Document jgGJL6RMpGdg2JXxN8vLV6nrR
STABILITY IN WATER (HYDROLYSIS)
TEST SUBSTANCE
Identity: N2-(N-methylperfluorooctanesulfonamido)-ethyl acrylate; may also be
referred to as N-MeFOSEA, or MeFOSEA. (2-Propenoic acid, 2-
[I(heptadecafluorooctyl)sulfonyllmethylaminoethyl ester, CAS #
25268-77-3)
Remarks: Material is an amber, waxy solid, coded THAR3F2. Sample purity was not characterized.
METHOD
Method: OPPTS 835.2110
GLP (YIN): No
Year completed: 1999
Type: Abiotic
Stock solution and test sample preparation: A 10,730 mg/L stock solution of
MeFOSEA in acetone was prepared. Test solutions were then prepared by
adding 10 uL of the stock solution to 1.0 mL of five solutions individually buffered
to pH values of 1.5, 5.0, 7.0, 9.0, and 11.0. This calculates to a 107.3 mg/L.
concentration of MeFOSEA in each buffered solution.
Remarks: Modification of the test method included using a wider rangeof pH and longer time periods foar more complete understanding of the behavior of the
test substance.
RESULTS
PH impact on Hydrolysis Half-lives at 50C
[p TT HalfiH ife(days) |
[18 T7927]
[850 178
|
[7 TT "0 99 --
[80 195
CTTo 79 --
[p |HalliH ifo (days) | pH impact on Hydrolysis Half-lives at 25C**
[fs ea
[7 1--"0 9--] [so--T93 ]
~ ExapoladtediToom valuesTo 155 79 --
000026
aRqeumeaorukss:pHThbueffaenraeldyssioslusthioonwsedwitthhatticmoe.ncentration of MeFOSEA declined in all The degradation rates fit second order kinetics better than first order kinetics. Nhaelvfe-ritfheealfetsers,sitxhetirmeepopretriaoudtsh.orGesnaersaslulym,edthfeircstalocrudleartekdinheatlicfs-faenidnccarlecausleadtewditthhe
time. The half-lives reported above are averagesof the half-lives calculated after each of the six time periods. The report does not explain how the extrapolation was made from the half-lives
aotne50orCdetroo2f5maC.gnAiuttuhdoer isntcarteeassaesisnuTmyedpeArG25=1C5.-18 kcal/mole which wouldgive CONCLUSIONS Tehnivsirsotnumdeyntianldliycarteelsevtahantt McoenFdiOtiSoEnsA. is hydrolytically unstable under Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul,
Minnesota, 55133
DATA QUALITY Reliability: Kiimisch ranking 1 REFERENCES
Study conducted by the 3M Company, Environmental Laboratory, St. Paul, MN. OTHER
Last changed: 5/17/00
000027
| IMEnonmanta Laboratory
FopotNo.W1883
Study of the Stability of MeFOSEA in Aqueous Buffers Using Gas Chromatography with Atomic Emission Detection
3MEnvironmentalLaboratory Contact `Thomas L. Hatfeid, Ph.D. Building 2-38-09 935 Bush Ave. PhSotneP:au(l,51M)N77585.1748463 FAX: (651) 778.6178 Requester 3M Company
+ Report Date; June 14, 1990
Report Summary
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1.82, 6.72, incubation,
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After with
chherxaonmea.togTrhaephhexwiatnheexatnracattsomwiecreemdirsiesdiownithdeatnehcyidorrou(sGCsIoAdEiDu)m. suTlfhaete aannadlyisnijsectsehdoinwteoda gthaast
'
W`ictohncteinmterwaititohnisneofacMhepFHOdSaEtAasdeetcalitn5e0dICn,aallvearqaugeionugs9.p4HdabuyfsfaertspwHith t1.5i,me1.7.8dHaaylstaivtespHIn5c.r0e,as5e.d9
dr5a.o0yo.sm9a9ttdepmaHpye7sr.aa0tt,ur8pHe.3(7d2.a50y,s9Ca)3tdreapsHyusl9ta.e0td,pianHnad8.7h0a.,l9atd-nivdae7sa9yatdvaesprHyasg1ai1nt.g0.p9H 4Exd1t1ar.ya0sp.oTalhtatepisoHenor1fe.s5t,uhlet1s7580idnaCdydis caatlathttpaaeoHt
MeFOSEA is hycrolyticaly unstable under environmentally relevant conditions.
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| IMEnvhorRmeentpa LoabrWor1ts0t8r.y8
1 INTRODUCTION...mses
Figure2. MFOSEAandPossibleDEGradation
ProGUCES..................................5
2 SAMPLERECEIPT cocoons
3 HOLDING TIMES....cccomsmssnsmsnmessesmsmessmmmsssmsssssseseso
4 4MA.E2T:SSHaONmDplASe-PGrAONP.AArLaYtiToInCAnLdAANNBDIPSIRSEDPIASRS:Ae TO.R.Y....o .s.s.c..s.s s.s.onrsorni osorromrcersn mmmmn8 8 ANALYSIS.ccssmmsssssmmsesssesssmmmsssmssssonnd.
55.238Sulrarnogkast.e.s........ h--name ssrs--e--r--e------cg J
5.6SampleRelated COMMONS.................... re------ 8 DFAiTguAr3Se.URMMeARpYc resGCo eIAnEDtCRc IaOMtAIiOGc TvAMeS...i ..o.orwn ....oroe rvoorera oenre.
`FTaibglue1r.4e.FiMtoofFOSSEeAConccenotraantndioLnindVeearrs-EuqsuaOtionrstodMTeeFiOSrmEAeDe.gra.dat.ion"Data..".j1o0 7 TCaOblNeC2L.UHSaIltO-NLi.veosocfcMeeFmOsSEsAsVesrssussTeimmes.s..esssssssmmssonrmo mmsn11n 8 DATA/SAMPLE RETENTION ..cconmmmsmsmmsmssessmsmmsemmssossss 9 SIGNATURES coosmssmmsisssssssnsmmssmsmsmmsmmonin 10 AAPpPpEeNnDdIiACx:ESEPc A Guis delinr es. smsssmsmessesesmessmmmsssssonnemsmmdnd
ApApppeennddiixxCB::SMaemFpOlSeEPrAepParreaptairoantiLoongasnhdeeAtnaslysis Method AAppppeendnidxiDEx:.SGpCr/eAadEsDheCehtrso:mGaCtIogArEaDmsRe(ssueletsseparate bound volumes) Appendix F: Spreadsheets: Calculationof Kinetic Parameters.
