Document ZL3V1Vx02kkMEg6V3GroveD8
ss PRT Hie
OKA1Y2 his g: 1g
Study Title
"TENNESSEE RIVER VALLEY SAMPLES
6 1733
i
Author
Mark E. Ellefson
Revised Report
September 12, 2003
PerfoMErnmviionnmgentLlaLabboroatroray tory Buiing 236.00 925 Bush Ave Spa, WNS5100
Project Identification
3M Environmental Laboratory Stud#y E02-0443
Total Number of Pages 28
_--_mmm Report E02.0443
Ton. RiverVatSamples
TABLE OF CONTENTS
Listof Tables...
----------
asl
SHAY INOMMEON
sss
SUMMEIY..cses
sms--------
[ -- com------------
Test andAnalytical Reference SUBSINGS................... mn"
fC
------
ml
MOtNOG SUTIMEIIES......cecocv
as----
won
PrODATDNONy MONOGS......cocorrn
smmsmm----
SAMPIOANBSIS.....crr sn
csm--------_
Analytical Result ......
----
mms
DBR SUB osm
smd
SHBSHCEI MONOGS ccc
smni2s
StatoefCmONeCIInSIOtN crn
rmms--------
ListofAHBCHMONS.......c.cocrc sn --
nmi
Signature Page... " m------
AttacAh:Amnaelytnictal Method and SOP DEVIBONS ......c...vssrsrvinsnnns 28
AMBCHMENtB:Data SUMMENYTaDIES.....crvrrnnrrsssnsonnniros 80
AHBChMIONCt: SAMPle CHIOMBOGEAS crores
81
AttachmenDt: Sample PrepSheets, Test SubsatndaTenstcSyeste,m Information................230
AttachmenEt: Notes 10 File..............
A -----
IM EmicnmentalLaboratory
Page2ar278
----------------------
ReportE02.0443
Torn. RiverVaseySamples
Li oFTs ABLtES
Tabl1e. Sample Location,Sample Type, and Analylical Data Summary. .. I
Table 2: Characterizationofthe Test and Analytical Reference SUBSIANCES. cv...
Table3a. DescripotfFiiosnhTissueAnalyzed i this Study.
mmm]
Table 3b. DescofrRivierpWalteriAnaolyzned in this Study... smn
`Table3c. Description ofRiverSedimentsAnalyzed i ths
SGY.....c...uvun
wondl
`Table4a. FishTissue Sample Preparation Method. cmmmm--_
`Table4b. Preparation ofExtractedCalibration CurvesfortheFish TISSue...............
9
`Table4c.Fish TissueAnalyical Data Quality Objectives. m--
Table 4d. River Water SamplePreparation Method............
mmm--
Table de. River Water Sample Data Quality OBJOCIVES ................crursvrrnsonsnsnne0]
`Table 41. RiverSedimentSample Preparation Meod.................wssmmsensec] 0
Table 4g. RiverSediment SampleDataQuality OBJEC ..............rurcvrusseencnd 1
Tabl5e. SampleAnalysis Information. a ----
:
`Table 6a. PFOSCalibration Standard Reprocessing SUMMAY .......ouwesommermsn] 4
`Table6b. FOSA Calibration StandardReprocessing SUMMANY ........... nonilB
`Table6c.PFOACalibration Standard Reprocessing SUmmary.............
wns
`Table6d. PFHS Calibration StandardReprocessing SUMMBIY ............
wn
Table Ge. PFBS Calibration Standard Reprocessing Summary. mm--_
Table 7a. Cafish ANGIYHCE! D2. corr
mmmm----]
Table 7b.Large moaundtSmahllmouthBassATBIYICal DBA. .....curcvsurvennnsns 22
Table 7c. RIVEr WaterAMICI DAB. ....ececeveeinesnsinsssiesvss 23
"Table 7d. River Sediment ANBIIal DBta................ moth
Table8. Sample Location, Sample Type,andAnalytical Data SUMMAIY.............
25
aM Envonmental Laboratory
Pagesal2re
_--mm m m--
----
Tar. ReVeySampls
STUDY INFORMATION
Requestor 3DaMleELnviBraocnmoenntal Laboratory B9i3d5g,Bu2s3h8.A0v0enue S0t5.1P.a7u7l8,.M47N3655105 SMtaurdkyE.DiErlelcitsoorn 3BiMdg.En2v.ir3o8n.m0ental Laboratory 9S3t5.PBauuslhMANve5n5u1e06 651.776.5405
`Study Location
3TeMstEinnvgiFraocnmietnytal Laboratory B9Slt3d.5gP.aBu2ul-s,3hEMA-N0v9e5n5u1e06 WMialricaLm KA.ndReerasgoenn,,ALnaalbyotriactaolrCyhMeamniasgter Cindy M. Carson, Analytical Chemist OExgpnejreinmkeantKarlupDlajtaonsi:n, Analytical Chemist `SSaammppllee AAnnaallyyssiiss nCotmipsloenti:o2n6: J1u2nNeo2v0e0m2ber 2002
LocationofArchives Aaclcoorridgiinnagltroa3wMdaSttaanadnadrtdh OpreerpaotritnhgaPvreocbeedeunreasr.chiRveemdaaitnhinog3sMpeEcnivmiernosnmpeenrttaailnLinagbooratthoery analyial phase of nis study wil bo archived at tha 3 Environmental Laboratofrory a ong as
the quality of the preparation affords evaluation.
aM Emicomentl ates
Pagoactzre
_--mmmm-- Report E02.0043
Ton,RiverValySamples
SUMMARY
eee
`FTisehn,nerisvseerewaRtievre,rannedarritvheer s3eMdiDmeecantturs,amApllaebsawmearfeacciotlyl.ectTehdefsraommptlhersewleorceatainonaslyiznetdhef.or p(ePrFfOlAu)o,ropbeurtfaunoersouolcftoannaetes(uiPfFoBnSy)l,ampiedrefl(uFoOroSh)e,xaannedsuplefrofnuaotreo(oPcFtHaSne),suplefrofnlautoero(oFcOtSan)o.ateThe tahneanlyasneaslywzeirneg tachceommupsliinsgheHdPLbCy-eExltercatctrionsgprthaeylSMaamspslSepseucsiirnogmeSlorlyd(PHhPaLsCe/EESxItMrSac)t.ion (SPE) and m`iSlaemp2l9i6n.g LSoecmaptiiionng1L(oScL+a1t)ionwa2s(SlLo-c2a)lewdadsowancrsoisrseathmeorfivtehref3rMomftachieit3yMnefaacriiFtoyxatCriveeerkmaitlreiv3e0r1 `Sampling location 3 (SL-3) was upstream from the 3M facilty at river mile3075.
Analytical results are presented in Table 1:
Table 1. Sample Location, Sample Type, and Analytical Data Summary. ETE
`SamplingLocation & `Species Sampled
[IEEE oi
PrHS gig)
[a [oe
[FooSeA [[oh2
SLA. (n=6) SL2.Cne7) SL3.C (n=6) CERT) Ere] ERT EER
<U0Q 100
4100 dl00
<u0Q 609 (ee) 113 (ey oa 10a ion
<100 4lo0 di0a <loa _is2(4e
<UoQ 4100 <od' <ioa sss
<U0Q 4100 <10Q <u00 169 (2.
<log <Ll00
dice ----<llo0
loa loa
dion <ioa
dion ion
pT
sSLL21.. RRWw SL3, RW
GParoms) pPgrmHlS) ePFOmA g[mTtY) (ppraoms) <ioa 400 <lod _ <dica _<ioa log <lioa oo <loo <ioa
PFBS [a
[ Fosa pros
[C2 [ [Cr [CE (9/9)
SL2G.eRls
5a377
<1w0oa
rdieog
d1w
sin | 457
EEE ``CS=odCiamteFniissh.,HLigWh
as =Largemobiass,
SH
<uoa =SmallmouthBase,
FW
127 = Riverwate,
pica value wesstalsticayeliminatedwing Dixons Tes.
am 6RS
=
ver
ate
wuarmbceraoflFifscrho>mtsLsLcOehQsadNmupmlibnegroofatFiisohnAnalyzed).Onlyone River Water and onaRiverSedimentsample
SM Envionmanta Laboratory
Page 501278
_--nmm Repent E02.0443
Ton. ver Vay Samplos
PURPOSE
n"Tdhe PpuFrOpSosien osfptohrits-csatuugdhytsfiosh,pfeirvefrorwamtqeura,ntaintdatiivveerscsreedeinmienngtsforfrPoFmBtSh,rPeHsSam,piPiFnOgAl,ocFaOtiSoAns,of the Tennessee River near Docatur, Alabama.
TEST AND ANALYTICAL REFERENCE SUBSTANCES
Table 2: Charactorizationofthe Testand Analytical Reference Substances.
`Compound
EE 3StMorLaagbeorCaotnordyfons
Physica Description (Rory
PFPeHrSf,uca rohexanesufonate|rPoeseuaorooctanesifroonn-|| ZEPeLorOlruNcraoonctanoals
BSiVg.Sp2e3c6i.a2l8y-M1a1laria, | aBiMdSp2o3c6a-l18y-M1a0taras, | 3BiMdSgpe2c3a6l-l18y-M1a0lorak,
|Froen
[Frozen
[Frown
|
y
Light yellowwarysod
oes
| Undetermined
950%
|
[rity iat Compound
prus
id
SuPfFoBnS,atPeolassium Perfuorobutane | PPeFrOfSu,orPoootcatsasnieusmufonete
3M Specialty Materials, Big.
