Document L4GnQoxVjQ0mqOROn40zVYoX

STABILITY IN WATER (HYDROLYSIS) TEST SUBSTANCE Identity:N2-(N-methylperfluorooctanesulfonamido)-etahcyrlylatem;ay alsobe referredto as N-MEFOSEA, or MEFOSEA. (2-Propenoicacid,2[[(heptadecafluorooctyl)sulfonyl]methylaminoe]settehry,ClAS 25268-77-3) Remarks: Materialisan amber, waxy solid,coded THAR3F2. Sample'purity was not characterized. METHOD Method: OPPTS 835.2110 GLP (YIN): No Year completed: 1999 Type: Abiotic Stock solutionand testsample preparation:A 10,730mg/L stocksolutioonf MEFOSEA inacetone was prepared. Test solutionswere then prepared by adding 10 uL of the stock solutionto 1.0 mL of fivesolutionsindividuallbyuffered to pH values of 1.5,5.0,7.0,9.0,and 11.0.This calculatesto a 107.3 mg/L concentrationof MEFOSEA ineach bufferedsolution. Remarks: Modificatioonfthe testmethod includedusinga widerrange of pH and longertime periodsfora more complete understandingofthe behaviorofthe testsubstance. RESULTS pH -impacton HydrolysisHalf-liveast50*C PH Half-lif(edays) 1.5 9.4 5.0 17.8 7.0 9.9 1 9.0 1 9.3 11.0 1 7.9 pH impact on Hydrol sisHalf-liveast250C** pH Half-lif(edays) 1.5 94 5.0 178 7.0 99 9.0 @93 11.0 79 Extrapolatefdromvaluesfor50*C. Remarks: The analysisshowed thatconcentrationM.EoFfOSEA declineidnall aqueous pH bufferedsolutionswithtime. The degradationratesfitsecond orderkineticsbetterthan firsotrderkinetics. Nevertheless,the reportauthorsassumed firsotrderkineticsand calculatedthe half-lifaeftersixtime periods.Generally,the calculatedhalf-liifnecreasedwith time.The half-liverseportedabove are averages ofthe half-livecsalculatedafter each ofthe sixtime periods. The reportdoes notexplainhow the extrapolatiownas made from the half-lives at 500C to250C. Author statesassumed AG = 15-18 kcal/molewhich would give one orderof magnitude increaseinTlj2 per 250C. CONCLUSIONS This study indicatesthatMEFOSEA ishydrolyticalulnystableunder environmentallyrelevantconditions. Submifter: 3M Company, EnvironmentalLaboratory,P.O. Box 33331, St.Paul, Minnesota,55133 DATA QUALITY ReliabilityK:JimischrankingI REFERENCES Study conducted by the 3M Company, EnvironmentalLaboratory,St.Paul,MN. OTHER Last changed: 5/17/00 3M &NkwmmntafLebmtoly ROM Ab.W 18M StudyoftheStabiliotfyMEFOSEA inAqueous BufferUssingGas Chromatography withAtomic Emission Detection 3M Environmental LaboratoryContact Thomas L.HatfieldP,h.D. Building2-3E-09 935 Bush Ave. St Paul,MN 55144 Phone: (651)778-7863 FAX (651)77MI76 Requester 3M Company ReportDate:June 14,1999 Report Summary A studywas conductedon 2-(N-mothylperfluorooctanesulforiamido)a-certyhlyalte(MEFOSEA) to determineitshalf4ifuender environmentallryelevanthydrolysisconditions.Itsbehaviorwas examined Inaqueous solutionbsuftred atfivepHs: 1.5,5.0,7.0,9.0,and 11.0. The analysis was performedaccordingtD 3M EnvironmentalLaboratoryMethod ETS-8-90.0,withmodifications thatfollowedthe U.S. EnvironmentalProtectionAgency's Fate,Transportand Transformation Test Guidelinesdocument OPPTS 835.2110,*Hydrolysiass a Functionof pH*. ModificaUons includedusing a wider range of pH and longerOrrieperiodsfora more complete understandingof the behaviorofMeFOSEk Data were collecteadtthestartofthestudy(Time 0) and after0.94, 1.92,6.72,13.90.20.71,and 27.77 days of sample agitatioannd incubationat 50*C. After incubabon,!swropylakx)hol(IPA)was added and the aqueous samplu were extractedwith hexane. The hexane exbaft were driedwithanhydrous sodium sulfateand Injectedintoa gas chromatographwith an atomic emissiondetector(GCIAED). The analysisshowed that concentrationosf MEFOSEA declinedInallaqueous pH buffem withtime. Half4ivesIncreased withtime withineach pH data set at50 OC, averaging9.4days atpH 1.5,17.8 days at pH 5.0,9.9 days atpH 7.0,9.3days atpH 9.0,and 7.9days atpH 11.0. Extrapolatioonfthe 50 OC data to room temperature(25 OC) resultedina haff-liveasveraging94 days at pH 1.6.178 days at pH 5.0,99 days atpH 7.0,93 days at pH 9.0,and 79 days at pH 11.0.These resultsindicatethat MEFOSEA Ishydro@@lty unstableunder environmentallryelevantconditions. AfforimyCflon~ Do Not Disdo" Pmduct P&*W Do Not Copy posm I of 13 3MEmkwdnwWLabomtofy ReportAb.W IBM I INTRODUCTION ..................................................................................3.......................... Figure1.Generic HydrolysiRseaction..........................................3......................... Figure2.MEFOSEA and PossibleDegradationProducts............................5........................ 2 SAMPLE RECEIPT ....... .................................................................................5............... 3 HOLDING TIMES ........................................................................................................... 4 METHODS- ANALYTICAL AND PREPARATORY .................................6.......................... 4.1 Standards:................................................................6.......................... 4.2 Sample Preparationand Analysis Dates: ........................................6........................... 5 ANALYSIS .....................................................................................................7................. 5.1 Calibratio.n..................................................................7........................... 5.2 Blanks .......................................................................8........................... 5.3 Surrogates....................................................................8.......................... 5.4 MatrixSpikes............................................................................8........................ 5.5 LaboratoryControlSamples .................................................8.......................... 5.6 Sample Related Comments ....................................................8........................... 6 DATA SUMMARY .................................................................8........................... Figure 3. RepresentativeGC./AED Chromatograms ...................................q.......................... Figure4. MEFOSEA ConcentrationVersus Time ....................................1.0.......................... Table 1.Fitof Second-Order and LinearEquations to MEFOSEA Degradation Data .....1.0. 7 CONCLUSION .. ....................................................................................I..I....................... Table 2. Half-LivesofMEFOSEA Versus Time ......................................i.i.......................... 8 DATAISAMPLE RETENTION .................................................................1..1....................... 9 SIGNATURES ..................................................................................1..2............................... 10 APPENDICES ..................................................................................1..3............................... Appendix A: EPA Guidelines Appendix S: MEFOSEA Preparationand Analysis Method Appendix C: Sample PreparationLogsheets Appendix D. GC/AED Chmmatogmms (em separate bound volumes) Appendb(E: Spreadsheets: GCIAED Results Appendb(F: Spreadsheets: Calculationof KJnetc Parametem AftotmyCLWt4VoikPnxkidPdvoggod Do NotDisdon DO Notcopy P"o 2 of13 3M&WftfwmwMLabmfwy IUPW ft.w low Hydrolysiissoneofthemainmechanismsbywhichorganiccompounds,bothnaturaalnd syntheticd,ecompose intheenvironment Testingforhydrolysiosfcompounds isrelevanto determiningthepomiawnce and environmentalfateofmany pe*Uckin and polymer* Such 83 polyestersp,olyethersa,nd polyarridesa,nd fordeterminingshelflifeof productscontaining such compounds (Appendb(A, EPA Guidelines). Hydmlysis Isa reactionbetween some species(inthiscase ofthetypeR-CO-X), wfthwater thatresultsInthe substitutioonf X with OH: Figure1. Generic HydrolysisReaction 0 II R-C-X + H20 0 II R-C-OH + HX R some hydrocarbon or fluorocarbonmaterial X - halogen,OFt,or NR Indilutseowons the ratelaw forchemicalI= by a hydrolysirseactionisshown withthe followinegquations,where "astermsignifietshestartinmgaterial.ItIsImportantto notethat the equationmust be modifiedinsolutionsthatare notdilute. d [ester] Tt-- k [ester] hyd or [A] In t kt pq 0 The rateconstantk isthe negativeslope ofthe linefito a plotofthe naturallogof the ftedon ofcompound remainingattimet,versus time.The half4ifoefthecompound ata specft pH IsreWW tothe rateofhydrolysisby: Afformy CWnMtrk Do Not Died*" Pmduct PtMbgsd Do Not Copy Page 3 of 13 0.693 tIr2 k 3M Eff4mn-nentLaalbmtoty R*pW ft.W ISM With the aboveequabonsandconsiderationsas guides,thestudy monitoredthe lossof MEFOSEA over an extended periodoftime to determinethe overallrAs of reaction.A predictedproductof hydrolysiosf MEFOSEA was N-MEFOSE alcohol.Analy@l difficulties were encountered inattemptingtD monitorthe appearance ofthisreactionproductInan eftrt to confirmthe degradationroute. The primarygoal ofthe studywas to determine,to a firsatpproximation,the hydrolytic stabilitoyfthe MEFOSEA. Since levelsof MEFOSEA steadildyeclinedover time,data collectiosntopped after28 days. Samples of MEFOSEA were preparedin buffersolutionsof pH 1.5,5.0,7.0,9.0,and 11.0 accordingtopublishedguideline(sAppendb(A and referencestherein)A. solutioonf MEFOSEA in 1.0mL ofeach bufferwas preparedby adding 10 pL ofa 10,730 ppm solution of MEFOSEA Inacetone. This correspondstD 107.3 ppm MEFOSEA Ineach buftr. SignificanetnvironmentalpHs were chosen (e.g.pH 1.5 isphysiologicalrleylevantas stomach pH incase of Ingestion)T.he additionof a pH 11.0bufferinthe presentstudywas made to betterunderstandthe behaviorof MEFOSEA Inbasicsolutions.The solventchosen for quenching was hexane, used toexbbd remainingMEFOSEA from the aqueous matrix. Thisallowedlnjecfioonfmatirialontothegas chromatograph. Previousstudieshave shown thatanalysisof dilutedaqueous buffersby gas chmmatography resultsInchromatographic anomalies and column degradation. Inthisstudy,biodegradationof MEFOSEA isruledoutfortwo reasons. Firstthe 500C temperatureused willImpede degradationdue to microbialgrowth inthe bufferedmedia. This temperatureishostilteo the growth of most mesophillimcicroorganisms,the type usuallyinhabitinlgaboratoriesT.hermophillicmicroorganisms,which do thriveat SO'C and above, typicallIynhabitenvironmentssuch as hotspringsand hydmthermal ventsat the bottomoftwbnlcallyactiveocean basins,butnotlaboratoriesA.lso,one can hypothesize thatthe maximum lossrateof MEFOSEA would occur ata ddferentpH ifaccomplished by hydrolysisversus biodegradation.Since acidsor bases typicallcyatalyzehydrolysis, hydrolysisratesare usuallynwamum under acidicor basicconditionsand minimalat or near neutralconditions.Thiscontrastsvaththe activitoyf microbes,which typicalldyemonstrate maximum growth rateator near neutralpH. Maximum ratesof hydrolysiwsere notobserved at pH 7.0 inthisstudy. A proposed mechanism forhydrolytidcegradationof MEFOSEA Isshown In Figure2. AftffpoyCUsnOVAx* Pmduct PrM*ogsd Do Not Disdo" DO Not copy PWgo 4 of 13 3MEnWmmwntafLabmtory RepaitAb.w law Figure2 MEFOSEA and PossibleDegradation Products MEFOSEA 0 0 H @02-N," --------- @02-N F17CS RR mw Me 511.27 F17CS RR mw Me 629.29 OH /-i @02-t@ or F17CS R @om F17Ce R 0 OR-OH + W-N F17ce R R mw Me 129.16 A sample of MEFOSEA (ooded THAR3F2) was obtained tom C. Elsbemd. 3M Chemicals, on October 13, 1998. The sample was placed Intothe hydrolysisstorage cabinet In ft 3M EnvironmentalLaboratory.The sample recemng date,an ekxamnle MSDS, the sample producuon methodology and predictivechemistrieswere entered Intothe 3M proprietary database "Hydro"is Tracking." The samples were prepared and analyzed withinthe applicableholding time cdtww. AND"Y CAW*Wtv* PMduct Pdv#ogod Do NotDisdo" Do Not Copy PSW 9 of 13 3M Emkmffmr" Laboratory ROW Ab.w 1868 3M EnvimnmentaLlaboratorMyethodETS-8-90.'0DeterminatiooftnheStabiliotfy MEFOSEA inAqueous SuffersUsing Gas Chrornatography withAtomic Emission Dekvton" was followedexcept where noted below. This rietiodIspresented InAppendbc B. The GC/AED systemusedwas a Hewlett-Packa(rHdP)5890Series11GC equippedwithan HP 5921A AED, and an HP 7673 auto-sampler.The column used was a J&W DBr)-MS,30 mm x 0.25mm x 0.25gm filmthickness.The oven program had an Inititaelmperatureof 50*C,initihaolldtimeof1.0min.,finatlemperatureof300*C,and a temperatureramp-rateof 150C perminute. 