A0t0oNmoetyDCilsacnoisMeorkProductPviooed
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1 Inrodigon i VRRS R deHstyyecrnrmtoihnliy,nigdstohenpeeocrfstiohsietnmamtnahceiepnanmnvediocerchnrsiamrnenanammtes.nbTteysawtlihnaigcehooorfrgmyaannidcycpesosmtpiocofiucdnedsosa,nbmdoptpholnoyatmueuerravslnasaundnctdhstaos puoclyhecstoemrps,oupnoydesth(rApsp,eanndidxpAolyEaPmAidGeus,idaenldinoers)Getomining nef Hoof products containing tHhyadtrroloyssuilssintahreesacutiobnbestwteoeifnXsuowmieotOsnpFecies (n tisc258 ofthe type R-CO-X),withwater
Figure 1. Generic Hydrolysl Reaction
f f R--C--X + H0 == R--C--OH + HX
R=somehX=yhdalrooOogrRf,eclounroar,oKRcarrbobnmaoternial
fIhonleldeoiwquiutnaegtseiqcounaotmniuossntsbt,hewehmaeotrdsei"faeswdtfrionr"scsohlieumgtioncnassltthlhoaessasbiryaernaionhtgymddraiotleeyrs.iisarea1ctioin nfs sphoow1natwnioattshnhetat
deste] _ --_-- dt or n7A[A,]
nya [ester]1
`
fTrhacetiroantoecfocnosmtpanotukndsrtehmeaniengiantgiave smleop,ovfertsheusnteef.0T.helhoatloffHtohoenfatthuercaloomgpofotuhaentad
`specific pH isrelatedtothe rateofhydrolysisby:
JOro Notlaine------
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SW EmbaromratrsoL.aWb8r8s8y
MWpiertFehdOitcShteEeadAbpaorvovedeurecaqtunoaeftxihtyoednnrsodlaeyndsdpicseoronifsoMiddoeefFraiOtmSieoEntAsoawdsaestgeuNri-dmMeisne,eFthOheeSsEotvuaeldrcyoahmioolrn.aitteAoonrfaelrydteitahccatlilodonisf.sfoiAcfulties w1e0rceoennfcoiunthteerdeedgriandaatttieomnptriountgs.to monfortheappearanceofthisreactionproduct nansffort TshtaebpilrliymaofrythgeoaMleoFfOtSheEsAt.udSyiwncaeslteovdeelstoefrmMieneF,OtSoEAfrsstteaapdpyrodxeicmlaitnieodn,otvheer thiymcer,odlayttac collection stopped afer 28 days. a`cScaomrpdliensgotfoMpeuFblOiSshEeAd gwuairdselpirneepsa(rAepdpeinnbduiffxeArasonldutroefnesroefncpeHs t1h.e5,rs5).0., 7A.0s,o8l.u0t,ioannodf11.0 SoMfiegMnFiefFOicOSanSEtEieAAnnvi1in.r0aocnmami.etonotfnae.lacpThHhisbsuwfceforemerewcsahpsoopsnredonsp(oaer.e1g0d7pb.Hy3a1.p5dpdmiisnMgpeh1yF0sOiuSoLlEoofAgiaicen a1al0cr,e7hl3e0bvpuafpnftemra.sscution sf`tomroamqduaeectnhocpbhHeitneignrwcuaanssdeehoresfxtaiannnegd,estuthiseoenbd)e.htToahveeixotarrdaoctftoMrneamFaoOif nSaiEnpgAH Mi1ne1bF.a0OsbSiuEsAfolrfurtiiontomnhste.hepTrahaqseuoesnootlsuvtseunmdtaytcwrhiaoxssen atThhnaiotsmaaanllailleoyswseiadsnojdfeccdotiluiutomendonfadqmeagurteaeodruaistailboounfn.fteorsthbeyggaasscchhrroommaattogorgarpahp.hyPrreesvuitosusinscthurdoiemsathoagvreapshhiocwn I"fnTortmihpsestrseatmtupuderyre,abtuiusorededesgwrilahldaaistmtipeoentdooeftdheMegegrFardoOawSttEihoAonifdsmuroeusltteodmomeisucorpofhboiiraltliwcgormroiewcatrshoooinrnsgta.hneiFsbmusfi,fottrrhheeeds6ym0ep,dCei:a. baubosotuvtaeol,myotifynpthieaccbaitltoliynniigcnahlaalbbyoiratacettonirvvieierso.ocnemTaehnnetrbsmaossipunhcsih,liabcustmhnioocttrsolpoarrbiognraganstioasrmniesds,.hwyhAdlirscooht,dheoorntmeharlcivavenehantyp5oa0tthteChseiazned: thhhyyaddrrtootllhyyessiimssarvxaeitremssuuasmrbeoisoudsseugarrlaaltdyeaotmfiaoMxn.eimFuSOimSnEcueAndawecoriudakscdokoriccbcaousrrebasatstiaypcdicciaoflenlrdyeicnitaotnpasHlyazfneadchcmydiornmoiplmlyaislssah,edorbnyear 8mneLaupxtrHiaml7.uc0m1ongdirttoiiwostnhsst.ruadTtyhe.aistcoorntnreaasrtsnewuittrhalthpeH.acMtiatxyiomfummicartoebseso,fhwyhdircohlytsyipsiwcearlsdenmootnosbtsreartveed
A proposed mechanism for hydrolytic degradation of MeFOSEA is shown n Figure 2.
DD o hoticir oss --
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DPouoonrsoCrotpsy
WErtorRempaotrtLeawsiaosos
MoFOSEA and PossFiibgluerDee2gradation Products MeFOSEA
ad " o
focd oNR R mw -- FocdsoRR mw
Me 51127
Me 62920
NN
OH
|
sory
Fuc{ R
or
OrN,
Food R
OH + Fuel
ad
HN R
Rw
Me 129.16
SR
A
Bi
`AEOncvstiaormbopenlrm1ee3no,tfa1Ml9e6L8Fa.bOoTSrhaEteAosra(yc.mopdTlehedewTsaHasAmpRpl3alFc2re)edcwiaantlsoitoghbetchaaytiedn,redoalnfyrsloiemscstCtr.oonErliascgbeMecrSanDbdSi,n,3etMtheCnthsehamemiSpclaMels, on
pdraotdaubcatsieon"HmyedtrhooldysoilsogTryacaknidngp.r"edictive chemisties were ented into the aM proprietary
Holl Tio SR A NT
Thesampleswere propared and analyzed within the appicable hoding ime criteria.
ADto rMoetytCacoionsis kPoetrtocnd
000032 oPeartcoonpy
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4 Meitioda:Analyiealans ProparstoryIhHERESEROSET SR +
M3M8FEOnvSiErAonimneAntqauleoLaubsorBautloreysMUestihnogdGEaTsS-C8h-r9o0m.a0t"oDgertaeprhmyinwaittihonAtoofmtihceESmtiasbsiiloynoDfetection" Was followedexceptwhere noted below. This method is presented in Appendix B.
THhPe5G3C2I1AAEADEsDy,staenmduasneHdPwa7s67a3 aHuetwol-esta-mPpalcerk.arTdh(eHPc)o5l8um9n0SuesreideswIalsGaCJeAqWuiDpBpSe-dMwSit,ha30n M1505mCC,x0pi.en2rti6mamlinhmuotledx.t0i.m2e6oufm1.f0immitnh.,icfkinneaslst.emTpheeraotvuerne opfr3og0r0amC,haadndaanitnetmipalertaetmurpeerraamtpu-rroaefte of
44 Standards:
ITnetsetrnAanlalSyttaen:da1r0d,:7390.p3p24m pMpemFONS-EEIAFiOnSaEceatkoonheo(lIDIn98h0e8x6a-3n-e1-61)% IPA
and ID -98080-15-16)
-
(ID 88086-3-19,
a8nplokridnegroSftmaangdanridt:ud4e7l3o.w4eprtphmanN-tMheeFamOoSuEntalicnotheonldiendmdeutehatnooalca(lIcDulWa3t9io8n-e1r1r1o7r)) (This is
4.2 Sample Preparation and Analysis Dates:
Time 0: 094Days
P`Sraemppalreesd 1a1n2d3i9m8m-eMdieaFtOeSlEyAq-u0e0n1chteod11o2n31618/2M4/e9F8.OSEA01S `Analysis by GC/AED was begun on 11/25/69.