SM Laboratory denticaton
`UWnhdietteePromwidneerd
SM Environmental Laboratory
Page or278
_--_-- Reporter ossa
Torn,Rie Vata Sams
TEST SYSTEMS
Table3a. Description of FishTissueAnalyzed nthisStudy Fotos:
[S[ ourcee ~m ~ essooRver|
"Types
LaCartgfiesMhouth Bass.
Small Mouth Bass
eoCo mi Downstream fom te Wi Tacit
`(Aicvreorsmsihoe3v0e1)r fomth 3M facity Upstreamofthe SH faciy
(river mile 307.5)
+The fish were fled and representative aliquots of the filets were analyzed.
Table3b. Description ofRiverWatarAnalyzed inthisStudy Ee
[Swe_
ont |r . lors eninas Location3
[TemessooRive|r Chiled (approximately C)
"Downstream from the 3M facility
`Acrosshe iverfrom the 3M faci U(ipvsetrrmeiaemo3f07h.e5)SW facly
Table 3c. DescriptionofRiverSediments Analyzed in this Study
[Sace ----
l ono s| ne [i omy bisiid
TTomemeorve|r
Chilled (approximately 4C)
Downstream from the 3M facility
"Across thfiverfrom the 3M faciy
Upstream of he SM facly
(iver mie 307.5)
aM Enveonmans Labs
Pageotare
EE Report E020043
-- Ton. RiverVaySamples
METHOD SUMMARIES
`RTihveercoSnecdeinmteranttisonwseorfePdFetBeSr,miPnFeHdSb,yuPsFiOnAg,SFolOiSdAP,haansdePExFtOraSctiinoFni(sShPTEi)ssaunsd, HRiivgehrPWeartfeorr,maanndce Liquid Chromatography-ElectrosprayMass Spectrometry (HPLCESIMS).
PREPARATORY METHODS + TWahteerfo,lalonwdinRgitvaebrlSeesddiemsecrnitbseatmhpelessa.mplDeatpareQpuaarlaittiyonObmieectthiovdess f(oDrQtOhe)FairsehaTlissosugei,veRnifvoerreach
`sample preparation method. Fish Tissue Sample Preparation Method
Table4a.FishTissueSamplePreparation Method
5
Fis TISUE SAPLE PREPARATION Mi
|[21]| Apeplroosmiomgamtln2e0voafsFcish rTisisueagndmiLoofASsTMmTyaipnodi1Weatonesrphwaerrooehrofomnoiogeesnotizemd
Esraacuhnhssomiohopog1oh.nno0eiimmtLoon.gwnaoganfsadtaho,molgenaelo edFtoo3FpseRpcaarDatseam1p5mleLs.cTohnwtasiabcgecoso.mpiehebdy
Meartis1xs.sp0pkimekedosfw(ihWtoShm)1ow0ge0orunoLaolpforwpar1s0e0Fduanmorsliv.oensreypdoeoasrncohtoohmenorg1ceo5nnatmta.ienc.inoIgnntahtcishecotafsutebeoat.neTashdtodMioSnsal
substances.
"s50mhLoffoara2c0skimoinnraoitew30an0stenpm.added & heconus bes.Tho boswerocappaendd
[6 `speomratmanit.ne camswarscried a306 or 0 ris Gy
"Thosupomatantwas Gecantodronow 50TLcartfugetubesanddictedwit40 mLof
"WeartoerpslaCc-e1d8oTounvcaicuounmalmaSradplPdask a1n3d,p6r0e0-SoPnEcclioornnodsnwihhaliaocnhegdm7a0nmneLrr.oservors ``mAOLp)np.raomWxohimseatntoemfloty1she0tommefLtihoasfnmwoealishhpaanudoblleowdaatnsopuualglcehd,dmtor0ro1ougwha,clAoelSruwTmaMnssTayanapddoe16dW(vo5a1lc0oumwu)am.swaWedhsdeaepndpt(lh5ed-r.1a0 WVaacsuounmyoathsmaclolalummonu.nTthofewcaoolarmentswertheenroetsleontw,edth1s0i0pdcockwas med 1810pthe [|aIumee0slpsuorhotnstwtaosmostco7lveceodrTsheecoluumnhswefrooaprloocwoendittiodenyadfoEatceaost .miserso . [70[heanaeswero hod romthe SPEcommswith 2.0m.ofmethanolnoauovias.
Soa he reparation worksfohroothcretxasctamounts, mes, speeds, ic.
SMEnvironmentalLaboratory
Paogr2e76
_--mmm----------
sms
I
Table 4, Proaraton of Extracted CalbrationCurves forth Fi Ts,
TRe oerotn omocriadnwPoesSsoocarp bcrAtLsabsnseadndterostC2abO0AoTrCeOS070
TFra otrpa ept e hriecscoe ssravp savirsee alncisde bbFeernoTTaeseo
es a
[= |] ]A1prp0ronexikmaaotrelly
10 gofFishTissueand 40mLof ASTM
oovasvoniorssvwspp
Ty
pe 1 Waterwere
omroribes
co
mb
ine
d
and
|
[3 Fahuowasspikedwintheprosotemindsmaurtofspesoon.
Tabledc.FahTiss Anaya DataCua Objectives
[1|RTAilesaymopwlaessweoorroopprnotpeooonddi4ne5ipcooatfre,oeTmmhoa%RShoDsssh.oyuK obfoo5r2o a54% EsA t BT P o E re lrR .corr ofon se oo Feao h eolr ScrinitkEsT w aconotSeave eSwebeoa TaIa SOOTpo om e mFaaahAa sooBeynn s i,
[5[Wc olo corio ngvarwasv] + River WatrSamplePreparaMttihoond
Tae46, RiverWatrSamplePrparatohons WnaryeC18rTeenaoeSeao e SE kie teag10amos `Ai pproximeartealyn1t0 rmmLofaeT mreptahsastnoeoloo wamsmanidedomeo edSotoosbtheecr oSerluvTmenisTai3nnedddthae(ivnTatcoarulue)smwwagiHssia1rpnptlio0eerd,. s om barit v Herver pa ons pcos PE To eT
I,
ramsatzms
_----
on szous
--
Table4d. RiverWaSampl Propastion Method
[3| hoaltoswooots romthcolumnswin 20mi.ofmethanol nk auovie
A-- frntaeci eeonrsi ooh Ss S e escbrSterlrostoHrtaac,Woate aorsansodas veer Eo537soacTm or aVAS
[3 Nomati spikeswer promoddung hosampleproparation of fo ivrWarsapien
+ Riv Sediment SampleProaraitohons
Tale4, RiverScSiampmlePrnopartaon Method Taa f r vre 3 veeSoianomtefsoe ay eaetien, Teo t So
|= rmeT alt ali |`Approximately20gofsedimentand WL Fg oT 35mLof 1%Acetic:AGH (9qUeoUs)werecombined info [s[o4rTiE honovoseasCwTbeurTnoEccaneppcsectvasoSoonmnaamndcTorv.fE noesmSaPkeoonr0emin HGF0eRTdPVTT,OoFLei
d sterroee brroorn peRreYpenhprbTrt rsyoaeetrssuhe he oo|bdoa iranld s),rWar eidne18 Te i pn riR oce R aeraa0ee,ny STR
oraoemrnaSnohvredweSamoOih.o.e4Freadtdrbce ghtehbtoS$h7racSsooins olePsET rEET [70]TTa hoockoloecrtadvmaostanclwsaseheomadhediowpprroosSmoatnly200mF.EofcAoSrTiM TypTeh1Siaer.
Sinem
--
_--_--m Report 02043
Ton.River VatSamples
Table4g.RiverSedimentSamploDataQuality Objectives
a
I rT,
[+ i sampleswer propareidcialn.ThoKRSDshui bo's25%
[2 vM alues, aworeps redi on acha cari.Ror shevi 50%of paced
prsTowecodlebsboscaGanoudnsaon]tahSloyadzeamdaswsi,uhgGoterhsnetesseaidmnpgwloefasss,pwiikomeprdowspsrabeiproocrooadr.rocdHovFeoousgphwedhhoaoanfraobrvimsasStoxifvoanmrcwiaaoscn,nhoetd
`xaWarttaoecrrtbwolhnaonpnkriso,ececrsosnss,eiwsdteirinagmpoerfwonaapntsaernu.otAtpcrcooofsveponittaebrevuanluTersowueghroh<ee7ntLrLeOprGepfoarratteiodnaaandsatin
whichthoywora un.
"cTuhroeR.ivVerSievdiemecnalttsvaamtpolnecsuwrverpeoqnuasrwiearlooudsUesidng38a CnoOrV-o.xiaciedSoVert Caloraion
SAMPLE ANALYSIS
``TEhnevisraomnpmelnetsalweLrabeoarnaatloyrzyeMdeutshiondg EHTPSL-G8/-E1S55I.M1S."AnTahleysainsaloyftWicaasltmeetShiroedawma,sWbaatseerdExotnratchtes3orM Other Systems Using HPLC-ElectrosprayMass Spectrometry" oTfheeafcohllsoawmipnglet.able details sample run informeion, including the sequence and the run start date Tabl5e. Sample Analysis Information.
