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22000099
8MMararcchh 22001100
& Minnesota Pollution Control Agency
22229955..00000011
STATE02010400
STATE_02010400
AMiinnnnee5ss2oo0ttaaLaPPfooalyllleuutttitiooennRCCooaondnttrrNooollrtAAhggeennccyy SS5aa2ii0nnttLPPaaafuaulyl,,eMMttNeN R555o51a1d5555N--44o11r9t9h44
hitttpp::///fwuwrww..ppecaa..ssttaattee..mmnn..uuss 651-296.6300 or 800-657-3864 toll free:
651-296-6300 or 800-657-3864 toll free
-TI-TI-YY 665511--228822--55333322 oorr 880000--665577--33886644 ttoollll ffrreeee Available in alternative formats
Available in alternative formats
AAuutthhoorrBssrauancndedMCCooonntnortnriibbuutotorsr.s
Bruce Monson
Laura Solem
Laura Solem
Poul Holt
Paul Hoff
Manin Hora
Marvin Hora
Pat McCann
Pat McCann
Wark
Mark
BBrriigggass
Joel sins
Joel Stiras
Steve Delain
Steve Detain
ocument number
Document number
XXA:\N\SS--S5PPL144\\vvoolI11\\AAggeennccyy__FFiileles\sE\AEAOO\\PPFFCCDDaattaa aanndd RReeppoorrttss --PPrreefliimmiinnaarryy\\DDaattaa\\FFiisshh\\22000093 FFiisshhddaattaa\\MMiissssiissssiippppii River Pool 2 Intensive Stud\Misisipp Pool2 PFCs 2009 Final Report SMARLO docx
River Pool 2 Intensive Study\Mississippi Pool 2 PFCs 2009 Final Report 8MARlO.docx
22229955..00000022
STATE02010401 STATE_02010401
`TTaabbllee ooff CCoonntteennttss
TABLE OF CONTENTS .......................................................................................................................................... 1 LIST OF TABLES ................................................................................................................................................... 2
ABBREVIATIONS GLOSSARY... LIST OF FIGURES ................................................................................................................................................. 2 ABBREVIATIONS GLOSSARY ................................................................................................................................ 3 INTRODUCTION... wn -- " nb EXECUTIVE SUMMARY ....................................................................................................................................... 4 INTRODUCTION .................................................................................................................................................. 6 MISSISSIPPI POOL 2 ........................................................................................................................................................ 6 pA WHAT ARE PFCs AND WHY ARE THEY AN ENVIRONMENTAL CONTAMINANT? .............................................................................. 6 SE -- AMBIENT MONITORING OF PFCs BEFORE 2009 ................................................................................................................... 7 Warns - J - s WHY THIS STUDY? .......................................................................................................................................................... 8 METHODS .......................................................................................................................................................... 8 FSHCOUECTON..... sa A -------- FISH COLLECTION ........................................................................................................................................................... 8 WATERCOULCION r emer JY WATER COLLECTION ....................................................................................................................................................... 9 Jr-- - - ee a LABORATORY ANALYSIS ................................................................................................................................................... 9 QUAI ASURANCE ee -- --------) QUALITY ASSU RANCE .................................................................................................................................................... 10 RESANUDDILSCUTSSISON... 10 RESULTS AND DISCUSSION ................................................................................................................................ 10 SAGE WAT SR ------ SURFACE WATER .......................................................................................................................................................... 10 . - - - n FISH ........................................................................................................................................................................... 11 Quay Assuronce un Quality Assuronce ............................................................................................................................................... 12 Spatial DistributionofPOSbySpecies. 1 Spatial Distribution o/ PFOS by Species ............................................................................................................... 11 TempoDistribution of 705 Concentrations. 2 Temporal Distribution of PFOS Con centr~tions................................................................................................... 12 ReltionsPhOiSlpevoelfs oh gender, age, and sie 3 Relationship o/ PFOS levels to/ish gender, age, and size.................................................................................... 13 BOACACTMER A0WAATER QTUALITOYCRNIA... 1 BIOACCUMULATION FACTORS AND WATER QUALITY CRITERIA .............................................................................................. 13 CONP10AOHGRRLOSGKTOONSN... - - - 1 COMPARISON TO OTHER LOCATIONS ................................................................................................................................ 14 CONCLUSIONS ................................................................................................................................................... 15 REFERENCES ...................................................................................................................................................... 17 TABLES .............................................................................................................................................................. 19 FIGURES ............................................................................................................................................................ 24 RESOURCES ....................................................................................................................................................... 37
A`AppppeennddixiAAx MMaapp ooff ffiisshh ccoolllleeccttiioonnss iinn PPoooll22 A`AppppeennddixixB8 RReesusltsuooflfPPtEFCCsss aannalayslisyoosfffiissshh ccoolllleecctteedd Iinn MMiissssiissssiippppli PPooool 22 nin 22000099
Mississippi Pool 2 PFCs 2009 + March 2010
Mississippi Pool 2 PFCs 2009 . March 2010
Ee
Minnesota Pollution Control Agency
Minnesota Pollution Control Agency
22229955..00000033
STATE02010402 STATE_02010402
LiofTsabltes List of Tables Table 1 Ancillary information about water sampling stat(i2oJnulsy 2009) 1 Table 1 Ancillary information about water sampling stations (2 July 2009) ............................................. 19
TTaabblele22 PPFFCC cconocenntrcatioensniinnwtwaatrteerraaattt1122isatoattiioonnnsssiinnMMIissssisssiippppi PPooool l2 2s ................................................. 1199
TTaabblel3e3 FFiisshh ccoolllleeccttiioonniinn MMiissssissspipppii PPooooll22 BbYy MDNR MONA... .............................................................................. 2211
TTaabblel4e4 SSuummmmaarryy ssttaattiissttiiccssffoorr PPFFOOSS cCoonnGceennttrraattiioonnssbbyy 5sppeeiceiess iint POOl2... 2. Pool 2 ..................................................
TTaabbllee'55
NNumuberomoffffissbhhcocelollleeccrtteedd
eeaacchh
EarBYSPECIES... year by species .............................................................................
22
22
Ta6 PbUlAePROS CONGEMIBHONS Is... 3 Table 6 Published PFOS concentrations in fish ........................................................................................... 23
LoifFs igut res List of Figures Figure 1 LOCaON OF MSS POOL 2. 28 Figure 1 Location of Mississippi Pool 2 ...................................................................................................... 24
FFiigguurer2e2 MMisisisssipspiPiPooosoll 22ssseeiccttpiioonnpss aainnddWwaatteerr Ssaammppllee tations... 5 stations ............................................................... 25
FFiigguurer3e3 CComopamrisponoaoffrAAXYiYSS s(rreedod,, ttnoopp bbaarr]) aanndd 33MM ((bblluuee)) rreessuullttss orfor PPFFOOSSccoonncceentnrattiornasitinniwwoaatnteesrr ffrroomm 1122ssttaattioinosniisnnPPooooll 22;; eemmbbeeddddeedd ffiigguurree sshhoowwssAAXXYYSS Vveerrssuuss 33MM PPFEOOSSWwIitthh 1106... 26 1:1 line .................................. 26
FFiigguurere4& CComopamrisponaooffrAAXXYiYSS s(rreeod,, otnopp bbaarr))aanndd33MM ((bBluuee)) rreessuullttss ffoorr PPEFOOSS ccoonncceennttrraattiioonnss frroomm ssaammee ffiisshh h homoogenamtes:o;eemmbgbeeddddeeeddffiingguurreesasnhoowwtssAAKXeYYSS Vvseerrssuus:s33MM PFWithO1:10S... 21 PFOS with 1:1 line .................................... 27
FiguresDistibutonsof
Figure 5 Distributions of
PFOSbyspecieswithin
PFOS by species within
achSection
each Section
(1-4)
(1-4)
andall
and all
sections
sections
combined
combined. ..............
2288
FFigiureg6uPPFFrOOSSeiinnSSpepceiceiess-SSeectcitioonnMMaattri;x;vveertrtiiccaall bbaarssaarree 4400 ppppbb aanndd 220000 PB... 29 ppb ....................................... 29
FFiigguurer7e7
DDisitribsutitonsroofif PPFFbOOSSubbyytyyeeiaarrfofoorrneeaascchh
ssppeecciieess
((allll
ectons).......cvvvevee: sections) .......................................................
30
30
FFiigguurer8e8 DDiissttrriibbuuttiioonnss ooff PPFFOOSSbbyyyyeeaarr ffoorreeaacchh ssppeecciieess lliimmiitteedd ttoo SSeeccttioino&n4 ........................................... a34
Figures PROS concentbyrgeandteiroofenacsh species 2 Figure 9 PFOS concentrations by gender of each species ......................................................................... 32
Figure 10 PFOS concentrationbyage fo each species 3 Figure 10 PFOS concentration by age for each species ............................................................................. 33
FiFgiguurree 1111 PPFFOOSSccooncnentcratieonsnbbyytlelenrnggttahh ofotrreeaiacchohspsenpceicseiess ....................................................................... u34
FFiigguurree 1122 PFSconcbeypnercetnt rpiasfotr eaichsopecnies. PFOS concentration by percent lipids for each species ............................................................. 335
FiFgiguurree
1133RRelealtaitioonnsshhiippbbeettwweeeenn
PPFFODAA
((CC1100))
aanndd
PPFFOOSS
ffrroomm
PPoocoll
2 2
al(all
ssppeecciieessaanndd
sections)
sections). . .................
36
36
Mississippi Pool 2 PFCs 2009 March 2010
Mississippi Pool 2 PFCs 2009 . March 2010
2
Minnesota Pollution Cantral Agency
Minnesota Pollution Control Agency
22229955..00000044
STSATTAETE0_202001100440033
AAbbbbrreevviiaattiioonnss GGlloossssaarryy
Groups PPFFCCss - ppeerrfflluuoorroocchheemmiiccaallss oorr ppeerrfflluuocrriinnaatteedd ccoommppoouunnddss. PPAASS:s --ppeerfrflluuoorrooaallli<yyll ssuurrffaaccttaannttss PPFCCAAss - ppeerrfflluuoorrooccaarrbbooxxvyllicc aacciidd PPFSSAAss-- ppoollvfflluuoorriinnaatteedd aallkkyyll ssuubbssttaanncceess FIO ~fluorotclomeralcohols PFETOARHS--fpleurofrloutoerlooamlkeyrlaalcciodhsols
PFAAs - perfluoroalkyl acids
IInnddiivviidduuPaallBA perfluorobutanoic acd (CA Acid)
PPFFBBAS--- ppeerrfflluuoorroobbuuttaanneoiscualfcoidna(tCe4 (ACc4idS)ulfonate)
Pipe - perfluoropentanoic acid (C5 Acid) PFBS- perfluorobutane sulfonate (C4 Sulfonate)
PFPeA - perfluoropentanoic acid (C5 Acid)
PFA PFHxA -~ppeerrfflluuoorroohheexxaannaoiicc aaccidd ((CC66 AAcciidd))
PFS PFHxS - ppeerrfflluuoorroohheexxaannee ssuullffoonnaattee ((CC66 SSuullffoonnaattee))
PPFFHDpAA - ppeerrfflluuocrroohheeppttaannooiicc aacciidd ((CC77 AAcciidd))
PPFFOOAA--ppeerrffluuoorrooocotcantoaincaoacicidcd ((CC88AAcciidd))
PPRFOOSSp-eprefrlfluuoorrooooccttaannee ssuullffoonnaattee ((CC88 SSuuflfoonnaattee))
PFOSA ~ perfluorooctane sullonamide (C8 Sulfonamide,
PENA ~perfluorononanic acid (C9 Acid) PFOSA - perfluorooctane sulfonamide (C8
PFNA - perfluorononanoic acid (C9 Acid)
Sulfonamide,
PPFFDDAA --ppeerrfflluuoorrooddeeccaannooiicc aaciidd ((CC1100 AAcciidd)}
PPFFUURnAA~- ppeerrfflluuoorroouunnddeeccaannooiicc aacciidd C(C11ll AAdcdid))
PPFFDDOoAA -~ ppeerrfflluuocrrooddooddeeccaannooiicc aacciidd ((CC1122 AAcciidd])
branched]
branched)
Other Abbreviations
Other
AFFE aqueous Abbreviations AFFF aqueous
fiirreffiigghhttiinngg
ffooaamm
EECCFF-- eelleeccttrroocchheemmiiccaall fflluuoorriinnaattiioonn
FFCCAA -~ffiisshh ccoonnssuummppttiioonn aaddvviissoorryy
MMODHH -~ MMiinnnneessoottaa DDeeppaarrttmmeenntt oof[ HHeeaalltthh
DDNNRA -- MMiinnnneessoottaa DDeeppaarrttmmeenntt ooff NNaattuurraall RReessoouurrcceess
WWWWTTPP--wwasatsetewwataeterrttrreeaattmmeenntt ppllaanntt
MMiissssiissssiippppii
PPooooll
22
PPFFCCss
22000099
+
.
MMaarrcchh
22001100
s
Minnesota Pollution Control Agency
Minnesota Pollution Control A~ency
22229955..00000055
STATE02010404 STATE_02010404
EExxeeccuuttiivvee SSuummmmaarryy Perfluorochemicals (PFCs) emerged asaglobal pollutant n 2001 when scientists reported pPeerrffluoorrooocchteamniecaslusl(lPoFnCats)e e(mPFeOrSg)ewdaass maegalsoubrael dpoilnluwtialnitfine t2h0r0o1uwghhoeunt stchieenwtoisrtls.reNpuomreterdous studies hpaevrefldueomroooncsttarnaetseudlftohnaattePF(OPSFiOsSt) hweparsimmaearsyfuroerdminofwPiFldC lfifeouthnrdouinghfiosuhtatnhdeotwhoerrldb.ioNtusm. e30ro1uCsomstpuadnieys's ChoatvteadgeemGroonvsetraftaeidtt,haitnPthFeOSsoisutthheeapstriemrnarTywfionrmGiotefsPFMCetfrooupnodliitnafnisAhreaan,dwas a other maior biota. m3aMnuCfaocmtpuarneyr'sof PCFoOttSagferoGmrotvhee 1950's to facility, in 2th0e02s.oTuhthee3aMsCteortntTawgeinGrCoitvieesfMaceitreopdoilsitcahnarAgreesat,rweaatsead mpraojcoersm s waantuefarcatundrer of cPoFoOlSinfgrwoamtethreto19o5o0l's 2toof20th0e2.MTishseis3sMippCioRtitvaegr.e Although the Grove facility fdiascchtargdeissctorentaitenudedprporcoedsusctwiaotnerofaPnEdOSin 2c0o0o2li,ngthweaftaecrilttoy Pdiosocl h2arogfethceonMtiisnsuiesssitpopihaRviveerm.eAalsthuroaubglhetPhFeOfSacciolintcyedntisrcaotinotinnsu.edPopolro2ids ucationenarolfyP3F3OSmiilne r20e02,aothfcethhfaecMiliitsyssdsisicohpiarRgievecrobnetintuweesentLoohcakve& Dam 1.and measurable LPoFcOkS& Dam 2. The Metropolitan concentrations. Pool 2 is a Wastewater nearly 33 mile TreraecahtmoefntthelaMnitss(isMseitprpoi Rplivanetr)b,etthweeleanrgeLsotckwa&stDeawmatierantdreLaotcmke&ntDpalmant2.inThMeinMneestorotap,olaitlaon dWiassctheawragteetros TPoroelat2m, eanndt alsoPlanth(aMsemteroaspulraanbt)l,ethle leargovefsPteOwSalsiteswtasteefrfltrueenatt.mWeansttpelwaantteinr Mcainnnbeesoatsai,gnailsfoicadnistcshoaurrgceesotfo PPEoCosl 2b,eacnadusaelstohehsaes cmheemaiscuaralsblhealveevebleseonf iPnFcOlSudineditisnaeffwluiednet.raWngaestoefwcaotnesrucmaenrbaenadsiingdnuisfticraianlt psrocudruccetosf tPhFaCtscbaencaevuesnetuthaellsye bcehedmisicpaoslsedhaovfeinbemeunniicnicplauldewdasitneawawtiedre sraysntgeemso,f Tchoinssurempoerrtadnodeisndnuotsterixaal mine the products tlhoaadticnagnfervoemnptousaslilyblbeesdisoposuoedfroPfFiCcnsmeouPnoisocilpa2l,wbautstreawthaeterrfsoycsutseems so.nTPhEisCsreipnoirsthdoaensd nwoatt eerxafmroinme the WloiasdiisnsgiforopmRivpeorssPiobolel 2s,oubracseesdoonfiPnFtCesntsoivPeoomlo2n,itbourtirnagthceormfpolceutseeds ionnthPeFCssuimnmfiesrh of 2009 and water from
Mississippi River Pool 2, based on intensive monitoring completed in the summer of 2009.
