1400 0830-1330 0830-1330 0830-1330 1400 1700 1400-1700 0830-1030 1130-1700 1130-1700 Spee Species FshOren(4t0) Freshwater Drum (FWD) Caes)as Wl White Bass (WB) BWuhintesSWah )565) White Bass (WB) CFaems) hOent(eFWsD) Freshwater Drum (FWD) SSueot sluBnto 6S)hB Bluegill Sunfish (BGS) WBNuBeapaSsNuRn0s5h] Bluegi~l Sunfish (BGS) Ce 6)nOune0l Freshwater Drum (FWD) |FrSesmheanelrOonsutOh1L Smallmouth Bass {SM8} | dFeprtbsuruDi un00e5OrL Bluegill Sunfish {BGS} SaWmhhieonoun 5t4) Carp { C} Sper Species ComCount 515 iws15 5i15 1115i15 13i15 HEi15 ":1 ii15 "i15 x15 Wisostppt Poot 2 cs 2009 March 010 Mississippi Pool 2 PFCs 2009 . March 2010 inesota olution control Asency Minnesota Pollution Control A~ency - 21- 33MM_MMNN0033004433008999 22556655..00002233 NetereSswstaitissstiec ET Nein Maxim um M~n~mum SSMeteondmdianangroiuscsrinon _suegi5ioss Bluegill (B(;S) :1350 8 1a45 Feetmes Carp T (0 T wo (C) Species Freshwater Drum (F-~ND) Sra Smallmouth Bass Twnam (SMB) 5 5 Bs 1340 3580 612 5 5 13 m 528 o 63 mSo41 White Bass tCwToa (WHB) w=764 38 i75m Tables Numbeorfohcollec ech yearbypcs TT am Year Species SMB WHB C WE BGS CHC BKS SAG FWD Total m2004 eu2mn1 ie ow ni 3 5 aw2006 ii ER6 15HE im32 Gang2009 60 60 60 57 60 i297 Wisostppt Poot 2 cs 2009 March 010 Mississippi Pool 2 PFCs 2009 . March 2010 inesota olution control Asency Minnesota Pollution Control A~ency - 22- 33MM_MMNN0033004433110000 22556655..00002244 species Location Species CommanCarp Mis51.Ckovai(4.n95) Common Carp (ren) Ni PfEsy ake indy (MAST) (fillet) keTrou (whe) LSaNkaiesgn.totiS,priLnagkaekech(iR3n10) Lake Trout (whole) sen Sculpin Location Mississippi R. - St. Cloud (R.M. 938) Miss. R. - Pig's Eye Lake vicinity (R.M. 833) Miss. R. -Spring Lake (R.M.816) Saginaw Bay, Lake Michigan Lake Ontario Rainbow Trout ewe Alewife hs Mysis Dporea Diporeia Towevow Lake Trout Golan) (4 yr old; whole) GeesLake Superior ake crea Lake Michisan Uke ron Lake Huron Like tre Lake Erie Uke omaro Lake Ontario hePFOS Nal) N (ng/g) 5a 9 8.1 10 26 10 26 nw 11 40 1 ia 10 124 7170 7 170 B50 15 450 30 110 nw 12 46 won NA 13 ww NA 280 0 5 10 4.8 36 10 16 nm 10 39 FE6 131 ww 10 46 erence Reference Veer Ye et a12008b (collection 2008) (collection 2006) meer Kannan et al 2005 Matineral 2008 Martin et al. 2004 (alecionz00r) (collection 2001) fdas mn Furdui et al. 2007 (olecion 2001) (collection 2001) Wisostppt Poot 2 cs 2009 March 010 Mississippi Pool 2 PFCs 2009 . March 2010 inesota olution control Asency Minnesotu Pollution Control A~ency - 23 - 33MM_MMNN0033004433110011 22556655..00002255 Figures 7Q MisissississsiippppiiPPooooll22 vv ? NTTaly {Je BR ---- TwinCities Metropolitan Area Sa . Cr a0| maonoixsaco[,f [Es ] rue ea mevesmiehse u|caB[=ger] | i i amoe EET paofLL r--------r---- re tnts wt % oo <TH issisinpi Poot 2 PFCs 2009 +March2010 Mississippi Pool 2 PFCs 2009 . li4arch 2010 Ce- 24 - MinnesotaPollutionControlAgency. Minnesota Pollution Control A~encV 33MM_MMNN0033004433110022 22556655..00002266 Fr --T ke | Me Se =" Section 2 Ee 02 ection 1AE $ VVest Ssint Pau ngt:m Mendota Heichts Eagan ~:!