4.1Standards: T"t AnaVe: 10,730ppm MEFOSEA inacetdne(ID98086-3-16) IntemalStandard:9.324 ppm N-ETFOSE alcoholIn hexane-l% IPA (ID 98086-3-19, and ID -98060-16-16) SpikingStendard:473.4ppm N-MEFOSE alcoholinmethanol(IDW3wlll7) (ThisIs an orderofmagnitudelowerthan theamount intendeddue toa calculatioenrror.) 4.2Sample Preparationand AnalysisDate*: Time 0: 0.94 Days Samples 112398-MeFOSEA-001 to 112398-MeFOSEA-015 Preparedand immediatelyquenched on 11/24198. Analysisby GCIAED was begun on 11/25/99. Samples 112398-MeFOSEA-016 to 112398-MeFOSEA-030 Incubatiosntartedat3:30PM on 11/23/98 Quenched at2:30 PM on 11/24/98 Analy@ by GC/AED was begun on 11/25/98(pH 1.5,5,7a)nd on 11/30198(pH 9.11) 1.92Days 6.72Days 13.90Days Samples 112398-MeFOSEA-031 to112398-MeFOSEA-045 Incubatiosntartedat3:30PM on 11/23/98 Incubatiosntoppedat2:10PM on 11/25/98 Analysisby GC/AED was begun on 11/26/98(pH 1.5.5,7a)nd on 12/l/98 (pH 9,11) Samples 1123MMeFOSEA4)46 to112398-MeFOSEA-060 Incubatiosntartedat3:30PM on 11/23/98 Incubatiosntoppedat8:54AM on 11/30/98 Analysisby GC/AED was begun on 12/22-23/98(pH 1.5,5,7)a,nd 1211/98(pH 9.11) Samples 112398-MeFOSEA-061 to 112398-MeFOSEA-075 Incubatiosntartedat3:30PM on 11/23/98 Incubatiosntoppedat 1:02PM on IZ7/98 Affwwy CUonVV#bf*ProductPrM%god Do Not Disdo" Do Not Copy P4p 6 of 13 3AoEfm*wwnntaf Lab"tmy ROW Ab.W 18M Analysisby GC/AED was begun on 12/23/98(pH 1.5,5,7a)nd on 12/89/98 (pH 9,11) 20.71 Days Samples 112398-MeFOSEA-076 to 112398-MeFOSEA-WO Incubationstartedat 3:30 PM on 11/23/98 Incubationstopped at 8:38 AM on 12/14/98 Analysisby GC/AED was begun on 12/28/98 (pH 1.5,5,7)and an 12/15I6M8 (pH 9,11) 27.77 Days Samples 112398-MeFOSEA-091 to 1123WMeFOSEA-105 Incubationstartedat3:30 PM on 11/23/98 Incubationstopped at 9:55 AM on 12/21/98 Analysisby GCIAED was begun on 12/29198 (pH 1.5.5,7,9) and on 12/30198(pH 11) Sample quenching was completed appmximately I hour afterincubationwas stopped. Sample preparationlogshosts are presented inAppendbc C. 5.1Calibration Standard calibratiocnurves were prepared using a mix of testanslyto(MEFOSEA) and degradationproduct(N-MEFOSE alcohol).Examinadw of the chmmatograms revealed that the intended internalstandard (N-ETFOSE alcohol)was in a region of chromatographic overlapof residualcomponents InMEFOSEA. Thus, N-ETFOSE alcohol could not be used as an Internalstandard with GCIAED testing. SolventfStandard Name Hexane solventused IPA solventused MEFOSEA standard N-MEFOSE alcoholstandard N-ETFOSE alcoholstandard Solvent/StandardNumberTN-A-2009 TN-A-2102 98086-3-16 8398-Ml S398-332 The calibratiosntandard setconsisted ofthe following: Reference 0 98086-46A 98086-46B 98086-46C 98086-46D 98086-46E 98086-46F 98086-46G 9 086-46H MEFOSEA (ppm) 64.38 48.28 32.19 16.09 6.438 4.828 3.219 r 1.609 N-MEFOSE alcohol(ppm) 63.12 47.34 31.56 15.78 6.312 4.734 3.156 1.578 N-ETFOSE alcohol(ppm) 9.324 9.324 9.324 9.324 9.324 9.324 9.324 9.324 Afimmy CftnWAx* PmductPdv&Wod Do Not Disdose Do MN Copy FVO 7 of13 30WEnWmm*nW Labwahxy ROPW Ab.W 1808 The standarcdurveswerelinearw,iththecoaftiontosfdeterminati(o@n)greatetrhan 0.990. Calibratiosntandardswere analyzed induplicateat the beginningofevery sample run. At regularinterval(se.g.after6 - 8 sample Injectionsb)lanksconsistinogf hexane with1% IPA and 9.324 ppm N-ETFOSE alcoholwere analyzed. A mid-mnge calibration standard was periodicalltyested throughouteach sequence. When the percent differencoef amount of measured analytowas greaterthan + 25% from ft truevalue, relativteo the initisatlandard curve,the run was discarded.Only samples analyzed beforethe lastacceptablecalibratiocnheck-standardwere consideredas validresults. 5.2Blanks The internasltandardwas a solutionof 9.32 ppm N-ETFOSE alcoholinhexanatl% IPA. Approximately1 mL aliqwtswere transferretdoautovialsand used as solventblanksin the analysis. These blanks served as an Instrumentaclheck foranalytocarryover. Acceptable valuesfbrthe blankswere lessthan halfthe practicaQluandtabon Limitof the method (theooncenb*ion oftheloweststandardused Inthecurve). 5.3Surrogates No,surrogateanwyto was used inthisanalysis. .5.4Matrix Spikes Mabix spike samples were prepared by introducinag known concentratioonfthe target ana" intoa sample.- These matrixspikesamples were carriedthroughthe entire sample preparationprocess. Comparison oftheamount quantifiefdrom the niabixspike with thatof the unspiked sample providedinformatioonn contributioonf the sample matrixto the analyticarlesults. One ofthe spildngsolutionsused was a 473.4 ppm N-MEFOSE alcoholstandard.This concentrationwas one-tenthof that which would have been optin*ml.As such,the amount of N-MEFOSE alcoholadded was lower than the lowestcalibratiosntandard, precludingquantitationS.pike samples on Day 21 and Day 28 alsocontained10 pL ofa 10,730 ppm solutionof MEFOSEA Inacetone. For allthe pHs extractedon Days 21 and 28,acceptableMEFOSEA recoveriesof80 to 123% were noted. The average recovery ofMEFOSEA was 95%. 5.5Labomtory ControlSamples Laboratorycontrolsamples were not preparedforthisanalysis. 5.6Sample RelatedConvnonts The MEFOSEA resultsforthe Day 2, pH 7 samples were rejecteda,s the mid-mnge calibratiosntandardthat followedthese samples did not pass qualitycontrolcriteria specifiedintheanalyticamlethod (AppendixB). The 3M Envimnmental Laboratorydeveloped a method forthequantitativdeeterminatioonf MEFOSEA using GC withatomic emwsion detection.This method was successfulusingfive pH buftr matrices.Sample chroniatogramsarepresentedInAppendb(D as separatebound Aftnwy CJ*WKtt* ProductPMA"D Do Not DiscJo" Do Not Copy POW a or 13 3M ErmhvwnontaLlaborahxy R*Md Ab.WINS volumes.A representatGiCv/eAED chmniatograomfa standarmdbcturaenda sampleare presented In Figure3a and 3b, respecuvely. Figure3 Representative GCIAED Chromatograms Peak retentioInmes are9.54minutes(N-MEFOSE alcohol)1,0.0minutes"rrml standard)a,nd 10.82 minutes(MEFOSEA) a. Standard (6.438ppm MEFOSEA, 121221987,:33:14PM) we' b. Sample (MeFOSEA-i.5-1-7,12/22=, 9:31:59PM. Quantifiedas L47 ppm MEFOSEA) Ali AfformyCUenVWoi*PioducPtiMbgsd Do NotDtadose DO Notcopy Ffte9 or13 3M Ew*onmentatLaboraftrl Repo4 No.W 1868 The calculactoendcentraoftainoamnesInsampled,uplicataen,dmetrbscokesamplesare presentedinspreadsheetformatinAppendb(E. These data,plottedas MEFOSEA conoentratiovnersus time inFigure4,show thatdegradationof MEFOSEA isingeneralnonlinearand a functionofpH. Samples from the pH 5.0 and 7.0 seriescan be fitequallywell witheithera linearorsewrxl.;ordeerquation(seeTable 1).A second-orderequation providesa betterfithan a linearequationforthe data atpH 1.5,9.0,and 11.0. Figure4 MEFOSEA ConcentrationVersus Time 12.000. io.ooo 9.000- 6.0004.000 2.000 0.000- 0 ?&FXMA Extract Concentradon (PPM pH = 1.5 0 pH= 5.0 ApH=7.0 OpH=9.0 pH= 11.0 100 200 300 400 500 600 700 Hours Table I Fitof Second-Order and Unear Equationsto MEFOSEA Degradation Daft 1-5 va 2oldY -O.Olgly +8.9477 5.0 yo 5@10 .4xa -0,009?x +OAN*- o@om v- -0-008dx+8.3400 yo -0.0067x+9.5230 o.ms 7.0 VO +2.8171 0,9449 va -0.0112K +9.149D 0,9119 9.0 yu 2slex2 -O-n2ni +9.2m O@9719 yu -0-01211 *9-0474 11.0 V. 30,eX2.0.on3X +9.02 1 0.9m I ym -0.0118x +8.8757 1 0,8025 1 Aftmoy CM*nVWot* Do Not Dhmkso Product Pdvgogod Do Mot edpy Page is of 13 3M EnvkonmentWLabonitoty ReportNo.W 1860 Attheconclusionftheexperimen(t27.77days)a,pproximate2l0y-30% oftheoriginal MEFOSEA remained forsamples hydrolyzingat pH 1.5,7.0.9.0,and 11.0. At pH 5, approximatelyhalfofthe originaMlEFOSEA was presentatthe end ofthe experiment. Calculationsof ldnetipcarameters are presentedInAppendix F. A generaltrendIsthatthe half-lioffeMEFOSEA Increasedwithincreasingtime,especiallyatpH 1.5,5.0,9.0,and 11.0 (Table2).Thisbehaviordoesnl match themathematicalmodel fora firsotrderreaction. However, the firsotrderappro)dmafionfora hydrolysisreactionassumes a singlecompound degrades to form onlytwo distincptroductspecies.The resultshown inTable 1 Indicatethis assumption may not be realistfiocrMEFOSEA. As ImpliedinFigure2.the degradationof MEFOSEA may Involvemultiplereactionpathways. MEFOSEA isa 3M controlcompound, whose behaviorisused to predictthatofothersynthetichemistries.Overall.the resultsof thisstudyare sufficiefnotrthatpurpose. Table 2 Haff-LJvesof MEFOSEA Versus rime 0.94 1.92 6.72 13.90 20.71 27.77 2.58 3.99 6.97 11.44 15.95 15.91 4.79 5.98 16.94 27.93 22.64 28.45 3.09 - 8.05 12.23 14.61 11.53 11.99 4.51 6.96 9.67 9.62 12.80 3.34 5.72 6.97 8.51 9.97 12.81 .......................... ......... ............. The 3M EnvironmentalLaboratorydeveloped a method forhydrolysiasnd analysisof MEFOSEA. The hydrolysistudy showed pH dependent half-livewshich Increasedwithtime withineach pH data setat 50 OC,averaging 9.4days at pH 1.5,17.8 days at pH 5.0,9.9days at pH 7.0,9.3 days at pH 9.0,and 7.9 days atpH 11.0. Extrapolatioonfthe 50 OC data to room temperature(25 OC) resultedina haff4ivesaveraging94 days at pH I.S.178 days at pH 5.0,99 days at pH 7.0.93 days at pH 9.0,and 79 days at pH 11.0. Itisthe conclusionof thisstudythatMEFOSEA Isunstableagainsthydrolysisunder environmentallryelevart conditions. ......... ...................................... . ................ ............................ Reserve samples and alloriginaplaper data willbe retainedinthe archivesof 3M ET&SS for a periodof ten yearsfollowingthe signingofthe finalreport. AttorneyC#ont4Vor* Product PrW*god Do Not Disclose DO Not copy Ptgo II of 13 3MEM*WnMWL&borniwy ROW Alaw.iwo Thomas L. Hatn-eTd Ph-D fe*6,Ceader Clestontings, Ph.D.,Agwst Gregory Maisel,Analyst Jmeo4.--&.-*-ok"Ch. D. Editor WilliamK. Reagen, Ph. D.,TechnicalReviewer Dal& DiO //7/177 Date c(ate Date Note: JeanetteWink, Analystdidthe majoritoyfft laboratorwyork forthisprojeclShe reviewedtheoriginadlata,buthas sinceleft3M EnvironmentalLaboratory.Her assistance duringthecourse ofthe study isappreciated. Affomey CfionvvftP*roductPMdVsd Do Not Disdon Do Not Copy P"o 12 of 13 30WEffhwwnontWLab"taty RoportA(wO.few 4c AppendixA:EPA Guidelines Appendb(B: MEFOSEA Preparationand AnalysisMethod Appendix C: Sample PreparationLogshosts Appendb(D. GC4AED Chmmatograms (am separatebound volumes) Appendix E: Spreadsheets:GC/AED Results Appendix F: Spreadsheets:Calculationof KJneticParameters A#Offwy CftWAVO* Do Not Dhxdo" Pmdud P&WOOod Do Not Copy P*go 13 of 13 3MEffAwwwjWLabmkly ROPOltAb.w 1868 Ypendix A: FateTrans ortand TransformadonTest didelingOsP,P, 835.11 Hydrolysiass a FuncdonofpH U.S.EnvironmentaPlrotectioAngency documentnumber k#A 712-C-98-05J7a,nuary1998 AMWW CftWKtik Pmductft%"W Do NotDhu*m DD Notcopy urum states AEgnevnicmynmontaPlrolsoion ProvwnionP.estcides andToWc Substances (7101) EPA 712-C-98-057 JarluarIjM IWYEPA Fate,Transport and Transformation Test G u*idelines OPPTS 835.2110 Hydrolys'a iass a Function. of pH INTRODUCNON This auidelineis one of a seriesof test,uidelinetshathave been developed by the Office of Prevention,Pesticidesand Toxic Substances, United StatesEnvironmentalProtectionAgency for use in the testingof pesticidesand toxicsubstances,and thedevelopment of testdam thatmust be submittedto theAgency f6rreview under Federalregulations. The Officeof Prevention,Pesticidesand Toxic Substances(OPPITS) has developed thisguidelinethrough a processof harmonizationthat blended the testingguidance and requirementsthatexistedin the Office of PollutionPreventionand Toxics (OPPT) and appearedin Title40, Chapter 1,SubchapterR of the Code of FederalRegulations(CFR), the Officeof PesticidePrograms (OPP) whicfiappearedinpublicationosf the NationalTechnicalInformationService(N71S) and the guidelinespublishedby the Organizationfor Econ6mic Cooperationand Development (OECD). The purpose of harmonizing theseguidelinesintoa singleset of OPPTS guidelinesisto minimize variationasmong the testingprocedures thatmust be perform@d tomeet thedatarequirementsof theU. S. Environmental ProtectionAgency under the Toxic SubstancesControlAct (15 U.S.C. 2601) and the FederalInsecticideF,ungicideand RodenticideAct (7 U.S.C. 136, etseq.). Final Guideline Release:This guidelineis availablefrom the U.S. Government PrintingOffice,Washington,DC 20402 on 77teFederal Bulletin Board. By modem dial 202-512-1387, telnet and ftp: fedbbs.access.gpo.go(vIP 162.140.64.19)o,r