Catfish [ ss 1owe| omic |
Large Mouth Bass
[2| Smolmosbass| s3 | ooeoozs |osunce |
[set RverWeter || Tsl2
| ooweiz | | ouaetz |
vzanoz | 2mgoz |
RverSodments [Sz
|
212 [12Nove| wet | f2Novoz |
w2tiz | ioNeve|z
SMEnvironmentsLaboratory
Page 1101276
_--_----
Repo 02043
Ton. RiverVay Samples
ANALYTICAL METHOD
SaOmthpelreSyasntaelymssisUswiansgbHaPsLeCd-EolnecEtTrSo-s8p-r1a5y5i.M1as"AsnSapleycstirsoomfetWrays'.teMSettrheaanmo,lWeaxtterarctEsxtwrearcet.s Or aPnFaOlySzeledvuelssinwgerHePLevCaIlEuSatIeMdSvienrtshuesnceagliablriavteiojnonstmaonddea.rdsPFrBanSg,inPgFiHnSc,onPcFenOtAr,atFioOnSfAroamnd1m10i0z0= n4g13an(alPyFtOe/Am)L,..mzTh=e4t9ar8g(etFOfSonAs),wearnedamszfo=lo4ws9: m(PzFO=S)2.69T(hPeFaSna)l,yimic/azl=me3t9h9o(dPFuHsSe)d, fionrdiavniadluyasliisnsistrpurmeesnetsn.ted below; modifications may be necessary to optimize the method for
AnalyticalEquipment ALniaqluyitdicCalhrcoolmuamtno:grKeaypsht:onAegieBnettHaaswisTMtC-Psa2cxk5a0rmdm,SeSruiemspa1r1ti0c0leLsiqiuzied Chromalograph system CCyoclluemTnitmeem:p9e.r5atmuirneu:t3es0 C FInljoewctriaotne:vo3l0u0mueL:i4mitno 20uL MobSiollevpenhtasAe: c2.o0mpmoMnenatmsm:onium acetate in water
Solvent B: HPLC Grade Methanol
Solvent Gradient: 0Ti0m0e
#08%
005800
6100%%
355500
110000%%
695500
1100%%
MSoafstwsarSep:ecAtgirloemnettCehre:mASgtiaetinotnHe~wAl.e0t8-.P0a3ckard Series 1100 APUMass Spectrometer Detector
Fragmentor Voltage: mm/zz239099== 112000V
mmilzz 44918.3== 1800V0.V
miz 490 = 140V
CGaapilnl=ar1y.V0oEltMagVe: 4000 V MGoadseT:eEmlpeecrtartousrper:ay3N5e0gatCive NDerybiunigzGearsP:re8s.s0uLre/:mi3n0. psig Analysis Type: Single lon Monioring (SIM)
SM Emvionmenta Laborstary
Page 1201276
--_-- Repon 02043
Tom. RiverVaySamples
--_--
ANALYTICAL RESULTS
Dataqualityobjectives outined in the Preparation Methodsseciion were met. Reigmrpersosveioqnuasn.iaQtuiaodnraotviecr tchuervceonfictewnatrsataipopnlireadntgoecaalpipbrroatpiroinastttaondtaherddsataa.ndAsllamcaplliebrdaatitoanfo
curves had least-square fis of 0.990 or greater. + Cv1ao0ll0iu0bmrneaotfigo1n0SwuteLar.neduIansresddso.mfoerSittnhasentdcaaanlcriedbssr,arttiahonengi1cn.u0grvniengsci.omnLTchesnettarsnatdtaainroddnarwfdaroscmuiranvjpeepcrptooeixdnitamstathsemaladylla1en.r0ivtnoojleuctmieosn.
(c1u,r2v,es2nwder5eurLu)n hbeifsowraesevdeornyeantaoleytxitceanldsethqeuelnocwee.ndPeorfctehnetcdaelviibarattiioonnscoufrveea.chCaclailbirbarattiioonn tsatragnedtacrodnwceenrteractalicounlawteerd.e eHxicglhu-deenddfcruormvtehpeociunrtvethcaatlcwuelartoioonust.sidLoowt-heand2c0u%rvcreipteoriinatsoftthhate wLeorweerouLtismiitdeofthQeu2an2t0a%ticorinte(rLiaLOwQe)r.e included in the curve calculations but excluded from the ComnatriniucialnigbraCtailoinbcrhateicoknwVaesriafniacaltyizoend(aCiClVe)a.st Feovrerqyuatnotnitsaatmivpeledestetormmionnaittioornsi,nsatrmuimde-nlteavleldri, witha mit of 20% deviation of the terget concentrations. + cLaoliwberratiLoinmicturovfe,Quwainthtiataletvieolnof(aLcLcOuQr)a.cyThwiethLiLnOQ20w%a,stheaqtuadlemtoontshterlaotweedstasrteasndpaorndsngrtehaeter than two times the response of analyte in the blank samples. + ScaylsibtreatmioSnuictuarbvileittoy.mFeiavseusryesttehme-spurietcaibsiilotnyosfttahnedarertdesntwieornetiamneaslyaznedd pbeeafokrasreeaa.chTihneital precision criterion of 5% for the mean area recovery was achieved. LianfborCmoanttiornolwaSspinkoetsu(sLeCdS)b.ecLauCsSestwheeraetpaersfuogrgmeesdtefodr itt hweaRsiviemrpoSsesdiibmleenttos.recHoovweervsepri,ktehde analytes from acidified water when river sediment was not presen. + ShMiaestdricimrxeitnSrtpii,skaempsl(eMsS.).DeMsaitriabxlsepmiaktersixwosrpeikpeerrefcoorvmeerdiefsorartoheF3i0s%h.TiNsostuealal nmdattrhiex sRpiivkeres met `aTnhde RFiivsehrTSiesdsuiemednattasawmapsloqusawnetriaetqeudaunstiinagteadnuesxitnrgacutneedxtcraalicbiroadticoanlicburravteiown hcuirvetsh.e RTivheer Water cdiaflfiebrreadt.ionThcuertvaeblreasngtheatthfaotlwloawscoinntjeacitnedeiwthaesr tfhreomca1iinbgra/tmioLntsot1an0d0a0rndgo/rmLth,ebsuatmtphleeraprnegpearuasteidon `almoentghowdiLhobwaetrcLhiumisteodfaQnudantthietaatniaolnys(iLsLdOaQt)e.foTr htheesaanmapllytoepsrfeoprareaatcihonsammeptlheodatLeLaOcQhSlowcilaltiboon annotated in the tabs.
IM Envionments Laboratory
Page 1301276
_--_--_--m wns
amr
i. 708Calbrtinstr pcaarny
o[nao r mmo |stowa| E[CEomTes| mwmearne | ow | [imonim53] omen sans |roms [mmm | mae| mw] [CT reer s |o rmrni crs| ET E e
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[r[oe m ev ne |ems n |
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es
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[[oemeasr|| ommmmmoenwee awmw
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[[mommnmias|m ] ome omnen |isom]|
[ [rve|eov on omeeninm e |s |iimoemnn s]] [Commas| oom nae |v]
om --------------
RS
ot
_--m mm----e-em e,e ----m
nt
en et
Tas. pr cartonsnr presi sry
C cms rE r ---- a
[mmmas] ommre | ows]
mr| ownome|im]
[mmm | meee| wows | [wom | omios | wows]arn
--
ra
_--m--mnmm
Mr
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--
I ----
EE ~
TIT
Crm |ommm|asnom a| [ems| ommane ew
[[iomrmmo ms[ |i mo s m n ni | romss
[revs| om enne| imw |
wr ES a uo
trams om
--
--_ Report E02:0443
"Torn.RiverValley Sampls
Blanks. Memtehasoudrebloafnmkse,thMioldlb-aQcwkagtreoruntda.kenInthtrhiosuegxhptehreimseonlitd,pthhaesyewoerxteralcatbieolnedpraosce"sWsE,"p.roOvniedesdeat wfuanswpirtheptahreeCdatfofrisehascahmlpolceast.ionA.ccIenptthaebFliesvhaTliusessufeorpotrhteiobnlaonfktshwe eexrpelreismsentth,atnh5e0y%weorfethe Lower Limit Of Quantitation (LLOQ). All method blanks in this study met tis criterion. ThcaretriFdigsehs.TisTshueesseewgemreentloabfetlheed aesxp"eSrBi"meanntdaclosnosicsotnetdaionfemdemtehatnhooldtbhlaatnwkassfourstehde SfoPE ebxltarnakcst mpreet-ctohnedpirteivoinoeudsccorlituemrinosn.that did not have any sample added. Al of these method Soclovnteanmitnabtliaonnk.siMAectcheapntoalblbelasnoklsve(nmtebtlhaannkosl miunjsetctcioonnst)aipnrolevviedlesdofa tmaeragseturaenoalfyitnesltersusmtehnatn t5h0s%croiftterhieonLoewxceerpLtimtihte OfoflQlouwainntgi:tation (LLOQ). Al of the solvent blanks in this study met Nthoetecr-itSeorliaveanrtoBnloatnrkesctohradtewdebreolobw. etfheoSyrstoemSutabiltyinjectionsanddidnotpass 0we2r0e6c2a6useexdtrbayctceadrsraymovpelrefsr0o0m5h0ig(hPerFBlSev,elPFstHaSn,daarnddcPurFvOeAp)oianntsd.00T5h1e (soPlHvSe)n.t blTahneksse that were run after these points showed minimal camyover. wDa0s20c6a2u8sesdambpylcear0r0y5o1ve(rPfFrBoSm,tPhFeHhSig,h-alnedvePlFsOtAa)n,da0r0d5c2ur(vPeFHpoSi)n,t.anTdh0e0s5o3lv(enPtFHbSl)a.nksThis that were run afer showed minimal carryover. D(P0F2H0S6,29PFsOaAm,plaensd0P0F5O9S()P.FHTSh,isPwFaOsA,caFuOsSeAd,byancdamPyovFer fO0r0o6mS0h(iPg)hF-OlSe,v)e,l astnadn0da0r6d1curve poonintthse. quTahleit0y0o6f1thMeedtahlaa.nolThBleannekxthasdaampsliegnhifaidcatnrtalceevaelmoofunantaslyotfeasnabluytttehiasnhdawdansobeeflfeocwt tshaempLleL.OQThfoer anlelxatnasloyltveesn.t bTlhaenrkef(o0r0e6,7)thhea0d06no1mMientahlaannoallyBtleacnokncdeindtrnaottiionn.fluence the D(P0F2O0S7)0,2 Tshaimspwlaess0c0a4u2se(dPFbOySc)a,rr0y0o5v9er(fPrFoHmSthaenhdigPhF-OlSev)e,l0s0t6an0d(aPrdFOcSu)r,veapnodin0t.061The solvent blanks that were run after showed minimal carryover. cDa0r2r0y8o1ve2r(4f)rosmamhipglheesr0le0v1e6l s(tPaFndOaArdancdurFvOeSpAoi)ntasndor0s0y3s1te(mPFsOuAit)a.bilTithyepsoeintwse.reThcaeussoeldvebnyt b(lPaFnOkRs)thaantwde0r0e39ru(nPFafBtSe,r tPhFeHsSe,poainndtsPsFhOoAw)edhamdinciamrrayl-coavrerryforveorm.saSmeplmepsl.esSu0b0s3e7quent blanks showed minimal contamination.