Since 2004, the Minnesota Pollution Control Agency (MPCA) and the Department of Natural Resources (rS(MMionODcmNeNRPR2)o0),o,0lww4i2,i.ttthhhAenppaaMrirtntiitincceniinpepsaaisttvoiieotsoanntuPoodfofylttlhouhefteioHHPneEeaCCalsltothhnitDDrfoeielspphAaargartentmmndecewynnatt(tMe((MPrMCDDwHAHa))s),,achhnoaadmvvpteehaleneatanDeladelyypzziaeendrdttmhffieiseshshnutaamonnfmddeNrrriiavvteeuorrfraww2la0aR0tt9eee.rsrofOfouofrrrctPePheFsFCCss f3r6o7mfiPshooaln2a.lyAznedinfternosmiv2e0s0t4udtoyporfesPeFnCts, 297 w in fish earned cwolalteecrtwedasinc2o0m09p.leItendadidnitthioen,suwm atmeresraomfp2l0e0s9.wOerf ethe c3o5l7leficsthedaantal1y2zesdtaftrioomns 2t0h0r4outgohporuetsPeonot,l 229i7n w20e0r9e. cToollecchtaerdacitner2i0z0e9t. hIne sapdadtiitailondi,swtraitbeurtisoanmopflePsFCwseirne Pcooolllec2,tetdheatr1e2acshtawtaiosndsitvhirdoeudgnhtoouftoPuorosle2ctiinon2s0,0w9i.tThoScehcatiraoncte1raizteththeemospsattiuapl sdtisrteraibmuetinodnaonfdPSFCesctinio4n aPbooovl e2,tthheeHraesatcihngwsaDsadmivi(dLeodci&nktoDfaomur2)seFctioinsg2, wuoiftrhtheSeecmtaioinn Ireaptotrhtesmhoowsst usepcsttrieoanmboeunnddarainedsaSencdtion 4 waabtoevre sthaempHlaesltioncgastiDonasm. (Lock & Dam 2). Figure 2 of the main report shows section boundaries and
water sample locations.
Afi and water samplos were analyzed fo PFCs by AXYS Analytical Ltd. Fo qualityassurance, water Asallmfpislhesanfdrowmaatlelr1s2atmaptlieosnswearneda3n0alryazneddofmolry-PsFeClsabcytdAXfYisSh samples wero Analytical Ltd. aFonr qaulaylibtyzyae3sMsdurEannvcier,ownametenrtal Lsaabmorpaletsorfyr.omThaelli1g2hsdtaetgiornese aonfdda3t0a rcaonrdreolmatlyio-snebleetcwteedefnisthhesawmoplelsawbeprreovaindaelyszceodnfbiyde3nMceEnntvhiroenqmuenatyal oLfatbhoerarteosruylt.sT.he high degree of data correlation between the two labs provides confidence in the quality
of the results.
The highest water concentraotfiPoEnCswerefound in Section 4 in particular, Station 11. Tpehrefhliugohreosbtuwtaanteicr caocndce(PnFtrBaAt)iownassodfePtFeCcstewdearte afolu1n2dstinatSioencs.tioFnO4S,,inppearrftlicuuolraorc, tSatnaotiioena1ci1d. (PFOA), and pPeerrfflluuoorroobhuextaannooiiccaacci(dP(PFFHBAA))wwaserdeetdeectteecdteadt inall S1e2ctsitaontison2s,3.,PaFOnS,4,pewirftluhotrhoeocHitagnheosict caocnidce(nPtFrOaAti),onasndin Speecrtfliuoonro4.hTehxraeneooicthaecridPF(PCFsH--xPAF)PweeAr,e PFBS, andPFHS --were detected in Section. detected in Sections 2, 3, and 4, with the highest concentratiot~s irr
Section 4. Three other PFCs--PFPeA, PFBS, and PFHxS--were detected in Section 4.
PFO wasdetected in nearly all fish from Pool 2. The highest PFOS concentrations infish coincidedwith hPFeOShiwghaesstdewtaetcetredcoinncneentarrlaytiaollnfsisihn fSroemctiPoo4on.l 2O.tThehre hPFigChseestrPeFOdSetceocntcedenntrafitisohntshaint hadfish higher coincided with tChoencheingthreasttiownasteofr PROS. Of the five concentrations intSaergcetitoend4f.isOhtshpeerciPeFsCisnwPeoroel d2e---tebcluteedgiiln sfiusnhfitshha,tcahrapd, hfrigehsehrwater dcrounmc,enstmraatliolmnosuotfhPbFaOssS,. and whitebass freshwater drum Of the five targeted fish species in hadPoolt2h-e-bhliugehgesiltl sPuFnOfSishc,onccaernpt,rfarteisohnws,atDerrum hdarudmn,otsmbeaellnmosuamthplbeadssp,raionrdtwoh2i0te09b,absesc-a-furseeshtwisatneortdcrounmsihdeardetdhe thyipgihcealstpPoFrOtSficsoh.ncBeansterdatoionntsh.e.Drum
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
Minnesota Pollution Control Asency
~innesot~ Pollution Control Agency
22229955..00000066
STSATATTEE0_202001100440055
MMDDNNRRs's oobbsseerrvvaattiioonn tthhaatt tthhee ddrruumm iiss aa ppooppuullaar ffiisshh hhaarrvveesstteedd iinn PPooooll22 ffoorr hhuummaann ccoonnssuummppttiioonn, iitt wwaass iinncclluuddeedd aass aa ttaarrggeett ssppeecciieess iinn 22000099..
The MDH has developed a reference dose for PFOS thatis used as the basis for fish consumption advice.
TMheeanMDPFHOShacsodnceevnetlorapteidonasreinfeirsehncbeedotsewf4oer0eaPFnnOdS2th00atpaisrtussepderabisllthioen b[apspisb)foarrfeisahssciognnseudmmpetaiolnaadvdivcicee.
oMfeoanncePpFeOrS wceoenkc;enbterattwioenesn i2n0f0ishanbde8tw00eepnpb4,0tahnedad2v0i0cepaisrtosnpeemr ebaillliopnerIpmpobn)tha,reaansdsiagbnoevdem8e0a0l papdbv,icdeo
nooftoneacte. piesrhwceoenks;ubmepttwieonenad2v0i0soarnieds8w0e0reppmbo,dtihfeieadfdovircePiosaoln2ebmaseeadl onpertmheon2t0h0,9arnedsualbtso.veFr8e0s0hwpaptbe,rdo
dnrotumeaht.adFisthhecohingshuemstpPtiFoOnScaodvniscoernietsrwaetreiaomnosddiwfiaesdtfhoeroPnoloyl 2fisbhassepedcioensthineP2o0o029 raessusltsi. gFarneosenhdewamteesr!
per month adiisory basedon amean PFOS drum had the highest PFOS concentrations
per month advisory based on a mean PFOS
concentration of and was the only
concentration of
229fish
229
ppb Smallmouth species in Pool 2
ppb. Smallmouth
bass also haamedan assigned a one meal
bass also had a mean
POS concentration of 209 ppb when data from 2004 to 2009arecombined; however, mesl advice is
oPFtOSgicvoenncfeornttrhaitsiosnpeocif e2s0i9 pPpobolw2hebnecdaautsaeforonm ly c2a0t0c4ht-oan2d0-0e9leaarseecfoimshbiningesd;alhloowweevder, meal advice is
( not givet n forhtehaie sltshpestcaietx se imnnP.ouosa l/2ivbsefceahs /ufsseho))n.l)y. catch-and-release fishing is allowed
NNoo ddiisscceerrnnaabbllee ttrreennddss wweerree sseeeenn iinn PPFFOOSS oovveerr ttiimmee ffoorr ssppeecciieess tthhaatt hhaadd bbeeeenn ssaammpplleedd ssiinnccee 22000084 oorr 22000055.. PPRFOOSScocnocnecnetnrtarattiioonnss iinn ffiisshhmmususcclleewweerree nnoott ccoorrrreellaatteedd wwiitthh ifisshh aaggeeoorrsisrizee,, aanndd tthheerree wwaass nnoo fdieffreerennccee bbeettwweeeenn ggeennddeersrs.. BBiiooaaccccuummulualattiioonn ffaaccttoorrss ((BBAAFFss)) wweerree ccaallcuclualteadtffeoodrr PPFFOOSSusuisinnggtthhee wwaatteerr aanndd ffiisshh ddaattaa.. BBAAFFss ffoorr PPFFOOSSwweerree iinntthhee rraannggee ooff 44000000 oto 66000000 Kg, L/Kg, wwhhiicchh sis tattthhee llooww eenndd ooff tthhee rraannggee ooff hhiigghhllyy bbiiooaaccccuummaulslattiivvee ccoommppoouunnddss..
Mississippi Pool 2 PFCs 2009 + March 2010
Mississippi Pool 2 PFCs 2009 . March 2010
5
Minnesota I~innesota P Poolllluuttiioonn CCoonnttrroo~l AAggeennccyy
22229955..00000077
STATE02010406 STATE_02010406
IInnttrroodduuccttiioonn
MMisisssiissssiippppii PPooooll 22
Wissssipi Mississippi
iver River
Pool
Pool
2
((FFiigguurree
11))
eexxtteennddss
ffrroomm
LLoocckk
&&
DDaamm
##22
aatt
HHaassttiinnggss,,
MMiinnnneessoottaa,,
uuppssttrreeaamm
nneeaarrllyy
33 miles 0 Lock & Dam #1 (Ford Dam). The Mississippi confluence with theMinnesota River sat the.
u33ppmerilers teo LaoofccPko&ohlD2aman#d1t(hFeorcdonDfalmue)n. cTehweitMhistshiesSstip.pCi rcooinxfliuevnrces jutwith belowLock & Dam 2. the Minnesota River isWaittthhien
Puopople2r,reaavcehraogfePaoonl 2nalnoudwtahies caobonufltue1n5c,e00w0cituhbtihcefeSett. pCerorixseRcivoenrdis(fjus)s.t Pbeollow2iLsoacrkec&eiDvaimng#w2a.tWerithfionr
tPhoeolla2r,gaesvterpaugdeliacnanluya-lofwlonwediswaasbtoeuwta1t5e,r00t0recautbmiecnfteepltapnetrisneMcionnndes(coftsa)., thePool M2etisroaproelcietiavninWgW-wTaPte,rwfiotrh
tahnealvaergraegsetdpiusbchliacraglley-oofw1n8e5d mwialsiotenwgaaltelorntsrepaetrmdeanyt(p2l8a6ntclin),MainndnetshoetaEa, gthlees MPoeintrtopWoWlTitaPn, WwiWthTPan, with
aatv1earvaegreagdiesdchisacrhgaergofe4o.f21m8g5d.mTillhioen3g1alCloonmsppaenrydCaoytt(2a8g6eGcrfso),vaendfatchlletyEiagnleesxtPtooi,ntaW ndWdToPw,nwstitrheaanm of,
tahveerEaaggeledsisPcohianrtgWeWoTfP4..2 Tmhged3. TMhfea3cM ltyCdoimscphaanrygeCsoitntadugsetrGiarlovperofcaecsilsitywaistenrexatntdo,coaonldindgowwantesrtr,ewaimthoaf,
tchoembEiangeleds fPlooiwntofW8WmTeP.. The 3M facility discharges industrial process water and cooling water, with a
combined flow of 8 mgd.
W Whhaatt aarree PPFFCCss aanndd wwhhyy aarree tthheeyy aann eennvviirroonnmmeennttaall ccoonnttaammiinnaanntt?? PPeerrfflluuoorroocchheem miiccaallss P(PFFCCs)s--)-a-allssoo kknnoowwnn aass ppeerrfflluuocrriinnaatteedd ccomopomunpds---o-aarrueecconommpdpoossseedd ooff aa ccaarrbboonn cchhaaiinn saturated with fluorine atoms, witha functional group at the endof the chain. The functional groups are: tsayturpatiedacswuailthflofnlluatoyerin(e-5a0to;omr)s,acwaritbhoxayfluinccaticoindaglrgoruopup(-aCOt OthH)e.eTnhdeoffutnhceticohnaaling. rTohuepfumnackteiosntahlegrPoFuCps are tsyopluicballelyina wsautlfeorn(ahteyc(r-oSpOh~i)lco)r,awhcaerrbeoaxsytlihceacciadrgbroonucpha(-iCnOmOaHk)e.sTthheefuPnFcCtimoonlaelcgurloeuspolmubalkeesnthliepiPdsFC (siopluobphleiiinc)waantderre(shiysdtraonpthtiolicw)a,twerhe(rheyadsrotphheobciacr)b.onThcehauinniqmuaekeprsotpheertPiFesC omfoPlFeCcsulheasvoelubbeleeninexlipplidoisted for numerous (lipophilic) caonndsruemseisrtapnrtodtoucwtsa,temros(htyndortoapbhloybficir)e. Tfihgehtuinngiqfuoeamp,rospteairntiepsrootfecPtFiCosn,haanved nbeoensntiecxkplsouitrefdacefos r
numerous consumer products, most notably fire fighting foam, stain protection, and non stick surfaces.