ISnacmupblateison1s1ta2r3t9ed8a-tM3e:F3O0SPEMA1on6 1t1o/1231/263808-MeFOSEA-030
Quenched at 2:30 PM on `Analysis by GC/AED was
1724/98 begun on
1725/98
(pH
1.5.5.7)
and
on
1730/88 (pH 9,11)
1620ays
InScaumbpaltieosn1s1t2ar3t9e8d-aMte3F:O3S0EPAM-0o3n1 1t1o/1213/283898-MeFOSEA-045 AInncaulbyastiisobnysGtCIoAEpaDptw2ea:s1d0bPegMunonon111/12/52/69/888 (pH 1.5,5,7) and on 1211/98 (BH9.11)
672Days
SInacmupblateison11st2a3r9te8d-aMte3F:O3S0EPA-M0o4n6 1t1o/1213/263898-MeFOSEA.080 AInnacluybsaitsiobnysGtoCpIpAeEdDatw8a:s54beAgMunonon111/23102/20-823/08 (pH 16,57), and 12/1188 (pH 9,11)
1390Days
ISnacmupblateison11s2ta3r9t8edMaetF3O:S30EPAM-06on 1t1o/1213/203896-MeFOSEA-O75 Incubationstoppedat 1:02 PM on 127/58
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000033
SW EmscoRmaepntaiL,awssoeeos A919n8 6aHb9ly11Gy)CIsAEDiwassbegunon 12/2398 (pH 1.65.7) and on 126-
2071Days SaInmcpulbaetsion1st1art2ed3at93380 P-MMonat1o1F/121O32/03S898E-MAeF.OS0EA70860 IAnalnysicsbyusGtoCbpIpAeaEdaDttw8a:is3b8eAogMuonnnon121/21142/891898 (5H 1.657)and on 12/1516198 (pH 9,11)
27.77 Days
ISnacmupblateison11s2t33a8r-aMtte3Fe:O3dS0EPAM-0o9n1 1t1o/1213/283898:MeFOSEA-105 Incubation stopped at 3:55 AM on 12/21/68 A1n2a/l3y0s/i9s8 b(yoHGC1/1)AED was begun on 12/20/98 (pH 1.5.5.7, 9) and on
`SSaammppllee pqruoepnacraitnognwoagsshceomepslaerteedpraopspernotxeidmaInteAlpype1ndhioxurC.afer incubation was stopped.
A TR I RERET
81 Calibration `Sdteagnrdaadratdiconalpbrroadtiuocnt (cuNr-vMeesFwOeSrEe aplrceophoalr)e.d uEsxianmginaatmiioxnoofftetshte cahnarloymtaet(oMgreaFmOsSEreAv)eaalnedd tcohhuarltodmatnthooetgbroiaunpstheiencddoaevdseraliannpteironnftaerlmeaslisdtsuaanldtcaordmpawo(tnNehn-nEtGFsCdF/iOnASaEMEDEFtraeOksSotEihdnoAgl..) Twhuass, Ni-nEAaFOSrEegaikocnohaolf
`SolventStandard Name | _Seivent/Standard Number [HIMPOeFAOsxoSlEvAeansttn aunsdeae drd s| [oN TvTe a Tn9n80z -t 8A6-23u-0i 160see d||
NN--MEeIFFOOSSEEaallccoohhoollssttaannddaarrdd|5398-331|
he calibration standard set consistedofthe folowing:
{--iepm)_|_scWoHhelFGSom)E || seNaEWlOSE
[seosedes | 4828 |[4e 734 3 | |1 oomsas2| |
[seosedec | 3210| [seose4eD | 1600|
3156 1578
| 0324 | | e324 |
[oeosdcE| 648| [oeossasF| "age |
eat 4734
| esa | | 03a |
[Cosomston| 13e21000||717 5703|| 1e5 wsaaa6||
a DoNettsciese ----
000034 oPooMeototcotpsy
| SMEmbormerts Laborer
Ropar. W 1068
T0.h9e90.staCnadlairbdratciuornvesstawnedraredlsinweearr,ewaintahltyhzeedcoienfdfuipcliienctasteaofttdehteerbmeigniantniionng (of)egvreeraytesramtphlaen WTuint.hA1t%rIePgAulaarndin9t.er3v2a4lsp(pem.g.N-afEtWerFOS-E8aslcaomhpollewienrjeecstnioanlsy)zebdl.ankAs mcoinds-iastnigneg coaflihberxaatnieo.n dsitfafnedraerndcewoafsamopeurnitodiocfalmleyastuersteeddantahlryotueghwoaust geraeactherstehqaunen+ce2.5% fWrhoemnthethteruepevracleusn,t rbeelfaotrievethteo ltahsteaicnoitaipaliasbtlaendcaalridbrcatuirovne,chtehcek:rsutnanwdaarsd dwiesrcearcdoedn.sidOenrleyd assamvpalliedsreasnulatlsy.zed 5.2 Blanks. A`pThperoixnitmeamtaellsyta1nmdaLrdalwiaqusotas swoelruteiotnraonfsf8e.r3r2edptpomauNt-ovEiWaFlsOSaEndalucsoehdolaisnshoelvxeannteb/l1a%nkIsPAi.n `tAhceceapntaalbylsiesv.aluTehsefsoer tbhelabnlkasnksserwveerde laesssatnhainnshtalrfumtehnetaprlaccthiceaclkQufaorntatnaatliyotneLicmairtryoofvetrh.e method (the concentrationofthe lowest standard used in the curve). 8:3 Surrogates Nosurrogate analytewas usedinthis analysis. 5.4 Matrix Spikes. Maatnarltyxtesipnitkoesaasmapmlpelsew.er- Tehperseepmaarterdixbyspiinktersodaumcpilnaegswkneorwencacrorinedctenhtorrftotahheetuetinagtroigrhenet w`istahmtplehporeafptathraetiuonnspprioceedsss.amCpolmepaprroivsiodneodftihe anmoufntoqounanctroinftiermdibfurtaoimontothfemtaihterisoxasmppnilkee. matrix to the analytical result.
O`ncoencoefnttrhaetisopniwkainsgosnoel-uttieonntshuosefdthwaatswahi4c7h3w.o4ulpdpmhNave-beMeneaolpctFiomhaolOl.sAtaSsndasErudc.h, Tthhies aprmeoculnudtinogf qNu-anMteaFtiOoSn.E SaplciokheolsaamdpdleedswoansDalyo2we1r atnhadnDtahye 2l8owaelssto ccaolnitbariatnieodn1s0tabnLdoarfda, 2180,,7a3c0ceppptmabsloeluMteioFnoOfSEMAeFrOecSoEvAerinioaecsfet8o0net.o F1o2r3a%lwethreepnHotsede.xtrTahcteedavoenraDgaeysre2c1ovaenrdy ofMeFOSEA was 05%.