1003231(1F1O2SsAa)m,p0l6e6s, 0(1P2FO(APFaBnSd,FPOFSOAA),,a0n6d8F(OFSOAS)A,),0a2n7d(0P7F1BS(,FOPSFAO)A.,aAlnldofFtOhSeAs)e,can be attributed to carryover from high-level standards or samples.
IM EnvironmentalLaboratory
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Report E02.0443
Toan, River Valley Samples
DATA SUMMARY aTavbelreasge7ad,at7ab,fo7rc,saamnpdl7edgrporuepsse.ntRtehperdeasteantfaotriivnedicvhidruoamlastaomgplreasm.s aTraebplree8sesnutmemdairniAztetsacthhement C. sTaambplleess.7a,A7lbs,o7icn,claundded7dardeistphleaayvtehreaogne-ccoonlcuemnntraantdiocnosrfroerceteadchcosnectenotfrsaatmiopnlsesforstiannddivairddual dceovriraetcitoend, faonrddi%lutCiooenf/fciocniceennttorfatViaorniaftaicotno,rwshientnroadpupcleicdadbuler.ingThseamfpinlael vparleupearsarteipoonratenddabryeinjection v`soolmuemoeftdihfeferseanmcpesl.esTwhiethirnepaorgtreoduvpawleuresew<eLrLeOnQo,t athdejuasvteerdafgoer MvaatlruiexfSopritkhee Rgercoouvpewriaess.calWchuelanted uTshiengabtbhreevrieaptoirotnesd aarnaelyatsicfaolllvoawlsu:eSfLor--saSmapmlpelse>LoLcLatOiQona,nCd--thCeatLiLsOh,QLvMalu--eLfaorrgseammopultehs <baLsLs,OQ. `SM -- Small mouth bass, RW -- River Water, and RS - River Sediment.
IMEnvironmental Laboratory
Page 2001276
_-- Report 02.0643
Tenn, RiverValleySamples
Table 7a. Catfish Analytical Data.
42rT| SStiicCrz|1
wSw40o0a|]
SwwOoQa ||
w1i0oaa| |
08399 sa
w5g07 55
SSTt.iCc2i1s|| alocaa|| awooaa| [ooaa|| s424 us2s0
SStiiiccazsz|| aacoaa|| wwoooa|| awcoaa|| 3429 saon7
SStiac.caez1|| sticas|
aaolao|| aca|
wwoaa|| woo |
waooaa awa |
[[7740 74
770058 738
sS4i.icc4a1z|| a4t0a0|| sticas| soa|
wooaa|| wteoaa| ico| ica|
a[37s 38
837 2
TET| SSSLiiTai.ccCeeess1||| waalooonaa||| iicooaan||| SwLiioooaaa|||
eent ss
%5710 gs
Te
SSLir1.cceesl|| Siices|
aawooaa|| dica |
taooaa || wo|
o<iaoa | wioa |
s[7s0 70
we1 es
SSSttZazccCiiaz|||
1di0o0a|| aioe|
ooaa|| wuoa |
<wiooaa || oa|
waood aioe
SSCtZacCa212|| Staczs|
a1i0o0a|| dca|
ooaa|| woo |
w<woioaa || wea |
w<teoa0 aioe
sSLiZaCcoe12|| Suzcas|
a4o0a0|| aca|
w<io0ag|| oa |
wwiooaa || wwoa|
w<oag aica
SSSiUtzZaccC4ae1zs]||
aaawcoaaa|||
i<wicooanq |||
aaSrricoooa|||
<wLeoag won
TE|
sSiz2cGsorz|| Si3ces|
w<iotoaa|| aoa|
w<ioona || ica |
1wi0oaa|| Sica|
<ona wica
sSCi2zccee1z] | Sis ces|
waoona|| arco|
wdoona || ica |
wooan|| woo|
wtoona ica
SSCtt2az6ce77r2s|| daaiocvaaa||| iicooaae||| wwwwooonaa||| aatioooase
SsSitas3iccrrrsz|||
aa4o0o0aa|||
w<wi0oo0aa|||
lwooaa|| Sica |
<wtoaa Gio
Te|
SSL3a.2C221|| St3cas|
amooaa|| <uoa|
iioon || ica |
wiicoaa|| arco|
w4rooea wica
SsStLi3a3Cc8aa31z3||| "<<wwooo0oa||| aadiiwocaaa||| <wiec0aa||| ia<wiciooaaa
TT|
SSLia3.cca4z1|| Stacas|
aIioona|| aca|
ooaa|| oa|
w<iooaa || wuca |
awooaa win
SsSLia33cCcs6s?1s|||
aaAcolaao|||
wwwo0oo0a|||
w<1o0aa || awco |
<o0a ico
SSLi33.cCee?1|| Staces|
adlooa|| aca|
w0oaa|| wioa |
w<o0aa || Sioa |
w4o0oa Sioa
EaI iE] ) 2 06
esaisn|| 110003 0073 ssmme
2G6a0 | s[ezs 4% | ss
s5i7s5 7o7s 1 53%
iisrs || miesr 26x| 102
m0o7a is
s7er wow
iSi | 2 Twies aTmo
swuss| t[eers 1s | 80
i280588 02
27095% I
awzs | [v5e9 575s5 a51m
oosux|| esoo 558077 10057%
iEonne
Pireo:
iooan
ooaa
Twoon
"wioaa
woeoa
g"irceay
awioae
wp"rirod)a
1T3S is
1T8S7 2775 60 60%
121 12
T1iss 22
a0TIdTT
ppoereae)
3357 io
3851 wh
TT2Tw
00a8
tooaa 23
25
wT
23 22
3MEnvironmentalLaboratory
Page21ct278
--------------------------------------------------------------------------------
Report E020443
Tonn, River Valley Samples
Table7b.Largemouthand Small mouthBassAnalytiDcataal.
a.
d
Fon
NE
" FR
gia)
9 gi) ing)
SstLiiLmi2| oLLaOQ|| <LLoOaQ|| <we0a Siva| aoa| <tica| sic
Sawooaq | [wTeos eweos 25821 aoa | eo wer dos
SSLUivzmeez|| aarooan|| <<ioaa|| aooaa suiimes| soa| <ioo| aco
Twooaa | [emse wwoa | sz
8e6mso ez
ssoerie
SSSCCCiiOwwsaTsz||| i<<i0coaaa||| owiwaooaa||| w<wiooonna
ioTocaaa || mm[risz esTEwrsr ao7mm5e
SSivi4we1z| i[4c10a0|| awwrooa| [i"eosn as | Tooa | T 77 CT wo m70m0
sutuwas| aco| aoa| woo a(@omienatod woo | ess ess 15%
SSCTimMwesTz|| <<w0oaa|| <tuooaa|| wtooaa SUimss| aioa| suca| wioa
rooaa | s[dsee aemsos 2p0r0)3 oa | swe mr o2%
SsiCamNmeTz || siiowes|
dooaa|| qica|
a<tooaa|| suoa|
d<wiooa aio
Mwooaa | <woa |
[swmse eso
s6m8n7 ew
a7=r3)m%s
SSiizziMwai1z|| stzowts|
aalooa|| swoa|
<mooao|| coo|
waooaa aca
wroaa|| <Lo0aa wwoa| ion
SSUZziMmza1z|| i4Io0aa|| <oaa|| <woia Sia ima| arco| ica| aio
rwooaa| ai[2c8a 5 wwoa| aica
SstZziMmostz|| 0<w0oa|| <<o0a|| awooaa SLzmss| aoa| ica| aio
oacaa | v[i87s coq | ss
w7ie 87
ie0eer
SSSCitZ zaems?|||
4ar0ooaaa|||
ooaa|| ion|
<ooaa suo
aIoa | si <iog | sss
sseeees
22m Sr
Sssiiessiiamrssz||| s4w0oo0ao||| oawioaoaa||| <aStioocaaa
ri<ioooano || [datioocaae
SsCt3aMm2a1z| [d1o0aa|| awooaa|| <wweoaa Sts mes| rca| <i| aica
<Siiooaa | i[coaa <ioa | dion
SsCt33omsy2|| wiooan|| <wo0n|| <wwoiona Si3imss| aroa| <tioa| wo
oSiaon | [aooaa <uoa | aica
SStL3aiDiWaTz|| St3.oues|
a<Looaa|| awoa|
liocaa|| wioa|
<wtooa awoa
arooaa || <iicoaa suca| wica
SSLC33OoMw5s1z| susumss|
<[1i0o0a|| sion|
4ai0oaa || ica|
w<ieoaa woo
aorao|| a<iooaa woa| ico
SSSCtt3saO.twwwese1sz|||
<awi1io0caao|||
aaooaa|| swoa|
w<woiona wica
oroaa || owiase Sioa | aica
SSCC33oDwMrTz|| sUs.wrs|
a<wiooaa|| ica|
awwooaa || wwoa|
iwooa aca
dooaa || <tooaa woa| ica
SSta3si5iz|| staswrs|
a0o0a|| Soa|
a0o0a|| aica|
w<o0e dion
owwwoaoaa||| iawiioocnae
WM Environments Laboratory
Page2201276
sev
en vr
--
= 8 e a= (u SLaisz
==
BI ET ishi [ar ---- pNa E
sy
hind
Rr a at
== EC I S oa E =
L E 5B B 0 |aa ET T E TT ) {ngimt) fe)
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pny
B zE E I | e L u= n = --- 2 pS u RL csaS toSE r
sername
_--
---- ------ e ee ee
Report E02.0843
Tenn, River Valy Samples
Table7d. RiverSediment AnalyticalData.