~}~ h Sairt ................. 7 45 ~ sectens Section 3 Inver Grove Heights : Wot \~oodbury Cottage Grove Conol UUanA~on - -- U Locka Dams === SSececttiioonnBBoorrddeerr (WaWtaeterrsSttaattiioonnss SA Lock & Dams River Mile ST MMisissississsipipppiiRRiivveerr SHES, 2 ) Sseecctioonnd4 Me 1 Jf= -| - Hast ngs fr Fis~re 2 Miss ssippi Pool 2 sections and water sample stations Mississippi Pool 2 PFCs 2009 . Merch 2010 - 25 - Minnesota Pollution Control A~ency 33MM_MMNN0033004433110033 22556655..00002277 eo . 120 i00 i: | i | =80 /, Ho / . |i. se | i | i, J gopm oy 4O 2O Lem 0 =| Tere 20 40 ~0 80 i00 120 M~ Lo sm AXYS PFOS | go : = 12 20 40 60 80 100 120 140 rm se woseuns STA PFOS (nglL) em Mississippi Pool 2 PFCs 2009 . March 2010 ---------- Minnesota Pollution Contro~ Agency - 26- moe 3M MN03043104 22556655..00002288 omc onion E-- Fish ID: samplelD-SP-Section 090051BGS1 ~ TE, -- E | 090206BGS4 ~ 090267BG53 =F 090054C1 090056CI ly 090123C2 Ee. 090191C3 090275C4 Er 090282C4 ~130 95 090009FWD1 090078FWD2 Eas EEEEEEEES 090096srvIB2 .7OO -600 500 iogi.400 i 300 2OO :IO0 0 0 1(30 A .NZ * // J _ somoiue 200 300 400 500 600 700 AXYS PFOS (ng/l) -- mr i00 200 300 400 500 600 700 Fillet PFOS Concentration(ng/g] rn Mississippi Pool 2 PFCs 2009 * March 2010 mm------ Minnesota Pollution Control A~ency - 27- annoanes105 3M MN03043105 22556655..00002299 11 i 4y 2 2 iB mer All Sections of Pool 2 ~ 100 0 LL D_ J10 ao] 3100 S898" I I I I I BGS C FVVD SMB WHB =Species enone] ot ye 03 100 0 LL ELlealBai: P 10 I BGS I I I C FWD SMB Species I VVHB ET4 1] - lOOO hs 100 piid .ml 1ooo ; Pr 09 100 O dpiE i H iI is & iosia we lO BGS C FWD SMB WHB Species i lO BGS C FVVD SMB WHB Species lO BGS C FWD SMB WHB Species Mississippi Pool 2 PFCs 2009 * March 2010 Minnesoto Pollution Contro~ A~ency - 28- 3M MN03043106 22556655..00003300 SMB ' CU i | THA i |] / i ' f C grr ge iA e be de hr J ---- Mississippi Pool 2 PFCs 2009 . March 2010 "ainesote Minnesota pPooltluutiioonn Cntr Control AA~seennccyy - 29- 33MM_MMNN0033004433110077 22556655..00003311 AAllll SSeectciontsoioffoPPoonoolls22 BBGGSS BBKKSS CC 1000 1000 1000 3 : $ lOO ................................................... u) O o_ 10 triad, 1 I I I I I I 2003 2004 2005 2006 2007 2008 2009 2010 YEAR CCHHCC 10 ................................................... digi. 1 I I I I I I 2003 2004 2005 2006 2007 2008 2009 2010 YEAR FWD sig:I 2003 2004 2005 2006 2007 2008 2009 2010 YEAR SSAAGG o & 10 ................ tri, 1 I I I I I I 2003 2004 2005 2006 2007 2008 2009 2010 YEAR SSMMBB Aer 1000 ........................................... '~ ...... lOO ....................................... 10 diggin, 1 I I I I I I 2003 2004 2005 2006 2007 2008 2009 2010 YEAR WE I-- ]0 dri. I 2003 2004 2005 2006 2007 2008 2009 2010 YEAR VW~H-tBB TE _ iSof llr hl =: AERCRE 2g sess 2 100 d=ldn +i 10 ds 1 I I 2003 2004 2005 RsBw I I I I 2006 2007 2008 2009 2010 YEAR 1 2003 or RE I I I I 2004 2005 2006 2007 weI 2008 I 2(309 0 2010 YEAR Fi~ re 7 # stributio~s of PFO5 by'~ear for each species [at sections} 2003 or 2004 2005 Ri2006 2007 owweI 2008 2009 2010 YEAR Mississippi Pool 2 PFCs 2009 . March 2010 - 30 - Minnesota Pollution Control Agencv 33MM_MMNN0033004433110088 22556655..00003322 `SeSctieonc44otoffiPPooooolln22 BBGGSS BBKKSS CCc 1000 tOO0 "~ 100 ........................... 