PFCs "are globally distributed, environmentally persistent, bioaccumulative, and potentially harmful"
(PGFiCessy"aarnedgKloabnanlalyn,di2s0t0r2ib).uteAldt,heonuvgihrotnhmereenatarellynapteurrsailsltyeonctc,ubriroiancgcfulmuourlaintiavtee,daonrdgapnoitcecnotimapllyouhnadrm s ftuhla"t
c(GonietsayinanadneKfalnunoarinn,e2a0t0o2m).,AalltlhFoCugshitnhtehreeearennvatuiralrlyaorocecanuntrrhimnrogpefolugnoenriintca.te(dGiocrsgyaannicdcKoamnnpaonu,nd2s00t2h)at
Vcaornitoauins toonreifleunodrpinoeinattsom ha,vaellbPeFeCnsmineathseureendviirnolnamboernattoarrey astnutdhireospaofgePFnCics.. (AGciceosrydianngd tKoaann2a0n0,72M00O2H)
pVraersiosurseltoeaxsice,eonbdspeorivnetsd ehfafveectbseoefnlmoweadsousreesdofinFlaObSoriantcolruydestduedcierseaosfePdFhCgs.hAdcecnosrdhiyngpotoprao2t0e0i7n MDH
cphreolsessrteelreoalse(H, DoLb)searnvdecdheafnfegcetss ionftlhoywrodidosHeosromfoPnFeOlS iencvliundeseoldmesecreaansimeadlsh.ighBiodleongiscitayl membranes lipoprotein are
prcihmoalreislteyrcool m(HpDoLs)eadndofcphhaonsgpehsoliinptihdysr,owidhihcohramroenaemplehvieplshiinicsomomleecaulneims.alsT.heBiaomlopghiicpahlilmiecmpbrorapneretsyaorfe
PpFriCmsamriilgyhctoemnphoasnecde cell membrane p of phospholipids,ewrhmicehabaireiotafm y pothhipehrilpicolmluotalenctsu,letsh.eTrheebyaminpdihriepchtillyicipndroucpienrgtyadovf erse
effects caubsyoethder chemicals (Waentag, 2009. PFCs might enhance cell membrane permeability of other
effects caused by other chemicals (Wang et al., 2009).
pollutants,
thereby
indirectly
inducing
adverse
Perfluorooctane sulfonate (PFOS) is the predominant PFCfound in mstfish (Houdeetal 2006). Fish
fPreormflucoornotoacmtainnaetseudlfaorneaatsem(aPFyObSe) aisstihgenipfirceadntomsoinuracnet oPfFCdifeotuanrydPRinOmSeoxsptofissuhr(eHo(uBedregeert aelt2a0l,062)0.09F)is.h The
ffriosm t rceoponrttamofinPatedFaasreOgalsom Sbaaly cboenatasmiginniafinctanitn swioludrlciefeowf dieatasrtysudPyFOfSunedxepdobsyur3e Giesy (Berger and Kannan, et al., 2009). The
f2i0r0s1t). When report ofPPFFOOSScaosncaegnltorbaatliconosntaarme ihniagnhtiinnfwisihldtliifsesuwe,aostahesrtuldoyngfucnadrebodn-b<yh3aM in (PGFiCess,ysauncdh asKannan,
p20e0r1f)l. uWohreondePcFOaSnaaccloiendc(eCn10tr)a,tiaornesoaftreenhdigehteicntefids.h tDisesteucet,iootnhleirmilotsnggecnaerrbaollny-crhaanignePfFroCms2,.5sutchoas5.
npaenrfolugorraomdsecpearnogircaamci(dng(/Cg1)0,)o, arpearotfstepnerdbeitlelcotned(.ppDb)e.teRcattiohnerlimthiatsn gbeeninegrallilyporpahinlgiec firkoemm2a.n5ytoot5her
persistent organic pollutants nanograms per gram (ng/g),
persistent organic pollutants
(POP), or parts
(POPs),
several studies have suggested that per billion (ppb). Rather than being
several studies have suggested that
PFCs are lipophilic
PFCs are
proteinophilc (Conder like many other
proteinophilic (Conder
etal. 2008). PFOS behaves very differently from other POPs, having differences in intinsic factors, such
aest saul.r, f2a0c0e8a)c.tiPvFiOtyS, bweahtearvessolvuebirlyitdyi,ffneoren-nmtleyafsruormabolteheorctPaOnPcsl,/whaatveinrgcodeiffffeirceinenctesvailnueins,triannsdicrfealcattoivrsel,ysluocwh
as surface activity, water solubility, non-measurable octanol/water coefficient values, and relatively low
Mississippi Pool 2 PFCs 2009 + March 2010
A4ississippi Pool 2 PFCs 2009 . March 2010
Minnesota Pollution Control Agency
~innesot~ Pollution Control Agency
22229955..00000088
STATE02010407 STATE_02010407
bcbioioonaascciccduuemmurulealadattiiPooOnnPpp(ootWteaenntnigtaiealt.la. lDD.eesspp2i0itt0ee9)tth.heessee ddiifffeerreenncceess,, PPFOOSS bbiioaocaccumcuulmautelsiainntffieissshh ttiissssuuee aanndd iiss
considered a POP (Wang et al., 20091.
AAmmbblieenntt m moonniittoorriinnggooff PPFFCCss bbeeffoorree 22000099
TThhee MMPPCCAA ssuummmmaarriizzeedd aammbbiieenntt mmoonintitoorriinngg tthhrroouugghh 22000088 iinn PPFFCCSs iinn MMiinnnneessoottaa''ss AAmmbbiieenntt EEnnvviirroonnmmeenntt::
22000088PPrrooggrreessss RReeppoorrtt ((ttp/ ww ca.state.mn.usfpublications/c fc1-02.54f). Inaction to fish, the
rreeppoorrtt
ccoovveerrss
PPRFCC
mmoonnititoorriinngg
iinn
ggrroouunndd
wwaatteerr,,
ssuurrffaaccee
wwaatteerr,,
wwaasstteewwaateterr,,
aanndd
ar.). In
air.
addition
to
fish,
the
FFiisshh iinn PPooooll 22 wweerree ffirrsstt etesstteedd ffoorr PFFCCSs Iinn AAuugguusstt 22000044 aannddffisshccolollleeccttiioonn ffoorr PPFFCCss hhaassccoonnttiinnuueeddeevveerryy
y9Yee5aa0rr
neegxx/ccge)eppattn22d000o07n7.e.
IIcnno22m00p00o44s,,i
tPPeFFCCsss wwaeermreeopddfefelttoeeueccrtteewddhininttethhbeeaffsiilllelfeittslseootfsf
ttwwoo (PFO
ssmmaallllmmoouutthh S: 138 ng/g).
bbaassss in 2
((PPFFOOSS::
105
105
005, 2006,
ng/g anngd/g
and
and
2905008,nga/dgd)iatnodnaolnteesctoemdpfoisshitsepseacmieplienoclfufodeudr wwahlliteeyeb,acssarfi,llecthsa(nPnFeOlSc:at1f3i8shn,gb/lga)c.kIncr2a0p0pi5e,,2s0m0a6l,lamnoduth
a2s0s08,,wahdidteitiobansasl,tessmtaeldlmfiosuhtshpbeucfifeasloin,celumdeerdalwdahlilenyeer,,caarnp, gcihzaanrndelshcaadt.fisFhi,lebtlatciksscureaspapmiep,lsems raallnmgoeudth
rombass, ownheitetobfaisfst,eesnmfaisllhmeorutshpebcuieffsa.loA,necimlearrayldmesahsinuerre, maenndtgsiziznacrldudsehdadl.enFgitllhe,t wtiesisguhet,saamgep,leasndrasnegx.edIn
2005, the from one
2005, the
highestPFOSconcentration was in to fifteen fish per species. Ancillary
highest PFOS concentration was in
white bas, with a rangeof 4 ng/tgo 1860 ng/g. measurements included length, weight, age, and
white bass, with a range of 84 ng/g to 1860 ng/g.
In 2006, sex. In
In 2006,
s5smm1a5al0lllmnmgoo/ugu.tthhSbbmaaasslsslhhmaaodduttthhheebahhsiigsghhheeasstdt PPtFhFeOOSShiccgoohnnecscetennctotrrnaactteiionontnrwwaataissoininnassmmgaalilllamnm2ooi0uut0tnhh8,bbaabssusst,, twwhiietthhraaanrrgaaenngwgeeasooff 1199 nngg/g/ttgoo
C5o1n5s0idnegr/agb.lySnmaarlrlmowoeurththbaanssnh2a0d0t6he(PhRiOgSh:es4t9cnonfce0ntr3a8ti0onnagg)ain in 2008, but the range was
considerably narrower than in 2006 (PFOS: 49 ng/g to 380 ng/g).
12006, background concentrations of FCs fish were estedbysamplitnhge upper St. roi River (above the t. oi Fas dam) and Lake Calhoun in Minneapolis The PFOS concentrations infish from In 2006, background concentrations of PFCs in fish were tested by sampling the upper St. Croix River
(above the St. Croix Falls dam) and Lake Calhoun in Minneapolis. The PFOS concentrations in fish from
tthheeSSt.t. Coriosix,,a easxpexepcetcetedd,, wweerree bbeellooww tthhee ddeetteeccttiioonn lleevveel.l. iInn LLaakkee CCaallhhoouunn tthhee bbulueeggiilllss hhaadd PPFFOOSS concentrations of 161 to 373 ng/g, prompting additions akemonitoringinthe following year.
concentrations of 181 to 373 ng/g, prompting additional lake monitoring in the following year.
In 2007, ONR's PEC monitoring in fish focuseodn30Twin Cites metro lakes, lower St. Croix River, and
hIne20u0p7p,erDNiRs'siPsFCpimoinvietorrinne8arinBfriasihnefordc.usievdeolnak3e0s--TEwlimnoC,itiGeesrvmaiest,roHalarkteis,,loJowhearnnSat.,CarnodixTRaivnenr,earn--sd
thhaed ufipsphewriMthisPsFisOsSipcpoinRceivnetrrnateiaornBsrgarineaetrder. Fthivaenla2k0e0sn-g-E/gl.moLa, kGeeErvmaios, hHaadrtriheet, hJioghhaenstnac,onacnednTtarnatnieorsn-o-f
PFS, ranging from had fish with PFOS
PFOS, ranging from
149 ng/g to 711 ng. Inthe concentrations greater than
149 ng/8 to 711 ng/g. In the
Upper Misissopi River 200 ng/g. Lake Elmo had
Upper Mississippi River
earBrainerd, PROS. the highest concentrations
near Brainerd, PFOS
of
ccoonncceennttrraattiioonnss iinn ffoouurr ffiisshh ssppeocciiees rraannggeedd ffrroomm oonnllyy 66 nngg/g/1tgoo 1188 gn/gg/g.. 1In aaddddiittiioonn ttoo tthhee mmeettrroo alakkee
sasammplpeless aannaallyyzzeedd bbyy AAXXYSS AAnnaalylyttiiccaall LLdtd,, ffiisshh hhoommooggeneanteasftfrreoomms 5595 llaakkeess ffrroomm tthhrroouugghhoouutt ththe ssttaattee aanndd
several Mississippi River locations were sen totheUSEPA lab in Research Triangle Park, North Carolina
(Delinsky etal. 2010}, USEPA's analyses several Mississippi River locations were
(Delinsky et al., 2010). USEPA's analyses
lookeda bluegill sent to the USEPA
looked at bluegill
andlab
and
pumpkinseed sunfish, and in Research Triangle Park,
pumpkinseed sunfish, and
black North
black
crappie. Carolina
crappie.
TThhee ssaammpplleess vweerree mmsotsltlyyccoommpopsoistiteess ((oonnlyy tthhrreeeeoofftthhee 7700 ssaammpplleess wweerree ssiinnggllee ffiillleettss)).. TThheeiirr hhiigghheesstt
rreeppoorrtteedd PPFOOSSccoonncceenntrtartioantsiwwoeenrrsee iinn bblluueeggiilll ffrroomm PPoool22(o(2200l0000 ng). ng/g). UUppsstrreeaamm ooffPPooooll 22, tthhee hhiigghheesstt
PPFFOOSS ccoonncceennttrraattiioonn wwaass 2200 nnegf/g.. TThheeiirr rreessuullttss ffoorr llaakkeess rraannggeedd ffrroomm PFFOOSS leessss tthhaenn ththe lliimmiitt ooff
Quantitation (L0G 1ng/g)to. high of 52 ng/g; 52 ofthe 59 lkes (885) had PFOS concentrations fess
tqhuaann3titnagti/ogn (LOQ - 1 ng/g) to a high of 52 ng/g; 52 of the 59 lakes (88%) had PFOS concentrations less
than 3 ng/g.
1In 22000088,, PPFFCC ssaammpplliinngg iinncclluuddeedd 2222mmeettrroo aarreaa llaakkeess aand2n2alakdkeess nneeaarr DDuulluutthh,, iinn aaddditiionttooimmooronere:
sampling in Pools 2nd3 ofthe Mississippi Aver. Thirteen of th lakes, ot including Calhoun and Elmo
which again showed high sampling in Pools 2 and 3
(which again showed high
PFOS of the
PFOS
concentrations), had species-mean PFOS concentrations above 40 Mississippi River. Thirteen of the lakes, not including Calhoun and
concentrations), had species-mean PFOS concentrations above 40
ng/g. Elmo
ng/g.
TThhrreeee llaakkeess----TTwwiinn ((BBrrooookkllyynn CCeennteterr)),, HHaarrrriieett,, aanndd LLaakkee ooff tthhee IIsslleess----hhaadd ssppeecciieess-mmeeaann PPFFOOSS
Mississippi Pool 2 PFCs 2009 + March 2010
A4ississippi Pool 2 PFCs 2009 . March 2010
;-7-
M3i4ninnneessoottaa PPoolllluuttiioonn CCoonnttrrooll AAsgeennccyy
22229955..00000099
STATE 02010408 STATE_02010408
ccoonncceennttrraattiioonnssaabboovvee 220000 nngg//gg.. IInn PPoooollss 22 aanndd 33,, aonneettooffiivvee ffiisshh ppeerr ssppeecciieess wweerree aannaallyyzzeedd;; bblluueeggiilllss aanndd ssmmaallllmmoouutthh bbaassss aaggaaiinn hhaadd mmaaxxiimmuumm PPFFOOSScocnocnecnetnrtarattiioonnss ggrreeaatteerr tthhaann 220000 nrigg//gg,, aalltthhoouugghh tthhee ssppeecciieessmmeeansaiinnnPPosoooll 22wweerree 117733 nngg//gg ffoorbblluueeggiilllssaanndd 116622nngg//ggffoorrssmmaallllmmoouutthh bbaassss..
W `Whhyy tthhiiss ssttuuddyy??