oi
[OC
036404s6 || s2e000aa4z4iSs1Li,t 11008s
Vol (0g) 5a33
[rey 55500
aT 5417
0so3us ||3s00s4o5a1s,s5st3t 15305
a1
3045 |300452 5L3 83
a
owrex pid
rr=y "
Seo0o4k5e | [s3p0o0a4s5y-1s50a2 15050
5i0s
046 | 30046252 52
31
a0r2 0
1o0r% 17
s330s40 | 30S0a4m8o352 On C1o7lumn AdjustpeHd]for ny Adjusteda3for Sample Average.SiStd Dew
MSE a Jr o38u04s4 || 3300004444-21,5SL11 2257
113%
CE138 2
and YC13V.0 (pig) 5
otouos eois
| |
[sReoass s3| ois2sts|
a2o5a <ioa
oi2a oa
w1o24n oa
prsxey oa
Sooios ||Weo0uesTs.sStLs2|| Laouoaa Jie | oaezsiz| woo
<000 oa
Taooaa Sioa
"wtoona oa
so0is | saEnsTaTsal ico E Sioa E <iioo PreT) E
us 36044
[ne | 30044-1501
E 62 y 3
3044 | 30442501
1
71
prey B1(0py) 708
E75R2 AT]
oroofi | 0r0i4t15)3 oaa7
IEtr))
3045 | 300452813 28
13
oEsre 130
Toa% <ioa
SSoouos || 0wo0u6s,s5is0i2s]| atooaa
aoloao
ou |wouezsi2| wo
oa
aoloao woa
0to0a ica
soi | se0ies sa] dion
oa
prey
Sioa
RI
[rire
380041, 5U1 77
ph 148
360442 SC 24
162
[rako i818
E3ro By
04s |330s004u541s,,5SC31 224s 30045 | 3s0452 513 12
2083 0s
i223
i 2
S00040s ois
|| |
0030844066-4152,35s51L232
7197 23
0185 13
T8as 128
1E8i}% i
32045_| 300463 SC2 hwios | Swe
32 eOn Crolu)mn
ie Adusptedyforin
Adsicd
io for
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re
Awrago 2S%ti Oc Eon
333000404444 ||| S330o00044-e41s2, SsSUUL1 5o30r4
285318
332851153
3i51052
004055 ois
||330000445521,5U33 | 304s sU3
81 1
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5805 105
2Ts 53
5is 25
1w=r%
`Summafroirtehse average analyte concentration per sampling group and location are given
below.
IM Envhonmenta Laboratory
Pago 2601276
--i --------------------------------------------
Report 020043
Ton.River VateySanpies
Table 8. Sample Location, Sample Type, andAnalytical Data Summary. ET
`4SSamppelciinegsLSoacmatpiloend [PSEFECBTCSY (ngoigy)
tngigA
[ os
ors
FEE
<oa <0 <UOQ 60.9 (887 113 (6l6
SL2.C (n=1) <uoa Loa oq <0 <ioa
ERY <toa <0
oa <loQ 15.246]
SLA. LM (n=6) SL2. LM (n=)
toa <a
Loa <oa
<Lioa' <oa
<loq 853 (6/6) <loa 169 (214)
SL3. LM (n=7) oq
oa toa <Loq <0
rE
<Lioa <oa <Lioa <iioa Loa
River Water
FEN sL2.RW SL3.RW
ey
PES
ey
[ee
PFOS
ee ee
[rene Lo) (pgimt)
84
196
550
25
491
"oa <0 <woa <ioq <oq
iio
Loa
oa <ioa <oa
River Sediment
PrBS
[a
ey
ey
PFOS
[2
[2
[
[
[2
LEE
517
130
732
1440
3130
sL2.RS
437
<Loa <oa
141
457
EER C= CatFish, LM
=Large
4s2 mou Gass,
<oa SW =Small mouthbuss,
R1N27= Riverwataer,d8RS
=
RiverSedime4n1ts6.
Hliguh rmplobcfaiFeivsharl>ueLwLaOsGsNtatiusticamolfFsiabmhinAaneiaeldyzuresidn.gOrDilxyoor'nseQR-iTveesrtWater andon RiverSedimentsamplewere
cOllacied from aach sampling locaton.
Attachment B contains additional data summary tables.
STATISTICAL METHODS v`Satraitaitsitiocnalanmdetshtaotdisstiwcealreexlaimmiinteadtitooncaolfcuolualtyiinnggadvaetraagpeosi,ntsstaunsidnagrdDidxevoina'tsiQo-nTse,s%t.coefficient of
IM Environmental Laboratory
Page2501276
orree--------------------------------------------------------------
Report 02013
Torn. RrVateySamples
STATEMENT OF CONCLUSION
Fish Tissue: FFiisshh iissssuueo oobbttaaiinneedd ffrroomm SSaammppllee LLooccaattiioonns12caonntdai3nceodnqluaainnteidfiqaubalnetilfeivaeblsleofleFveOlsSAofaPnFdOPSFOonSl.y. River Water: WPaFtOeSr. fWraotmeSraombptlaiinngedLofcraotmiosnam1pcloentLaoicnaetdioqnusan2tiafniadbl3edliedvenlostocfonPtFaiSn,quPaFntHiSf,iabPlFeOeAv,elFsOoSfA, and anaiytes. River Sediments: RPiFvOeAr,SeFdOiSmAe,ntaonbdtPaiFnOeSd.atRSiavemrplSeedLiomceanttioonbt1 acionnetdaaitnesdamqupalnetiLfoicabalteiolnev2elcsoonftaPiFnEeSd,quPeFniHiSf,iable l`qeuvaenltsifoifabPlFeBlSe,velFsOoSfAP,FaBnSd, PPFFOOSA., FROivSeAr,SeadnidmPeFntOSo.btained at sample Location 3 contained
REFERENCES 1. 3SyMstEnevmisroUnsmienngtaHlPLMCe-tEhloodctErToSs-p8r-a15y5M.a1ss"SApenciarloomfyeWlsarysitse Stream, Water Extracts Or Other
LIST OF ATTACHMENTS
AttachmenAt: Analytical Method and SOP Davitions + Attachment B: Data Summary Tables. + Attachment C: Sample Chromatograms + Attachment D: Sample Prep Sheets, Test Substance, and Test System Information Attachment E: Notes to Fie
REPORT REVISIONS TTyhpeognruampbheicralofefrirsohrssafmorplteheduantieadceshilgoncaattoirosnfwoarsTaabllseos1ad,d6e2d-1,6 7Taa,bl7ebs, 71da,nadnd8.8Twheeredecsocrrriepcttieodn.s ohfotshee rseapmoprltiendgnlotchaetiEonntsriwxerreepoardtj,uJsutle,d 2in00th3e(psruojmemcatr#y17a8n4d01n).tabRleesmo3av,e3d,twaondva3lcuetsofeofriPecFtHS iPnFfOivSeriwnaftiesrh aitn tsaabmlpelsin1galnodca8tiboencsa2usaendth3eyanwderPeF<OLALOiQn.sedRiem-ecnaltcautiastaemdplaivnegralgoceatviaolnue3sifnotrables 12nd 8 using LLOQ values for samples < LLOQ.