5.5 Laboratory Control Samples Laboratory control sampleswere not preparedforthis analysis
5:6 Sample Related Comments. TcahleibrMaetiFonOSstEaAndarredsutshatforfotlhleowDedayth2e,speHsa7mpslaemspldeisd wneortepraesjsectqeuda,litays ctohnetrmoild-crriatnergiea specifiedintheanalytical method (Appendix B).
6 C DataSrey RR R.
`MTeheF3OMSEEAnvuisrionngmeGnCtawliLthabaotroamtiocryemdiesvseiloonpededteactmieont.hoTdhfiosr mtehethquoadntwiatastisvueccdeestsefrumlinuastiinogn fovfe
PHbuffermatrices. Sample chromataoregprresaenmtesdIn AppeDanssdepiaraxte bound
ADtoNootDilscelnosteoProductPrvinged.
ootCopy Pogesorss
000035
I
SMEmRoosnatiLawbissttrsy Vporleusmeenste.dAnreFpirgeurseen3taaatnivdeG3G,IAreEsDpcehcrtovmaya.togramof standard ixursand asampleare
Representative GFiAgurDesChromatograms PionadkielseMtaiFoOnSEeRs)ar 0.54 minutos(4MOFOSEsch, 10.0ites(dam standard, an 1082
Standard (8.43 pomMAFOSEA, 122258, 7:35:14 PM)
Ed
5
-
.
-
[
1
Ao
5. Sample (MFOSEA-.61.7, --
=
122298, 8:31:89 PM. Quaas5.n47poir MOeFOSdER)
-l
|
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000036 DFoaNseotcrosnsy
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`pTrheesecnaltceudlantsedprcooadnshcoeetnftorrmoaaftiainnaoAlnpytpseeinndsiaExm.pTeh,edsuepdlactatae,,palnotdemdaats MespFkOeSEsaAmples are concentrationversustime inFigure 4, show thatdogradation of MeFOSEAis ingeneralnon-
linear and afunctoifopHn.SamplesfromthepH 5.0 and7.0serles canbefitequallywell
pr`woivthiedietshearabeltienerarotrhsaneaconenadro-qoeuaqrtuiadotenioronr(tsheeedTaatbalaet 1p).H A1s.5e,c5o.n0d,-aonrdde1r1.0e.quation --M-- eFOSEACMOeFnOScEAeComnFticgeumrn4ettVriearsotusiTniomVne ersusTme
| ; nao . 'MeFOSEAExtractConcentra(tPiPoMn) 1000
om 138
n
| f ew
-
2
oi-s
=pH=50
fApHe=70o
opH=110
-
wf
*
89
| ooo re
------
|
Wm MW Ww ww ww
m-
Fit ofSecond-OradnedrLinsar EqTuaabtilo1ens to MeFOSEADegradationData
so1vese'ioce|ncaowe me|veomen|comoem m|
A`DtomNoatDCishioossirProus rege
.
000037
PDaogenetr0coto1p3y
SMEmonReportLe,awrs1888
Aho conclusion of the experiment (27.77 days). approximately 20 - 30%ofthe orginal
MeFOSEA remainedfor samples hydrolyzingatpH 1.5, 7.0, 9.0, and 11.0. AtpH 5, `approximately halfof the original MeFOSEA was present at the end of the experiment.
`DCaallcuelatoifonMseoFfOnSeEtAinpcarreaamseotderwsitahreinpcrreesaesnitnegdimIne,ApepsepnedciixalF.y aAt pgHene1.r5a,l5t.r0e,nd.s0, tahnadt t1h1e.0 (HToawbelveer2),. hTehifsbsethaavridoerr aoppsrsox!imamtaitocnhftrheamhaytdhreolmyastiiscarloamctoidoenlafsosrumiersoarsdienrgrleeaccotimopno.und dasesgurmapdteisotnomfaorymnoontlybtewreoaldisitsitcfionrprMoedFuOctSEspAe.ciesA.s iTmhpelerdesiuFsigsuhroew2n, itnheTadbelgera1daitnidiocnatoefthis `hMWiehsoFssOteSubdEeyAhaarmvoiaosyrufiifsnivcuioselnevtdefom1rultpthriapetldeipcurretpahocasttei.oonf opatthhewrasyysn.theMtiecFcOheSmEisAtriiseas.3MOvecornatlr,oltcheomrpoosuufnsd,of -- HalvesolMeFTaOble2SEAVemusTme
[00s0 258'T a7 |300|11o0|334| [102 T3500T 508 | 145i|
[aso T28451iss|280|1pm|
PE omen SRE ER
"MTehFeO3SMEAE.nviTrohnemheyndtraollyLsaibsorsautdoyrysdheovweeldoppeHd daempeetnhdoedntfohrahlyfdIrvoelsyswihsiacnhdinacnraleyassiesdowfith tm. `fwioptohHmin7t.ee0am,cp9he.rp3aHdtd auryesa a(s2t5ept tHaC)ta 85.r00e,sualCnt,deda7vI.e9rdaaaghyilnstgait9v.pe4sHdaay1v1se.r0a.atgipEnHgx19.4t5,dra17y.sa8dapoafypotsHhale1t5.5pa0,H1t57C.8i0d,da9ato.yats9nodaatys. PhcoiHnsd5is.tt0i,uond9sy9.tdhaaytsMaetFpOHSE7.A0,Is93udnastyasbaletapgHai9n.s0t, hayncdr7ol0ysdisauynadsterpeHnv11i.r0.onImteisnttahle rcloencvlaunstion of
Datars Ratwation {17111
cl
aRepseerriovdeosfatmepnleyseaarnsdfoalloowriinggintahlepsaipgenrindgaotfa wthielfbinarerteapionretd. in the archives of 3M ET&SS for
ADorneytCtalcoitorhs ProducPrtged
000038 P0ogMoottocrotpsy
OS
RR SR
eo
< "ThomaLs. a rs
GistonEge, Pr0.
G Poiacd
GregoryMaisel, Analyst
Erfomteursiornnierdy
RSA 5:7 ,
4
&D/a1tee
4/17/39
Date
b.Eaor
efit
il amK Reagan, oh. Tot c--ca Reviewer d yDatfs
Nroertviei:newJehedeatcnhoeaurtorWigiionkfat.lhdeAasna,aysbu,shiastpshpenrmoaclaotrotSyoMfEthnevilonamenbtsowLearrbkaoforrttai.sophrerseecyi.suSnhcee
ADatmCiansnProtrnd
000039 oPoaanctoa
MEmbmometteabtnersy 0ARREST ST BT RRSTR A
Appendix A: EPA Guidelines AAAppppppeeennndddiiixxx CBD:.: MGSaGemIFpAOlESeDEPACrhePrpraoermpaaatrtoaontgirLoanomgastnhd(oeAnensalsyosipsrMaetbhooudnd volumes) AAppppenednidx EF:: SSpprreeaaddsshheeeettss:, CGaCk/cAuEaDtoRnesouflKtsvtc Parametrs
ADsaetCthoinskProc rd
000020
ovoat Crony
Sm--y a Xs srnenol, Aj dix A: Fate, Transportand Transformation Test
712-C-98-057, January 1998 gency
Sspwp----
000041
--
-
SEPA
Fate, Transport and
Transformation Test Guidelines
OPPTS 835.2110
' Hydrolysis as a Function
of pH
:
000042
INTRODUCTION
This developed
guideline is one of a series by the Office of Prevention,
of test guidelines that have been Pesticides and Toxic Substances,
pUensittiecdideSstaatnesd be submitted t
EtonxviicrosnumbsetnatnaclePsr,otaencdttihoendeAvgeelnocpymefnotr o the Agency for review under Federal
use in
of test
the
data
regulations.