call202-512-0132 for disks or paper copies.This guidelineis alsoavailablelectronicalilny ASCII and PDF (portabledocument format)from EPA's World Wide Web site (http://www.epa.gov/epahome/research.hutnmd)er theheading "Researchers and Scientists/TesMtethods and Guidelines/OPPTS Harmonized Test Guidelines." OPPTS835.2110 Hydrolysiass a functioonfpH. (a)Scope---1()ApplicabiliTthyi.scruideliisnientendetdomeettest- ing requirementsof both the Federal InsecticideF.ungicide.and RodenticidAect (FEFRA) (7U.S.C.136,etseq.)and theToxicSubstances ControlAct (TSCA) (15U.S.C.2601). (2) Background. The source materialused in developingthisharmonized OPPTS testguidelineare40 CFR 796.3500 Hydrolysisas a Functionof PH at 25 *C,.and OECD guideline111 Hydrolysisas a Function of pH. (b)Guidance information--(I)I?rerequisiteW&ater solubilitdyata; suitableanalyticamlethod; vapor pressurexurve. (2) Qualifying statements.Pure and commercial gmde substances can be Wted with the method descn"oedhere,but the potentiaelffectof impuritieson the resultshould be considered.This testguidelineapplies only to water solublecompounds. There is uncertaintyin extrapolating high temperatureresultsto environmentallyrelevanttemperaturesas a change inreactionmechanism could occur. (3) Standard documents. This testguidelineis based on methods givenin paragraph(f)of thisguidelineand on thePreliminaryDraftGuidance forPremanufactureNotificatioEnPA, @ug'ust 18,1978. (c)Method--@1) Purpose, relevance,application,and limitsof test (i)The.testingof substancesforhydkolysisisrelevantto theirpersistence. Hydrolysisis one of the most common reactionscontrollinagbioticdegradationand isthereforeone of the main degradationpaths of substances in the envirommenl (ii)A procedureto determinehydrolysisratesisimportantalsoin indicatingwhether other testingshould be carriedout on a parent compound or on itshydrolysisproducts.Itisthedegradationproductsthat are crucial.Hydrolysisbehaviorneeds to be examined atpH valuesnormallyfound in theenvironment(pH 4-9) and undermore acidicconditions (pH 1-2)forphysiologicaplurposes. (iii)Surface-controllreedactionscan sometimes predominateover bulk solutionhydrolysise,speciallyin the soilenvirommenl This may resultindifferentdegradationratesthan would be predictedfrom thisguidelinebased upon ratesinhomogeneous solutions. (2)Deflnitionasnd units.The definitionisn section3 of theToxic SubstancesControlAct (TSCA) and thedefinitionisn40 CFR Part792Good LaboratoryPracticeStandardsapply to thistestguidelineI.le following definitionaslsoapplytothistestguideline. Hydrolysisrefersto a reactionof a chemical RX with water,with the netexchange of thegroup X with OH atthereactioncenter: RX + HOH > ROH + Hx Hydrolysisrate,therateat which theconcentratioonf RX decreases in thissimpfifiedprocessisgivenby: second orderreactionrate= k CH20] M or firsotrderreactionrate= k [RX] depending on the ratedeterminingstep.Because water ispresentin great excess compared to the chemical,thisbr;@eof reactionisusuallydescribed as a pseudo-firsotrderreactioninwhich theobservedrateconstantisgiven by therelationship: kobg = k [H201 and can be determined-fromthe expression K@be = 2.303/tlogin(colct) where t time,and Co and Ct = concenotionsof RX at times0 and L The unitsof thisconstanthave the,dimensionof (time)-'and the halflifeof thereaction(timefor50 percentofRX toreact)isgivenby tl/2= 0.693/kb, (3)Reference substances.(i)Aspirinand Diazinon are used as references.These substancesneed not be employed in allcaseswhen investigatinga new substance.These dataareprovidedprimarilyso thatcalibmtionof the method may be performedfrom time to dm and to offerthe chance tocompare therrsultswhen anothermethod isapplied.The results of theOECD/EEC-Laboratory IntercomparisoTnestingareincludedin the followingTables 1.and 2.: Table I.--Valuesof Rate Constants and Half-Uves forAsplrlnl,2 PH K (105sec--il ti/(2h) 3.5 ...... ..................... 0.065 300 5.0 ....... ................................0...1.5........ 130 7.4 ....... 0.13 ISO 9.5 ........ 0.37 52 11.3 ......................................................16.................. 1.2 I Data taken at 17 OC 2 Aspirin(CAS no. 50-78-2) (2-acetylsalWicacid)data from Li. Edwards, Transac#ons of the F&Mday Soc@@ty 723.-735 (1950). 2 Table 2.-Values of Rate Constants and Half.Uves forDiazinant 10 OC 20 OC 1 40 OC 60 OC pH K [10s tt/2 K (105 tir- K (105 tir. K (101 ti/2 sec-1) (h) sec-lj (h) sec-11 (h) 3ec-li (h) 10-43 ..........................0...0.6.1....3.1.0......0..13 150 0.41 48 9.0 ..............................-.......-......0..0.0.59 3300 - - 7.4 ...............................-........-......0...00043 4400 - 5.0 ..............................-.......-.......0...0.26 740 - - is 12 - - 3.1 .............................0...7.5..1..2.6.0...1....1...6. 1 120 1 6.6 29 1 25 7.8 Diazinon(CAS no. 333-41--S)(0.0-dethyl-O.(2-isopmpyl-@ethyg-6-pyrimidpihnoyslphomthloate) datafrom H.M. Gomma stal.Residue Reviews 29:171 (1969). (ii)Furtherresultosf OECD-EEC Laboratoryintacompanson testing followin Tables 3. through12.In some casestheresultspresentedhave a variabiliwthyich exceedswhat iscalledforin the testguidelineT.his mfty particularbley the resultof the use of differenbtuffersin the test systems and the influenceof oxygen.These resultsarepresented, however,as theyhave been obtainedusingtheTestGuidelinesin the OECD/ EEC IntercomparisonTestingProgramme, PartH. Tb"eguidelinehas been modifiedinthelightof theseresults. (A) Substance:Aspirin Table 3.-Reaction Rate Constint in lOssea-I coeffl- tem- stand-- clent pH pera- mean ard Of range ture,OC value devi- vari- ation atlon, % 1.2 ..................................3.5.-.4.0.....1...0.1.3...1...2.7.8. 3.0 ...................................2.0.......0..0.8.0...0...0.5.6. 40 0.556 0.112 7.0 ...................................2.0......0..2.0.5....0...0.3.3. 40 1.339 0.004 9.0 .....................................2.0......0...3.0.9....0...160 40 0.953 0.006 126.2 70.3 20.1 15.9 0.3 0.109-1.916 0.040-0.119 0.477-0.635 0.182-0.228 1.336-1.341 51.7 0.196-0."2 0.6 0.949-0.957 n* ofresub 2 2 2 2 2 2 2 3 Table 4.--Hait-41tion hours tom- stand- coefficient pH pera- mveaalnue daervdi- ofvariation, -ange n* of results turs,OC ation % 1.2 ...........................3.5.-.4.0......9.3...7.1.. 118.3 3.0 .............................2.0......3.1.9...7... . 40 35.4 7.0 ............................2.0........9.5...1... 40 14.4 9.0 ............................2.0........7.2...1... 1 40 1 20.2 1 222.5 7.1 15.1 0.0 37.3 9-1 1 (B)Subs=ce: Di 126 70 20 20 .- 50 0.01 10.O-r-177.36 162.3--477.0 30.3-40.4 84.4-105.8 14.4-14.4 45.7-98.5 20.1-20.3 1 2 2 2 (1lab) 2 2 (1lab) 2 2 (1lab) Table &-Reaction Rate Consbmt In 1CPseer-I coom- tem- stand- clent PH pera- mean ard de- ot range n* ofresults turs,IOC value viatlon Vdd- aflon, % 12 ........................................3.0...3.6......8..40 3.0 .................................2.0....... 2.866 4.825 40 9.038 '2.447 so 5.77 4.27 60 36.085 11.088 7.0 .................................2.0........0..9.3.3....1..796 40 0231 0.294 so 0.200 0.023 60 1.638 3.154 9.0 .................................2.0.......1..1.0.3.....2..113 40 2.568 6.900 so 0.292 0.034 60 2.801 4.125 27.0 28.8 27.1 74.0 30.7 192.4 127.3 11.3 192.6 191.6 268.7 11.6 147.3 21.40-W.46 1.675-3.841 5.70814.165 0.86-8.58 25.535-51.449 . 0.005-3.626 0.042-0.895 0.184--0.216 0.303-9.413 0.007-4.271 0.06420.955 0.268-0.316 0.24112.604 4 7 11 (10tabs) 3 (2labs) 6 4 a 2 8 (7labs) 4 9 2 8 (7labs) Table S.-Helf-lifienhours tem- mean standard coefficient pH pom- value deviation of variabon, range n' of results ture,OC % 1.2 ......................3.5.-.4.0....... 0.672 3.0 .......................2.0......... 7.27 40 2.25 so 9.00 60 0.57 7.0 ..........;..............2.0. 40 so 1707.75 215.16 97.07 so 38.68 9.0 .......................2.0.......1.1.50.75 40 124.38 so 66.40 60 25.13 0.187 2.40 0.57 11.53 0.17 1875.18 166.12 10.97 20.98 IW.58 102.45 7.74 25.67 27.9 0.501-0.900 33 5.0-11.5 25 1.4-3.3 128 2.24-22.31 29 0.37-0.75 110 5.3-3660.9 77 21.5-460.7 11 89.31- 104.83 54 2.0-M.5 116 4.5-2840.5 82 0.9--298.7 12 60.92-71.87 102, 1.5-79.8 4 7 11 (10labs) 3 (2labs) 6 4 8 2 8 (7labs) 4 9 2 8 (7labs) (C) Substance:Aft-azine Table.7.--ReactionRat* Constant in lossoo-t tom- stand- Loefficient pH POM- mveaalnue daorvdl- of variation, range n* of results turs,"C agon % 1.2 ............................3.5.-.4.0.....0...5.4.a...0..416 76.3 0.76-0.948 4 3.0 ..............................2.0......0...0.1.4...0..008 40 0.140 0.082 60 0.808 0.397 7.0 40 0.009 0.011 56.8 0.005-0.020 3 58.4 0.028-0.222 6 49.1 0.282-1.283 5 124.8 0.001-0.016 2 9.0 ..............................2.0......0...0.1.3...0..018 130.1 0.001-0.024 - 1 40 1 0.0081 0.0101 123.7 10.001-0.015 2 Table S.-Half-iffIen hours tom- mean pH pom- value turs,OC 1.2 .......................3.5.-.4.0.......5.4.76 3.0 ........................2.0.......1.8.6.7.88 40 240.50 60 31.42 7.0 ........................4.0.......9.0.0.0-15 9.0 ........................2.0......1.7.9.2.105 40 8005.35 standard coefficient deviation ofvariation, % range n* ofresults 44.36 1446.58 239.61 21.51 11033.77 24188.21 9539.51 81.0 20.3-115.35 4 77.0 980.7- 3 3537.14 99.6 111.71- 6 696.79 69.0 15.0-68.3 5 123.0 1198.1- 2 16802.2 135.0 817.4- 2 35024.7 119.0 1259.9- 2 14750.8 5 (D) Subs=ce: Di(2-ethylhexplh)thalat(eDOP) Table9.-ReactionRate ConstantInI(Psecr-I tom@ stand- coefficient pH pera- mean ard of variation, value devi- range lure,OC avon % n'ofresults 3.0 ...............2.0..... 9.0 ................2.0.... 40 60 7.0 ................2.0.... 40 60 40 0.048 0.040 0.166 0.084 0.073 i1oo:'10'29272l@ 0.051 0.047 0.202 0.022 0.064 - 107.8 116.7 121.8 26.3 $8.8 0.009-0.106 3 0.007-0.073 2 0.023-0.309 2 0.068-0.099 2 0.027-0.118 2 1 1 Table10.-Half-4ffIonhours pH tompam- mean-. standard coefficient devi- ofvariation, turs,OC value ation % range 3.0 .............2.0. 40 60 7.0 .............2.0. 40 60 40 990.20 452.56 239.33 440.30 (1. 208.19 1152.53 996.32 551.98 63.75 391.35 - 101 122 27 - 89 182.4-2103.5 622-5-842.86 194.25-284.41 163.57-717.02 - (E) Substance:Ethylacetate TableII.-ReactionRateConstantInI(Psec-I pH tomPOM- mean standard coefficient devl- ofvariation, range lure,OC value agon % 3.0 .......................2.0.......(.0...0.0.1.2) - - 40 @0.012) - - 60 0.355) - - 7.0 .......................2.0......0...0.0.3) - - 40 0.008) - - 60 @0.137) - - 9.0 .......................2.0........... 40 0.153) 60 (1-547) n* of results 3 2 2 2 1 n* of results I 1 1 1 1 1 1 Table 12.-Half-4ifienhour3 tom- mean standard coefficient devi- ofvariation. range pH pera- lure,OC value ation % 3.0 ........................2.0......-.(.1656) - - - 40 (1612.85) - - - 60 (54.30) - - - 7.0 ........................2.0.......(.7553.1) - - - 40 2511-81) - - - 60 (140.38) - - - 9.0...........................2.0.... (305.55) - - - 40 (125.71) - - so (12.44) - n' ofresults (4)Principleof the testmethod. (i)In theenviromnent@chemicals usuallyoccur in dilutesolutionw,hich means thatwater ispresentin large excess,and, thereforet,hatthe concentrationof water remains essentially constantduringhydrolysisH.ence, thekineticsof hydrolysisare generally pseudo-firsotrderatfixedpH and temperature. (iiT)he hydrolysisreactionmay be influencedby acidicor basicspeciesH30+, (H+),and OH-, in which caseitis'referretdo as specificacid or specificbase catalysis. (iiiT)he concentratioonf the testsubstanceisdeterminedas a functionof time.The logaridunsof the concentrationasre plottedagainsttime and theslopeof theresultinsgtraighltine(assumingfint-orderor pseudofirstorderbehavior)givesthe rateconstantfrom the formula (ifloglo isused): kobs slopex 2.303 (iv)When itisnot practicablteo determinea rateconstantfora particulartemperaturedirectlyi,tisusuallypossibleto estimatethe constant throughthe use of the-Arrheniurselationshiipn which the logarithmof rateconstantsatothertemperaturesisplottedagainstthereciprocalof the absolutetemperature(K). (5)Quality criteria--@Rie)producibility.Measurements of hydrolysisrateconstantson 13 classesof organicstructurecsan be of high preciSion,oftenwith lessthan2 percentstandarddeviation(seeparagraph(f)(2) of thisguideline)7.be rateconstantsfor one pH and one temperature should be determinedinduplicatewith a deviationof lessam 2.5 percent unlessunusualcircumstances(e.g.analyticadlifficultiepsr)eventachieving thisand then the detailsof thesecircumstancesshould be reported.Ime reproducibilictayn be improved by an improved controlof the sensitive parameters,inparticulaprH and oxygen. 