TThhee MMPPCCAAsis lleeggaallllyy rreeqquuiirreedd tos to list wwaatteerrss aassImimpapiarireedd iiff tthhe ffiisshh ccoonnssuummppttiioonn aadvdisvoryiffoorsraaoalakrkeeoyorr rriivveerr
that is more restrictive than a mealperweek (Minn. R. pt. 7050.0150, sub. 7). Pool 2 has been listed as
tihmapat iisremdodrueeretsotPriFctOivSeinthfaisnh asimnceeal20p0e8r,wbeaesked(Moinnna.oRn.cpet.pe7r05m0o.n01t5h0a,dsvuibsopr.y7)f.orPobloul e2gihlassibne2e0n07l.isted as
AimddpiatiiroendalduPeFCtodaPtFaOwSeirnefiswharsrianncete2d0g0i8v,ebnatshee sdmoanlal osnacmeplpeersimzeosnotfh faisdhviisnoyreyafrosr pblrueigtooills2i0n0920a0n7d.
because bothwater Additional PFC data
because both water
and fish PFOS concentrations are needed to were warranted given the small sample sizes
and fish PFOS concentrations are needed to
establishsitespecific water quality of fish in years prior to 2009 and
establish site-specific water quality
icrtiteeiraia,. MMPPCCAA,, MMDDHH,, MMDDNNRR,, aanndd 33MMstsataffff mmeett oonn 1133 MMaayy 22000099 ttoo ddiissccuussss tthhe iinntteennssiivvee mmoonintitoorriinngg
ssttuuddyy ooff PPooooll 22..33MM ssoolicliteid caapiprrootppoeossadall ffoorraa ssttuuddyy ffrroomm tthhee ccoonnssuullttiinngg ffiirrmm,, Ent, Entrix, wwhhiicchh wwaass tthhee bbaassiss
ffoorraa ddiissccuussssiioonn.. TThhee MMDDNNRR oofffefrreed oto ccoolllleecctt tthheeffiisshh aanndd MMPPCCAAwwaanntteedd ttoo oovveerrsseeee tthhee ssttuydy;;
tthheerreeffoorree,, iittwwaassaaggrreeeedd tthhaatt MMDDNNRR wwoouulldd ccoolllleecctt tthheffiisshhaanndd MMPPCCAAwwoouulldd ccoooorrddiinnaattee tthhee llaabboorraattoorryy
aannaallyyssiiss aanndd aannaallyyzzee tthhee rreessuultltss.. 33MM wwaass pprroovviiddeedd wwiitthh ssppilitt ssaammpplleessooffffiisshh aanndd wwataer ofotrr aaennaallyyrssiiss iinn
330M1'ss EEnnvviirroonnmmeennttaall LLaabboorraattoorryy ((mmoorree ddeettaaiillss uunnddeerr MMeeththoodds)s.).
M Meetthhooddss FFiisshh CCoolllleeccttiioonn FFoorrtthhiiss ssttuuddyy,, PPoool 22owwalass ddiivviiddeedd iinnttoo ffoouurrsseeccttiioonnss ((FFiigguurree 22)),, bbaasseedd oonn tthhee pprrooffeessssiioonnaall jjuuddgmgmeentnootff JJooeell tSitirraass,, MMDDNNRR FFiisshheerriieess;; aanndd wweerree aaggrreeeadd ttoo bbyy tthhee rreepprreesseennttaattiivveess ffrroomm MMODHH,, MMPPCCAA,, aanndd 33MM.. DDeessccririppttiioonn ooff tthhee ffoouurr PPooaoll22 SSeecctitioonnss:: SSeeccttiioonn 21::33..66 irivveerrmmilileessffrroomm FFoorrdd DDaamm ttooccoonnfflluueennccee wwiitthh MMiinnnneessoottaa FRiivveerr. SSeeccttiioonn 22::99.:55 irivveerrmmilileessffrroomm ccoonnfflluueennccee wwiitthh MMiinnnneessoottaaRRiviveerrttoo lloowweerrcchhaannnneellttoo HHoogg LLaakkee aanndd PPiigg'ss EEyyee LLaakkee,, bbuutt nnoott iinncclluuddiinngg HHoogg aanndd PPiigg''ss EEvyee llaakkeess;; MMeetrtrooppoolliittaann ((MMeettrroo)) wwaasstteewwaatteerr ttrreeasttmmeenntt ppllaanntt aanndd HHoollmmaann FFiieelldd asiirrppoorrtt aarree iinn tthhiisssseectcitioonn.. SSeeccttiioonn 33::1133.7.7 rriivveerr mmiilleess iinncclluuddee HHoogg LLaakkee aanndd PPiigg'ss EEvyee LLaakkee aass wweellll aass iRvivre,r, BBaallddwwiinn,, MMooooeerrss,, aanndd SSoprriinngg llaakkeess aanndd LLoowweerr GGrreeyy CClloouudd SSlloouugghh.. SSeeccttiioonn a4::44..77 rriivveerr mmiillelss ttoo LLoocckk && DDaamm 2#2 iinn HHaassttiinnggss;; EEaagglleess PPooiinntt wwaasstteewwataeterrttrreeaattmmeenntt ppllaanntt aanndd 33MM CCoottttaaggee GGrroovvee ffaaciiilittyy aarree iinn tthhisi sseecctitioonn.. FFiivvee ttaarrggeett ffiisshh ssppaecciieess wweerree aaggrreeeedd uuppoonn:: Bblluueeggiilll ssuunnffiisshh ((B36GSS)),, ccaarpp ((CC)),, ffrreesshhwwaatteerr ddrruumm ((FFWWDD)),, ssmmaallllmmoouutthh bbaassss ((SSMMIB)),, aanndd wwhhiittee bbaassss ((WWHHEB)).. FFWWDD hhaadd nnoott bbeeeenn ccoolllleecctteedd pprreevviioouussllyy;; ccrreeeel ssuurrvveeyyss aanndd ffiieelldd oobbsseerrvvaattiioonnss bbyy tthhee MMDDNNRR hhaavveesshhoowwnn ffiisshheerrss ccaattcchh aanndd eeaatt FFWD.D.
Mississippi Pool 2 PFCs 2009 + March 2010
Mississippi Pool 2 PFCs 2009 . March 2010
5
Minnesota 34innesoto P Poolllluuttiioonn CCoonnttrrooll AAggeennccyy
22229955..00001100
STATE02010409 STATE_02010409
MONAcolleics tferodm the 33 mile reach of Pool 2in late May 2009. Jol tras, MONR Fisheries, and SMtDevNeRDceloallienc,teMdDfNishRfErcoomlogthiceal33RemsoiluerrceeaschLoonfgP-oToelrm2 iRneslaotuerM ceaMyo2n0i0t9o.riJnogelPSrtoirgarsa, mM,DcoNlRleFctisehdefriieshs,inand tShterevee dDaeyLsaiuns,inMgDeNleRctErcooslhoogcickailngRceasuoiuprcmeesntL.oTnhge-Tfeirsmh cRoelsleocutricoen MloonitcorianwgetPrrieomgoarapmnp,escdoll(eActpepdefinshdAiinlx tFhisrehewedraeyswursaipnpgeedlienctarolsuhmoicnkuinmgfeoiqluaipndmeimnmt.edTihaetfeislhy fcroolzleenc.tioTnheflorcoaztieonnsfiwsherweermealpapbeedle(dAwppeinaduitxniAq)h.ue sFaismhpwleerIeD wberafoprpeedshiinppailungmoinvuermnifgohitl tothe laboratory. and immediately frozen. The frozen fish were labeled with a unique
sample ID before shipping overnight to the laboratory.
W Waatteerr CCoolllleeccttiioonn Water samples were collcted at 12 stations--3 stations per section--corresponding to areaswhere ish W wearteercasuagmhtp.leWsatweerresacmopllleecstedwearte12coslltaectitoendso--n3Jusltayt2io,n2s00p9e.r MsPeCctAiocno-l-lceocrtreedsptohnedeinsgamtoplaerseaas each where fish wsaetrieoncaaungdht3. MWcaotellrescatemdpdleusplwicearteescopllleusctsepdikoensJaumlpyl2e,s2a0t0a9l.l M12PCstAatcioolnlescatsedweltlh.reAellssaammpplleesswaet reeach csotalltieocnteadn3d23gMrabcoslalemcptleedsdjuupslibcealteoswtphlues wspatikeerssaumrfpalecse uastianlgl a12lsartagetiopnoslyaesthwyellel.neAlbl ostatmlepltehsatwweares used tc0o5lplelcittetdheaswgartaebr ssaammpplleess among 3M and PCA bottles. just below the water surface using a large polyethylene bottle that was used
to split the water samples among 3M and MPCA bottles.
Description
Description
ooff
1122
wwaatteerrssaammpelestsatattiioonnss
((FFiigguurree
2)2):
1. Section 1; main channel a iver mile 847
1. Section 1; main channel at river mile 847
2. Section 1; old Minnesota River channel, near river mile 845.4
2. Section 1; old Minnesota River channel, near river mile 845.4
3. Section 1; main channel upstream of confluence with Minnesota River at river mile 844
3. Section 1; main channel upstream of confluence with Minnesota River at river mile 844
4. Section 2; main channel near boat launch at river mile 842
4. Section 2; main channel near boat launch at river mile 842
5. Section 2; main channel adjacent to Holman Feld atrivermile 837
5. Section 2; main channel adjacent to Holman Field at river mile 837
6. SSeeccttiioonn 22;; bbaayy ssoouutthh ooff PPiiggss EeEye LLaakkee nneeaarr rriivveerr mmiillee 883344
6.
7. Section 3; main channel near boat launch and downstream from Ashland Oil refinery at river 7. mSielcetio8n2.35; moraiignincahlalnynienltneenadredbotoatbleaunnecahr 4an9d4dborwidngse,treatamuppfreormenAdsohflaSnedctOiiol nre3f,inbeurty naot fishriver
wmeirlee8c2o9l.l5ec(toerdigiinnathllaytinreteanchd)ed to be near 1494 bridge, at upper end of Section 3, but no fish
were collected in that reach)
8. Section 3; main channel upstreaofm land 112 at river mile 827.5
8. Section 3; main channel upstream of Island 112 at river mile 827.5
5. SSeeccttiioonn 33;; SSpprriinngg LLaakkee,, nneeaarrrriivveerrmm ililee 882211
9.
10. Section 4; main channel, downsotfGrreey Calomud Slough at river mile 819
10. Section 4; main channel, downstream of Grey Cloud Slough at river mile 819
1111..
Section
Section
&;
4;
near
near
shoreline,
shoreline,
downstream
downstream
of
of
31
3M
Cottage
Cottage
Grove
Grove
discharge,
discharge,
near
near
river
river
mile
mile
817.5
817.5
12. Section 4; main channel, upstream of Loc&k Dam #2 at river mile 816.
12. Section 4; main channel, upstream of Lock & Dam #2 at river mile 816
LLaabboorraattoorryy AAnnaallyyssiiss
AXYSAnalytical AXYS Analytical
SSeerrvviicceess
1dLtd
aannaallyyzzeedd
alall
wwaatteerr
aanndd
ffiisshh
ssaammpplleess
ffoorr
PPEFCCss..
EEmmppttyy
ccoooolleerrss
wweerree
sshhiippppeedd
bbyy.
AXYStothe MPCA fo ish samples and coolers with botties were shipped for water samples.Thewhole
AfiXshYSshtoiptpheed MtoPACXAYSfowrefriseh msaemaspulersedanfdorcoleonlegtrsh andwithwbeoigtthlet;s awlesor,egsehnipdepredanfodrawgaetweerrseamrepcleorsd.eTdh.eAXYS whole
fish shipped to AXYS were measured for length and weight; also, gender and age were recorded. AXYS
Mississippi Pool 2 PFCs 2009 + March 2010
A4ississippi Pool 2 PFCs 2009 . March 2010
5
M3i4ninnneessoottoa PPoolllluuttiioonn CCoonnttrrooll AAggeennccyy
22229955..00001111
STATE02010410 STATE_02010410
Homgenized fish filets with scales off and sion, which sth protocol used for fish contaminant ahnoamlyosgisenwihzeednfrisehsuflitllsetasrewuitshedscfaorlesiohffcaonndsusmkipntioonn, wachvicshoriisetsh.e protocol used for fish contaminant
analysis when results are used for fish consumption advisories.
The USEPA as not yet approved an analytical method for PEC; however, al laboratories conducting TPFhCeaUnaSlEyPsAishaosn environmental samples use a method of quid h not yet approved an analytical method for PFCs; rhoomwaetvoegrr,aphy-eictrosp all laboratoriesray tandem conducting mass spectr PFC analysis oomneternyvi(rLoCn/mMSe/nMtSa)l.saSmapmlpesleusheomaogmeentihzoadtioofn,liqeuxitdracchtiroonm,aatnodgrcalpehayn--eulpecsttreopsspcraayn varytandem ammaossngspaebcotrraotmoreitreys(LACX/YMSSd/eMscSr)i.bSeasmthpeleir method a5, AXYS homogenization, Method MLA 060: Analytical Proc extraction, and clean-up steps canevdaurrye for tahmeAonnaglylasbisoroaftoPreieuso.rAiXnYaStdeedsOcrrgibaensitcheCiormmpoeuthnoddsians,AqueousSamples by LCMSIVS AXYS Method MLA-060: Analytica! Procedure]~or
the Analysis o]~ Perfluorinated Organic Compounds in Aqueous 5emples by L C-MSIMS.
The reporting eve is thelimitof quantitation (OQ) defined a the lowest non-zero calfration standard TRahveirnegpaocrctuinrgaclyeovfel 100 430%. is the limit of quantitation (LOQ), defined as the lowest non-zero calibration standard
having accuracy of 100 _+30%.
QIQnuauadaldiilitttiyyonAAtsossstuuherrmaaunnlctcieeple level quay assurance protocol at XYS Wiliam Scruton, Quality Assurance Coordinator for MPCA' En In addition to the multiple vironmental level quality Ansys and Outcomes Divison, reviewed ll assurance protocol at AXYS, William Scruton, Od,autaalitpyacAksasguersanfcreom ANS and dtd any Coordinator for MPCA's rEensuvlirtosnnmeeednitnagl AtnoablyesqisuaalnifdieOduat5c.oameesstDiimvaistieoni, ll QArequirementswere n reviewed all data packages otfrom metAXYS and identified any results needing to be qualified as an estimate if all O,A requirements were not
met.
Samples wresplit fr sh and water with 3M to verify AXYS laboratory result. i ish of each of the fSiavme fpilsehsswpeecrieesspwleitrfoerrfaisnhdoamnldywsaelteecrtwedithbe3fMoretobevienrgifyanAaXYlSyzlaebfoorraPtoECrys and homogenates from those results. Six fish of each of the ffiivseh were shipped back to MPCA and delivered tothe fish species were randomly selected before being3aMnaElynzveidrofonmrePnFtCaslaLnadbohraotmoroyg.enAastemsentioned from those faisbhovwe,erweatsehripspaemdplbeasckwteoreMcoPlClAecatnedd at the same delivered to tihmee3Mby MPCAand 3M Environmental aLtablolr1a2tosryta.tAiosnsm. eTnhtieonreesdults from 3 above, are watergsiavmenplienstwhee3reMcoEnllevicrteodnmaetntthael sLaambeeratitmoerybFyinMalPCAnAalayntidca3lMReaptoarltl s12Nos.tati0o9n-s0.3T6h5e(rseusrufaltcse fwraotmer3)ManadreNog.ive0n8.in0t3h7e2 (fish filet homogenates). 3M Environmental Laboratory Final Analytical Reports No. E09-0365 (surface
water) and No. E09-0372 (fish fillet homogenates).