MEmonment Laboratory
Page 8276
Repo 02043
eee Tenn. Rover VoySampes
`SIGNATURE PAGE
We certiy that this reportisatrue and complete representationofthedata or this study:
<<
Eefson, `Study Director
2g [12 fpz
Date
ez Wiliam K_Reagen, Testing Facilty Management
0123 Date
MEnvionments Laboratory
Pogo 270t276
C-- e----------------------
Report E020443
__. Ton River atey Samples
ATTACHMENT A: ANALYTICAL METHOD AND SOP DEVIATIONS
SM Emironmentl Laorstary
Pagoasotzre
Reon E020843
A
----
Torn River Vay Sansios
`Document may be used,if current, for 14 days from 11/21/2002 33E MM EN NVIV RONMI ENTR ALLLAAO BORN ATOM RRYY ENTAL
MeTHOD ANA OFWL ASTY ESTRS EAMI ,WATSER EXTRACTS OR OTHER SYSTEMS USING
'HPLC-ELECTROSPRAY/MASS SPECTROMETRY
Method Number:ETS-8.155.1
AdoptionDate: {1/0 / RevisionDate: S/30/(0(
Author: MarkL. AndeMarrksE.oEllnefs,on
Approved By:
plz --
Laboratory Manager
L
oly
Date
/3io0 fo)
M Environments Laborstory
Page 2901276
Report 02043
Ton.RiverVatey Sapes
Document may be used, if current, for 14 days from 11/21/2002 10__ SCOPEANDAPPLICATION 11 Ssycsotpeer:usTuhsiisngmeHtPhLCo-dedleseccrtirboessptrhaye/amnaaslsyssipsecotfrwoamsettersy.tream,watersamples orother
111 Sstpaencdiafridc(asn)aalyntdeso,thieornsp,amraatmreitceerss, swiolllvebnetsd,efsoilnuetdioinnst,hqeuparloittyoccoolntorroltsh,eisnatmerpnlael preparation worksheet(s).
12 Applicable Compounds: Electrospray ionizable compounds. 13 Matrices:
13.1 WsyasstteemsSotrreaasmdseasnidgontatheedrisnysttheepmrsomtaocyocloonrssiastmopflaepqrueepoaursatainodn/owroorrkgshaeneitc(ss)o.lvent 132 WsaotluetrioSnasm.pTlheesmiantcrliuxdewitlalpwbaetedre,fginreodubnydtwhaeteprr,owtaocsotlewoartsearmapnldeoptrhepearraaqtuieonous
`worksheet(s).
20 SuMmARYOFMETHOD 21 This method describes the analysisof electrospray ionizable compounds, using HPLC-
seelleeccttrioosnproayfamsaisnsglsepeiocntrcohmaeratcrtyer(iHsPtiLcCo-EfS/pMarSt)i.culTarhecoamnpaloyusnids.isperformed by the mass
30 _ peanmions 31 qAutamdorsuppholeersiycsPtreemsssaulrleowIofnoirzvaatriionou(sAmPe)t:hoCdosmomfeirocniiazlatliyonavbaiyluatbilleiHziPnLgCa-vaErSi/etMySosfingle
sIoounriczeast,iporno(bEeSsT),,anAtdminotseprhfearciesc.PTrhesessueriencchleumdiecbaultIaorneinzaottiolnim(iAtPedCt)o,:ETlheecrtmroosspprraayy, et. `vTahceiuounmi)z.ationintheseprocessesoccursatatmosphericpressure(i,notunder a. 32 `Eplreescsturroe,swphrearyeIboyniizoantsiionns(oElSu,tiEonSDa:reAtramnestfheorrdoedftiootnhizeaglaisopnhpaesrefvoirmetdinaytcahtamrogsephderic: droplets. These droplets are produced by the application ofa strong electrical field. 33 siMnagslseSqpecutroametdmearsr(sVsSeu)l:ecCtpoimvemodeertcelicatloelrys.maTnounfsaarcetsuerleedcMteSdosnytstheembsasairesoefqumiapspsedtoith charge ratio (w/z) and subsequently detected. 34 MspieccrifoimcaospserMataisosnoLfyannx /HPHLPC-ChEeSm/SMtSa.tiPolneaSsoefrtewfaerre0: Sthyestmeamnusaolftfwoarrtehdeesspiegcinfeidcf:orthe instrument software.
SMEnmonmeo Laborer WM Envronmertal Laboratory
wns Fst
Peszaro Page 001276
_--------
Rogert E20443
Tenn. RrValey Samples
Document may be used,if current, for 14 days from 11/21/2002
40 WARNANIDCNAUGTIOSNS
41 Health and Safety Warnings: 4.1.1 tUhseepcraoubteioenmpwiltohysthaevvoloagleocfatbalpepsrafooxrigtmhaeteeellyec5t0r0o0spVroalytpsr.obe. When engaged, 412 aWnhdeenyehwaenadrl.ing samples or solvents wear appropriate protective clothing, gloves,
42 Cautions: 42.1 bOapcekrparteesssuolrveeenxtcpeuemdsp4sb0e0lboawr,tahbeacPk1pr1e0ss0uwrieollfi4n0it0isbteearu(t5o8m0a0tipscis)h.uItfdtohwen. 422 Do not run solvent pumps to dryness.
50 INTenrRences 51 Tstoomriagneiomriazneyipnatesrtfoefrienncsetsrwumheenntaatniaolnytzhiantgcsoammpelseisn,coTnetfalocntswhiotuhltdhnesoatbmepulseoerdefxotrrsaacmt.ple
60 Equipment
61 E`quimpmeontdlisitinedtbhfeelroaiwwmdaactyabaaesmmotedtihfiioedddoeivninaotridoesrns.0optimizethesystem.Documentany 6.1.1 eMlieccrtoromsapsrsayPliaontifzoartmioLnCsZouMrcaes.s Spectrometer (or equivalent) equipped with an 6.12 HP1100 low pulse solvent pump,solventdegasser, column compartment, and autosampler or equivalent HPLC system.
70 SurruesAND MATERIALS 71 Supplies
7.1.1 Highpuritygradenitrogen gasregulated toapproximately 100psi(orhouasier system).
7.12 HsiPzeL)Coraneaqluyitviaclaelntc.olumn, sausacBetahsil C18 column (502mm, 5pmparticle: 7.13 Cappedautovialsorcapped 15 mLcentrifugetubes.
80 REAGANEDSTNANTDARSDS
81 Reagents: 8.1.1 Methanol, HPLC grade or equivalent.
3M Emon Libor AisUsoHPLC.sBaies)y pecomety
Lr
3M Environmental Laboratory
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Report E020443
Tom. River Vatey Samples
Document may be used, if current, for 14 days from 11/21/2002
8.12 M`wialtlerio-QTMeqwuaitvealre(atA,SaTnMd mtyapyebIe)palrlovwiadteedr ubsyeadMiinltlhii-sQmTetOhCodPlsuhsouslydstbeemMoirlli-QTM `another vendor.
8.13 Ammonium acetate, reagent grade or equivalent. 8.13.1 When preparing different amountsthanthose listed, adjust accordingly. 8132 `2a.m0mmonMiuammsmcoetnaituem.Paoceutraitnetsoolau2ti0o0n:0WLeviogluhmaeptprriocxfilmaastke,alydd0t.3h0e0 g aSptporroepraitartoeovmoltuemmpeeorfatMuirel.li-Q watmiexurnt,il allsoalrediissdolvesd.
8.1.4 Optrheeparrsaotlivoennwtosraknsdhseeotl.utionsmaybeusedassatedintheprotocolorthesample 82 Calibration Standards:
82.1 TyopfiScsaolllveynttwsotamnedtahrdosdabrleaannkasl(yMizleldwi-iQtwhactaecrh),gtrwooumpaotfrsiaxmbpllaensk.s,and aminimum
o90TSAMrLLiEHANDLING 9.1 cSetnatnrdiafrudgseatnudbepsreopraortehdesrasmupitlaeblsemcaoyntbaeinsetrosreundtiinlcaanaplpyesidss.utovials,capped 15mL 92 `Ifaapnparloyxismiaswteillylb4edCeluanyieda,nsatlaynsdeasrcdasnanbdeppreerpfaorremdesda(mtpelfeigsemraatyobretermepferriagteurraetesdmaaty have a detrimental affect on the solubilityofsaturated solutions)
100 Quaurry ControL,
104 Blanks:
10.8.1 `Seoalcvhesnatmbpllaenskes,tm0etdhetoedrbmlianneksc,onatnadmimnaattriioxnoblracnakrsrayorveprr.epared and analyzed with
10.1.11 `WwhateenrotrheHPstLuCdygrmaatdreiocregsacnoincssiosltovefnhtisg,htlhyempuertihfioeddasnoldvmeanttrsisxucbhlaanskTsmypaey1
be represented by a ingle solvent blank.
10.12 aSnodlvmeanttriblxabnlkasnskhsosuhlodubledbaenaalnyazleydzeprdiaofrtetrotehaechnictailailbrcatiaonlcuirvecb.urrMveeatbhutotdpirbilooarntnkos
thestudysamples. necessary.
Ifcarryoveris
problem,consecutivesolventblanksmaybe
102 Matrix Spikes:
10.2.1 Matrixspikesmaybeprepared foreachset ofextractedsamples(ifspplicabtloe the study) andanalyzedto determine extraction efficiency.
IM EmreLitorory
ingHPLCEBriasce Sosy
Prd"otio
3M Environments Laboratory
Pogedzotz1e
ee Report E2043
Tenn.RiverVaty Samos
Document may be used, if current, for 14 days from 11/21/2002 10.2.2 Matrix spike duplicates may be prepared periodically tomeasurethe precision
associated with the analysis. 10.2.3 Analyze the matrix spike and matrix spike duplicate (ifprepared) in the same run
as the original sample. 10.2.4Matrixspikeandmatixspike duplicateconcentrationsshouldfal inthemid-
range oftheinital calibration curveor shouldbepreparedat1.5-Stimesthe endogenousconcentrationoftheanalyte. Spikeconcentshroualdtfailloinnthse low-angeofth initialcalibrationcurveifextremely low levels are expected.