7 (iiS)ensitivitMyo.st hydrolysriesactiofnosllowapparenftlrsotrder reactionratesand. thereforeh.alf-liveasre independentof concentration ti,2= 0.693/klbs This usuallypermitsthe applicatioonf laboratoryresultsdetermined at 10-2-10-3 M to environmentalconditions(< 10-6 M) under paragraph (f)(2o)f thisguideline. (iiiS)pecificityS.everalexamples of good agreement between rates of hydrolysismeasured in both pure and naturalwaters for a varietyof chemicals providingboth pH and temperaturehave been measured (see paragraph(f)(2o)f thisguideline). (d)Descriptionof the testprocedure.(1)Ifthe watersolubilitoyf thesubstanceislessthan2 x 10-2 M, a half-satumtesdolutionin water is@prepared.If the solubilitiys greaterthan 2 x 10@-2,the testsolution is preparedat lessthan 10-2 M. Substancesknown to be hydrolyticauy unstableare testedat7atleasttwo temperaturesbetween 0-40 *C. Other substancesareput throughpreliminarytestingS.ubstancesfound to be stable under these conditionsare consideredhydrolyticauystable(tj/2at 25 *C is greaterthan I year).Those not stableart 50 *C for one week are submittedto testingat at leasttwo temperaturesbetween 0-40 *C, or, as appropriatea,t at leastthreeelevatedtemperatures,and the data extrapolatedtoproduce k at25"C. (2)Preparations--(i)MateriaLs-(A) Buffer solutions.(1)The hydrolysistestshouldbe performedatfourdifferenptH's: atpH 1.2(ifphysiologicalliymportant);pH 4.0;pH 7.0;and pH 9.0.Eitherbuffersas describedbelow or a ph-statmay be used.Use of a ph-statavoidspotential problems due tobufferc.atalysis. (2)For thispurpose,0.05 M sterilbeuffersolutionshould be prepared using reagentgrade chemicalsand distillesdt,erilweater.Ile buffer systems are based upon theanalyticarlequirementsforthechemical being tested.It should be noted thatthe buffersystem used may influencethe rateof hydrolysisand where thisisobserved an alternatbeuffersystem should be employed. The use of bomte or acetatebuffersinsteadof phosphatehas been recommended under paragraph(f)(2)of thisguidelineT.he pH of each buffersolutionmust be checked with a calibmtedpH meter at the requiredtemperatureto a precisionof at least0.1 pH units.Some usefulbuffersystems are presentedin the followingTables 13.,14.,and Table13.-BuffeMrixtureosfClarkand Lubsl,2 Composition pH 0.2N HCI and 0.2N KCI 47.5mi HC1 + 25 mlKC1 dilutetdo100mi ...........................................1.0.................... 32.25 ml HC1 + 25 ml KC1 dilutedto 100 mi .........................................1..2.................... 8 Table 13.-13uHer Mixtures of Clark and Luba ','-Continued Composition pH 20.75 mi HC1 + 25 mi KC1 dilutedto 100 mi ............................................1..4.................. 13.15 mi HCI + 25 mi KC1 dilutedto 100 ml .............................................1..6................. 8.3 mi HC1 + 25 mi KC1 dilutedto 100 mi .........................................................1...8............. 5.3 ml HC1 + 25 mi KC1 dilutedto 100 mi ..............................................2...0.................. 3.35 ml HC1 + 25 mi KC1 dilutedto 100 mi .............................................2..2.................. 0.1 M potassium biphthalate+ 0.1 N HC1 46.70 mi 0.1 N HCI + 50 mi biphthalatteo 100 mi ........................................2...2.................. 39.60 mi 0.1 N HC1 + 50 ml biphthalatteo 100 mi ........................................2...4.................. 32.95 ml 0.1 N HC1 + 50 mi biphthalatteo 100 mi ........................................2...6.................. 26.42 mi 0.1 N HCI + 50 ml biphthalatteo 100 mi ........................................2...8.................. 20.32 ml 0.1 N HCI + 50 ml biphthalatteo 100 mi ................................................3...0. 14.70 mi 0.1 N HCI + 50 mi biphthalatteo 100 mi ......!@.....................................3..2............... 9.90 mi 0.1 N HCI + 50 mi biphthalatteo 100 mi ..............................:...............3...4............ 5.97 ml 0.1 N HC1 + 50 mi biphthalateto 100 mi .. ........................................3..6. 2.63 ml 0.1 N HC I + 50 mi biphthalatteo 100 ml ..........................................3...8.................. 0.1 M potassium biphthalate + 0.1 N NAOH 0.40 ml 0.1 N NAOH + 50 mi biphMWate to 100 mi .......................................4...0................... 3.70 ml 0.1 N NAOH + 50 mi piphthalateto 100 mi .......................................4...2................... 7.50 ml 0.1 N NAOH + 50 ml biphthalateto 100 ml .......................................4.4 12.15 mi 0.1 N NAOH + 50 ml biphthalatteo 100 mi .............................................4..6.... 17.70 mi 0.1 N NAOH + 50 mi biphthalatteo 100 mi ......................................4...8................... 0.1 M potassium biphthalate+'O.lNAOH 23.85 mi 0.1 N NAOH + 50 mi biphthalatteo 100 ml .......................................5...0.................. 29.95 mi 0.1 N NAOH + 50 ml biphthalateto 100 rrd.........e...,.................................5..2.......... 35.45 ml 0.1 N NaO 50 mi biph#uftteto 100 mi .......k....................................5...4............ 39.85 mi 0.1 N NaO A + 50 ml biphthalatteo 100 ffd.......................................5...6.................. 43.00 mi 0.1 N NaO I + 50 mi biphthalatteo 100 mi ......................................5...8................... 45.45 mi 0.1 N NaO q + 50 ml biphthalateto 100 ml ......................................6...0................... 0.1 M monapotassium phosphate + 0.1 N NAOH 5.70 ml 0.1 NAOH + 50 mi phosphale to 100 ml ........................................6...0................... 8.60 mi 0.1 N NAOH + 50 mi phosphate to 100 ml ........................................6...2................... 12.60 ml 0.1 N NAOH + 50 mi phosphate to 100 mi .......................................6...4.................. 17.80 ml 0.1 N NAOH + 50 mi phosphate to 100 mi .......................................6...6................... 23.45 ml 0.1 N NAOH + 50 ml phosphate to 100 mi .......................................6...8................... 29.63 mi 0.1 N NAOH + 50 ml phosphate to 100 ffd.......................................7...0................... 35.00 mi 0.1 N NAOH + 50 ml phosphate to100 mi .......................................7...2................... 39.50 mi 0.1 N NaO 50 mi phosphate to 100 mi .......................................7...4................... 42.80 ml 0.1 N NaO -i++ 50 mi phosphate to100 mi .......................................7...6................... 45.20 mi 0.1 N.NaO -1+ 50 mi phosphate to 100 mi .......................................7...8................... 46.80 ml 0.1 N NaO -1 00 mi .......................................8...0................... 0.1 M H2BO2 in 0.1 M KC1 + 0.1 N NAOH 2.61 ml 0.1 N NAOH + 50 mi boricacidto100 ml ........................................7..8................... 3.97 ml 0.1 N NAOH + 50 mi boricacidto 100 mi .........................................8...0.................. 5.90 ml 0.1 N NAOH + 50 mi boricacidto100 ml .........................................8...2.................. 8.50 ml 0.1 N NAOH + 50 ml boricacidto 100 mi ........................................8...4................... 12.00 mi 0.1 N NAOH + 50 mi boricacid to 100 ml .......................................8...6................... 16.30 ml 0.1 N NAOH + 50 ml boricacidto 100 mi .......................................8...8................... 21.30 ml 0.1 N NAOH + 50 mi boricacid to 100 mi .......................................9...0................... 26.70 ml 0.1 N NAOH + 50 mi boricacid to 100 mi .......................................9...2................... 32.00 mi 0.1 N NAOH 36.85 mi 0.1 N NAOH 40.80 ml 0.1 N NAOH 43.90 ml 0.1 N NAOH + 50 mi boricacid to 100 mi .......................................9...4................... + 50 mi boricacidto 100 mi .......................................9..6................... + 50 ml boricacidto 100 mi .......................................9...8................... + 50 mi boricacidto 100 mi . ......................................1.0...0.................. Data taken at 20 OC. 2 The. pH values reported in these tables have been calculatedfrom the patentw measurements Sorenson'sstandardequations(1909).The correspondingpH values are0.04 unithigherthan the =ted values. 9 Table 14.--CitratBeuffersof Kolthoffand Vioeschouwerl2 Composition pH 0.1 M monapotassium citrateand 0.1 N HCI 49.7 mi 0.1 N HCI + 50 mi citratteo 100 ml .............................................2...2...................... 43.4 ml 0.1 N HCI + 50 mi eltmtoto 100 mi .............................................2...4...................... 36.8 mi 0.1 N HCI + 50 mi citmtoto 100 mi .............................................2...6...................... 30.2 mi 0.1 N HC1 + 50 ml citmtoto 100 mi .............................................2...8...................... 23.6 mi 0.1 N HCI + 50 ml citmtoto 100 mi .............................................3...0...................... 17.2 mi 0.1 N HC1 + 50 mi citmtoto 100 mi .............................................3...2...................... 10.7 mi 0.1 N HC1 + 50 mi citmte'to100 mi .............................................3...4...................... 4.2 mi 0.1 N HC1 + 50 ml eftrateto 100 ml ..............................................3...6...................... 0.1 M monapatassium citrateand 0.1N NAOH 2.0 mi 0.1 N NAOH + 50 mi cftme to 100 ml .............................................3...8...................... 9.0 ml 0.1 N NAOH + 50 mi citmtoto100 ml ...........f..........................................4..0.............. 16.3 mi 0.1 N NAOH + 50 mi cftratteo 100 mi ...........................................4..2...................... 23.7 mi 0.1 N NAOH + 50 mi cftratteo 100 ml ............................................4...4...................... 31.5 mi 0.1 N N&OH + 50 rrdcitmtoto100 ml ............................................4...6...................... 39.2 mi 0.1 N NAOH + 50 mi citmtoto 100 mi ............................................4...8...................... 46.7 mi 0.1 N NAOH + 50 ml citratteo 100 mi . ..........................................5...0...................... 54.2 ml 0.1 N NAOH + 50 ml eftratteo 100 mi ............................................5...2...................... 61.0 mi 0.1 N NAOH + 50 mi cftratteo 100 ml ............................................5...4...................... 68.0 mi 0.1 N NAOH + 50-mi cftratteo 100 mi ............................................5...6...................... 74.4 mi 0.1 N NAOH + 50 ml chrateto 100 mi ............................................5...8...................... 81.2 mi 0.1 N NAOH + 50 mi eftratteo 100 ml ............................................6...0...................... I Data taken at 18 cc. 2 Add tinycrystalof thymol or a few milligramsof mercury..o@mrercuricIodideto preventgmwth of molds. Table IS.-Bars% BufferMixturesof Sorensen Composition 0.05 M borax (mi) 0.01 N HCI (mi) 5.25 ...............4..75 5.50 ...............4..50 5.75 ...............4..25 6.00 ...............4..00 6.50 ...............3..50 7.00 ...............3..00 7.50 ................2..5.0 8.00 ...............2..00 8.50 ...............1..50 9.00 ...............1..00 9.50 ...............0..50 10.00 ...............0.00 10.0 ...............0..00 9.0 .................0..00 8.0 .................0..00 7.0 .................0..00 6.0 ....;.............. 0.00 0.01N NAOH (ml) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 -0.00 0.00 0.00 0.00 0.0 1.0 2.0 3.0 4.0 Sorensen (18-C) 7.62 7.94 8.14 8.29 8.51 8.08 8.80 8.91 9.01 9.09 9.17 9.24 9.24 9.36 9.50 9.68 9.97 10 OC 7.64 7.98 8.17 8.32 S.S4 8.72 8.84 8.96 9.06 9.14 9.22 9.30 9.30 9.42 9.57 9.76 10.06 Walbum, pH at 40 OC 7.55 7.86 8.06 8.19 8.40 8.56 8.67 8.77 8.86 8.94 9.01 9.08 9.08 9.18 9.30 9." 