RReessuullttss aanndd DDiissccuussssiioonn
SuSSruufrarfcfaaewccaeetW Wearatsteaemrrples were callcied on 2 ly 2009 frothm 12 water samplestationsslected for
Pool 2 Surface the Wisisppi iver. Addition! water samples were collected on 2inJfuolyrm2a0t0i9onfrcoomlcttheed1t2owcahtaerrscstaemipzleeeach ie stations included selected for
Pool 2 of the Mississippi River. Additional information collected to characterize each
rteemmapienriantguwriethiisns2l4v-e2d6 Coxyrgaenng,edtehprtohu,gahnodutcoPndouct2.ivDiitsys(oTlavbeldeo1x).ygTeenmpderroaptpuerdefwraosm temperature, dissolved oxygen, depth, and conductivity (Table 1). Temperature was
r9rsee.itl2leaatmtiiinvvceLellluyydaccetoodnSnststattaainnottn,,
1107.3 me/Lat Staion remaining within 24-26 1C2. Water depths ra range throushoutnPgoeodl from 1.2m 106.7 m. 2. Dissolved oxygen dSrpoepcipfeidc cfroonm duc9t.i2vimtyg/iLncarteasedStation
afI ttoe7t.h3eraMgi/s/aitsSptpaticoonnf1l2u. eWncaetewridthetphthesMriannngeesdotfraomive1r.2, bmettowe6e.7n Stati3oannsd 4 (382 5/em 10 536 m. Specific conductivity increased
after the Mississippi confluence with the Minnesota River, between Stations
freemami)nedansdtaibnlceroearsetdhselriegshttoyfaPgaoiin 2. tween Stations 5 an(5d25 S/cm to l~S/cm), and increased slightly again between Stations 5 and 6 (525 l~S/cm to
S80 u/cbu)tth,en 3 and 4 (382 I~S/cm to
580 l~S/cm), but then
536
remained stable for the rest of Pool 2.
CiCnoonTncaceebnnltt2rer.aattSioianomnsplffooerrsaaalrl ePPFFiCdCenaatnniaaflliyyettdeebssyiinnSeeecaatccihhontrrsiitppaliitcciaaottneersseaaplmmippclaleeteff.rroPommOttShhceeon11c22ewwnatatrteeartrissoaanmmsppllee rssettapaottiriotonnissngarereevggeiilvveenn arinlTiasbtleed2i.nStahmepsleescoanred toast co identifiedlbuymSneacntdioanv-sertaatgioens-orerpleicxacthe.saPtFiOoSn re sted nthe concentrations ofrinraelpcoorltiunmgn.levWehlsen
are listed in the second to last column and averages for each station are listed in the final column. When
Wisissippi Pool 2 PFCs 2009 + March 2010 Mississippi Pool 2 PFCs 2009 . March 2010 0.-I0-
Minnesota pollution Control Agency
~it~nesot~ Pollution Control Agency
22229955..00001122
STATE 02010411 STATE_02010411
tthhee ccoonncceennttrraattiioonn wwaass bbeellooww tthhee rreeppoorrttiinngg lliimmiitt,, 4 tthhee rreeppoorrttiinngg lleevveell wwaass uusseedd ttoo ccaallccuullaattee ddeessccrriippttiivvee ssttaattiissttiiccs..
VVaarriiaabbiiltityy,, aass iinnddiiccaatteedd bbyycoceofeffificcieennttooffvvaaririaattiioonn ((CCVVS%6)) aammoonngg ttrriippllicicaattee wwaatteerr ssaammpplleess wwaass bbeellooww 1100%% ffoorr PPFFOOSS aatt aallll ssttaattiioonnsseexxcceepptt sttaattiioonn 1122,, wwhhiicchh hhaadd aa CCVV%S ooff 2266%%.. TThhee aavveerraaggeeCCVV3%ffoorr PPFFOOSS aatt tthhee ffiivvee stsatattiioonnsswwhheerree PPFFOOSS wwaass ddeetetcteabclewtwaaassb99.l.00%e%..TThheeCCVV3%5 ffoorr PPFFBBAA,, ddeettecetacbtleaabattlaalelll 1122 ssttaattiioonnss,, wwaass. 113..22%%.
AA ccoommppaarriissoonn ooff PPRFOOSSccoonncceennttrraattioionns ffrroommAAXXYYSSaanndd 33MM sshhooww ggoooodd aaggrreeeemmeenntt ((Fiigguurree 33).). RReessuullttss ooff PROS inwaterfrom 3M Environmental Laboratory were generally higher than from AXYS for the same. sPaFtOiSonin water from 3M Environmental Laboratory were generally higher than from AXYS for the same
station.
MMoosstt ooff tthhee ootthheerr PPFFCCss wweerree lesless tthhaann tthhee rreeppoorrttiinngg lev, level, latlthhoouugghh nniinnee ooff tthhee 1133 aannaallyytteess wweerree
ddeetteecctteedd iinn ssttaattiioonnss 1111 aanndd 1122.. TThhee hhiigghheesstt ccoonncceennttrraattiioonnss ofalof all ddeetteecctteedd aannaallyytteess wweerree iinn ssatattiioonn 1111..
PHBAwas the onlyoneof the 13 measured PECs that was measured in detectable concentrations at all
wPaFtBeArwstaastitohnes.onPlFyOoAnweaosf tdheete1c3temdeaatstuarteidoPnsFC6s:t1h2aatnwdaPsFmHxeAaswuaresddinedetteectaactbsltteacteioondncse7n-t1r2a.tioPnFsOSatwaalls
wdeatteecrtasbtalteioinnss.tPatFiOonAsw6a7s,8de,te11c,teadndat1s2.tatTiohnesa6v-e:1r2agaenPdFPOFSHcxoAnwcaesntdreatetcitaoentd saattsitaotnio1n1s.w7a-s12$.0PnFgO/LS.wTahse.
ndeexttechtiagbhleestinPsRtOaStiocnosnc6e,n7t,r8a,ti1o1n, awnads 1512. nThegaatve/SrtaagtLeioPnF1O2.S Tchoenctehnetrrattiohrneeatsstatatitioonns w1i1twhadset9e0ctnagb/lLe The
PnFeOxSt (h6ig,h7e,sat nPdFO8)ShcaodnPcFeOnStraavtieornawgeass o1f5 7.n, g1/L0a3t,Staantidon8.152n.gT/hL,e roetshpeecrttihvreelye. The high FOS. stations with detectable
cPoFnOcSen(t6r, a7t, iaonndat8)sthaatdioPnF1O1Swaavseraabgoeustoefq7u.a7l, 1t0o.t3h,eancodn8c.e5ntrriga/tLi,ornesopfePcFtiOvAely(.94Thneg/hL)igahnPdFoOnSe-half the.
concentration concentration
concentration
ofat
of
PFBAat that station (168 ng/L). station 11 was about equal to the
PFBA at that station (168 rig/L).
concentration
of
PFOA
(94
ng/L)
and
one-half
the
TThhee MMPPCCAA hhaass eessttaabblliisshheeddsistitee-ssppeecicfifiicc wwaatteerr qquuaallittyy ccrriitteerriiaa ffoorr PPFFOOSSaannddPPFFOOAA iinn PPooooll 22 (ht:oro pea state mn us/leanup)pleindex. ham) nd for PFAstatewide,The PFOS criterias 7 g(h/Ltt.p:T//hwew2w0.0p9cwaa.tstearteq.umalni.tuyst/calteiaonnuapv/eprfcag/iensdeexxc.hetemdl)thoisndcrifetePriPaFaBtAstsattaiteonws6ide7 . T8h,e1P1,FOaSndcr1it2e.riNaoirse7of tnhge/Ls.tTathieon2s00e9xcweaedteerdqtuhaeliPtyFOsAtactirointeraivaeorafg2es uegx/cLee(d2,th70is0 cnrgi/teL)riaoratthsetaPtiFoBnAs c6r,it7e,ri8a, o1f1,1amngd/L1.2. None of
the stations exceeded the PFOA criteria of 2.7 #g/L (2,700 ng/L) or the PFBA criteria of I mg/L
FFiisshh
QFQiuusahalwliiettyryeAAscsossluulrercaatnnecdceeon 28-29May2009 and 1June 2009, throughout the lengthofPool 2 (Tabl3)e. The
tFaisrhgewt efroer ecaocllhecsteecdtioonn 2of8-1259 iMndaiyvi2d0ua0l9s apnedr t2aJrugnete s2p0e0c9ie, sthwraosugahchoiuetvtehdefloernaglthseocftPioonosl e2x(cTeapbtlefo3r). The
bluegil in target for
bluegill in
Section 1,where 12 individuals were collected.Despite some of the each section of 15 individuals per target species was achieved for all
Section 1, where 12 individuals were collected. Despite some of the
bluegils sections
bluegills
being extremely except for
being extremely
ssmmalalll,, tthheeyy wweerree aannaallyyzzeedd iinnddiivviidduuaallllyy rraatthheerr tthhaann ccoommpopsoistiteedd..
The interfab comparison of PFOS concentrations inthe 30 fish homogenates show good agreement (FTihgeuirnetea)r.-laIbn ccoomnptarritsaoontshotf PiFnOeSr-caobncceomnptraartiiosnosn ifnorthPeF3O0S in wfish ahtoemr,otgheenaretesusltsshoofwPgFoOoSdnagirsehefmreonmt 314 E(Fnivgiurroen4m)e.nItnacloLnatbraosrat ttoortyheweirnetegr-elnaebraclolmy plaowriesrotnhafonr fPrFoOmS AinXYwSatfeor,tthheesraemsueltfsisho.f PFOS in fish from 3M
Environmental Laboratory were generally lower than from AXYS for the same fish.
`SSppaattiiaall DDiissttrriibbuuttiioonn ooff PPFFOOSS bbyy SSppeecciieess
The distribouftPiRoOnS concentrations ae shown in series of box-whisker plots. Individual
concentrations for The distribution of
concentrations for
each fish are shown a circles. The PFOS concentrations are shown in
each fish are shown as circles. The
bos is boundedbyhorizontal a series of box-whisker plots.
box is bounded by horizontal
sides representing Individual
sides representing
the 25 and 75thpercentiles--the boundariesofthe interquartile range (IQ)--with the median line
the 25th and 75 percentiles--the boundaries of the interquartile range (IQR)--with the median line
Mississippi Pool 2 PFCs 2009 + March 2010
A4ississippi Pool 2 PFCs 2009 . March 2010
"e -11-
M3i4ninnneessoottoa PPoolllluuttiioonn CCoonnttrrooll AAggeennccyy
22229955..00001133
STATE02010412 STATE_02010412
((5500th ppeerrcceenntitillee)) wwiitthhiinn tthhee bboosx.. IInn ootthheerr wwoorrddss,, tthhee bboorx sshhoowwss tthhee arannggee ooff tthhee cceennttrraall S500%%ooff tthhee vvaalluueess.. TThhee wwhhiisskkeerrss sshowhtthheeosspprrweeaadd ooffvvaalluueess tthhaatt aarree wwiitthhiinn 11.5.5xx QIQRRaabboovveeaanndd bbeellooww tthhee aaccttuuaall 10.IO,R. VVaalluueess bbeeyyoonndd tthhee wwhhiisskkeerrss aarree ccoonnssiiddeerreedd oouutltliieerrss.. CCoonncceentnrtraattiioonn iisggiivveennoonnaa lloogg-ssccaallee ttoo iimmpprroovvee tthhee ssyymmmmeettrryy oonn eeiitthheerr isiddeeooff tthhee mmeeddiiaann ((ii.ee..,ttoo bbeetttteerr aapppprrooxxiimmaattee aannoorrmmaallddisistrtriibbuuttiioonn))..
A ccoommppaarriissoonn ooffffisishh ssppeecciieess wwiitthhiinn eeaacchh SSeeccttiioonn aanndd aallll SSeeccttiioonnss ccoommbbiinneeddsshhoowwsstthhee PPFFOOSS.
concentrations were generally below 100 ng/g (ppb) in Sectio1ns,2, an3 (igure 5. Section 4, in
ccoonntcraesntt,rahtaiodnshiwgheerrePgFeOnSercaolnlycebnetlroawti1o0n0s innga/gl (spppebci)einsexSceectpiotnwshi1t, e2,baansds 3(W(HFEi)g.ureFr5e).shSweacttieornd4r,uinm
(FWD) had the highest PFOS concentration in a contrast, had higher PFOS concentrations in all
(FWD) had the highest PFOS concentration in a
single fish fillet (3580 ng/g). The species except white bass (WHB).
single fish fillet (3,580 ng/g). The
PFOS concentrations Freshwater drum
PFOS concentrations
iinn
WWHHBB rreemmaaiinneedd sabboouutt tthhee ssaammee iinn lalll irivveerr sseeccttiioonnss,, iinn ccoonnttrraasstt ttoo tthhee ootthheerr ssppeecciieess;; wwhheenn aallll sseeccttiioonnss
wweerree ccoommbbiinneedd,, WWHHBB hhaadd tthhee hhiigghheesstt ssppeecciieess--ssppeecicfifiicc PPFFOOSSmmeeddiiaann ((7755 nngg//gg)).
CCoommbbiinniinngg tthheeddaattaa rfroommaalll ffoouurr SSeectciotnsioofofPPonoosoll 22,, ccaarrpp hhaadd tthhee lloowweesstt aarriitthhmmeettiicc mmeeaann PPFFOOSS ccoonncceenntrtraattiioonn,, 7777 nngg//gg, ((TTaabbllee 44)),, aanndd FFWWDD hhaadd tthhee hhiigghheesstt ssppeecciieess--mmeeaann,, 222299 nneg//gg,. TThhee ootthheerr tthhrreeee ssppeecciieess hhaadd ssiimmiillaarr aavveerraaggeess ((aapppprrooxxiimmaatteellyy 110000 nngg//gg)).. FFiisshh ccoonnssuummppttiioonn aaddvviicceeiss aassssiiggnneedd ttoo eeaacchh ssppeecciieess bbaasseedd oonn tthhee ssppeecclieess--aarritthhmmeettiiccmmeeaann PPFFOOSSccoonncecnetnrtarattiioonn ffrroomm aalll sseeccttiioonnss ooff PPooooll 22.. MMDDHH rreecocmommemnedsnttdhhaastt ccoonnssuummppttiioonnooffffiissh ffiillleettss wwiitthh PPFFOOSS ccoonncceennttrraattiioonnss iinn tthhee rraannggee 4400--220000 nngg//gg bbee lliimmiitteedd ttoo oonnee mmeesall ppeerr wweeeekk.. FFoorrffiisshh ffiilllelettss wwiitthh PPFFOOSS ccoonncceennttrraattioinons iinn tthhee rraannggee 220000--880000 nngg//gg,, tthhee aaddvviicceeiissoonnee mmeeaall ppeerr mmoonnthth.. MMDDHHadavdivsiseessnnoott ttoo aeatt ffiisshh ssppeecciieess tthhaatt eexxcceeeedd PPFFOOSS ccoonncceennttrraatitoinosonosff 880000 nngg//gg.. MMODHH ccaallccuullaatteess mmeeaall aaddvviiccee uussiinngg mmuultltiippllee yyeeaarrss ooff ddaattaa,, ddeeppeennddiinngg oonn tthheetteemmppoorraall ttrreennddss iinn tthhee ccoonnttaammininanatn.t. FFWWDD aarriitthhmmeettiicc mmeeaann ddooeess nnoott cchhaannggeebbeeccaauussee tthheeyy wweerree oonnllyy ccoolllleecctteedd iinn 22000099.. TThheerreeffoorree,, FFWWDD wwiilll hhaavvee tthhee mmoorree rreessttrriiccttiivvee aaddsviiccee ooff oonnee mmeeaall ppeerr mmoonntthh aanndd tthhee ootthheerr ssppeecicesiefaalsll wwiitthhiinn tthhee oonnee mmeeaallppeerrwweeeekk aaddvviissoorryy..