103 Continuing Calibration Verifications: 103.1 `Csocnctuirnacuyionfgtchaelibcraaltiibornatvieornifciucravtei.ons (CCV) are analyzed to verify the continued 1032 Analyze a mid-range calibration standard ater every teath sample, with a `minimumofonepersample set.
104 Internal Standard/Surrogate Standard: 104.1 Anintemalstandard(S)maybeusedtoquantifythetargetanalytesby establishing arelationshipbetwentheratio ofanalyte responseto ISresponse: and aknownconcentraotfiothne anaolfiyntetreset. TheISshobeuspilkeddat `anamountthatwillfallwithinthemid-rangeofthecalibration curve. The IS shouldbe addedafertheextractionprocessandbeforeanalysis. 10.42 Asurrogatestandardmaybeusedforqualitycontrol.Thesurroisgusaetdteo quantitatively evaluate the entire analytical procedure including sample preparanadatnailyosins.Thesurrogateshouldbespikedatthebeginningofthe Sempleprepaarndashtouildofanll witthheloiwtno mid-ofrtheacalnibrgatieon curve.
bo
111 Analyzethestacnurdvesaprirordtoandfolleacohsewtofisamnplegs.Theaveragofe twostandardcurvesmaybeplottedby linearregression(y =mx +b) weighted1/x,or qcuaaldirbartaitcionitcu(ryv=es2xs'ho+ubldxn+oct)buesifonrgcMeadstshrLoyungxhozreorot.hersuitablesoftware. The 11.1.1 The closing calibration curve may be excludedifthe CCV"s meet acceptable criteria. Ifonlythefirstcurve isused,thecalibration andstandardization `parameters are the same.
112 maIfitnhteeinnaitnicalecoalripbrreatpiaornecaunrveewdsoteansdnaortdcmuerevtea(ifcneccesseacrryip)taernitdapreeraafnoarnlmyzreco.utiene: 113 For purposesofaccuracywhen quantitating low levels ofanalyte, it may be necessary to
use the low endofthe calibration curve rather than the full range. Example: when
SMErvionmenalLabora
Amiri sgHsCBssotSapc n
Pesaro
aM Environments Laborer
Pose 3301276
--Repon 02043
TonRiver VaySamples:
Document may be used, if current, for 14 days from 11/21/2002 attempting toquantitateapproximately 10 ppb ofanalyte,generate acalibrationcurve. `consistingofthestandardsfrom 5ppbto 100ppbratherthantheful rangeofthecurve. (5 pp010b00 ppb).Thiswilleduce inaccuracyattributedto linearregressionweighting of highconcentrationstandards. 11.4 Highand/orlowpointsmaybeexcludedfromthecalibrationcurvestoprovide abetterfit overthelinear rangeappropriatetothedataorbecausetheydidnotmeetthepreaderteearcmoiunnetdsaacrceenpottaantcleecarsittterwiiac.eLtohwa-tloefvtehlecmuertvhepoodibnltasnskhso.ulJdaulssobteiexffcoliruecdxecadliutfsitihoenoiornf calibrationcurvepointswillbenotedintherawdata. 11.4.1 Aminimunof 5poiatswil beusedtoconstructthecalibrationcurve.
120 _Procepures 121 Acquisitionset-up ~pleasereferencethe SOP thatpertainstothespecific
instrument. Actualparameters will be recorded ontheinstrument printouts. 12.1.1 Sethetsamuplep lit.
12.111 Assign asamplelst filenameusingthefirs eterofthenameof the iannsdtrtuhmeednaty((T fo0rT0uck1efro)r,0Otch1teoyb2eearr(120,02f0o0r02o0n00T)u,ctkheerm).onItfhmo(r04eftohraAnpornile), listismade onthesameday,useincreasingletersofthealphabetstarting with Aattheendofth lst.
12.012 Assaimegthond (MS) fle. 12.013 Assignan HPLCprog(Inrletafilme). 12.014 Typeinsampledescriptionsand vialposition mummbers.
12.1.2 sTpoeccrteraotmeetaemrheetahdoidn,gcslaicnkdosnem lecteSIRi.t nStehtehiAcqouoisintdioimnocdzoentara3oalppaptrnoeplirtihaoetenamnnasds `mass10.499orotherapproprmiasastese. Afullseanisusualycollectiedn additotthieSIoRsn.Saveacquisitionmethod. SeetheMicromass MassLynx GUIDE TO DATA ACQUISITION foradditionalinformation.
12.1.3Typicallytheanalyticalbatch runsequencebeginsandendswith asetofsolvent standards.
12.1.4Saaftmeprleevesrayrteeanntalhsyazmepdlwei.tShoalcvoennttibnluainnkgscsahlioburladtiboenavnerailfyizceatdiopner(iCoCdVi)cianljtleoycted `monitorforpossibleanalytecarryover.
122 Usingthe Autosampler/Column Heater 12.2.1 Placesamplevialsintothesampletrayaccordingtothesamplelstpreparedin Section12.1.1.
TM Envksomesnl Litenory Aoki slog PLECrBsemisps Spc
Pagtotto
SMEmonment Laborstoy
Page s4o1278
Repent E2043
Torn. RrVatey Samples
Document may be used, if current, for 14 days from 11/21/2002
12.2.2 Attach the proper analytical column in the column heater compartment. Ifusing theswitchingvalve, ensurethatthetubing i runtotheappropriateports.
123 Using the Inlet Editor
123.1 Set-up the HP1100 using the following conditioonrs at conditions the analyst considersapprfooropptrimailraesptonsee. Recordactualconditinotnhse instrument logbook:
123.41 Sample siz=e 10 kL injection
123.42 Flowrate= 300 ulmi. 12313 Cycle time = 10.0 minutes
1231.4 Mobile phase components:
Solvent A: 2.0 mM Ammoniun Acetate in Water
SSoollvveenntt BGr:adMieetnht:anol (TMiemOeH()min) %B
000
500%
1.00
5.00%
450
950%
800
950%
850
500%
100
Stop
124 InstrumentSet-up 12.4.1 Refer to the Platform LCZ User's Guide, the MassLyNnTx User's Guide, the ETS-9-36, "Operation and Maintenanceofthe Micromass Platform LCZ Electrospray/Mass Spectrometer",orthe SOPthatpertains to the specific instrument. 12.42Check thesolventlevelinreservoirsand refillifnecessary. 1243Checkthetipofthestainless steelcapillaryattheendoftheprobewithan eyepiece. Thetipshouldbeflatwithnojaggededges.Ifthetipisfoutnobde unsatisfactory, disassemble the probe and replace the stainless steel capillary. 124.4 Tum on the nebulizing gas. 12.4.5 Otphete unepn age. Cloni`Opcerakte'toinitiatethedesolvahteaiteorns. 12.4.6Opeathe InletEditor. 12.461 SetHPLC pump to "On". 12462 Setthesolventflowtothedesiredflowrate. 124.63 Observedroplets cooumtofithetnpofgthe probe.Afinemistshould be `expelledwithnonebulizing gasleakingaroundthetipoftheprobe. Readjust the tipofthe probeifno mist is observed.
3MEmber Libor AyingHBsPLCesnsya Specs
Per0t10
IM Environmental Laboratory
Pages ar276
Roper E02.0443
ToonRiverValey Samples
Document may be used,ifcurrent, for 14 days from 11/21/2002
12.464 Allow to equilibrate for at least 10 minutes. 12.4.7 T`mhaeyicnhsatnrguemienntoursdeesrtthoeospetpiamriazmeettheersraetstphonosfeo.lAlcotwuianglspetaingrs.aThwmeisleelsbetetrteeicnogrrsdsed
on theinstrument printouts. 1247.1 Dryinggas250-425 litershour 12472 ESInebulizing gas 10-15 lters/hour 12473 HPLC constantflowmode, flow rate 10 - 500 wLimin 12.474 Pressure<400bar(Thisparameterisnotset,it iaguidetoensurethe
HPLC is operating correctly.) 1247.5 Source Block temperature 150. 1247.6 Desolvationtemperature 250. 12.4.8P`rsipnetcttrhoemteutnerepinafgoerwmaittihoint,sapnadraamleltoetrhse,rtahpepLlailceatblpeagien,fosrammaptlieonliastn,dmsatsorse it in the
studybinderwith copics taped into theinstrumeatrun logbook. 1248.1 All copies must be initialed and dated. 1249Clickon statbuttonontheMassLyntoolbar.Ensurebeginanndeindningg
`sample numbers encompass all samples 10 be analyzed.
13.0 DATAANALYSISAND CALCULATIONS 131 Calculations (including, but not limited fo):
13.1.1 Calculate matsix spike percent recoveries using the following equation:
%Recovery= Observed Result - BackgroReusnuldt x 100 Expected Result
13.1.2 Calculatepercentdifferenceusingthefollowing equation: %Differenc=e ExpCone.-c CalcutlateedCodne. x 100 Expected Conc.
13.13 Calculate actual concentrationofanalyte in matrix (g/mL): On-ColumnConcentration (g/mL) x Dilution Factors = Calculated Concentration
140 METHODPERFORMANCE 14.1 The LiofmQuanititattion (LOQ) is method, analyte, and matrix specific. For many
analytes, the LOQ concentration is selected as the lowest acceptable non-zero standard in the calibration curve.