9.67 70 OC 7.47 7.76 7.95 8.08 8.28 8.40 8.50 8.59 8.67 8.74 8.80 8.86 8.86 8.94 9.02 9.12 9.28 (B) Test soludons. The chemical substance should be dissolved in distilleds,terilewater with sterilebuffer medium added to it.The concentrationsshould not exceed the lesserof 0.01 M or half the saturation concentration(see OPPTS 830.7840, Water solubility,shake fluk method), and the purest availableform of the substance should be employed 10 in making up the solutionsT.he use of mixed solventsis recommended only in case substanceswith low watersolubilitTvh.e amount of solvent should be lessthan I percent@and the solvent@hould not interferewith the hydrolysisprocess. (C) Glassware. Allglassware,which must be inertin the pH range studied,should be sterilizeSdt.opperedvolumetricflasks(no grease) should be used for carryingout the hydrolysisreactionsI.f the chemical or buffersystem is volatileo,r ifthe testisbeingconductedat elevated temperatures,sealedor septum-closedtubes are preferredand head-space should be avoided. (3)AzWytical method. The analyticamlethod willbe determined by the natureof the substancebeing tested.Itmust be sufficientlsyensitive and specificto allow determinationof thedifferenstpeciesatthe testsolutionconcentrationasnd may wellconsistof some combinationof pH eleca-odes,UV-visiblespectrophotometryc,onductivityg,as chromatography, high pressure liquidchromatography,extractionand formation of derivative(sa)n,d determinationby a suitablaenalyticamlethod. (4) Test conditions-(i)Temperature. For extrapolatiopnurposes, itisimportantto maintainthetemperatureof thedem=ffiationsto atleast -O.l*C. An appropriateconstanttemperature'batshhould be employed. Ifthe hydrolyticbehaviorof thesubstanceitunimown. a preliminarytest at50 *C isrequired.For testsbeyond thispreliminarystagedatafor temperamms inthe range0-40 *C aresought.They may be obtainedby measurement at two temperaturesin this'rangeor by extrapolatiofnrom three higher temperatures.In any event,the determinationshould be done at temperaftiredsifferingfrom each otherby atleast10 *C. (ii)Light and oxygen. AD of thehydrolysisreactionshould be carriedout using any suitablmeethod to avoidphotolytiecffectsA.U suitable measures should be taken to excludeoxygen (e.g.by bubblingnitrogen or argpn through thesolventfor5 minutesbeforepreparatioonf the solution). (5)Performance of the test--(iP)reliminarytest.A preliminary testshould be performed on the substanceat 50 t 0.1 *C at each of pH 4.0, 7.0,and 9.0.Iflessthan 10 percentof thereactionisobserved after 5 days (ti/2> 1 year),the chemicalisconsideredhydrolyticauystable and no additionaltestingisrequired.Ifthesubstanceisknown to be unstable at environmentallyrelevanttemperaturest,he preliminarytestis not required.7be analyticamlethod must be sufficientplryeciseand sensitive todetecta reductionof 10 percentintheinitiacloncentration. (ii)Hydrolysisof unstablesubstances.Ifthe substanceis unstable as definedby the preliminarytest,the testprocedureisto be as follows: The bufferedtestsolutionsof the substanceshould be thermostattedat the selectedtemperaturesT.o testfor first-ordebrehavioreach reaction solutionshould be analyzedin time intervalwshich providea minimum of six spaced data points,normally between 20 percentand 70 percent of hydrolysisof thattestchemical.The reactionshould be examined at three(4,7. 9) pH's at each of the selectedtemperatureswith replication atone of them (themiddle temperaturein thecase of elevatedtemperature determinations). (iiiH)ydrolysisat pH 1.2.The above testfora hydrolyti@alluynstable compound should alsobe carriedo.ut at pH 1.2,employing a single, physiologicallsyignificanttemperature(37 OC). (e)Data and reporting-(I) Treatment of results---(Cio)nffwmation of ffrstorder ldnetics.The daW obtainedshould be plottedat logloCc versus t and the reactionrateconstantlcb.calculatedby regressionanalysisor from theslope: k,.t.= 2.303 x slope" (ii)Interpretationof results.If the data do not fallon a straight line,thereactionisnot fintorder,and thedatamusrbe analyzedby methods beyond thescope of thistestprinciple. (2)Test reporl (i)Tne testreportshoula includeinformationon: (A) Sample purity. (B) Any resultsappropriatteotheprocedureemploying referencesubstances. (C) Detailedtestprocedureincludingthetempemmm, pH and, buffer foreach setof experiments. (D) Detailedanalyticamlethod used forthe testedsubstance,includingdetailedmethod of extractioannd recoverydataifan extractiomnethod isused toseparatethechemical from the aqueous phase. (E) All concentration-timdeatapointsforreactionswhich were observedtooriginatea no@linearlog concentration-timpelot. (F)Possibilitoyf acidorbase catalysis. (ii)A suggestedformatfor sample reportingform, which can be duplicatedi,spresented: 12 solutionshould be analyzedin time intervalwshich providea minimum of six spaced data points,normally between 20 percentand 70 percent of hydrolysisof thattestchemical.Tne reactionshould be examined at three(4,7. 9) pH's at each of the selectedtemperatureswith replication atone of them (themiddle temperaturein thecaseof elevatedtemperature determinations). (iiiH)ydrolysisat pH 1.2.7be above testfora hydrolyti@alulnystable compound should alsobe carriedo.ut at pH 1.2,employing a single, physiologicallsyignificanttemperature(37 OC). (e)Data and reporting--@1)Treatment of result;-4i)C.onfirmndon of firstorder ldnedcs. 7be date obtained should be plottedat logloC, versus t and the reactionrateconstantkb. calculatedby regressionanalysisor from the slope: kb. = 2.303x slope (ii)Iziterpretadoo@fn results.Ifthe datado not fallon a straight line,thereactionisnot fmt order,and thedatamust-beanalyzedby methods beyond thescope of thistestprinciple. (2)Test reporl (i)The testreportshould includeinformationon.: (A) Sample purity. (B) Any resultsappropriatteo thr.procedureemploying referencesubstances. (C) Detailedtestprocedureincludingthetemperaturep,H and, buffer foreach setof experiments. (D) Detailedanalyticamlethod used for the testedsubstance,includ9 detailedmethod of extractioannd recoverydataifan extractionmethod isused toseparatethe chemical from the aqueous phase. (E) AU concentration-tidmaeta pointsforreactionswhich were observedtooriginatea no@linearlog concentration-timpelol (F)Possibilitoyf acidor base catalysis. (ii)A suggestedformatforsample reportingform, which can be duplicatedi,spresented: 12 DATA SHEET FOR HYDROLYSIS Laboratory: Date: TestSubstance: Formula: Name (IUPAC): Testprotocol A. Prelhnhuirytest yesno_ buffersystemsused: pH 4.0 pH 7.0 pH 9.0 STUDIES Approximatseaturatioonncenftdon pH mole/L 4.0 7.0 9.0 C@D:Initicaolncentratio.n.................... Cn:Finalconcentratiaofntertdays; 5 ....................................................................... t ........................................................................................................................... (Co- C4/icxoTOO at50 :tO.l*C .............................................................................. 13 B.Determinadon SeparatreunsatpH 4.0,7.0,and 9.0atthechosentempemtm(s) withreplicataitoonneofthes(ethemiddlteemperatuirnethecaseof determinatioantelevatedtempem=e). The same formatwhould be used foreach pH. Buffersolutionused Temperamm,- Approximate saturatiocnoncentration, t 0 Ci [mole/Ll................................. ................................................................................. 109ct ................................................................................................................................ HydrolysisatpH 1-2 Buffersolutiounsed Temperamm- Approximate saturatiocnoncentration tE 0 r-t[mole/L]...!...................................................................................................................... logCt ......................................................................................................................... Finaldata temperature initicaoln- reaction half-litfie/,i contmt[on, ratecon- cooftio pH OC co stantk,lbl ofcorrela- [h] tion, r2 (moleA.) (1/3x 1031 .............................................................................................................................. ........................................................... ....................................................... . 14 C.Reporton tesmtethod Providdeetaildeedscriptoifotnheexperimenctoanlditioen.sg,f.ormainmining sterilittyo;avoidphotolytiecffectst;o excludeoxygen; to prepare thetestsolutione,tc.(Pleaseuse separatesheetof paper.) Ana"cal combinationussed h h pH electrodes............................................................................. UV-visible spectrophotometry .................:....................................................... Conductivity................................................................................ Gas chromatography .................................................................. High pressureliquid chmmatograpny ....................................................................... 11Ile Extracdonand formationofderivative(sI).................................................................. Demils of theanalvticaplerform@nce: Type of apparatus Testconditions Was theaccuracyof thisresultdeterminedinany additionawlay ? Particulairncidents: Comments: (f)References.Ile followingreferencesshouldbe consultedforadditionablackground materialon thistestguideline. (1)Kolthoff,I.M.and Laitinen,H.A. pH and Electro-Titration2sn,d Ed.,Wiley,pp 34-36 (1941). (2)Mabey, W. and MUI, T..CriticaRleview ofHydrolysisofOrganic Compounds in Water Under EnvironmentalConditionsJ.ournalof PhysicalChemist?yReferenceData 7:383-415(1978). (3)Gomaa, H.M. etal.Kineticsof Hydrolysisof Diazoxon.'Residue Reviews29:171(1969). (4) OECD Document A80.30,Summary of OECD-EEC Laboratory ,te=mpanson TesiangProgramme, Part 2, Umwelthundesamt@ Berlin,, May 1980. 16 3MEn4WWwWLabomtmy ROW ft.wing pendixB:3M EnvironmentaLlaborato ethodETS-8-90.0 @&PtonninadonoftheStabfflotfyMeFOSWI@n Aqueous Buffers UsingGas Chromatography*IthAtomicEmissidnDetecdon" AUMMY CftWV^* PWLD ftWagW Do NotIW&ckm Do NW Copy 3M ENVIRONMENTAL LABORATORY METHOD DETERNANATION OF THE STABMITY OF MizFOSEA IN AQuEous BuFnRs USING GAS CIRROMATOGRAPHY WITH ATOBUC ENUSSION DETECTION Method Number: ETS-8-90.0 Adoption date: 6 4 /,o RevisionDate: NA Author: Thomas Hatfield,Ph.DJCleston Lange, Ph.DJGregory Maisel/JewetteWink Approved by: Laboratory Manager Date <4up Leader TechnicaRl@i4ewer 6131'7 Date 1.0 SCOPE AND APPLICATION 1.1 This procedure definesthestepsforpreparationand analysisof 2-(Nmethylperfluorooctanesulfonamido)-ethayclrylate(MEFOSEA) from aqueous hydrolysisby gas chromatography with atomic emissiondetection(GC/AED). 1.2 Acceptable Matrices: Aqueous solutionsatvariousbufferedpHs. Word 6.0/95 Method ETS-8-90.0 StabilitoyfMEFOSEA by OCTAED Page I of 13 2.0 SUMMARY OF THE METHOD 2.1 One millilitoefr bufferedaqueous sample from thehydrolysisofMEFOSEA is quenched with 0.5mL isopropylalcohol(EPA)and extractewdith 10 mL hexane. A portion(1-2mL) oftheseparatedhexane phaseisdriedthroughan anhydrous sodium sulfatecolumn and then analyzedon a gas chromatographwith an atomic emissiondetector. 3.0 DEFINITIONS 3.1 Duplicate analyses.Analysesor measurements of theanalyteof interespterformed identicalloyn thesame sample. The resultsfrom duplicateanalysesareused to evaluateanalyticaolrmeasurement precisionbutnotprecisionof smpling, preservationor storageinternatlo thelaboratory. 3.2 Sample duplicates.Two samples taken from and representativoef the same sample sourceand carriedthrough allstepsof thesamplingand analyticaplroceduresin an identicamlanner. Duplicatesamples areused to assessvarianceof thetotalmethod, includingsampling and analysis. 3.3 Matrix spike.Prepared by adding a known mass of targetanalyteto specified amount of a sample matrixforwhich an independentestimateof targetanalyte concentrationisavailable.Matrix spikesareused todeterminetheeffectof the matrixon themethod's recoveryefficiency. 3.4 Solvent blank. A sample ofanalyte-fremeedium towhich allreagentsareadded in thesame volumes or proportionsas used insample processingbut isnot carried through the complete sa*mplepreparationand analyticaplrocedure. 3.5 Continuing Calibration Verification(CCV). A standardanalyzedperiodically during an analyticarluntoverifythecontinuedaccuracyofthecalibratiocnurve. This solutionmay be preparedfrom a differenstourceof lotnumber than the calibratiocnurve standards. 