GGooiinngg ffrroomm SSeeccttiioonn 1IttooSSeeccttiioonn 44,, ccuummuulalattiivvee ddiissttrriibbuuttiioonnss ooff PPFOSFbbyysOsppeecSciieess sshohwaaocclleewaarr sshhiifftt ffrroomm olowwererttoo hhiigghheerr ccoonncceennttrraattiioonnss iinn ffoouurroofftthhee ffiivvee ssppeecciieess,, wwhheerreeaass iinn wwhhiittee bbaassss ((WWHHEB)) FPFOOSS ddiissttrriibbuuttiioonnss rreemmaaiinn rreellaattiivveellyy ccoonnssttaanntt F(Fiigguurree 66).). AAllsoo,, tthhee rranagensoogff PePFFOOsSS ccoonncceennttrraattiioonnss aarree nnaarrrrooww iinn HWHBB ccoommppaarreedd ttoo tthhee tohtheerr ssppeecciieess.. TThhee mmoovveemmeenntt ooff FPFCCss tthhrroouugghh ffoooodd wweebbss iis nnoott uunnddeerrssttoooodd.. OOnnee ppoossisbibllee eexxppllaannaattiioonn ccoonnssiisstteenntt wwiitthh tthheessee rreessuullttss iiss tthhaatt aalll tthhee ffiisshh ssppeecciieess,, eexxcceepptt WWHHBB hhaavvee lliimmiitteedd hhoommee rraannggeess.. W Whhiittee bbaasss hhaavvee bbeeeenn ddooccuummeenntteedd ttoo ttrraavveell lloonngg ddiissttaanncceess:: 4400 mmiilleess nin tthhee MMiissssoouurrii RRiivveerr aanndd tthhrroouugghhoouutt tthhee eennttiirreeLLaakkeeErEiriee bbaassiinn ((MMoorrggaann aanndd HHaarrrreell,, 22000066).). HHoommee rraannggeess iinn bugil bluegill ssuunnffiisshh hhaavvee bbeeeenn rreepoprtoedraatttoeonnldlyy 3300 ssqquuaarree mmeetteerrss ((PPaarrrr,, 22000022)),, aalltthhoouugghh aassttuuddyy iinn MMiinnnneessoottaa llaakkeess ffoouunndd ssoommee bblluueeggiilll aanndd bbllaacckk ccrraappppiieess mmoovvee aammoonngg ccoonnnneecctteedd llaakkeess ((PPaarrssoonnss aanndd RReeeedd,, 22000055).). TThheerree iiss ssoommee eevviiddeenncceeiinnddiiccaattiinngg tthhee mmajaojoririttyy ooff ccoommmmoonn ccaarrpp rreemmaaiinn wwiitthhiinn 110000 mmeetteerrssoofftthhierir nneessttiinngg aarreeaa aalltthhoouugghh ssoommee mmaayy ttrraavveell lloonngg ddiissttaanncceess J(JonoesaannnddSetSutausratr,t, 22000088).).
`Temporal
Temporal
Distribution
Distribution
ooff
PPFFOOSS
CCoonncceenntrtraattiioonnss
FFiisshh wweerree ccoolllleecctteedd ffoorr PPFCCss iinn 22000044,, 22000055,, 22000066,, 22000088,, aanndd 22000099,. OOlnylytthhreaeffiisshh wweerree ccaolllaecctteedd iinn 22000014
((TTaabbllee 55).). MMaorree ffiisshh wweerree ccoollleecctteedd iinn ssuubbsseeqquueenntt yyeeaarrss,, aalltthhoouugghh tthhee ttoottaall ppeerr ssppeecciieess rreemmaaiinneedd llooww
ntiuntil tthhee ssaammppllee ccoolllleeccttiioonn iinn 22000099.. BBeeccaausuesooeff tthhee llooww nnuummbbeerrsswwitithhiinn mmoosstt yyeeaarrss,, aasssseessssiinngg tteemmppoorraall
trendsisdificult. A plot ofthe concentration distributions by species for each year suggests a
downward trend trends is difficult.
downward trend
iAn
in
PFOS concentrations, especialy in smallmouthbass (Figure 7). plot of the concentration distributions by species for each year
PFOS concentrations, especially in smallmouth bass (Figure 7).
However, suggests
However,
paprriioorrttoo
Mississippi Pool 2 PFCs 2009 + March 2010
Mississippi Pool 2 PFCs 2009 . March 2010
"- -12-
Minnesota Pollution Control Agency
Minnesota Pollution Control Agency
22229955..00001144
STSATATTEE0_200210100441133
S2200e0099ctthth4eeififirossohhnmwwee2r0ree09ccoodllolleeecsctteenddotoonsnllhyy oiinnwaSSeenccotttiioiocnne4a4;b;lrreee:-dpploloowttmtiiwnnaggrttdhheetraaennnnnduuaialnltddhieisPtsrFibtOuSrtiocionbnscbuebyntystipsrpeaoectciinioeesnssww(iFittihhguoornnell8yy).
appearsadaitional Section 4 from 2009
It appears additional
years are needed tomake a does not show a noticeable
years are needed to make a
properassessment downward trend in
proper assessment
of temporal treonfPdFOsS in ish the PFOS concentrations (Figure 8).
of temporal trends of Pros in fish
from pool 2
from Pool 2.
PRRFeeOllaSattciiooonnncssehhniitppraootfifoPPnFFsOaOSSmolleenvveellfssemttaooleffsiis,shhmggaeleennsdd,eerar,,naaggjueev,,enaainnledds
size: didsize
not
sahnotoiceawble
difference
(Figure
9), except blveilavenies were lower than PFOS concentrations among females, males,
9), except bluegill juveniles were lower than
aduls, There and juveniles
adults. There
wasdid
was
also not much difference among not show a noticeable difference
also not much difference among
age(Figure
age
lasses within ach species (igre 10], Th twohighest FOS concentrations inthe freshwater drum
werein classes 3 yearod within each an8yedar old species (Figure f1i0sh).. TThheestewroeshuilgthseisntdPicFaOtSe PFOSdoesnot concentrations biniothacecfuremuslhawtaetewirtdhruamge as
itwedroeesinian m3oysetarbiooldacacnudmu8layteiavreocldomfipsho.uTndhess,esurecshualtssmercury indicate aPnFdOSPCdBose.sAnnootthbeioraoccbumsuelartevwairthotmatigheoeasnse
concentration distributionsby age class s the wide range within age classes in most species, especially it does in most bioaccumulative compounds, such as mercury and PCBs. Another observation from these
concentration distributions by age class is the wide range within age classes in most species, especially
the freshwater drum, whereas the white bas shows very le range inconcentrationsamong and
twhiethfirnesahgwe aclteasrsdesru. m, whereas the white bass shows very little range in concentrations among and
within age classes.
AAilssoa,,ntdthhe1e2rr)ee.wwaassnnoo rreellaattiioonnsshhiipp bbeettwweeeenn PPFFOOSScocnocnecnetnrtarattiioonnss aanndd ffiisshh lleennggtthh oorrppeercrceenntt pid lipids ((FFiigguurreess
11 and 12).
BBiiooaaccccuummuullaattiioonn FFaaccttoorrss aanndd WWaatteerr QQuuaalliittyy CCrriitteerriiaa
Bioaccumulation factors (8AFs)for FOSwere calculated for each specie, i each section. Water
cBoinocaecncturmatuiloantisonfrfoamctothrs t(hBrAeres)sftoatriPonrsowsitwheirneecaaclhcuselactteidonfowreeraechavsepreacgieeds., inIenachdsiecfvtiisohin.fidW leutaPtearOlS
ccoonncceennttrraattiioonnss wfreorme tdheitvhriebedytsethadetioanvsewraitgheinPFeOaSchcosneccetniotrnatwieonre. Th individual BAFs averaged. Individual were then fish fillet PFOS
combine 3. geometric man concentrations were divided by (theeomaveearna)gefoPrFcOaSchcosnpceecniter.at(ioAng.eoTmheetirnidcivmideuaanl BisAtFhs waenrieothgeonfthe
acvoemrbaigneedofalsoga:tgreaonmsfeotrrimcemdevaanlu(gee.om Theeafni)naflorBAeFacih 2 geomean species. (A goefoaml esptreiccim esegaenomisetahnes.anthiliosgcoalfcthuleation
had been done in previcus years, usinag much smaller dataset average of log-transformed values.) ,he final BAI- is a geomean
had been done in previous years, using a much smaller dataset
(STS Consultants, 2007). of all species geomeans.
(STS Consultants, 2007).
TheThis
The
resulting calculation
resulting
water quality criteria basoneidsh consumption refered to as fish consumption criteria, CCwere 6
ng/L for Pool3 and 4 water quality criteria nbga/sLedfoornPofioslh 2c. oTnhseum20p0ti9osntuIrdeyfehraresdaltoloawsedfisfhoraconrsabuumstptrioencaclcriutleartiai,onfCoCf,twheerBeA6Fs
anngd//wfaotreProqoula3liatnydcr4itnergi/oLn.for Pool 2. The 2009 study has allowed for a robust recalculation of the BAFs
and water quality criterion.
PFOS
PFOS
water
water
concentrations
concentrations
iinnthe
upper the upper
33SSeecctiotnsioofofPnPooosoll
22 wweerree
pprreeddoommininaatteellyy
lleessss
tthhaann
tthhee
rreeppoorrttiinngg
level Le, Love of Quantitation, LOGY. For water concentrations below the rearting eve, one-half the
wrlreeeevppreooelrrt(tliii.nlengg.a,bllLeoeevvvveeelel ltwwohaaefssOruu,eusspeaeodndr.tt.iitAAantgBBioAeAnFr,vwwLaaOtessQoacc)l.aavllFocc,oiuurdllawathetadeteaffroovcrrtooononinluclyyesnSneSetcernatcoittniiooo-nnndse,4tb,eewwclhthoaeewbrrleetehPPecForrnOoecSsepnwwotararttaitneetgrirocclneoosvn.necTcle,ehnonetnsrtraepate-tihicooainnlefsssth.e
wspeecriefiacll BAFs ranged from 2,519 IK above the reporting level, to afovrocidarhpatvoin7g,t0o10usKe anofno-rdferteeschtawbatleercodnrucem.ntTrahteiogneso.mTehteriscpemceieasn- of
aslpescpieficcieBsAirns Sraencgteido4nfr1om3,28,75719KgL/.K~Tfhoer gcaeorpmetotr7i,c01m0eaLn/Kogfaflolrsfrpeecsihewsafterormdraulm l S.eTchtieognseoism7e,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.
TheseBAFscan be applied tothe equation or calculating aish consumption rterion (IC). The TeqheusaetiBoAnFss can be applied to the equation for calculating a fish consumption criterion (fCC). The
equation is
ED BW +E Cwhe=re,STEN BAF
where,
Mississippi Pool 2 PFCs 2009 + March 2010
A4ississippi Pool 2 PFCs 2009 . kiarch 2010
ae
-13-
Minnesota 34innesota Pollution Pollution Control Control Asency Aylency
22229955..00001155
STATE 02010414 STATE_02010414
RRIfDD ==rereffeerreennccee ddoossee,, 00..0000000088 mmgg//kkgg//dd BBWW == bbooddyy wweeiigghhtt,, 1700kk.g KK==eexxppoossuurreeffrraaccttiioonnaattrtiribbuutteedd ttoowwaatteerraanndd ffiisshh ccoonnssuummptpitioonn,, 00..22 1WIW == iinncciiddeennttaall iinnggeessttiioonn ooff wwaatteerr,, 00..0011 LL//dd RCR== ffiisshh ccoonnssuummppttiioonn rraattee,, 00..003300 kKgg//dd
A`Appppllyyiinngg tthhee BBAAFF ffrroomm 22000099,, tthhee rreessuullttiinngg CCfCC sis 77 nngg//LL uussiinngg aallll PPooooll 22 ish.fish.
CCoommpparariissoonn ttoo OOtthheerr LLooccaattiioonnss (OOnnee mmiigghhtt rreeaassoonnaabbllyy aassssuummee tthhaatt bbaacckkggrroouunndd ccoonncceennttrraattiioonnss aarree zzeerroo bbeeccaauussee PPFOFSiissOssttrriiSccttllyy aann anthropogenic compound; however, PFOS has been found in widife, including fis, throughout the waonrthlrdo(pGoigeesyniacncdoKmapnonuannd2;0h0o1;weHvoeurd, ePFeOtaS h2a0s06b]e.enPEfoCsunardeginlowbialdllliyfed,iisntcrliubduitnegd andfish, tthheroluegvehlosuitncthreease. wwiotrhldpr(Gosieimsiytayntdo Kurabnanannar2e0a01H;oHuoduedeeteatl.al 2200060)6.). PFCs are globally distributed and the levels increase
with proximity to urban area (Houde et al., 2006).
AAccoommpapriasornoioffwswhhooolnlee ffiisshh ccoommppoossiitteess ((oonnee ssmmaallll ffiisshh aanndd oonnee llaarrggee ffiisshh ccoommppoossiittee ppeerr ssiittee)ffrroomm3300 istiteess wwiitthhiinn tthhee MMiissssoouuriri,, OOhhiioo,, aanndd MMiissssiisssiippppii RRiivveerrss ffoouunnddmmedeidainanPPFFOOSS ccoonncceennttrraattiioonnss ooff 224.42.2ngn/gg/g,, 3311.88 nngg//gg., aanndd 553.38.8nngg/g, rreessppeeccttiivveellyy ((YYee tetaall.,, 22000088a)a.). AAlltthhoouugghhtthhee MMiissssiissssiippppii hhaass tthhee hhiigghheerr PPFFOOSS. lleevveell, tthhee tteenn fiisshh ssaammpplleess aabboovvee220000 nngg//gg PPFFOOSS wweerree ddiissttrriibbuutteedd tthhrroouugghhoouutt tthhee tthhrreeee rriivveerrss,, iinnddiiccaattiinngg tthhee PPFFOOSS ccoonnttaammiinnaattiioonn iiss wwiiddeesspprreeaadd..