ttehsattinmgusotf
has
The Office of Prevention, Pesticides and Toxic Substances (OPPTS) developed this guideline through a process of harmoniz
blended
the
testing
guidance
and
requirements
that
existed
in
ation that the Office
. OCofhffaipPctoelelrouftIi,PoeSnsutbPiccrhiedavepetnPterirooRgnraaomnfsdt(hTOeoPxCPio)cdsweh(ioOcfPhPFaTepd)pereaaanlrdeRdeagipnuplepaautbrileoidncsaitni(oCTnFisRt)loe,f4t0thh,ee
lNiasthieodnably TtehcehnOircgaalniIznaftoiromnatfioorn ESceornvoicmeic(NCToIoSp)eraatnidonthaengduiDdeevlienleospmpeunbt-
(OECD).
OPPTTShegupiuderlpionsees oisf thoamrimnoinmiizziengvatrhieasteiongsuiadmeloinngesthienttoesatinsginpgrloecesdeutreosf
tmheanttmaulstPrboetepcetrifoonrmAegdetnocymeuentdtehredthaetaTroexqiucirSeumbesnttasnocfesthCeoUn.tro$,l EAncvtiro(1n5.
U.S.C. 2601) and the Federal (TUS.C. 136, et seq.).
Insecticide,
Fungicide '
and
Rodenticide
Act
GoverFinnmaelntGuPirdientliinnge ORffeilceea,seW:asThhiinsgtgouni,deDliCne 2i0s4a0v2aiolnabTlehefrFoedmerthael
U.S. Bul-
oflfeetdipbnabps.eBarocaccreosdpis.e.sg.pBoT.yhgiosv mg(oIuPiddee1l6mi2n.e14d0iis.a6la4l.s12o90)a,2v-ao5ir1la2cba-ll1le328e07le2,c-t5r1otn2eil-cn0ael1tl3y2aifnnodrASfdiCtsIpkI:s
(ahnidtpP:/D/Fssr(wp.ocrptaa.bgloev/deopcauhmoemne/trefsoeramratc)h.fhrtomm) EunPdAe'rsthWeorheladdiWnigde"ReWseebarcsiht.e
ers and Scientists/Test Guidelines."
Methods
and
Guidelines/OPPTS
Harmonized
Test
i
000043
!
OPPTS 835.2110 Hydrolysis as a function of PH.
iRnogden(rtaei)qcSuiidcreoemApecentt--s(F1)IoFAfRppAl)bioc(ta7hbiUl.itSht.eyC.. TF1he3id6se.rgaeultidseeIqln.is)neecatniisdciitdnhet.eenTdoFexudincgtioScuimdbeese,ttantacesnetsdControl Act (TSCA) (15 U.S.C. 2601).
(2) Background. The source material used in developing this har`toimfoopnnHio.zfedpOHPaPtT2S5 tesCt,gauinddelOinEeCaDre g4u0idCelFiRne79161.135H0yd0rHoyldyrsoilsysaissaasFuanFcutnico-n
suitab(lbe) aGnualiydtaicnaclemeitnhfoodr;mavtaipoonrp--r(e1s)sPurreerceuqruvies.ites. Water solubility data;
cimapnurb(ie2t)iteesQsutoaenlditwfhiyetihnregstuhslettsamtesethmoheuonldtds.dbeesPcucrroienbseiaddnehdreercdeo.,mTmbhueitrsctithaeesltpoggtureianddteeilailsnueebfsaftpeapcnltcieeossf
only high
ttoemwpaetreatrurseolurbelseultcsomtpoouennvdisr.onTmheenrteallisy
urnecleervtaanitnttyemipnereaxtturarpeoslaatsinag
.
change in reaction mechanism could occur.
.
given(i3n) pSatraangdraaprhdd(of)coufmtehnistgsu.idTehliisnteeasntdgounidehliinPeirsebalseidmoDniramnfetatGhuroiydds
ance for Premanufacture Notification EPA, August 18, 1978.
-
()
Th(e)
tMesettihngodof--(su1b)stPaunrcpeossfeo,r
relevance, hydrolysis
aipsprleilceavtainotn,toatnhdeilripmeirtssiosftteenscet..
rHayddartoiloynsiasndisisonteheroeffotrhee omnoestofctohmemmoaninredaecgtriaodnsatcioonntrpoaltlhisngofabsiuobtsitcandceegs.
in the environment.
cinodmipca(oitfui)nngdA owrphreootncheiedtrus rheoytdthroeorldysetitesesrtpmirniogndeuschthysod.urlIodtlyissbietshecraadrteergsireaiddsatoiiumotpnoroptrnaondtuacatplsasrotehniattn amraellcyrufcoiauln.dHiyndtrhoelyesnivsirboenhmaevnitor(pnHee4d-s9)toanbde uenxdaemrinmeodreatacpidHicvacloundeistinoonrs(PH 1-2) for physiological purposes.
(iii) Surface-controlled reactions can sometimes predominate over
sbuulltkinsodliuftfieornenhtyddreoglryasdiast,ioenspreactieaslltyhainn wtohuelsdoibleepnrveidriocntmeedntf.ro`mThtihsismaguyidree.-
line based upon rates in homogeneous solutions.
(2) Definitions and units. The definitions in section 3 of the Toxic
GSuobosdtaLnacbeosrCaotnotrryolPrAaccttic(eTSStCaAn)daarndds
the definitions in
apply to this test
40 CFR Part 792--
guideline. The fol-
lowing definitions also apply to this test guideline.
the
Hydrolysis refers
net exchange of the
to a reaction
group X with
of a chemical RX with water,
OH at the reaction center:
with
1 000044
RX + HOH -- 5 ROH + HX
in
Hydrolysis rate, the rate at which
this simplified process is given by:
the
concentration
of
RXdecreases
second order reaction rate = k [(H;0] [RX]
or
first order reaction rate = k [RX]
edxae5cpeaesnpsdscieoundmgopo-afnirrteshdtetorroadtteheredreectahecetrmimioicnnaiilnn,tgwhshitisectphy.ptBeheeocfoabruseseaercvtweiadotneriraisteusscpuoranelsstleaynnttdieinsscggrriievbaeendt by the relationship:
Kobe =k [HzO]
.