3.6 Limit ofQuantitation(LOQ). The lowestconcentratiotnhatcan be reliably achievedwithinspecifieldimitsofprecisionand accuracyduringroutinelaboratory operatingconditionsI.tmay be nominallychosen withintheseguidelinetso simplify datareporting.For many analytest,heLOQ analyteconcentratioinsselectedas the lowestnon-zerostandardinthecalibratiocnurve.Sample LOQs arehighlymatrix dependent. Method ETS-8-90.0 Stabilitoyf MEFOSEA by GC/AED Page 2 of 13 4.0 WARNINGS AND CAUTIONS 4.1 Health and SafetyWarnings: 4.1.1 Wear theproperlabattirfeorallpartsof theseprocedures.Wear gloves at alltimes. 4.1.2 Handle allsolventina hood forallpartsofthedescribedsample preparationprocedure. 4.1.3 For potentiahlazardsof each chemicalused,refertomaterialsafetydata sheets,packingmaterialsand 3M EnvirorunentaLlabomtorys Chemical Hazard Review. 4.1.4 Use carewhen working with C7CJAED because high temperaturesand ultravioleltightarepresent. 4.2 Cautions: 4.2.1 Rinse with solventsallglasswareused topreparestandardstoreduce the possibilitoyf contamination. 5.0 INTERFERIZNCES 5.1 Contaminantsinsolventsr,eagentsg,lasswarea,nd othersample processingor analysishardware may causeinterferencesR.outinelyanalyzelaboratorysolvent blanksto demonstratethatno interferenceasrepresentduringtheanalysis. 6.0 EouipmENT 6.1 Balance,capableof measuring to 0.1 mg. 6.2 Shaker,incubatingc,apableofholdingat50*C 3*C. 6.3 pH meter,Coming Model 308 pH/Temperature Meter with 3-in-1gelfilled combinationelectrode(pli/refcrence/temperatoure)quivalent. 6.4 Gas Chromatograph, HP 5890 SeriesII,withBI? 5921A Atomic Emission Detector (AED) orequivalent. 6.5 Colunm, J & W ScientifiIcncorporatedD,B-5MS, 30 m x .25mm x .25 Am or equivalent. Method ETS-9-90.0 StabditoyfMEFOSEA by GCIAED Page 3 of 13 6.6 Data RecordingSystem,HP ChemStation Rev. A.05.04with Windows NT software. 6.7 Autosampler,HP 7673 or equivalent. 6.8 Clock. 7.0 SUPPLIES AND MATEIUALS 7.1 Autovials,crimp top,1.5raL. 7.2 Vials,glassscrew top,40 mL, I-CHEM or equivalent 7.3 Labels,Avery 5160 orequivalent. 7.4 Graduated pipettesg,lass,disposable,varioussizes. 7.5 Pasteurpipettesg,lass,disposable. 7.6 Volumetricflasks,varioussizes. 7.7 Beakers, glass,various sizes. 8.0 REAGENTS AND STANDARDS 8.1 Buffersolutions Preparethebuffersolutionisn1000mL quantitieAsd.justpH withNAOH orHCI. Use a portablepH meter to calibrateallbuffer solutions.Record finalpH measurements of buffers.Store the buffersolutionsin sealed 1000 mL flasks. Prepare buffers as follows: 8.1.1 pH 1.5 + 0.3 a) 250 mL of 0.1 M HCI, b) 125 mL of 0.2M KCI, c) Bringtoa finavlolumeofIL withASTM Type IH20- Method ETS-9-90.0 StabilitoyfMEFOSEA by GC/AED Page 4 of 13 8.1.2pH 5.0+ 0.3 a) Dissolv3e.57g ammonium acetatien200mL ASTM TypeIH2.0. b) Add 230 mL of 0.052M aceticacid(3mL glaciaalceticacidintoI L ASTM Type IH20) c) Bringtoa finalvolume of I L withASTM Type IH20. 8.1.3pH 7.0 0.3 a) Dissolve7.9g Trizma&HCI in200 mL ASTM Type I H20. b) AdjustpH to7.0withO.INNAOH. c) Bringtoa finalvolume of I L withASTM Type I H20. 8.IA pH 9.0+ 0.3 a) 46 mL of0.1N HCI. b) 125 mL of0.1-M borax(sodium bomte, 10 hydrate). c) AdjustpH to9.0. d) BringtoafinavlolwneofIL withASTM TypeIH20. 9.1.5pH 11.0+ 0.3 a) 250mLofO.INNaOH. b) 250 mL of 0.1 M borax. c) AdjustpH to 11.0. d) Bring toa finalvolume of I L withASTM Type IH30. 8.2 Acetone, spectroscopygrade orequivalent 8.3 IPA, spectroscopygradeor equivalent. 8.4 Hexane, 85% n-Hexane, spectroscopygradeor equivalent.Use hexane in postinjectiosnolventwashes fortheGC/AED. Preparea one L hexane solution containing10 mL of IPA (hexane-1% EPA) touse forextractioannd forsolvent blanks. Method ETS-8-90.0 StabihtoyfMEFOSEA by GCIAED Page 5 of 13 9.5 MEFOSEA, preparedinacetone,approximately10,000ppm. Weigh 0.1 g of MEFOSEA and dissolvein 10 mL acetone.Use thissolutionforcalibration standards,testanalytesamples and spikes. 8.6 Sodium sulfate,anhydrous,60 mesh, reagentgmde. 9.0 SAMPLE HANDLirir, 9.1 Handle allsamples and standards in a well-ventilatedarea Wear gloves when handling solutions. 9.2 Prepare hydrolysis sample prep worksheets for each sample set.(Attachment A.) Prepare a traeldng schedule for sample extraction. 9.3 Analyze allsamples as soon as possibleafterextraction.If samples cannot be analyzed immediately, storein refrigeratoart approximately 4*C. 10.0 OuALrry CONTROL 10.1 Solvent blank. Prepare solventblanks (hexane-l% EPA). This servesas an instrumentalcheck for any analyte carryover. 10.2 Duplicates. Prepare a sample and a duplicate. Perform two injectionsof each. 10.3 Matrix spikes.Prepare a post-hydrolysismatrix spikefor each of the pHs used in the study.Perform two injectionsof each spike. 10.4 CCV. Run a CCV every 15 or fewer injections. 11.0 CALIBRATION AND STANDARDIZATION 11.1 Standard preparation. Prepare sixcalibrationstandardsof MEFOSEA. from approxiznately 1.6to 32 ppm are suggested. Standards 11.2 Calibration standards. Analyze calibrationstandardsat the beginning of the run. 11.3 Coefricient of Determination. The acceptablecoefficientof determination(t@)is 0.990 or greater.Curves should be examined closelyfor linearityand intercept, particularlyfor accuracy of quantitationat the high and low ends of the curve. Method ETS-8-90.0 StabilitoyfMEFOSEA by GCIAED Page 6 of 13 12.0PROCEDURE 12.1Samplepreparation. 12.1.1 Establishtimepointsforsample analysis.Typicaltimepointsareatdays 0, 1,2, 7, 14,21 and 28. 12.1.2 For each pH tobe testeds,etup the40 mL I-Chem vialstoallow fora sample, a duplicateand a spikeforthe durationof theexperiment.Each timepointhas 3 samplesperpH and fivepHs fora totalof 15 vialsper time point. 12.1.3 Create L-ibelasnd affixtovials.Label informationshould includedate,a sample number; thepH; whether thevialcontainssample,duplicateor spike;thetimepoint;and theinitialosftheanalyst.An example using June 15,1999 is:61599-MeFOSEA-002 pH 1.5 Duplicate Day 0 CCL 12.1.4 Remove vialcap.With a pipettea,dd I mL ofbuffertothebottom of each vial,takingcaretoavoidthewallsofthevial.Always replacecap immediatelyafterany additiontomin@e evaporation. 12.1.5 Using a 25 pL gas-tighstyringea,dd 10p.LofMEFOSEA testanalyte solutiontoeach vialwithbuffer,exceptforthosemarked Day 0. Tiltthe vialso thebufferrunstoone sideof thebottom ofthevial.Add thetest analytesolutionon theoppositesideofthevial,away from thebuffer. 12.1.6 Preparetimezerosampleswhen adequatetimeisavailabletoimmediately quench thesamples.Setup each sample individuallyE.xtracteach one with hexane-I% EPA beforestartinagnotherto geta truetime zero. 12.1.7 Fillout hydrolysisampleprepworksheets(AttachmentA) foreach swnple set. 12.1.8 Placethesamplesinthe50'C incubator.Set for100 rpm shaking.Note time,date,and temperatureon worksheets. 12.1.9 At thespecifiedtimepoin@ remove samples from theincubator.Let cool toroom temperaturefor15 minutes. 12.1.10 Add 10 ILLoftheMEFOSEA spikesolutiontothebottom of each spike vialso itmixes withbuffer. Method ETS-8-90.0 Stabilitoyf MEFOSEA by GCIAED Page 7 of 13 12.1.11 Add 0.5mL of EPA toallvials.Swirltomix. 12.1.12 Add 10 mL ofthehexane-1% IPA tovials.Recap vialsand shake vigorouslyfor10-15 seconds.LetsettlfeorI minute.The waterphase is on thebottom;thehexane phase ison the top. 12.1.13 With apipettep,ulloffaportion(1-2ML) of thetopphase.Dispensethe hexane ontoa column consistinogfapproximatelyI inchheightof Na,SO,,ina Pasteurpipette.Allow thehexane extractoflow throughthe column intoa prelabeleadutovialU.se two autovialpsersample.Cap the vials.Storeone setofvialsinthefreezeartapproximately-20*C. Place theothersetof vialsintheautosarnplefroranalysisI.fsamplescannotbe immediatelyanalyzed,storeinrefrigerataotrapproximately4*C. 12.2 Solventblanks. 12.2.1 To 40 mL I-Chem vialsa,dd 10 mL ofhexane-l% IPA. Analyze inthe same manner asthesamples. 12.3 Sample analysb. 12.3.1 Instaltlheanalyticaclolilmnand establisihnstnunentconditionsA.llow thesystem toequilibratfeor30 minutesbeforestartintgheanalysis. TABLE 1. SUGGESTED GC CONDITIONS FOR SAMIPLE ANALYSIS PARAMETER Uet temperature: Wet liner: Detecttemperature: Carriergas: Oven Program: Initiatlemperature: Initiatlime: Rate: Finaltemperature: Finaltime: SUGGESTED VALUE 1800C 4 mm ID,singlegooseneck,glass 2800 Helium 500C 1.00min. 15.OOC/min. 3000C 0.00min. Method ETS-8-90.0 Stabilitoyf MEFOSEA by GCIAED Page 8 of 13 12.3.2 Sethead pressurefora linearvelocitythroughcolumn between 28-32 cm/sec. TABLE 2. SUGGESTED AED CONDITIONS FOR SAMPLE ANALYSIS PARAMETER Transferline: Cavity: Min. peak width: Data rate: Solvent ventprogram: On time: Off time: Elements: I Spectra: SUGGLWED 280*C 2800C 0.054 min. 5.0 hz VALUE 0.00 3.50 minutes Carbon 193,Sulfii1r81,Nitrogen174d Save 12.3.3 TABLE 3. SUGGESTED AuTOSAP4PLER CONDITIONS FOR SAMPLE ANALYSIS PARAMETER Autosampler injector. Smnple washes: Sample pumps: Injectiovnolume: Syringesize: On column: -Nanoliteradapter: PostInjectionSolv A washes: -PostInjectionSolv B washes: -Viscositdyelay: -Plungerspeed: SUGGESTED 7673 I 3 1.0 ILL 5.0gL Off Off 4 (hexane) 4 (hexane) 0 sec Fast VALUE 12.3.4 Enterthestandardand sample informationintothesequencetable. Analyze calibratiosntandardsfirstt,hen a sample setof 15 or fewer injectionsf,ollowedby eitherthecontinuingcalibratiovnerification standardor by thefullsetofcalibratiosntandards.Run a solventblank afterthehighestcalibratiosntandardand aftera setof 15 or fewer injectiontsocheck forany analytecarryover. Method ETS-8-90.0 StabiliotfyMEFOSEA by GCIAED Page 9 of 13 12.3.5 Placethestandardss,amplesand QC (duplicatemsa,trixspikesa,nd blanks)intotheautosamplertrayaccordingtotheordertheyarelisteidn thesequencetableoftheHP ChemStation. 12.3.6 Startthesequence. 13.0 DATA ANALysis 13.1 Matrix spikerecoveriesC.alculatsepikerecoverieussingtheformulabelow: %recovery- (spgcesdampleresu-lt sampleresult) x 100 actualspiked amount .13.2MEFOSEA concentrationsC.alculatteheconcentrationf MEFOSEA inthe hexane extwt by externamlethod usingthecalibratiocnurve. 13.3 Data plot Obtaina plotofMEFOSEA concentratioinnthehexane extracatsa functionof time foreach pH. Use thesedatafordegradatiornatedeterminations. 14.0 MzTHop PERFoRmANcE 14.1 Solventblanks.The measuredvalueforthesolventblankshouldbe lessthanhalf theLOQ ofthemethod. 14.2 Sample duplicatesT.he warninglimitsaretheaverage:ktwicetherelativpeercent differenceT.he controllimitsaretheaverage-thteetimestherelativpeercent differenceI.fthelowervalueofthewarningorcontrollimitcalculatetsobe less thanzero,use zeroasthelow limit. 14.3 Matrix spikes.The recoverywarninglimitsaretheaveragespikerecovery:ktwice thestandarddeviation.The recoverycontrolimitsaretheaveragespikerecovery:k threetimesthestandarddeviation. 14.4 CCV. Analyze a mid-rangecalibratiosntandardand a solventblankafter15 or fewersample injectionasnd attheend oftherun.Ifthepercentdifferencfeorthe amount ofmeasured analyteexceeds+ 25% ofthetruevalue,relativteotheinitial standardcurve,stoptherun. Use onlythosesamplesanalyzedbeforethe last acceptablecalibratiocnheckstandard.Reanalyzetheremainingsampleswitha new calibratiocnurve. Method ETS-8-90.0 Stabilitoyf MEFOSEA by GCIAED Page 10 of 13 14.5CoefficieonftDeterminationT.hecoefficioefndteterminat(iro)nshoulbde 0.990 orgreater.The curvesshould be examined closelyforlinearitaynd intercept, particularlfyoraccuracyofquantitatioantthelow and highends ofthecurve. 14.6 LOQ. The LOQ isequaltotheloweststandardinthecalibratiocnurve. 15.0 POLLUTION PREVE:NTION ArqD WASTE MANAGEMENT 15.1 Dispose of sample waste accordingtoacceptablelaboratorpyractice.Refertothe 3M Waste Stream procedureforfin-theirnformation. 16.0 RFcoRDs 16.1 Printouthard copiesof allgraphicsand dataanalysissummaries forarchiving. 16.2 Sign and dateallgraphicsand labelwith instrumentID. 16.3 Record sample weightsand extractioinnformationon thehydrolysissample prep worksheets (Attachment-A). 16.4 Printout the sample sequence table,reduce the sizewith photocopying and tape the photocopy into the instrument log. Keep allthe originalcopies in the raw data files package. 16.5 Printchromatograins and internalstandard reports forallanalyses. 