40 lOO ................................................... brig). 10 ................................................... 1 I I I I I I 2003 2004 2005 2006 2007 2008 2009 2010 YEAR CCHHCC gra. 10 ................................................... 1 I I I I I I 2003 2004 2005 2006 2007 2008 2009 2010 YEAR FWD digred. I 2003 2004 2005 2006 2007 2008 2009 2010 YEAR SSAAGG 100 ....................................... o & 10 ................ 10 10 br4it. sega. drag. 1 I I I I I I 2003 2004 2005 2006 2007 2008 2009 2010 1 I I I I I I 2003 2004 2005 2006 2007 2008 2009 2010 I 2003 2004 2005 2006 2007 2008 200g 2010 YEAR YEAR YEAR SSMMBB WE WHB elofl l IOO0 ~ 100 O LL : 100 5 & 13- 10 TE ds RsBw 1 I I I I I I 2003 2004 2005 2006 2007 2008 2009 2010 YEAR or RE we 0 1 I I I I I I 2003 2004 2005 2006 2007 2008 2(309 2010 YEAR Fi~ re 8 D stributio~s of PFOS by year for each species limited to Se~t on 4 or Ri owweI 2003 2004 2005 2006 2007 2008 2009 2010 YEAR Mississippi Pool 2 PFCs 2009 . March 2010 -31 - hlinnesota Pollution Control Agencv 33MM_MMNN0033004433110099 22556655..00003333 oss rou2c2008 wo BGS Pool 2 2009 C FWD 1000 1000 1000 S E Ht EET i 8 100 bir A g ~ od " I0,3 ~00 "EY i a. 10 I I I _J M F Sex SSMMBB. eee N 1000 ................................................... zr5 ri Eg+ g8 li]2 ~o 8! i 1000 5 I0,3 RE I I I _J M F Sex WWHHBB Lo ................................................... de3 .................................... beI I I _J M F Sex R--_ I I I J M F Sex -- I ~ex ~iss#ssipp# Pool 2 PFCs 2009 . Merch 2010 - 32 - Minnesota Pollution Control A~encV 33MM_MMNN0033004433111100 22556655..00003344 puaaon Pool 2 2009 BBGGSS CCc Eir 1000 100 bi d~i 10CO 1C0 wih E:T 1000 ~0 10 oe4 6 8 Age (yr) SMB 10 12 we 0 2 4 6 8 10 12 Age (yr) ~B 10C0 ................................................... : 100 Hie Lh~'~ IC0 ............................. I I I I I 2 4 6 8 10 12 Age (gr) 0 2 4 6 8 10 12 Age (yr) Figure 10 PFOS #centratio# by age for each species FFWWDD | 4 6 8 Age (yr) 10 12 ~ississippi Pool 2 PFCs 200 4terch 2010 - 33 - Minnesota Pollution Control A~encV 33MM_MMNN0033004433111111 22556655..00003355 I 8 100g LlLOO0 --_ 2g = wr 100 a o % c0o 8OO oF x x at 5b AA~AA * aA aa_ x X 6." X % IE? A a adh EK CBoE ldEgy X oF FE 8So o atma4 bx X% o - 1000 3B ed % 1 ox Xx x 00 1100 2200 LLeennggtthh ((iinn)) Figure 11 FOS concentrationsby length foreach species Yi~re EE PFOS concentrations by ensth for each spe~cies 08SS6ppeescciieess. BGS ZexC FWD -Sue WHWSMHEBB 3300 Wissisippt Pool 2 PFCs 2009 + March 2010 ~ississippi Pool 2 PFCs 200 ~erch 2010 3- 34 - M Wiinnnneessoottaa PPoolllluuttiioonn C Coonnttrrooll AAg~eennccVy 33MM_MMNN0033004433111122 22556655..00003366 1000 1000 =~ 2 =0v o M1O00F IaL 10 x o X ........................................................... :i: ................................................................................................ 