andcan be determined from theexpression
-
Kaba =2.303/t 10gio(Co/C) |
w2here t = time, andCoandC. = concentryationsofRX attimes 0and
liTfheeofuntihtesreoafcttihiosn c(otnismtefanotr h5a0vpethee driomfecRnXsiteoonrenoafct(t)tiismgei)v!enabndythe half-
ti = 0.693/kots
El [Krome| t wm erenc(e3s). RTehfeesreesnucbestsaunbcsetsannceeesd. n(oi)t AbsepiermipnlaonydedDiianzailnlocnasaerse wuhseedn aisnvreesf.-
tcitihogananotcifentgthaoencmeoemwtphsauorbdesmttaahnecyerb,eseTulhptesesrewfhodeartnmaeaadnrfoerthpoermrovtmiiedmteehdtopodritimsiamarpieplalyinesddo.ttTohahotefcfraeelrsitublhrtesa of the OECD/EEC-Laboratory Intercomparison Testing are included in the
following Tables 1. and 2.:
`Table 1.--Values of Rate Constants and Half-Lives for Aspirin2'
BE cosrrrerermrmrmeme--------
300
cay R 2500 (AGe ASS1n6a,5e 865.768-2)) (22acaisalictcicaacck) datadata fromromLLJo., ExEdwards,Transactionsofthe Far
2
000045
Table 2--Vaiuss of Rate Constants and Halt-Lives for Diazinon
[oc [we |wv [we PH
sKo[c10]8
Ks[e1c0]|| tia
t&ia
10I43O csr -- ClE00E s| E as00 | F
12
3H III os
6 | 120| 6s
78
ES RERE Sa erm pont fa olvalroi(waib)iinlFiuTtryatwbhhleeirscrhe3s.eultxthcsreooeufdgOshEw1Ch2.aDt-IinEsEscoCamLealbcoflarsoaeerstiodntrhyetihrneettseuerlstctsogmppuraeirsidesneotnledtieTnhsthaeiivn.esg
}
mesavyeysrt,peamarsstitachnuedlyatrhhlaeyvbeienbfteluehenenrcoeebstuoalfitnoeoxdfyguteshnien.ugTstheheeosfeTedsrietfsufGleutrisedneatlrbieunfperfseoisrnesnitthneedtOh,eEhtoCowsD.s .
EmoEdCifIinetdeirncotmhepalriigshtoonfTtehsetsiengrePsrulotgsr,amme, Part IT. The guideline has been
(A) Substance: Aspirin
.
Table 3--Reaction Rats Conatnt In 10%sec-:
stang- | Sant
PH
d Some.
daavrd | aonf
n. of results
ton.
3102
c n n s ||
36"20940|| 0|1o00s18s3e0]||
1278 | 0oi0i8z8| |
1272080327|| 000041000o10e1s19s9||1833a
7 c:ss| 2"0 | 0[210350|900000343| 105931[3001862-r0308281|| 35
90 corms| 2"0| | o0s3s08a||oo01o6s0|| 5`107|4|001s0i0o-o0s0r2|] 23
3
000046
|
Table 4--Hll-tfe in hours
on
steoo.yGC EdoEw || sVearVa2asonn,| range | notreosns
| Wa [wn Tes 80 mn | 2| 0 ||3197| 22=25
wwlews9ae5r%o| BIST]
|: 2a m
70 mes 00 ns |
2D|oE984 | 144 2 | 723 | a7
2| sol
srHhoeEinoEsss|||
22m oa
40 20.2 91
0.0] 20.1-203 2(1lab)
(B)SubstancTea:bDlieaSzin--onRoRataeCocnsttantiin1o0senc
i ; i Fordco
.
treats
dharc
Vln | ya5r
S 12 || 32B40B|R[232)0m%]| p4aBwy)| Bewetl TemrinRemae]d ee
08 || o7ls]| iaza|| omoo)l 0ob'mS%|| suoy e
790 mss | 3Qo0 |||| 0T0o9me35o3e|] 3aG17mEB9l0 1m1W9y25s4|3oc03cmoa1senm0gnzo3ns|| on48o e
80mi 38)0 | 81330)3| 2G14h33 E 1358| ou oongan|*C0
50
60
Ye 0292 0034| 11602680316
2801 | 4125| 1473 0.241~
2
8(7 labs)
4
000047
Table 8.--Hait-ie in hours
12 * B | 340E | coma]E oar
30 ron| 020 || 8212%:7||| 182s4%0
70 inne] w2&o0 | || 1'7H0og7i7we5||| 1e87a55r.1%s8
0| eo |
So| ase |
2o00w8y
90 ine | .
2wo0 so
|| |
1a1`5a0e7ak5|||
1N339E855E8
| 293| aser
coefficient |
Se27n9||0sorie09n00|| otr4 os
12258|| 2s250o92r5233s1 |'[3(1217a0)0
120| 77|
s2Siaasdrdeoersossr||| C84
7) se)
2T"00a65i83e55
|
2 87iane)
ni@e|l2|aadossoaorzsieaisrs||| 2o4
102) "55705 | 6 cane)
(C)Substance:Atrazine
.
Table 7~Reacton Rate Constantin 10%sec-:
oH
ddoo.|w|rofovaarmioIVaeaEtniotn,
nofresus
3120 errsone || 35@2040||| 0000514048]]| d00.6o010e68
9700 ers|
"@ || c0o8o0l8| oooeiir| 20 | 0013] o018|
|ooos|ooo|
sS76653]84||o00o07sm60o00z00e4|||
4 8
aGeos1|0|ozseoaricostee|| 38
13i0%1a|7|oS0c0b1i0o0o2s8|| 3=
.
oH Q12o III|
'
70 evs |
90co
|
Table 8.--HaiI-nhlofuros
poomr.: b
standard afcvoanfaitcioennt,
oofresults
| $540 | ] 5476] ao3n a0 | vseres| vassse
* o10|200rmsas| 770] sor
4 a
| 2050| amen ss| aTrai 5
40 || 90a0u0e1|8| 103a37s7] 12@300|] 1to659i06mn4.78e93 | 25
20 | 1792105| 2010821 | 40 | 0s3s| sans
1350] noo
ais3sreaes.
2 2
en
5
000048
(D) SubstancTea:blDei(92---eetshcylthoenxl)RapthetChoanlasttean(tDiOnP1)05sec-t
aaT| eciavatniaotnons,
ation
%
390 0] | a220 ||| oo0f0oe4s8| [|0oo0o5a1r| 70 cn| i2&o0 ||| 0gcen0o7s3e||| 0o08z4
o& || o fooeac|Z
e1i0m7ar8l] ooooosoocdraors-ooms|
wsS|| z
Goosce=zorooime
:
-
o of resus 22a 2zii i
:
`Table 10.--Half-iife in hours
oH
stGaaanovdnaird||| of"cvoaorfiiactieonnt.
30 | B@2Q0 ||| 9i22k002)0|| sB`oeoEr2s2 i1Z02|]f. s1i8ar2ss4s2a1sa0is0ae8n
70
&20
||
eia0i3se0 |
30138 z
:- of
|Gesy] = | oC
ase ::
(E) Substance: Ethyl acetate
Table 11.--Resction Rate Constant In 10sec
of resus 232 1233
pH
"| Farain.
woltrosuts
30 lo | 70 i| FL --
.
i820 ||| o((6030o50182)
22@0 ||pfe0min
2+ | a4s8
1ii
i1i
.
i1i
6 000049
Table 12.--Halt-ife in hours
oH
Taounda ||Sa"daewr"]| ocf voannattoon, || range
valis ation
%
30 wis | 2s]o0 || (e16r358)a0s)| -|Z
70 wn|
2a00 6
|| |
(a78s8i33a)n| (ao3g|
==|Z
0
| ER oc
60
(12.44) =
|T n of resuts
|
11 1 11 1
i
1
usi.all(4y)oPcrciunrciinpldeiloutfetshoelutteisotn,mwehtihcohd.me(ia)nIsntthahte wcaatveirroinsmpernets,encthienmilcaarlgse pcesoxencusedtsosa-,nftiardnsdut,riotnrhgdeerhreyfdaotrroefl,iyxsetihdsa.tpHHtehaennccdeo,ntcetemhnpeterrkaaintteiutorienc,sofofwahtye~drrorleysmiasinasreesgseennetriaallllyy
cies H(si)O+T,he(Hh+y)d,roalynsdisOHr-ea,ctiinonwhmiacyh bcaesienfitliusernecfederbryedactiodaisc osrpebcaisfiicc sapceid-
or specific base catalysis.