16.6 Print calibrationtablesand curve information and storein raw data file. 16.7 Store hydrolysis sample prep worksheets in the raw data file. 16.8 Enter allstandard preparationinformation in the standardspreparation logbook. 16.9 Backup allelectronicdata to appropriatemedia. 17.0 TABLES, DIAGRAms, FLOWCHARTS. AND VALIDATioN DATA 17.1 Method validationhas not been performed forthismethod. Method ETS-9-90.0 Stabilitoyf MEFOSEA by GC/AED Page II of 13 18.0 RIEFERENCES 18.1 Fate,Transportand TransformationTest Guidelines,Officeof Prevention, Pesticidesand Toxic Substances.(OPPTS). 835.2110. Hydrolysisas a Function of pH and Temperature. EPA. 712-C-98-057. January 1998. 18.2 Fate,Transportand TransformationTest Guidelines,Officeof Prevention, Pesticidesand Toxic Substances.(OPPTS). 835.2130. Hydrolysisas a Function of pH and Temperature. EPA. 712-C-96-059. April 1996. 18.3 Handbook of Chemical Property Estimation Methods. Rate of Hydrolysis.pp. 7-1 through 7-48. 18.4 CRC Handbook of Che?nist?yand Physics, I$tStudent Edition."Buffer Solutions OperationalDefinitionsof pH." Robert C. -Weast,Ph.D. 1988,p. D-97. 19.0 AFNCTED DOCUMENTS 19.1 None 20.0 RizVISIONS Rev number Revisionreason Rev dat Method M-8-90.0 StabdityofMEFOSEA by OCTAED Page 12 of 13 TEST ANALYTE: HOURS: Sample No. FluorochemicDaelgradatio(nHydrolysAinsa)lysis Time ofInitial Description Prop SWer pH ISTD Spike BufferVolume TestAnslyto Solution Solution Time of (ML) Solutio(npL) (UL) (pL) OA*mNng So sa;;e Duplicate Spike 1.5 1.0 1.5 1.0 1.5 1.0 Sample Duplicate Spike 6 1.0 5 1.0 5 1.0 Sample Duplicate Spike 7 1.0 7 1.0 7 1.0 Sample Duplicate Spike 9 1.0 9 1.0 9 1.0 Sample Duplicate Spke [--] Date of InMalPmp: 11 1.0 11 1.0 11 1.0 SWndardITraceabNky Test An*M Solution No. CWPMmt C4rmntmdon (4ffL) ISM Solution Spike Solution Ouenching Sdution NA Date ofQuenching: Tompambire of IncubatorCC): IncubationStart(Dateand Thm): IncubationStop (Dateand Tkm): Total IncubationThm: BufferAddition by. ISM Additionby. Ted Armlyto Addtion by. Oumching by, Sp*s Addition@2: AutovW Aliqwgng by: 7um-cHm-ni it Cw*MWdon 2mnm: RPM: Tkm: By: Yes I No rNn Method ETS-8-90.0 Stabifityof MEFOSEA by GCTAED FfftrationY:es/ No S)r Pore Size: um, Brdnd: RwWwod by. Page 13 of 13 3MEM*Mnontal Laboratory Raw Ab.wim AppendixC.-MEFOSEA SampleProperadonLogsheets AfformyCLI*nb%tiPkrodudPdvhgod Do NotDiSdam Do NotCopy TEST ANAYLTE: HOURS: Sample No. 10 998 -MeFOSEA-001 10 98 -MeFOSEA-002 10 998 -MeFOSEA-003 FluorochemicDaelgradatio(nHydrolysiAsn)alysis MethylFOSEA C -Tb,4kliFl.) Date 11/23/98 day 0 ISTD Spike Time ofInitial BufferVolume TestAnalyto Solution Solution I Description Prop BufferpH (mL) Solution(pL) (pL) (pL) Qu Sample 2- "*1.-2 1.5 1.0 Duplicate_ oo/.-?I).2y 1.5 1.0 Spike L2p 2'-02.//-Z'i 1.5 1.0 10 inquench 10 inquench 12 10 inquench 10 10 998 -MeFOSEA-004 Sample 2,02- 5 1.0 10 998 -MeFOSEA-005 Duplicate 1-&%/ 5 1.0 101998 -MeFOSEA-006 Spike Ui L, c.L.l 5 1.0 10 inquench a 10 inquench a 10 Inquench JD 1 998 -MeFOSEA-007 1 998 -MeFOSEA-008 10 9988 -MeFOSEA-009 Sample Duplicate Spike QW 7 1.0 oto 7 1.0 o@r 7 1.0 10 -inquench Q 10 in_quench a 10 inquerich J.Q 10 998 -MeFOSEA-010 Sample 2-,.Oa- 9 1.0 10 10 -MeFOSEA-01 I Duplicate Z -./0 9 1.0 10 101 8 -MeFOSEA-012 Spike 9 1.0 10 99988 101 98 -MeFOSEA-013 Sample '2,1 11 1.0 10 1OP28 10oO1IlJ9998 -MeFOSEA-014 Duplicate ?- t 1-7 11 1.0 10 -MeFOSEA-01 5 Spike [a) L *kt 11 1.0 10 n2to o%flniflaPlrep: 11-2 TestAnalyle 57flietC Quenching Solution ISTD Solution - tJ.7 Solution Standard/TraceabilNiot.y 1 Component 1 403"-itar Yo*o@-3-If ICA Alf#9 14e;fi,"-r rsTO Cmmtration (pg/mL) _/Oo1304e.-i BuffeArdditiobny: s cex_ Ltllii,9@ i ee Y" No Cenbifugs:Roujan TestAnalyteAdditionby: t?C I- L q, RPM: -A@@'by-i Time: min -,ApftAddift.by*. i cull -By: inquench 0 inquench 11 -inquerich io inquench inquench inquench 0 .0 im Date ofQuenc Teff"ratureoflncu IncubatioSntart(Date IncubatioSntop (Datea TotalIricu 4MR!!@2* Yes By: Pore Size: Reviewed by: 3M EnvironimntLaalbomtorRyequeg No:U2744 TEST ANAYLTE: HOURS: IVP$ Sample No. FluorochemicDaelgradatio(nHydrolysiAsn)alysis Methyl FOSEA Date 11/23/98 day I Time of Initial BufferVolume Description Prop BufferpH (MLi TestAnalyto Solutio(npL) ISTO Solution (PL) Spike Solution (pL) Wit A JQIJC.B#.MeFOSEA-016 Sample $*.oo^ 1.5 1.0 10IJ98 -MeFOSEA-017 Duplicate :S,9,0^ 1.5 1.0 101 - 8 0 10 inquench a 10 Inquench a 10118-MeFOSEA-019 Sample 1019PS -MeFOSEA-020 Duplicate Y05 1019PB -MeFOSEA-021 Spike 5 1.0 5 1.0 5 1.0 10 inquench a 10 Inquench a 10 Inquench io 10118 -MeFOSEA-022 Sample Lis 7 1.0 101$8 -MeFOSEA-023 Duplicate,, .1.*,)5 7 1.0 101$8 -MeFOSEA-024 Spike ?.'05 7 1.0 10 Inquench (I 10 Inquench a 10 inquench 112 10118 -MeFOSEA-025 Sample 9 1.0 101198 -MeFOSEA-026 Duplicate -1@ZO 9 1.0 101498 -MeFOSEA-027 Spike t0 9 1.0 10 inquench 0. 10 inquench a 10 inquench JD lOlj98 -MeFOSEA-028 101 98 -MeFOSEA-029 101 98 -MeFOSEA-030 T9 Standard/TraceabilNiot.y Comporwnt Conoentragon(pgtml) IkUWMon! tw: Sample /,o li 1.0 Duplicate 1/0 11 1.0 SPiike Date of'ln[UaPlrep: 11 1.0 Test Ana@to Solution PICFOS&-* /00 7.ID mm SeK Quenching ISTD Solution Solution Solution ?,FOe6-5-Jl A/31M,9 -7 1"1=4 by Yes CenWfuge: Roujan RPM: Time: rnin By: 10 inquench Q 10 inquench a 10 inquench in Date of Quenc TemperatureofInc Yes By: Pom Size: RevWwod by: 3M EnvironrnLaarbtoarlatRoerqyuedNo:U2744 TEST ANAYLTE: HOURS: Sample No. b"-.MeFOSEA-031 101 98 -MeFOSEA-032 101 98 -MeFOSEA-033 FluorochemicDaelgradatio(nHydrolysiAsn)alysis Methyl FOSEA Date 11/23198 day 2 Descdpgon Time ofInitial BufferVolume TestAna" Prop BufferpH (mL) Solutio(npL) ISTD Spike Solution Solution (PL) (pL) Q Sample Duplicate Spike 1.5 1.0 j:2L 1.5 1.0 1.5 1.0 10 inquench .0 10 inquench a 10 Inquench IQ 101I98 -MeFOSEA-034 Sample 5 1.0 101 98 -MeFOSEA-035 Duplicate 5 1.0 101 8 -MeFOSEA-036 Spike 1!,77 5 1.0 10118 -MeFOSEA-037 Sample 7,0,7 7 1.0 lol9p8 -MeFOSEA-038 Duplicate I.-Ol 7 1.0 1019PB -MeFOSEA-039 Spike LY 7,W 7 1.0 101@8 -MeFOSEA-040 Sample -3'10 9 1.0 lolq28 -MeFOSEA-041 Duplicate tv 9 1.0 101498 -MeFOSEA-042 Spike L@@6 10 9 1.0 10 Inquench 'a 10 Inquench a 10 inquench in 10 Inquench .0 10 inquench Q 10 Inquench JD 10 inquench .0 10 Inquench 12 10 Inquench JD 101 8 -MeFOSEA-043 Sample 3"$/o 11 1.0 10 101. 8 -MeFOSEA-044 Duplicate 11 1.0 10 101 8 -MeFOSEA-045 Spike 11 1.0: 10 Date ofInMal Prop: @tg TestAnave Solution spi@. Quenching ISTDSolution Solution Solution--- Staridard/TraceabiNloi.ty Component CmmtraUon (pg/mL) ip, tj3,i4,-ll)l rl @4.rll > Yam V=XM lftl.t -7 BuffeArddkion by: ISTD Additionby: TestAnalytoAddffiw by: Quenching by: SpikeAddMm by-. AutovialAJiquobng by: (51 -rit4b CentrifugatioYn 0 CenWMge: Roujan RPM: Time: min By: Inquench inquench inquench .0 .0 IQ oq Date of Quenc TemperatureofIna lZbDatiZon Start(Date ..$fA(pOdti Tobdlncu Fiftration:Yes By: Pore Size: Reviewed by: op fW44@ Ah.3MEnvimnrrwLnatbmoimtoRieyquesNto:L2t744 TEST ANAYLTE: HOURS: Sample No. w,.Jp@g$WeFOSEA-046 101 98 -MeF?)-SEA-047 101 98 -MeFOSEA-048 FluorochemicalDegradation(HydrolysisA)nalysis MethylFOSEA Date 11/23/98 day 7 Time ofInitial BufferVolume Description Prop BufferpH (mL) TestAnaVe Solutio(npL) ISTD Solution (PL) Spike Solution T (pL) Qu Sample Duplicate 1.5 1.0 Z:si( 1.5 1.0 Spike [Z] t 1.5 1.0 10 inquench Q 10 Inquench a 10 Inquench J.Q 101 98 -MeFOSEA-049 101 98 -MeFOSEA-050 101 98 -MeFOSEA-051 Sample Duplicate Spike 5 1.0 5 1.0 5 1.0 10 Inquench 11 10 Inquench a 10 inquench i.Q 101 98 -MeFOSEA-052 101 98 -MeFOSEA-053 101 98 -MeFOSEA-054 Sample Duplicate Spike ;!Of 7 1.0 .7.,Vl 7 1.0 7 1.0 10 inquench a 10 -inquench a 10 inquench JLQ 101 98 -MeFOSEA-055 101 98 -MeFOSEA-056 101 98 -MeFOSEA-057 Sample Duplicate Spike Liy 9 1.0 9 1.0 I'> 9 1.0 10 inquench .0 10 Inquench a 10 inquench im 101 98 -MeFOSEA-058 Sample 18 11 1.0 10 101 98 -MeFOSEA-059 Duplicate 7tqlo 11 1.0 10 129P -MeFOSEA-060 Spike [::Sj -71teo I1 1.0 10 v DateoflnidaPlrop: ty-a.T-9e StandardfTraceabilNiot.y Component Concentradon(pg/mL) TestAnalyte Solution 3 by* CCA.- W4MikWMon bys 'IAAk VTA,KA n*W AdObw byv czk..., Quenching by: :I SpikeAddUon by: lm6i AutovialAliquodngby: 'TAArm 4d4d 0. 5- rn L -rPA 7$ .,eAe@i Sil K- Quenching ISTD Solution Solution Solution TIO&O-7-6 lw;f -.-IeM -@yf4' M 475.@a&. 8,w '-IPW Yes No ConbifugReo:ujan RPM: Time: min By: EnvironrmntLaalbomiorRyeqtmt No:U2744 _IAA Cn inquench inquench inquench Q 11 im Date of Quench Temperatum ofIricu (DaOt lncubagonStop(Datea Yes By: Pore Size: u Reviewed by: TEST ANAYLTE: HOURS: 1121V t.- Sample No. t@ ?-MeFOSEA-061 10 1 98 -MeFOSEA-062 101 98 -MeFOSEA-063 FluorochemicDaelgradatio(nHydrolysiAsn)alysis Methyl FOSEA Date 1M3/98 day 14 Descrip0on Time ofInitial BufferVolume Prop BufferpH (mL) TestAnalyto Solutio(npL) ISTD Spike Solution Solution I (PL) (PL) Ou Sample Duplicate Spike t;f& 1.5 1.0 L;S(o 1.5 1.0 ZSb 1.5 1.0 10 inquench Q 10 Inquench a 10 Inquench io 101 98 -MeFOSEA-064 Sample 3:11 5 1.01 101@98 -MeFOSEA-065 Duplicate $Vt 5 1.0 101 8 -MeFOSEA-066 98 Spike 5 1.0 101 988 -MeFOSEA-067 10 98 -MeFOSEA-068 101 98 -MeFOSEA-069 Sample Duplicate Spike EA 7 1.0 7 1.0 7 1.0 10 Inquench 0 10 Inquench a .2: 10 Inquench -jp --3?! 10 Inquench 12 .21 10 Inquench 12 19.1 10 inquench im ;@w., 101 98 -MeFOSEA-070 Sample 9 1.0 101 98 -MeFOSEA-071 Dupikate 1.0 9 1.0 101 98 -MeFOSEA-072 Spike LE Tt-S0 9 1.0 10 inquench 12 10 Inquench ii 10 Inquench ia a! 10198 -MeFOSEA-073 Sample lo 11 1.0 10 101 98 -MeFOSEA-074 Duplicate 11 1.0 10 101 8 -MeFOSEA-075 Spike LiZ @D 11 1.0 10 DateoflnftlParlop: )V TestAnalyto Quenctdng Soiudon ISTDSoluUon S tition StandardrrraceabilNiot.y $R*@ @bko- iS-& v Cornpornnt &V~ cflq Concentrabon(pg/mL) SoWj,#*kdon by; CtA- Quenctdngby:--.-. SpikeAddifionby: AutoviaAlliquobngby: -IAI& ,4do6d @o ID %ti.4) dA 4@en@e-. RPM: nme: By: YW. ifYes No Roujan ffdn 3M EnvironffwUnbtoarlatorRyoqwg No:U2744 inquench Inquench inquench Q 9 Q la @2! -,"DatoefQuenct Temperatureof lncu 9M (Do* IncubatioSntop (Datea -I"mn:g Yes ijy: Pore Size: L Reviewed by: TEST ANAYLTE: HOURS: t 10 Sample No. W@M -MEFO SEA-076 101$98 -MeFOSEA-077 101498 -MeFOSEA-078 FluorochemicDaelgradatio(nHydrolysiAsn)alysis Methyl FOSEA Date 11/23/98 day 21 Time of initial BufferVolume Description Prop BufferpH (mL) TestAnalyto Solutio(npL) ISTD Solution (pL) Spike Solution 71 (PL) Quo Sample t: C.P 1.5 1.0 DWkWe IF 's, ro* 1.5 1.0 Spike z:fr 1.5 1.0 10 inquench a 10 Inquench 9 io Inquench J.Q 1019 8 -MeFOSEA-079 Sample ; ,iv 5 1.0 1019 8 -MeFOSEA-080 Duplicate -1:,03 5 1.0 1019 8 -MeFOSEA-081 Spike LZJ ;.-11 5 1.0 10 Inquench a 10 Inquench .0 10 inquench ig 101-gi8 -MeFOSEA-082 Sample 7 1.0 101498 -MeFOSEA-083 Duplicat 31-5 7 1.0 101 8 -MeFOSEA-084 -Spike @Z 10 3:15 7 1.0 10 Inquench (I 10 Inquench 11 10 Inquench ia 101 98 -MeFOSEA-085 Sample 1 9 1.0 101 98 -MeFOSEA-086 Duplicate 315,0 9 1.0 101 98 -MeFOSEA-087 Spike Co -1."3v 9 1.0 10 inquench_ a 10 inquench 2 10 inquench JQ 101 98 -MeFOSEA-088 Sample 3:.(o 11 1.0 101 98 -MeFOSEA-089 Duplicate _I:g-o 11 1.0 10 @9I99998 -MeFOSEA-090 Spike r7l (ij 3:5-0 - 11 1.0 %Y DateofInWalProp: 11-7,.7-9r TestAnalyte Solution ISTDSoludon SYUP Quenching Solution Standard/TraceabilNkoy. Component Corwentratio(npg/mL) BoNsAddift by: OT3@ 17AAW-.r-lkp)?4x-lilt A*"W E'16FAFIfd & -h6 - eq -W.JW.-.t --Stil i-E 7TjF.7C*t@- ('1yccL 60-1 f-IFI@% I NN. o ISM Additiobny: -TOWAn*b AddMm Quenching by: SpikeAddfflwby: ---r-AAb blg LUL, _iv 6 CenWfug RPM: Time: By: Roujan min Autovial Aliquobng by: :TM C, Alltr@,@ latal 1 Vtq ID A set o 10 Inquench a 10 inquench a 10 inquench JU Vale ofOuench Temperatureof lncu W.pkdlonSW (Dde IncubatioSntop(Date -1"@ Y@es By: Pore Size: u Reviewed by: tac4 plw JM(A U2744 -Mirolw tja"i"tytId.) TEST ANAYLTE: HOURS: Sample No. eFOSEA-091 8 -MeFOSEA-092 ii1009F118898 ---mMmeFOSEA-093 FluorochemicDaelgradatio(nHydrolysiAsn)alysis MethylFOSEA Date 11123198 day 28 Time of Initial BuftrVolume Description Prop BufferpH (mL) TestAnalyto Solution(pL) ISTD Solution (pL) Spike Solution (PL) Ot Sample Dupkete Spike 1; O.D 1.5 1.0 T- ou 1.5 1.0 1.5 1.0 10 inquench Q 10 inquench 12 10 inquench JD 10IJ98 -MeFOSEA-094 101498 -MeFOSEA-095 101498 -MeFOSEA-096 Sample Duplicate Spike 5 1.0 5 1.0 5 1.0 10 Inquench a 10 inquench a 10 Inquench JD 10118-MeFOSEA-097 Sample 3:i@' 7 1.0 101498 -MeFOSEA-098 Duplicate 7.'I.C 7 1.0 101$8 -MeFOSEA-099 Spike 7 1I1-C 7 1.0 10 Inquench 0 10 Inquench (I 10 inquench JD 10118 -MeFOSEA-100 Sample 9 1.0 101SP8 -MeFOSEA-101 Duplicate fv 9 1.0 lolq98 -MeFOSEA-102 Spike [Zitf) ft) 9 1.0 10 inquench Q 10 inquench a 10 inquench JD 101198 -MeFOSEA-1 03 Sample '3!S,9 11 1.0 10 101198 -MeFOSEA-1 04 Duplicate T.