2"8o4t Lx . ea ah sfooo rwEolfbeov,yey x xX LS5 bRErTHIR AFSLRNL WC aSw cRrooDu8 py xX3x%xex x a x 00.,11 11.,00 1100..00 %% LLiippiiddss Species Species BGS Hd XC FaFWD SuSMB WHB isto! pant 1 PECs 2000 + march 200 Mississippi Pool 2 PFCs 200 ~erch 2010 ase- 35 - Minnesota atutian Control Agency Minnesota Pollution Control Agency 33MM_MMNN0033004433111133 22556655..00003377 JlIIIIIIII 32 , 3&| <~ 20 2& o, be &=0o 1i o0 daw 200 som 400 0 1,000 PPFFOO2SS,00((0ppppbb)) 3,000 4,000 Fre 13 Rlationsisbetween PFOA (C10) andPFOS fom Po 2 all speciesand sectors) ississippi Pao 7 PFCs 7009 March 7010 Mississippi Pool 2 PFCs 200 March 2010 3- 35 - Winnesota Pollution Control Agency Minnesota Pollution Control A~encv 33MM_MMNN0033004433111144 22556655..00003388 RReessoouurrcceess CCoovveerr PPhhoototo:: UUppppeerr MMiiddwweesstt EEnnvviirroonnmmeennttaall SScciieenncceess CCeenntteerr.. bihtttpp:f//uwnwsws.uummeesscc.uusRsss.g~oovvJ/aaeiraiall phpohtoetoss//ss/!ss3311~511 119999770obb.hhtimll FFoorr mmoorree iinnffoorrmmaattiioonn oonn tthhiiss rreeppoorrtt ccoonntatactc:t: Bruce Monson RBerusceearMchonScsioenntist Minnesota Pollution Research Scientist Minnesota Pollution CCoonntrtrooll AAggeennccyy 552200 LLaaffaayyeettttee RRooaad dN St.Paul, MN 55155 PSht.onPea:ul,(6M5N1)5755175-52579 Phone: (651) 757-2579 MMiinnnneessoottaa PPoolllluuttiioonn CCoonntrtrooll AAggeennccyy PPFFCCss hit urvs castate mnuscleanup/ofe/index imi http:/iwww.pca.state.mn.us/deanu p/pfc/index.html MMiinnnneessoottaa DDeeppaarrttmmeenntt ooff HHeeaalltthh PPFFCCss https heath sate mn. use/h dhaziardvous topcs/ofes index him http://www.health.state.mn.us/divs/eh/hazardous/topics/pfcs/index.html MMiinnnneessoottaa DDeeppaarrttmmeenntt ooff HHeeaalltthh FFiisshh CCoonnssuummppttiioonn GGuuiiddeelliinneess https heath sate mn.us/dfisihivndeexh hm http://www.health.state.mn.us/divs/eh/fish!index.html Mississippi Pool 2 PFCs 2009 + March 2010 ivlississippi Pool 2 PFCs 2009 . ~arch 2010 37 - 37- Minnesota Pollution Control Agency Minnesota Pollution Control AgentV 33MM_MMNN0033004433111155 22556655..00003399 AAppppeennddiixx AA MMaapp ooff ffiisshh ccoolllleeccttiioonnss iinn PPooooll 22 Atstssippl Poo 2 PECs 2009 + January 2010 Mississippi Pool 2 PFCs 2009 . January 2010 Minnesota ottutin control Agency Minnesota Pollution Control Agency 33MM_MMNN0033004433111166 22556655..00004400 M Miissssiissssiippppii PPooooll 22 PPFFCCss 22000099 +. JJaannuuaarryy 22001100 M Miinnnneessoottaa PPoolllluuttiioonn C Coonnttrrooll AAggeennccyy 33MM_MMNN0033004433111177 22556655..00004411 AAppppeennddiixx BB RReessuullttss ooff PPFFCCss aannaallyyssiiss ooff ffiisshh ccoolllleecctteedd i~nn M Misisssiissssiippppii PPooooll 22 iinn 22000099 Misisiop Pool 2 PECs 2009 + January 2010 Mississippi Pool 2 PFCs 2009 . January 2010 Minnesota Pottation contro Agency Minnesota Pollution Control Agency 33MM_MMNN0033004433111188 22556655..00004422