'
~ atinodn to(hifeidt)silmToehp.eeTochfoentchleeongtrarerasiuttlithoimnnsgoofsfttrthaheieghtcetostnlcisneuenbt(sratasatsniucomensiinsagrdefeiptrlesotrt-mtoirenddeeradgoaarisnpsasteftuuindmcoeifsirustsedo)r:der behavior) gives the rate constant from the formula (if logy
Kobe ==slope x 2.303
ticula(rivt)emWpheerantuitreisdinroetctplrya,ctiticiasbluesutaolldyetpeorsmsiinbleeatroateestciomnastteantthefocronasipaanrt-
through the use
rate constants at
of the Arthenius relationship in which
other temperatures is plotted against the
the logarithm of
reciprocal of the
absolute temperature (K).
+
is
ra(t5e)
cQounastlainttys
eornite1r3ical--a(sis)esReopfroodrugcainbiiclsittryu.ctMuereassucraenmbeentosf
of hydrolyhigh preci
osifont,hiosftgeunidweiltihnel)e.ssTthheanr2atpeerccoennsttasnttasndfaorrd odenveiaptiHona(nsdeeopnaeratgermappehra(ft)u(r2e)
should
unless
ubneusdueatlercmiirnceudmsitnandcueplsi(cea.tge.
awniatlhytaicdaelvidaitffiiocnulotfielse)ssprtehvaennt2.a5chpieervcienngt
prtheaiprsraomadeuntcdeirbsti,hleiintnytpahcreatnidcebutleaairlismppoHrfoatvnhededsoexbyycgierancn.umismtparnocveesdschoonutlrdolbeofretphoertseedn.sitTihvee
7
000050
1
tz = 0.693/kops (ii) Sensitivity. Most hydrolysis reactions follow apparent first order
reaction rates and. therefore. half-lives are independent of concentration
This usually permits the application of laboratory results determined at (1D0-22)-1o0f-t>hisMguitdoeleinnvei.ronmental conditions (S106 M) under paragraph
of hy(diriio)lySspiescifmiecaistyu.reSdevienrablotehxapmuprleesanodf ngaotourdalagwraeteermsenftorbaetwveareinetryatoesf
chemicals paragraph
(pfr)o(2v)iodfitnhgisbogtuhidpelHinea)n.d
temper.ature
have
been
measured
(see
the
(d) Descriptionofthe substance is less than 2
txest10p-r2ocMe,duareh.al(f1-)saItfurtahteedwastoleurtisoonlubiinliwtayteorf
is is
prepared. prepared
atIfltehsse
solubility than 10-2
iMs.grSeuabtsetrantcheasn
k2nxown10-t2o,
btehehytderstolsyotliuctaliloyn
.
unstable are tested at at least two temperaures between 040 C. Other
`substances ble under
are put through preliminary testing. Substances found to these conditions are considered hydrolytically stable
be sta(tz at
25 are
sCubimsigttredeatotthteeasrnting1yeatara)t.
Thosenot least two
stable at 50 temperatures
C forone week between 0-40 C,
"or, as appropriate, at at least three elevated temperatures, and the data
extrapolated to produce kat 25C.
:
(2) drolysis
tPerset psahroautlidobnes--p(eir)foMramteedraitaflosu--r(dAi)ffBeruefnfteprH'sosl:uattiopnHs.
(1) 1.2
The hy(if phys-
-
iologically importan
scribed below or a
t);
pH-
pH
stat
4.0;
may
pH
be
7.0;
used.
and pH
Use of
9.0. Either buffers as de.
a pH-stat avoids potential
problems due to buffer catalysis.
pared(2u)siFnogrrtehaigsenpturgproasdee, c0h.e0m5icMalsstaenrdiledibstuiflfleerd, ssotleurtilieonwsatsehro,uTldhebebufpfree-r
steysstteed.msItarsehobualsdedbeupnoontetdhethaantaltyhteicablufrfeeqruisryesmteenmtsusfeord tmheaychienmfilcuaelncbeeitnhge
srahtoeulodf bheydermopllysoiyseda.nTdhweheursee otfhibsorisatoebosreravceedtataen baulftfeerrnsatiensbtuefafderofsypshtose-m
phate has been recommended under paragraph ()(2) of this guideline, The
PatHthoef reeaqcuhirbeudffteermpseorlauttuiroen
mtousatprbeecicshieocnkoefd
with a
at least
calibrated pH
0.1 pH units.
meter
Some
useful buffer systems are presented in the following Tables 13., 14., and
15:
Table 13.--Buffer Mixtures of Clark and Lubs'*
Composition
oH
430722.:52N6mHmICIHlHCCTa1nd++202828MNlmiKKKeCClHGdIiLl0uGt1et0do.110000Mmil.I .. Ie||| 1109
8 000051
`Table 13.--Buffer MixturesofClark and Lubs',:--Continued
Compostion
oH
2403..1755 mMiI HHCO1Y S3mIHC1 +
++ 2255 25 mI
mMiI KKCC1T dGilOutOed KC1 diluted to
t1o0.110000 100 mi
mMil... .....
III
$3 mi HC1 + 25 mi KC1 diluted to 100 mi
1184 18
3.35 mi HC1 + 25 mi KC1 diluted to 100 mi1.....I . T II I
2220
406.1.7M0 39.60
mmpiiot00a..11ssNNiuHHmCCT1bi'p++ht55h00almMaiiteDbIi+PpAhMt0.Nh1EaIlNaaIteeHCt1o01110000
mMiI
I ..co..coeoesemsssssennes
22
2362..4925 20.32
mmli mi
00..11 0.1
NN N
HHCC11 HC
++ +
5500 50
mmii mi
bbiipphhtthhaallaattee biphthalate
ttoo to
110000 100
mmii mi
[I I
|
224 28
52d:499.0770mmiImi00..011.1NNN HHHCCC1T1+++550050mmiimlbbiibppihhptthhhtaahllaaalttaeetettooto110010000mmi.im.. " i... I T IT I|| 263 ml 0.1N HC1 + 50 mi bipht
330 338
0.1
M
potassium
biphthalate
+
halate to 100 0.1 N NaOH
mi
"ITI|
3
1779:2493.501998.mmmimil000.-.0111.1NNNNNNNNaaaaOOOOHHHH++++55250000MmmiImiipDibbIoiiDphpHhthtAnthahIalalAalaNtatSeetett1oo0to111010000000mmMilm i " [ ...I oI cseI sI msI smI nes||
4480 42
17.70 mi 0.1 N NaOH + 50 mi biphthalate to 100mi Ii ." ".ZI.."