AAnnEEPPAA sstutdyouoffdPPFFyCCss iinn ccaarrpp ccoolllleecctteedd iinn 22000066 ffrroomm tthhee UUppppeerr MMiissssiissssiipppii RRiivveerr,, rreeppoorrtteedd mmeeddiaiann. ccoonncceennttrraattiioonnss ooff PPFFOOSS rraannggiinngg frroomm88 nngg//gg uuppssttrreeaamm ooff SStt.. CClloouudd ttoo 2266 nngl~//gg aanndd 4400 nngg/g/aagt PPiigg''ss EEvyee LLaakkee aanndd ddoowwnnssttrreeaamm aatt SSpprriinngg LLaakkee ((YYeee ettal.l.,, 22000088bb)) ((TTaabbllee 66)).. TThheellaatttteerrttwwoo ssiitteess aarree iinn SSeectciotn2i2 oaannndd SSeecctiotni33ooonff PPooooll 22,, rreessppeectcitivveelyly.. NNoo ccaarrppwweerreeccoolllelcteedcbbtyytethhdee MMDNDRoorrNMMPPCCRAAiinn 22000066 ffrroomm tthhee Mississippi River. Median concentrations of PFOS incarp from our 2009studywere 28 ng/g forallof PMoioslsi2s,si1p3pinReivferf.orMSeedctiainonco2 nacnedn8tr7atniongs foofrPSFeOcStiino4cnarp from our 2009 study were 28 ng/g for all of
Pool 2, 13 ng/g for Section 2 and 87 ng/g for Section 4.
PROS
PFOS
levelinwhole,
levels in whole,
four
four
year-old
year-old
llaakkee
ttrroouutt
ccoolllaecctteedd
ffrroomm
tthhee
GGrreesatt
LLaakkeess
iinn
22000011
((FFuurrdduui
eett
a,al.,
22000077))
were
were
lowest
lowest
in
in
Lake
Lake
Superior
Superior
((44..88nnggf/gg))
aanndd
hhiigghheesstt
iinn
LLaakkee EErriee
((112211.
nngg//gg).).
IInn
sa espeapraarattee
ssttuuddyy
ooff
PPEFCCss
in the Lake Ontario food web, mean PFOS concentration in slimy sculpin was 450 ng/g, while whole lake:
tinrothutewLearkee 1O7n0tanrgio/gfo(oMd awerbet, miaeln,an20P0F4O)S Lcooknecternoturtateioatnsinleswliimfey(s9c0u%l)piannwdassm4el5t0 7n-g8ig5,),;wshciulelpwinheoalet lake
mys trout waendreDi1p7o0reniga./gB(eMcaaurtsine tehteals.,cu2l0p0i4n)d.iLeatkies btreonutht iecatbaasleewdifreat(h9e0r%t)haanndpeslmageilct,(7th-8e%a)u;tshcourlspisnugegaetsted
thmeyssiesdainmdeDntipwoaresiath.eBepcraiumsaerythseousrccuelpoinf PFO. diet is bTheentrheiscu-lbtassoefdtrhaeth2e0r09thaPonolpe2lasgicu, thpetahpuestheoodrisrmesnuttg.gested
tshoeursceedhimypeonthtewsaiss,thbeecparuim seatryhesohuigrcheesotfPPFFOOSSc.onTcheenrtersautlitsonosf twheere20n09frPeosohlw2atseurpdprourmt ,thwehsiechdimi eant-
bsooutrtcoemhfyepeodethr.esTish,eybemcaavuseertohcekshaignhdesst PuFObS sctotonfclreunsatrhattthioeenis pwreeyre, winhifrcehshawreapterirmdarruilmy,awquhaictihc iis nasects,
sbmoatltolmfisfhe,eadnecr.mTolhleuyskms.ovTeheroycakrseaknndoswunbsfotrraeteattiongfluzsehbrtahemuirssperelys, (wShuiscshaanrde Harrel, 2006). primarily aquatic insects,
small fish, and mollusks. They are known for eating zebra mussels (Sluss and Harrel, 2006).
RReeppoorrtteedd BBAAFFs ffoorr PPFFO0SS hhaavveevavaririeedd ggrreeaatltlyy ffrroommssttuuddyy ttoo ssttuuddyy aanndd aammoonnggspsepceiceiesswwitithhiinn ssttuuddiieess.. IInn
tthhee LLaakkee OOnnttaarriioo ffooocdd wweebb BBAAFFss rraannggeedd ffrroomm 89,,880000 LL//KKgg ffoorr aalleewwiffee ttoo 55,,000000 ffoorr ssccuullppiinn;; llaakkee ttrroouutt BBAAF
was 16,000 (Houde et al, 2008). Inacomparison of year old lak trout among the Great Lakes, the
wBAaFs r1a6n,0g0e0d (fHrooumd5e,0e0t0a0l., 22000,800).0InKagco(mFupradriisoetn aol,f 240-y07e)a;r tohldislsatkuedtyroruet pamoornagtatehkedeGtrreouatt BLAaFkeosf, th50e00
U/Ke. In Pool 2, species BAF ranged from 5,000
L/Kg. In Pool 2, species
geometric to 20,000
geometric
mean values L/l<g (Furdui
mean values
ranged from 2500 0 7000 L/Ke et al, 2007); this study reported
ranged from 2500 to 7000 L/Kg
fo Section a lake trout
for Section
4and 4,400 BAF of 5000
4 and 4,400
ttoo
Mississippi Pool 2 PFCs 2009 + March 2010
Mississippi Pool 2 PFCs 2009 . March 2010
re - 14-
M3i4ninnneessoottoa PPoolllluuttiioonn CCoonnttrrooll AAggeennccyy
22229955..00001166
STATE02010415 STATE_02010415
1111,50,05ofor0raa0llll sseeccttiioonnss ccoommbbiinneedd.. OOnn aann oorrddeerr--ooff-mmagangintituuddee ssccaallee ic.(i.e., lloogg-:ssccaalle)) tthheessee DBAATFss llooookk mmoorere. ssiimmiillaarr;; tthhaattis,, tthhee lIooggBBAAFF iiss aabboouutt 44~, wwhhiicchh ccaannbbeeccoommppaarreedd ttoo PPCCBBSs aanndd mmeerrccuurryy ologgBBAAFFss aarrouonudn6odorr 771(1--1100 mmiillllioonn kL/eK)g.). PPFFCCsswwitithh sseevveenn oorr lleessss fflluuoorriinnaatteedd ccaarrbboonnss aarree nnoott ccoonnssiiddeerreedd bbiiooaaccccuurmmuullaattivvee aaccccoorrddiinnggttoo rreegguullaattoorryy ddeeffiinniittiioonnss ((CCoonnddeerreettalal., 22000088).). TThheeeevviiddeennccee ssuuppppoortrtss tthhaatt lam claim bbeeccaauussee PPFFCCss esless tthhaannCC38 ((PPFOFAaOannAdd PPRFOOSS)) aarree oofftteenn nnoott ddeetteecctteedd iinn ffiisshh ((PPoowwileeyy eett aaLl.,, 22000088).). OOnn tthhee ootthheerr ssiiddee,, CC38-CC1122 PPFFCCss hhaavvee bbeeeenn ddeetteecctteedd aattiinn ffiisshh,, aalltthhoouugghh tthhee nnoonn--PPFFOOSS PPFFCCss ooccccuurr aatt mmuucchh lloowweer ccoonncceennttrraattiioonnss tthhaann PPFFOOSS.. AA pprreevviioouuss ssttuuddyy rreeppoorrtteedd tthhaatt tthheerreeiiss aassigignnififiiccaanntt ccoorrrreellaattiioonn bbeettwweeeenn PPFFOOSSaanndd tthhee PPFFCCAASs ggrreeaatteerr tthhaann CC88((PPoowweleyy eettaall.,, 22000088).). TThhiiss wwaass rreeppoortretd ffoorr ffiisshh iinnLLaakkeeCCaallhhoouunnaanndd MMiissssiissssiippppii RRiivveerr PPoooollss 22:-55a3 ccoolllleecctteedd iinn 22000066 ((DDeellinisnksyekeytt aa,l.,22000099)),, aannddiit iisttrruueeffoorrtthhee 22000099 rreessuullttss ffoorr PPooooll 22. IInn tthhee 22000099 PPooooll 22 rreessuullttss,, wwhheenn PPFFOOSS ccoonncceennttrraattiioonn wwaass vveerryy hhiigghh, tthhee lloonnggeerr ccaarrbboonn--<chhaaiinn PPFFCCss wweerree aallssoo ddeetteeccttaabbllee ((FFiigguurree 1144)).. PPFFDOAA ((CC1100)) wwaass hhiigghhllyy ccoorrrreellaatteedd wwiitthh tthhee PPFFOOSS ccoonncceenntrtraattiioonnss.. TThhee PPeeaarrssoonn ccoorrrreellaattiioonn cosfficients between PFOS andtheC9 (PFA), C10 (PFDA), and C11 (PFURA), and C12 (PFDOR) were. 0c.o0e1ff0i,c0ie.n9t4s3,b0e.t7w3e2e,n3nPdFO0S.2a80n.d Tthhee Cco9rr(PeFlaNtAi)o,nCw1i0th(PPFFDOAS)A, was 0.717. and Cll (PFUnA), and C12 (PFDoA) were
0.010, 0.943, 0.732, and 0.280. The correlation with PFOSA was 0.717.
((DDeelliinnsskkyy eettaall.., 22000099))nnootteedd tthhaatt tthhee CC1100--CC1122 ccoonncceennttrraattiioonnss iin tthhee HHaaww aanndd DDeeeepp rriivveerrss iinn NNoorrtthh CCaraorloilinnaa---w-witithh nnoo ddooccuummeenntteedd ssoouurrcceeooff PPFFCCs---w-weerreessoommeeooff tthhee hhiigghheesstt iinn tthhe lliiteterraattuurree~; LLaakkee CCaallhhoouunn wwass aallssoo hhiigghh aanndd hhiigghheerr tthhaann ihfish ffrroomm PPoooollss 22:-55a3 ((ffroomm 22000066coclolleleccttiioonn));; tthhee oonnllyy ssttuuddyy rreeppoorrtteedd hhiigghheerr CC1100 aanndd C C1l1l lleevveellss wwaass ffromraaoccrreemeekk iinn CCaannaaddaawwhheerreeaaqquueeoouussffiirree--ffiigghhttiinnggffooaamm hhaadd bbeeeenn rreelleeaasseedd ((MMooooddyy eettaall.,2020020)2.). MMaaxxiimmuumm ccoonncceenntrtraattiioonnssooff CC1100 aannddCC1122 iinn PPooooll 22 frroomm 22000099 wweerree: 3322..11aanndd 2289..88 nngg//gg aanndd eexxcceeeeddeedd tthhee mmaaxxiimmaa rreeppoorrtteedd ffoorrtthheettwwoo NNoorrtthh CCaarroolliinnaa rriivveerrss.. CC1l1l mmaaxxiimmaa frroomm tthheettwwoo rriivveerrss wweerree mmuucchh hhiigghheerr tthhaann iinn PPooooll 22 ((442.22.2 aanndd 5500..55nngg//gg,, ccoommpapreadtrtooe11d11..88 nngg//gg iinn PPooooll 22).). IInntthhee 22000099,, PPooooll 22 rreessuullttss,, aallll PPFFCCss ootthheerr tthhaann PPFFOOSS hhaadd mmeeddiiaann ccoonncceenntrtatrioantsaiaotnoosrr bbeellooww tthhee LLOOQG, bbuutt nneeaarrllyy aallll ooff tthheemm hhaadd aa ddeetteeccttaabbllee ccoonncceenntrtraattiioonn aatt ssoommee ppooinint.t. (OOnnee ffiinnaall ppooiinnttttoo aaddddrreessssiisstthhee bbiioommaagaginfifiiccaattiioonn ooffPPFFOOSS aanndd tthhee aappppaarreenntt ddiissccrreeppaannccyy bbeettwweeeenn Iliiteterraattuurree rreessuullttss aanndd tthhiiss ssttuuddyy.. NNuummeerroouuss ssttuuddiieess hhaavvee rreeppoorrtteedd PPFFOOSSlelevveellss Iinnccrreeaassee wwiitthh ttrroopphhiicc elevveell iinn ffrreesshhwwaatteerr aanndd mmaarriinnee ffoooodd wweebbss ((KKaannnnaann eettaall.,, 22000055)),, ssoommeettiimmeess bbyy aass mmuucchh aass aa ffacatocrooftftthohrreeree. bbeettwweeeenn ttrroopphhiicc lleevveellss..TTihsiswwaass nnoottsseeeenn ffoorr PPFFOOSS ccoonncceennttrraattiioonnss iinn ffiisshh ffrroomm MMisisssiissssiippppii ARviveerr PPooooll22. TThhee wwiiddee aanndd oovveerrllaappppiinngg rraannggeess ooff PPFFOOSScocnocnecnetnrtarattiioonnss wwiitthhiinn aanndd aammoonngg ssppeecciieess iinn PPooooll 22 mmaayy hhiiddee tthhee ppoossssiibblleeddififffeerreenncceess aammoonnggttrroopphhiicc lleevveelsls.. CComoparmisonpooffaPPFFOOrSSccoioncnecsnetnrtaoratitioonnnss Iinn llaarrggeemmoouutthh bbaassss `aanndd bblluueeggililll ssuunnffiisshh ffrroomm tthhee ssaammee llaakkeess iinn MMiinnnneessoottaa ssuuggggeesstt tthheerree mmaayy bbee ttrroopphhiicc mmaaggrnififcicaattiioonn ooff PPFOOSS ((ddaattaa nnoott pprreesseenntteedd iinntthhiiss rreeppoorrtt.). TThhee ffiisshh ffrroomm PPooooll 22ccannaotbbeenppaiarirneeddbbyo ylolocactatitioonn.. FFuurrtthheerrmmoorree,, tthheeyy aarreeaalll ccaarrnniivvoorreess,, aallbbeeiitt aatt ssoommeewwhhaatt ddiifffeerreenntt elevveells..