SMEon Laboraoy
rt sgHPLFCBraesrsSpecs
Pusbario
IM Envionmental Laboratory
Pages or276
--_------_--_--_--_--_--_----
ReportE0203
JE vr --
Document may be used,if current, for 14 days from 11/21/2002
142 Scoallvibernattaionndcmuervteh.odblankareacounts mustbe < %thatofthe loweststandardusedinthe 143 oTrheequcoaelffti0ci0e.n9t8o0.fdetermination (7) value for the calibration curve must be greater than 144 sCtoanntdianrudicnognCcaelnitbrraattiioonn. Verification (CCV) percent recoveries must be + 30%ofthe 145 Intemal Standard recoveries should be within + 50%ofthespikedconcentration. 14.6 I`fpecrrfioterrmieadliosnttedhienstyhsitsemmeatnhoddspaemrpfloersmreaanncaelsyezcteidoonraortehneortamcteito,nmsaaisndteetnearnmcienemdabyybtehe
analyst. Docallauctiom nsine the n rawdatta. 14.7 f1ofodtantoatiesdtoonbteabrleeposratneddwdihsecnuspseerdfionrmtahencteexctriotfetrhieahraepvoernto. tbeen met,thedatamustbe
115590 _PPOOLLLLUUTTIIOONNPPRREEVVEENNTTIIOONNAANNDDWWaASSTTEEMMaAvNaAcGEEMMEENNTY
0+oo
151 SgalamspslpeiepextttreacwtawsatsetiesadnisdpfolsaemdmianbblreoskoelnveglnatssidcoinstpaoisneedrsinlhociagthedBiTnUthceonltaabionraetrosr,ya.nd
160 _Recomss
16.1 Bachpagegeneratedforastudymusthavethefollowinginformationincludedcitherin thinethegeraadteiornormehtahnoddw,rsiatmtepnloenntahmeep,aegxet:rascttuidoynodratper,odjielcuttniuonmbfaecrt,ora(ciqfuaipspiltiicoanbmlee)t,hoadn,d analyst.
162 tPoriinnctltuhdeetiunntehpeaagep, spamrploeplssttru,daiycfqaouiltsdieetri.onCmoeptyhtohedsaenpdaaglelsoathnedrtaapppeliinctabotleheiinfnosrtmrautmieonnt run logbook.
163 Plotthecalibrationcurvethenprintthesegraphsandstoreinthestudyfolder. 164 Prsitundtydabtiandienrt.egrationsummary,integrationmethod,andchromatogramsandfileinthe
165 Summarizedatausingsuitablesoftwareandstore inthestudybinder.
166
Back-up electronic data to appropriate medium. backed-up electronic data in the study binder.
Record the file names and location of
167 DTootc#usm,enptuarittiyo,neoxfpiarnaatliyotn,e(asn)danstdoarlalgerecfoenrdeintcieonssu.bstances wil include trace numbers,
170 ATracHMENTS 171 None
MEeveoamr Labor
ii higPLECrBsoassso)n pcm
Peesarto
SU Environmental Laboratory
Page 37 ot 276
Repo 02046
ee
---------- Ten. RiverVatey Samples
Document may be used,if current, for 14 days from 11/21/2002
180 RerERsnces 18.1 SPlZat;foorrmFlLoCatZsRUsoeard',sWGuyitdhee,nMsihcarwoemMa2ss3U9KLZL;imUintietde,dKTiudnogrdRooma.d,Altrincham,WAL4 182 MSaRsZs;LoyrnFxloNaTts URsoeard',sGWuyitdhee,nMsihcarwoemMa2s3sULKZL;imUintietedd,TKuidnogrdRoome.d,Altrincham,WAL4 183 M`AalstsiLnychnaxmN,TWGAu1i4deSTRZo;DoartFalAocaqtusiRsoiatdio,nW,yMtihcernosmhaaswseUMK2L3im9iLtZe;d,UTnuitdeodrKRionagdd,om. 184 EEqTuSi-p9p-3e4d.w0i,t"hOpaeMraatsisonSapencdtMroamientteernDaentceecotforHaenwdl/eotrt2PPahcoktaorDdiHoPdLeCAr1r1a0y0DSeytesctteomr". 18.5 ElEeTcSt-r9-o3s6p.r0a,y/"MOpaesrsaStpieocntarnodmeMtaeirn"t.enanceoftheMicromassPlatform LCZ.
190 AFFECTEDDOCUMENTS 191 None
200 Revisions
Revislon
Rew
Number
Reason ForRevision
Date
1 `Section 1: EalrgedthsopoofTtihelmeeCtohuondgbeyincludingaddionalmatics. Also sdded 09May01
Sections `1acoamdm2e:ntRsesmboovuetsdpeecfiefriccapcaersatmoestpeercsiwfiicllcoemdpeofuinndesd,i hi protocolo prepsheets.
S`Seeccttiioonn33:; CRheamnogveeddtpoaarlalgorwapdihafemrCeonntvseynstteimosnsn!vdss.oZf-wSaprraey.probe erfce.
SSeecctioo8n:n: BArdoaadsednpeadnthegthylpeoswoifnsgtorfoagetchon4ta5i0neofrasahnedrcmoanidvistoilovnesn.tssadsolitons.
Section 10; Adsdeducomndmdenpitplsiceaablilsloyw.for exitinqualitycontrolsfordifereatypesof
SSeeccttiioonn111:: AAddddeeddappaurraaggrraapphha(l1l.o4wi)nglofvoritnhgefeoxrclhueddirnogoppfiaheosfeccoenvdecpurovie.s sadmisiur
`Section 12: Audmdbeerdocofmcmuernvetpsototsereeendcede.hespecificSOP's forsep.
S`eScecttiioonn1126:: ACdomdeecdtperdgnrumabpehrionng,records of naysandsubstances.
Section18: Addedreferenceto hemethodfo theHowlen-PackardLMS.
SM EmitLatetoy SMEnonmerta Laboratory
imE]ss -
Pas100o110 Pagessarars
Ropon Enzous
Record of Deviation
Ton. RiverVatey Samples
1. Identification
Study / Project No.
Deviation Type: (Check one)
TN River Valley E02-0443
0sop
AMethod 0 Equipment Procedure
O Protocol 0 Other:
Document Number: ETS4-04.0
Date(s)ofoccurrence:
Ti. Descrip0tionTe:ws Joos -- JE 20
Required Procedure/process: _ETS-4-04.0 section 4 states, "It i the responsibility ofanyone:
`handling
form."
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movementofthose
samples
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chainofcustody
AthcetucaolurPsreoocfetdhuries/sptruodcye.ss: The internal chainof custody forms were not generatedorused in
Til. Actions Taken:
No
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a
ction
w_i_ ll(sbuecthaaksena,maesntdhmeeinntfoirsmsauteid,o
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Recorded By:
E ntp nfi
7
-
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IV. Impact on Study / Project
`This deviation does not adversely affect the qualityofthe data.
Date:
7 Nem
Authorized By:(Study Di oye Lead)
Date:
/
3M EnvironmentalLaboratory
3MEnvironmentalLaboratory
(aig vy Sud Dict DevPicattioLnodNo. o__/ doiy) Page3901276
em Report E02.0043
ATTACHMENT B: DATA SUMMARY TABLES
-------------------- Ton. RiverVasey Samples
SM Environmental Laboratory
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ATTACHMENT E: NOTES TO FILE
Tem.RiverVatey Samples
3M Environment! Laboratory
Page270 ot 276
_--mmmm--m--
Resort 02043
Toon.River leySamples
_3M-- ENVIRONMENTAL LABORATORY
Note to File
Project or Study Number: E02-0443
LIMS Number: NA
Affected
Data:
D020626Extracted, (Fish Tissue)
D020628,
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Project or Study Number: E02-0443 LIMS Number: NA Affected Data: All Data
N1ote: This stoexplainhow the quantitation wasperformoednthe dat. Tcihnaesstsean,ntciherisegihnclawelvihebilracctuitroivnsecpwuoraivsnetdswoanwsee,reenhte"eDrdiesidasibbltleoeddt"hcieunrqtvuaehnptsoioitfnatttwsiaosrnhesooawfntdawawrreeecroavnrederymthooevec0fud%rfvreowmatshethcuervaenaclaylzceld.atoInn.manTyy al dLneoottewursmeeindnd.atcTiuhornevseoefptophoieinnsLtsOtGhw.aeehasdti4l nRceclouvdeerdieisnttchhaaltiebxrcaetedieodntchuercvretcarlicuolratwieornse,<ho2wXevteher,sotlhveeyntwebrleannksolweveedlsfwnetrhee 2Ilnotwhoerraanwedgaattaivtehavtcaloumeears faosmigtnheedTaanrgeexttrsoefmtewaproes,ticvonecveanlturea.tiTohnsestehavtawlouueldarneocramsailllyynobteiqcueadndtiuteatteodthaesira very oafbaquoarnmtailtlatyiloanr,gaerveaclhueasnagleodntgow"itBhLvOeQry stmoaelllirmienaatceoaunntys.poTsshiebslee vcaolnufeuss,ioanl.ong with values that are blow the limit
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Page S of6. Page 275276
_--_--
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3M ENVIRONMENA TALALAOBORRATOORYY
Note to File
Ton FerVoteSampen
Project or Study Number: E02-0443
LIMS Number: NA
Affected Data: Fish Tissue
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