-fe 11 1.0 10 IOIQB -MeFOSEA-105 Spike_ LO(P 3: re) 11 1.0 10 v Date of InitliPlmp: z;-Tf - StarWardITraceabilNiot.y cwnpwmt Concentrati(opncj/mL) TestAnalyte VKO Quenching Solution ISTD Solution Solution Solution V014 -7 -Ile %W.141 W;qg,ln-f qp AfecoL-.4 glgw-oll tA7t1hlp@sg,moo inquench Inquench Inquench a 12 IQ Date ofQuenc Temperatureoflnc4 "LbationSW pa% IncubationStop (Date BuffeArdditionby: ISM Additiobny: %a.A-,"AddgwLW. Quenching by: SpikeAdditionby: AutoviaAlliqwbng by: :sm(:a JKAG 41@o /Oka 04 lj"n&nlyt %;(A -. to,33opem t;v,fNctta,/- yrZNoNo CenWfugs: Roujan RPM: Tkm: min - By: iqd4ed0. 1,lpttAtea 0,41 d57,fW.reA,' 3@i'm 3M Envimnffwftl Laborawy = No,t27;,"u4 a --Jpraoo: Yes By: Pore Size: Reviewed by: P14 AppendixD: GCIAED Chromatograms S" separefbtoundvoluffies. 3M EffAwvmNaiLaboratoly RWd No.WISOO AHMMY CMW*W:N* PMDLW PMWW*D 00 NCWDiseftm DoNotCopy 3MEnWMMWWLabmbty ROPM ft.W 1M AppendixE.,SpreadsheetsG:C(AED Results AffamyCAWWVbfkPmdud Pdvisgod I)ohW Diselo" DoNotCopy MEFOSEA GCIAED results Note thateach extractwas injectedInduplicate. pH 1.5 DATA day Sample numbe, 0 112398-MeFOSEA-Wi 112398-MeFOSEA-Ml 0 112398-MeFOSEA-002 112398-MeFOSE44)02 0 112398-MeFOSEA-003 112398-MeFOSEA-003 0.94 0.94 0.94 11239"eFOSEA-016 112398-MeFOSEA-016 112398-MeFOSEA-017 112398-MeFOSEA-017 112398-MeFOSEA-018 1123WMeFOSEA-018 1.92 112398-MeFOSEA-031 112398-MeFOSEA-031 1.92 112398-MeFOSEA-032 112398-MeFOSEA-02 1.92 112398-MeFOSEA-033 1123984AeFOSEA-033 6.72 6.72 6.72 112398-MeFOSEA-046 112398-MeFOSEA-046 112398-MeFOSEA-047 112398-MeFOSEA-D47 112398-MeFOSEA-048 112398-MeFOSEA-048 13.90 13.90 13.90 112398-MeFOSEA@Wl. 112398-MeFOSEA-061 112398,-MeFOSEA-062 112398-MeFOSEA-062 112398-MeFOSEA-063 11239"eFOSEA-063 20.71 20.71 20.71 112398-MeFOSEA-076 112398-MeFOSEA-076 112398-WFOSEA-077 112398-MeFOSEA-077 112398-MeFOSEA-078 112398-MeFOSEA-078 27.77 27.77 27.77 112398-MeFOSEA-091 112398-MeFOSEA-091 11239"eFOSEA-092 112398-MeFOSEA-092 112396-MeFOSEA-W3 1123MMeFOSEA-093 MeFOSEA(ppm) 9.896 9.891 9.872 9.858 9.722 10.132 7.590 8.021 8.079 8.385 8.919 8.9" 7.502 7.605 7.612 7.666 7.987 7.735 5.537 5.467 4.752 5.830 5.561 5.540 4.211 4.246 4.365 4.420 5.320 5.168 3.644 3.650 5.058 5.003 12.952 12.795 2.764 2.826 3.543 3.666 13.411 13.154 averag* ppm 9.894 9.865 9.927 % spike rtcovery for MEFOSEA %RPD calculatons 0.3 n/a 7.806 5.3 8.232 8.957 n/a 7.554 1.1 7.639 7.861 n/a 5.502 3.9 5.291 5.551 n/a 4.229 3.8 4.393 5.244 n/a 3.647 5.031 12.874 79.5 31.9 2.795 3.605 13.283 94.0 25.3 MEFOSEA GCIAED results Note thateach extractwas injectedinduplicate. pH iiDATA day Sample number 0 1123984AeFOSEA-004 112398-MeFOSEA-004 0 112398-MeFOSEA-005 112398-MeFOSEA-005 0 112398-MeFOSEA-M 112398-MeFOSEA-006 0.94 0.94 0.94 112398-MeFOSEA-019 112398-MeFOSEA-019 112398-MeFOSEA-020 112398-MeFOSEA-020 112398-MeFOSEA-021 112398-MeFOSEA-021 1.92 112398-MeFOSEA-034 112398-MeFOSEA-aU 1.92 1123W4MFOSEA-035 112398-MeFOSEA-035 1.92 11239"eFOSEA-036 112398-MeFOSEA-036 6.72 6.72 6.72 112398-MeFOSEA-049 i12398-MeFOSEA-049 112398-MeFOSEA-OW 112398-MeFOSEA-050 112398-MeFOSEA-051 112398-MeFOSEA-051 13.90 13.90 13.90 112398-MeFOSEA-064 112398-MeFOSEA-064 112398-MeFOSEA-066 112398-MeFOSEA-065 112398-MeFOSEA-W6 112398-MeFOSEA-066 20.71 20.71 20.71 112398-MeFOSEA-079 112398-MeFOSEA,079 112398-MeFOSEA-M 112398-MeFOSE44)80 112398-MeFOSEA-Ml 112398-MeFOSEA-Ml 27.77 27.77 27.77 112398-MeFOSEA4)94 112398-MeFOSEA-094 11239"eFOSEA-095 112398-MeFOSEA-095 112398-MeFOSEA-M 112398-MeFOSEA-OW MeFOSEA(ppm) 10.323 10.208 10.368 10.493 10.416 10.236 9.466 9.408 9.285 9.402 9.431 9.198 8.491 8.660 8.467 8.823 8.496 8.592 7.910 8.592 7.702 7.718 8.518 8.457 7.131 7.431 7.864 7.744 7.710 bad injection bad injection 5.789 5.639 5.546 18.636 19.054 5.448 5.215 5.636 5.518 15.199 15.132 average ppm 10.266 10.431 10.326 % spike recovery forMoF03EA %RPD calculations 1.6 ri/a 9.437 1.0 9.344 9.315 n/a 8.576 0.8 8.645 8.544 nla 8.251 6.8 7.710 8.488 nla 7.281 6.9 7.804 7.710 n/a 5.789 3.5 5.593 18.845 122.9 5.332 4.5 5.677 15.166 90.5 MEFOSEA GC/AED results Note thateach extractwas Injecteidn duplicate. RH 7 DATA day Sample number 0 112398-MeFOSEA-007 112398-MeFOSEA-007 0 112398-MeFOSEA-008 112398-MeFOSEA-008 0 112398-MeFOSEA-009 112398-MeFOSEA-&.)g MeFOSEA(ppm) 10.598 10.573 10.440 10.356 10.453 10.785 average ppm 10.586 10.398 10.619 % spike recovery for MEFOSEA %RPD calculations 1.8 n/a 0.94 0.94 0.94 112398-MeFOSEA-022 112398-MeFOSEA-022 112398-MeFOSEA-023 112398-MeFOSEA-023 112398-MeFOSEA-024 112398-MeFOSEA-024 8.535 8.603 8.627 8.547 9.023 8.882 8.519 0.8 8.587 8.953 n/a 1.92 112398-MeFOSEA-037 112398-MeFOSEA-037 1.92 112398-MeFOSEA-M 112398-MeFOSEA-OU 1.92 112398-MeFOSEA-039 n/a 112398-MeFOSEA-039 6.72 6.72 6.72 112398-MeFOSEA-052 112398-MeFOSEA-052 112398-MeFOSEA-053 112398-MeFOSEA-M 112398-MeFOSEA-054 112398-MeFOSEA-054 6.534 6.871 5.410 5.542 5.947 5.801 6.703 6.476 5.874 20.1 n/a 13.90 13.90 13.90 112398-MeFOSEA-067 112398-MeFOSEA-067 112398-MeFOSEA-U!8. 112398-MeFOSEA-068 112398-MeFOSEA-069 112398-MeFOSEA-069 4.793 4.940 4.278 4.180 5.507 5.585 4.867 14.0 4.229 5.546 n/a 20.71 20.71 20.71 112398-MeFOSEA-082 112398-MeFOSEA-082 112398-MeFOSEA-083 112398-MeFOSEA-W3 112398-MeFOSEA-084 112398-MeFOSEA-084 4.506 4.684 3.512 3.360 14.152 13.941 4.595 28.9 3.436 14.047 93.5 27.77 27.77 27.77 112398-MeFOSEA-097 112398-MeFOSEA-097 112398-MeFOSEA-098 112398-MeFOSEA-098 112398-MeFOSEA-099 112398-MeFOSEA-M 1.958 2.041 2.021 2.060 14.490 14.089 2.000 2.0 2.041 14.290 114.3 ResultsforDay 1.92were notincludedinft graph,due tofailedQC crtteda. MEFOSEA GCIAED resulfs Notethateachextracwtas Injecteidndupilaft. pH 2 13ATA day Sampb number 0 1123WMeFOSEA-010 112398-M&FOSEA-010 0 112398-MeFOSEA-011 112398-MeFOSEA-011 0 112398-M*FOSEA-012 112398-M*FOSEA-012 0.9.4 0.94 0.94 112398-MeFOSEA-025 112398-M*FOSEA-025 112398-M*FOSEA-M 11239&WOSE4-026 112398-MeFOSEA-027 112398-MeFOSEA-W .1.92 112398-WFOSEA-040 112398-MeFOSEA-040 1.92 112398-MeFOSEA-041 112398-M@FOSEA-&;l 1.92 1123ga-MeFOSEA-042 112398-MeFOSEA-042 6.72 6.72 6.72 112398-MeFOSEA-M 112398-MeFOSEA-055 112398-MeFOSEA-056 112398-MeFOSEA-M 112398-MeFOSEA-M 112398-MeFOSEA-057 13.90 13.90 13.90 112398-MeFOSEA-070 112396-M*FOSEA-070 112398-MeFOSEA-071 l12398-WFOSEA-071 11239SMeFOSEA-072 112398-MeFOSEA-072 20.71 20.71 20.71 112398-MeFOSEA-M 112398-MeFOSEA-M 112398-MeFOSEA-M 112398-MeFOSEA-OW 112398MeFOSEA-W7 112398-MeFOSEA-Oa7 27.77 27.77 27.77 112398-MeFOSEA-100 112398-MeFOSEA-100 112398-M&FOSEA-101 112398-MeFOSEA-101 112398-MeFOSEA-102 112398-MeFOSEA-102 M@FOSEA(ppm) 9.998 9.469 10.312 10.533 10.313 9.881 10.998 li.m 11.386 10.059 8.713 8.517 g.a97 8.8w 7M 7.326 7.457 7.189 5.036 4.992 6.114 5.082 6.263 5.4al 4.436 4.394 4.365 4.624 2.980 2.960 2.601 2.476 Z312 2.289 11.365 11.252 2.392 2.371 2.415 2.361 11.798 11.972 average PPM 9.734 10.423 10.097 % spike recovery fbr MEFOSEA %RPD calcubtions a.a n/a 11.145 3.9 10.723 8.615 nla 9.349 7.295 7.323 24.7 rva 5.014 11.0 5.598 6.872 rvs 4.415 i.a 4.495 2.970 fva 2.538 10.3 2.291 11.309 62.9 2.382 0.3 2.388 11.885 88.5 MEFOSEA GC/AED results Notethateachextracwtas ifqecteidnduplicate. pH 11 DATA day Sample number 0 1123M3-M*FOSEA,013 11239"eFOSEA-013 0 112398-MeFOSEA-014 112398-MeFOSEA-014 0 112398-MeFOSEA-015 112396-M@FOSEA-0'5 0.94 0.94 0.94 11239&MeFOSEA-028 1123MMeFOSEA-028 112398-MeFOSEA-029 112398-MeFOSEA-029 112398-M*FOSEA-M 112398-MeFOSEA-030 1.92 112398-MeFOSEA-043 11239S-MoFOSEA-043 1.92 112398-MeFOSEA-044 112398-MeFOSEA-044 - 1.92 112398-M@FOSEA-045 112398-MeFOSEA-045 6.72 6.72 6.72 112398-MeFOSEA4)W 112398-MeFOSEA-OW 112398-MeFOSEA-059 11239SWoFOSEA-09 112398-MeFOSEA-WO 1123913-MeFOSEA-060 13.90 13.90 13.90 112398-MeFOSEA-073 112398-MeFOSEA-073' 112398-MeFOSEA-0@4 112398-MeFOSEA-074 1123984"FOSEA-076 112395-MeFOSEA-075 20.71 20.71 20.71 112398-MeFOSEA4)88 112398-MeFOSEA-M 112398-MeFOSEA-M9 112398-MeFOSEA4)B9 112398-MeFOSEA4)90 112398-MeFOSEA-OW 27.77 27.77 27.77 112398-MeFOSEA-103 112398-WFOSEA-103 112398-MeFOSEA-104 112398-MeFOSEA-104 112398-MeFOSEA-1 05 112398-MeFOSEA-105 MeFOSEA(ppm) 12.496 10.362 9.650 10.302 10.306 9.674 8.971 8.648 9.218 8.988 8.596 8.527 7.316 8.749 9.143 8.833 8.525 8.434 5.947 5.630 6.966 5.103 5.315 5.035 3.360 3.260 3.471 3.325 3.545 3.802 2.144 2.354 2.885 2.795 12.385 12.647 2.268 2.300 2.497 2.488 12.028 12.442 average PPM 11.429 9.976 9.990 % spike recovery forU*FOSEA %RPO calcumons 13.6 n/a 8.810 3.3 9.103 8.562 nis 8.032 11.2 8.988 8.480 n/a 5.789 4.5 5.535 5.175 n/a 3.310 2.6 3.398 3.674 rvs 2.249 23.2 2.840 12.616 92.9 2.284 8.7 2.493 12.235 91.8 QA/QC calculations MatftOP&Omcovm eakulaftm RH Aumk 1.5 1123W-MeFOSEA-078 1.5 1123984"FOSEA-M 5 112398-M*FOSEA-Ml 5 112398-WOSEA-M 7 112398-M&FOSEA-M4 7 112398-M&FOSEA-M 9 112398-MeFOSEA-M7 9 1123984AeFOSEA-102 it 112398-MeFOSEA-M 11 1123984WOSEA-105 Average recovery Standard deviabon %Ralab" standarddeviation Lowerwarninglin* Upper warninglimit Lower controlimit Upper controlknit % 79.5 94.0 122.9 90.5 93.5 114.3 SZ9 88.5 92.9 91.8 95.1 12.7 13.4% 69.6 120.5 56.9 133.3 Sample precisioncakulatkm, usingthesample and duplicateto calculattehe RPO Average RPD 8.5 Standard deviabon 9.0 Lower warningBmk 0.0 Upper warningIn* 28.6 Lower controlby* 0.0 Upper controlirnk 35.6 3MEn4mmenWLaboraloy ROPortAbw.im AppendixF.,SpreadsheetsC:alculadoonfKinedcParameters Atbmy CMw*Ktt*PiodudPDAWW Do NotOhmi*M DO Notcopy Kinetics Equtlou wed: The hydrolysinso co=tan@ k.=[IRKP-X@-ln(RX) I t whom RX isMolarconcmtnom 0.6931k, MEFOSEA was testedbytheswitionof10 microliteoifs10,730ppiMnEFOSEA Thisisequivalentto 107.3niicrograwmiofMEFOSEA. The forfnulawreightofMethylFOSEA isequalto6'1127 Ibisimkcs theiniticaolncentratiofnMcFOSFA equalto 1.7554FA MOW. inwdone toI.Omlofbu pH 1.5Data Avmo Md4MA Day WO) 0 .9.90 0.94 8.33 1.92 7.69 &72 5.45 13.90 4.62 'M 71 4.34 27.77 3.2D lMeFOSEAI (M*kr) 1.619E-04 1.363M 1.257E-04 8.912E-OS 7.561E-05 7.09$FA)S 5.23SE-05 pH 5 Data Day 0 0.94 1.92 6.72 13.90 20.71 27.77 A"rW MeFOSIrA Wb) 10.34 9.36 8.59 8.15 7.60 5.69 5.45 (?&nMFAI @nd (Mohr) 1.692E-04 1.532E-04 1.40SE-04 1.333FA)4 1.243E-04 9.310E-05 2.923E-05 MeFOSLA6 0.922 Ci.777 0.716 O.SOS 0.431 0.4C#4 0.298 LNWMSLALJMEMZAI, 0.964 0.273 0.301 0.760 0.708 0.530 0.308 malmlbg of OKRWAL [NDKWAII -0.081 -0.253 .0.334 -0.672 -0.842 -0.905 -1.210 A"rW Stm&rdDw. k 0.2690 0.1738 O.IODB 0.0606 0.0437 0.0436 0.1152 0.09M tga(dar, 2.6 4.0 6.9 11.4 15.9 15.9 9.4 5.8 oaftrbaglof IMCMU&L RAeFOSRAIg -0.037 -0.136 -0.222 .0.275 -0.345 -0.634 -0.676 AvoW Stambrd Dev. k 0.1445 0.1159 0.0409 0.0248 0.0306 0.0244 0.0635 0.0528 us (gh 4.9 6.0 16.9 27.9 22.6 28.4 17.8 lo.s Pap I pH 7 Data Day 0 0.94 6.72 13.90 20.71 27.77 Average MOMRA (ppb) 10.53 8.69 6.02 4.88 4.02 2.02 lr&FOSRAI @red (bbbr) 1.723E-04 1.421E-04 9.344E-OS 7.984E-05 6.569&05 3.305E.05 pH 9 Data Day 0 0.94 1.92 6.72 13.90 20.71 27.77 Average MEFOSFA (ppb) 10.09 10.16 7.99 5.49 3.96 2.41 2.38 IMWFOWAI @m tmakr) 1.650E-04 1.662E-04 1.307E-04 8.989E-OS 6.47$E-05 3.93DE-OS 3.901E-05 pH 11 Data 0 -0.94 -1.92 -6.72 -13.9 -20.71 -27.77 I)ay 0 0.94 1.92 6.72 13.90 20.71 27.77 AverageMEMFA Wb) 10.47 8.92 8.50 5.50 3.46 2.54 2.39 [MEFWFAI mmumd (Mobr) 1.712E-04 1.444E-04 1.391E-04 S.ME-OS 3.66IB-05 4.163E.05 3.907E-0 fteocs LNdMSFA6[MtFMZAk 0.982 0.810 0.561 0.455 0.374 0.198 LMdDSU6WOSEAk 0.940 0.947 0.745 0.512 0369 0.22S 02M gidESUUMtFMIA]f 0.976 0.823 O.M 0.513 0.323 0.237 02M Page 2 meemliogof ludm"AL [MEFWKAI@ -0.018 -0.211 -0.578 -0.7U -0.983 -1.670 Average StooftrdIX-r. k 0.2246 0.0960 0.0567 0.0474 0.0601 0.0950 0.0739 tln(da 3.1 8.1 12.2 14.6 ii.s 9.9 4.5 misra1l%of INDMM" IMOMFAlo -0.062 -0.054 -0.295 -0.669 -O.M -1.491 -I-iw Avenp SUMardDa. k 0.0578 0.1535 0.0996 0.0717 0.0720 0.0-Ul 0.0848 0.0373 tin(da@ 12.0 4.S 7.0 9.7 9.6 12.8 9.3 3.1 mt" bg of obeau&L lhkMZAI, -0.025 -0.1" -0.233 -0.668 -1.131 -1.439 -1.502 Average Standard Dew. k 0.2079 0.1212 0.0994 0.0814 0.069S 0.0541 0.1056 0.0552 tn (d 3.3 5.7 7.0 8.5 10.0 12.9 7.9 3.3