CCoonncclluussiioonnss AAllllffiisshh aanndd wwaatteerr ssaammpplleess wweerree aannaallyyzzeedd ffoorr PPFFCCss bbyy AAXXYYSS AAnnaalylyttiiccaall L11tdd.. AAllll wwaatteerr ssaammpplleess aanndd 3300 ffiisshh ssaammpplleess wweerree aallssoo aannaallyyzzeeddbbyy 33MM EEnnvviirroonnmmeennttaall LLaabboorraattoorryyffoorr qquuaalilittyy aassssuurraannccee.. TThhee mmaattcchh bbeettwweeeenn
Mississippi Pool 2 PFCs 2009 + March 2010
Mississippi Pool 2 PFCs 2009 . March 2010
5 -15-
Minnesota Pollution Control Agency
~innesot~ Pollution Control Agency
22229955..00001177
STATE02010416 STATE_02010416
rreessuullttss ooff sspplliittssaammpplleessffrroomm tthhee ttwwoollaabbsswwaassvveerryy ggoooodd ffoorr bbootthh iwtaeterr aanndd ffiisshh,, wwhhiicchh rreeiinnffoorrcceedd ccoonnffiiddeennccee iinn tthhee qquuaalilittyyooffththee rreessuulsts.. W Waatteerr ccoonncceennttrraattiioonnss ooff PPFFCCss wwierree hhiigghheesstt iinn SSeeccttiioonn 44 aanndd iinn ppaarrttiiccuullaarr,,SStatattiioonn 1111.. PPeerrfflluuoorroobbuuttaannooiicc aacciidd ((PPFFBOAA)) wwaass ddeetteecctteedd atl at all ssttaattiioonnss.. PPFFOOSS,, ppeerrfflluuoorrooooccttaannooiicc aacciidd ((PPFFOOAA)),, aanndd ppeerrfflluuoorroohheexxaannooiicc aacciiddee ((PPFFHHYxAA))wweerree ddeetteecctteedd iinn SSeeccttiioonnss 22,, 33,, aanndd 44,,wwiitthhtthhee hhiigghheesstt ccoonncceennttrraattiioonnss iinn SSeeccttiioonn 44.. TThhrreeee. ootthheerrss----PPFEPPeeAA,, PPEFGBSS,, aannddPPEFAHSxS---w-weerreededteetecctteedd iinn SSeeccttiioonn 48.. PPRFOOSS wwaass ddeetteeccttaabbllee iinn nneeaarrllyy alall ihfish ffrroomm PPooooll 22,, wwiitthh tthhee hhiigghheesstt ccoonncceennttrraattiioonnss iinn ffiisshh aanndd wwaatteerr iinn SSeeccttiioonn 44,, tthhee mst most ddoowwnnssttrreeaamm sseeccttiioonn ooff PPooooll 22.. MMoossttootthheerr PPFFCCss wweerree nneeaarroorr bbeellooww tthhee rreeppoorrttiinngg level, although longer carbon-chain PFC were detectawbhleen PFOS concentrations were high. Ofthe fleivveelt,aarlgthetoeudghfislohnsgpeecriceasribnoPno-oclha2in-bPlFuCesgiwlesreunfdiesthe,ctcaabrple, fwrheesnhwPaFtOerSdrcuonmc,esnmtaraltliomnosutwherbeashs,igha.ndOwf hthiete basfivest--afrgreestehdwafitsehr drum h species aind thePool h2i-g-hbelsutegPFillOSscuonnficsehn,tcraartpi,ofnrse.shDwruamtehraddrum no,tsbmeeanllmsoaumtphled pr bass,iaornd0.w2h0i0te9 bbeacsasu-s-feretsihwnaottercodnrsuimdehraedd athteyphiicgahlesspt oPrFOfiSshc,obnuctetnwtraatsioinnsc.lDudreudm5hadtnarogtebteedenspseacmiepslebdecpariuosretoof2t0h0e9 DNs servation tha tis a popular because it is not considered a typical sfpisohrtkfeispht,fobruht uitmwaans cinocnlsuudmepdtiaosn a taanrdl~ehtaesdbsepeenciheasrvbeesctaeudsebyof the cDoNmRm'esrocbisaelrfviasthioinngtohpaetraittiisoanspopular fish kept for human consumption and has been harvested by
commercial fishing operations.
NNoo ddiisscceerrnnaabbllee ttrreennddss wweerree sseeenn nin PPRFOOSS oovveerr ttiimmee ffoorr ssppeecciieess tthhaatt hhaadd bbeeeenn ssaammpplleedd ssiinnccee 22000044 oorr 22000055.. PPFFOOSS ccoonncceenntrtraattiioonnss iinn ffiisshhmmususcclleewweerree nnoott ccoorrrreellaatteedd wwiitthh ifisshh aaggeeoorriseiz,e, aannd tthheerree wwaass nnoo ddiifffeerreennccee bbeettwweeeenn ggeennddeersrs.. BBiiooaaccccuummulualattiioonn ffaaccttoorrss ((BBAAFFss)) wweerree ccaallcuclualteadtffeoodrr PPFFOOSSusuisinnggtthheewwaatteerr and fish data. BAFs for PFOSwere inthe range of 4000 o 6000 Kg, which s at the low end of the range oafndhifgishhlydbaitoaa.cBcAuFmsalfaotriPvFeOcSomwpeoruenidnst.he range of 4000 to 6000 L/Kg, which is at the low end of the range
of highly bioaccumulative compounds.
Mississippi Pool 2 PFCs 2009 + March 2010
Mississippi Pool 2 PFCs 2009 . March 2010
- -16-
Minnesota I~innesot~ P Poolllluuttiioonn CCoonnttrrooll AAggeennccyy
22229955..00001188
STATE02010417 STATE_02010417
RReeffeerreenncceess
BBeerrggeerUrUa,.4,: GGsllyyonnnn uAA,.o, rfHHhooluclmmmssaettnrroomem KKx.CE.., pBBetroeoglpurrnsfdlMguMuc,.rl,AirAnnuknaaktearenrdbbeaedrlrkggylEEs.HHu,.b,sTTtooanrrnckkevvssisitnt AAS.w((e22d00e00n89)-) iFAnsisahhlyccsooinnsssouufmmeppdtitiiboolnne
ffa1iiss0shh.a1fts0rroo1oum6mr/cjLLecaahokkeeefmhVoVuasamtptthtaeeenrrrnnee.aax2nnp0ddo0s9tthu.hre0ee4BB.toa0at4ltip4icce.rSSfeleaua.o. rCCinhhaeetmmeodossapplhkheyerlreesu77b66s::t77a99n99c-e-88s004i4n..
DOL:Sweden
DOI:
-
Analysis
of
edible
CCoonnddeerrJr1.eM10vM..1i,,e0HHw1oo6akk/neje.dcRRhc.AeoAm.m.,pDoDaserepWihWsoeolorneflf.w2WWi0t,.0h,9RRr.ue0usg4ssus.el0ela4lllt4oMM.rH.yH,l.,ipBBoupuhccikkli.RcC.cC.o. m2(2p00o00u88n))dsAA.rreeEPPnFFvCCiArAsosnbbmiieoonaatccaccluumSmuculialeatnticivevee&??
A
A
critical
critical
DelinsTkTreeyecvchAihLenDn,woSoltlaorongygdnyyac44ro22mM::99Jp99,a55-r-i1N1s0o0a0n03k3.wa. yiDDthOaOLm:Ir:eaS1g1.0F0u,,.la11V0t0o22ar11y//erelissp00oL77Lp,00hY88ie9l9i5c5X.gc.8.o,mpMocuCnadnsn.
Environmental Science &
P.L Lindstrom A. 2008)
DelinskyEDDAnee.vtDtiee.rr,rommSniitmnnreayantnttiiaoaornlnMooR.fJef.tst,eeeNnanrappckeeharryf1fall0umu9oo:arr9iin7Sna5.aF-tt.e9,ed8dV4acc,roonDmmsOpIpJo:.oLuu.1,nn0Yd.de1ss0X1iin.n6B/bb.,jlluuMeeencggviCirlllaensssuunn2nf0Pfii0.sJs9h.h,.0L((L8Lin.eed0pp1soo3tmmr.oiimss mmAaa.cBrc.oroc(2hc0ih0riru9us)s))ffiillleettss..
DeliALnD,Sstrkynyar M.J, McCann P.J, Varn Environmental Research 109:975-984.
Delinsky A.D., Strynar M.J., McCann P.J., Varns
LL,DOI:
J.L.,
McMillaLn, Nakayama S.., Lindstrom 78. 10.1016/j.envres.2009.08.013.
McMillan L., Nakayama S.F., Lindstrom A.B.
((22001100))
`RGiGveeeoorggsr.raapEphnhivicciaarlloDnDimissetntrrtiibabuluttiSioonncooff iPP&eerTrelfeluucoonrhrininnocaalttoeeegddyCCAooSmmAppPoou1un7nFddEssB2nin01iF0iss.hh DffrOroI:omm1MM0iin1nn0n2ee1ss/ooettsaa90LL3aa7kk7ee7ss5aa.nndd
FFuurrdduuiiVV.5R..I..,i,vAe.SSr(tts2oo.0ccE0kk7nNN)vL.iSLr,po.,aEntElmillalieslsndDDtiaA.sAlt..rS,icBBbiuueuttnttictoeCCn M.&oM.fT.,peeWWcrhhfihlntiuottotlllroeeogaDDyl.k.AMMy,Sl.A,CcPCroonr1ozt7ziaFiemeErirBnPP2a.0nYWt1.s.0,. RiRDneeiOlinnaI:ekeerr1t0rE.o.11Ju,.0,t2MM1fuur/ieoirrsm9DD0t..C3hCe.7.GG7G..7r, esMMa.ata.bbuurryy
Giesy 1.LSL2a,a.AkkKe.eass(.n2.n0EEa0nnn7vv)iKi.rrSoop(nn2amm0t0eiae1nl)ntdtaGaillslotSSrbcicabiileuenntdiccoeeni&&osTTf eepctcehhrnfnrlouoololfioorpggobeyyarl44kfu11yl::lu11toc55ro55ion44o-t-cao11tm55a5n5in9n9e.a.nsDDutOslOIf:iIon:n11ala00tk.e.e11i00tn2r2ow11i/u/leedtssif00freo66.2m200E4t4n8h8v4ei4.r.Gonremaetntal
Giesy
(Giesy
1J..PSS.,cKiKecaannncnneia&a&nnTeTeKK.ec.nc(h(2h2n00noc00ol21loo))eggGPyyelor33fb55l:a:u11lo33dr33io9s9c-t-hr11ie3b3m4u4i2t2c.ioa. lnDDOsOIou:Ifr:pf11ae00cr.t.f1l1au00not22rs11o//ioeencsstht00ae00n11ee88n33sv44uikkrl.f.oonnmaetnet.in
wildlife. Environmental
Environmental Scienc&e
Giesy
Technology36:146A-152A. J.P., Kannan K. (2002) Perfluorochemical Technology 36:146A-152A.
surfactants
in
the
environment.
Environmental
Science
&
HHoouuddee
MM,., MMaarrttininJ.LWI.,, polyfluoroaliy
LLeettcchheerr RR..,J.,SSoolloommoonn substances: A review.
EKKm.RRi..r, oMMnuumeiirnrDt.aCD.lC..GGS..ci2(2e00n0c06e6))&BTBieiooclloohggniioccalallogmmyoon4n0ii:tto3or4ir6n3ig-no3ogf4f73.
DOL:
Jones MLp11,00o..lyS11ft00luu22ao11r/r/toeea.ssG0lO.k55y22(l552s880u0006bb8.s.)taLnacteersa:lAmorevveiemwe.nEtnovfircoonmmmeontnalcSarcpien(Ccyep&rinTuescchanroslioogyL)4i0n:a34l6a3r-g3e4l7o3w.lDanOdI:
JKoanemsaMKn.irJ,ivv.,eeTrSrataaounnadLdr,tfflISlo.Goioon.ddcp(pl2lala0aii0inrn8.,.) PEELcacaooteltloorvagglyya5m.oo0f,foFvFJrerueemdssehehw0nwa.tat1otee,frGrFciiFoseimshshmy118o18:.n1:17c7-(a8-2r820p2.0.5(C)yPperrinluusorcianraptioedL.c) oinmpaolaurngdesloinwland
Kannan aEaKqnq.,uvuTaiatartiooiccnLmoo.e,rrgngSatainanncliislsamCmiorssnaEta.t,atmPvviaaanrsraiitovotuauissoSntt.rDroao.,pnpJhhdiuicTcdoellxeeiDvvcee.Joll.sls,ioGignnyiea4as8GyG:rJ5ree.5Paa9.tt-(5L2Laa60kk50ee.5ss)DffOPooLoe:odrdf1lucc0hho,aari1ini0nn.0a.A7tAre/cr5dch0hic0ivo2ve4ems4sop-oo0f0uf 4n-d0s13in3-x.
MMaarrttiinnLJfWE.Wr.no.v,mWirW holianhkmtietlteOleennttaDDalrM.MiC,o.o.,MnMEtianuvmriirirnDDoa.n.tCCmio..eGGnn,.t,aaMMnladaSbTbuuorcrxyyicSSoiA.&lAo..geT(y(e22c400nh800n4:45o)c)5lPP9oee-egr5ryf6fllu63u.o8rr:oDo5aOa3l7Ilk:k9yy-l!Ol53cc.18oo05nn0.tt7aa/mmDsiOOinnIOaan2nt4tss4-ii0nn0aa4-foOooo1dd3w3w-exeb.b.
10.1021/es0193315. from lake Ontario. Environmental Science & Technology 38:5379-5385. DOI:
MMooooddyy
CCS1.uA0Ar...f1,a0MMc2ata1ratrn/ettiisnsn0iJJ1n.W9Wi.3.o3,tlKKaaww.aaannnd
WW..CC.., MMuuiirr Surface Wa
DD..CC..GG,., ter Sa
MMaabbuurryy SS.AA.. ((22000022)) MMoonnititoorriinngg mples Following an Accidental R
PPeerrfflluuoorriinnaatteedd elease of Fire-f
i
g
h
t
i
n
g
Surfactants in Biota and Surface Water Samples Following an Accidental Release of
F10o.a1m02n1t/oe5E0t1o1b0i0c1o+k.eCrack. Environmental Science &Technology 36:545-551. DOI: Foam into Etobicoke Creek. Environmental Science & Technology 36:545-551. DOI:
Fire-Fighting
PMMoaorrrggr.aann(12TT.,00.,0.12HH)0aar2rLr1reee/lpel osS5.m0. i1((2s12000m000a661c))+rMM.ocoohrrioounnsee,ccAhhnrriyymssaoolppssD,,ivAAennriismmiatayll WDDeiivvbee.rrssiittyy W Weebb..
PPPaaarrrssrooCnn.ss(2M8Bi0..nG0Gn2,.e,)sRRoLeeteeeapdd.omJ].NRRios..r(m(t22ha00c00A5r5mo))ecrMMhiircoouavsnev,mAJeoenunirmmtnoaaofellfSoDBnafilavcFtcekikrsshCCietryrraaipWpepspeiiMeebass. naaanngddeBBmllueueneggtililll2ss5/aa6mm8o9o-nn6gg95II.nntteDeOrrIcc:oonn1nn0eecc1tt5ee7dd7/LLaaMkkOeeAss-iinn
211. Minnesota. North American Journal of Fisheries Management 25:689-695. DOh 10.1577/M04-
Powley CR,George 021.1.
Powley C.R., George
spatially and
SW, S.W., RRuusssseellll MMH.H,.,HHookkee RA.R.A., BBuucckk temporally integrated foodweb in
RR..CC.. the
W((e22s00t00e88r))nPPoAorlclyvtfifllcu.uoorrCiinhnaeatmteeoddscpchhheeemmrieiccaa7l0lss:6iin6n4aa-672
001: 10.1016/,chemosphere.2007.06.067. spatially and temporally integrated food web
DOI: 10.1016/j.chemosphere.2007.06.067.
in
the
Western
Arctic.
Chemosphere
70:664-672.
Mississippi Pool 2 PFCs 2009 + March 2010
t~ississippi Pool 2 PFCs 2009 . March 2010
"- -17-
Minnesota Pollution Control Agency
~it~nesot~ Pollution Control A~ency
22229955..00001199
STATE02010418 STATE_02010418
STS Consultants. (2007) Surface Water Quality Citeron for PefluorooctaneSulfonicAcid Minnesota
STS
Wa
nCgoT,n,sPPouWolltllalauuntntitiosogn.n
(CCY2.o0Won.0nt7Ltrr)iooslSlouAACgrl~fYeaen.cncecyCy.W a.i a.tQe.r,QJuaalnitygCG.r8. it(e2ri0o0n9
for Perfluorooctane Sulfonic Acid
) Perspectives on the Inclusionf
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