|| 448d
B 0.1 M potR assium biE phthalate
29.95 mi 0.1 N NaOH + 50 mi
S+ 0.a1 tNasOH0
biphthalate to
100.1
100
mi
coc
"
2
35.45 mi 0.1N NaOH + 50 mi biphthalateo 10
| 50
| 29
4332..0805mmii 45.45 mi
00..11 0.1
NN N
NNNaaaOOOHHH
++ +
5500 50
mmii mi
bbiipphhtthhaallaattee biphthalate
tttooo
1000 110000
mmii mmii
Z .... 2 I " II I I
|
5584 2
SS0.7P10oMmmImo00c.n!1opMNoNNtAaaCsOsKHiu++m5590p.hMmoiisppPhhHoasOtpeShaP+tA0e.1t1o0N1100N00aOmMiIHU .* vv.ecoessesmmsmesmns [0
38 89
1172::8800 mmii 3.45mi
00..11 0.1
NNN
NNaaOOHH NaOH
++ +
5500 50
mmli mi
pphhoosspphhaattee phosphate
ttoo to
110000 100
mmii.[ .." II II I| mi "III
8828 86
3259.:0603 39.50
mmii mi
00..11 0.1
NN N
NNaaOOHH NaOH
++ +
5500 50
mmii mi
ppphhhooosssppphhhaaattteee
ttoo to
110000 100
mmii _" .. I mi _. II
|[0 8888 72
4452:.2800 46.80
mmii mi
00..11 0.1
NN-NNaaOOHH N NaOH
++ +
5500 50
mmii mi
pphhoosspphhaattee phosphate
ttoo to
110000 100
mmii mi
" [ II I I _...I
7784 0 870
820.:81917MmmliH;008..101,'NNinNN0aa.OO1HHM++K55C001 mM+i! 0bB.o1OriCNc a2Nc6ai1d0Ot1Ho0 110000 mMil cI esL ses
78
851..29.80000mmiimi00..011.1NNNNNNaaaOOOHHH+++550500mmiimibboobrroiirccicaaccaiicddidttooto111000000mmiimi..I . T II I
8820 84
2116..3300 26.70
mmii mi
00..11 0.1
NN N
NNaaOOHH NaOH
++ +
5500 50
mmii mi
bboorriicc boric
aacciidd acid
ttoo to
110000 100
mmii mi
[II II I I II
8886 90
3$82..8050 4403..8900
mmii mmii
00..11 00..11
NN NN
NNaaOOHH NNaaOOHH
++ ++
5500 5500
mmil mmii
bboorriicc bboorriicc
aacciidd aacciidd
ttoo ttoo
110000 110000
mmii mmii
.I III ___I Ir
9224 9986
"Lee | BE
{an21 gDTaShtoeareptnaHkseevnnal'autes2st0arneCdp.aorrdteedquiantitohnesse(19t0a9b)l.esThheavceorbreeesnponcdailncuglpatHedvaflruoems tabulated values.
tahreo
go6.t0a4nutnailt
hmiegahserutrhoamnentthes.
9
000052
'
Table 14.--Cilrate Buffers of Kolthott and Vieeschouwer's
4003.--.1:4_7M--m1im0o0.n11opNNoHHtCaC1ss++iu55m00McmilitrcCartea0taend0to.0C1.1T1o00m00eNpmMoriHhsCieIt.sioe.n I.I .coonmmns|||
wpwH 22
233630:828mmmili 17.2 mi
000..:111 01
NNN HHHCCC NHC1
+++ +
555000mmmiiiccciriaaattteee 50 mi cra
t0too fo
111000000 100
mmmiii mi
[I I II II
|| 222828 | 28
4120m7Im0i.011NNHHCCI1+35050mmliGirartaete0.to101000M1mir L rre ee||| 833289
0102.801.m3mMmIIm00:.a011.n1oNNpNoNNNtaOaaOsHOHsHi++u+55m500c0mIitmiriaSGtIcaeArt1aa0ent.ed1t0ot0o.111010000N0mMNmlIaic Ov H n e r ee|||| 433988
323931:.527 26.7
mmmiii mi
000...111 0.1
NNNN
NNNaaaOOOHHH NaOH
+++ +
555000 mmmiiicccrrraatateetttetooo 50miciate to
111000000 100
mmmlii mi
1 r r. e e 5 e s ee||| | Le|
444824 48
1858.4.020 74.4
mmmiii mi
000...111 0.1
NNN N
NNNNaaaaOOOOHHHH
+++ +
555000 50
mmmili mi
cccrriaaattteee citrate
fttooo to
111000000mmmiii 100mi
r L om rs e||| es|
8239820 28
81:2 m1 0.1 N NaOH + 50 mi crate 1 100 ml "rors| 89
mol2dADs:adtdatitnaykcernyastta1l8ofC.thymolor afowmillgrameofmercury,ofmercuric did topreventgrowth of
Table 15.--Borate Butter MixtufesofSorensen
Gomposion
"
Walbum, pH at
0.M0bo5raxrx|| 00of 7 N HOI
hit
s52oL5io.ln[ ] aAae Rm [Bi20e0000n| 778524 sys] 438 000 8%
87738874 7a730a5
r7747e78 738
er800so1 oom| 3430%%0
TOI
280
002000000 000
8a802589 880
8887532 a88s41s0 884 857
588802458800
Ssa0o0oso] B3i8dR0e
S80
00
202000000 000
525090118 817
558099846 a88s97e47 52 501
5287&547 840
s01o0n00.7 SUIT
00680800 0%
9570000 20
5983234 950
89933%8 857
895001888 930
55888588 962
TsOoUu]] 68%% 030 905578 1567.088 sS6i7 59322
(B) Test solutions. The chemical substance should be dissolved in distilled, sterile water with sterile buffer medium added to it. The concentrations should not exceed the lesser of 0.01 M or half thesaturation
codo)n,ceanntrdattihoenpu(sreeestOaPvPaiTlSabl8e30f.o7r8m40o,fWtahteersubsosltuabnicleitys,hosuhladkebefleasmkplmoeytehd-
10
000053
oinnlmyaiknincgaseupsutbhsetasnocleutsiownist.h Tlhoew uwsaeteorfsomliubxielidtys.olTvhenetsamios urnetcoofmmseolnvdeendt
should be less than | percent. and the solvent should not intertere with the hydrolysis process.
(C) Glassware. All glassware, which must be inert in the pH range
ssthuoduiledd,beshuosueldd fbore or buffer system is
cvsaotrlearrtyiililinezg,ed.oourtSitftohtpehpeehyrtdeersdtolviysosilbsuemirenetagrcitccioonnsfd,luacstIkfesdth(aentocehlgeermveiaactsaeeld)
sthemopuelrdabtuereasv,oisdeeadl.ed or septum-closed tubes are preferred and head space
the n(a3t)urAenaolfyttihceaslubmsettahnocde.bTehinegatneasltyetdi.caIlt mmeutshtodbewislulffbiecidenettleyrmsiennseidtibvye tainodn scpoencciefnitcrtaotiaolnlsowanddetmearyminwaetlilocnoonfstihsteodfisffoemreentcosmpebciineastiatonthoeftpesHt seolleuc.trodes, UV-visible spectrophotometry, conductivity, gas chromatography, dheirgihvatipvree(sss)u,reandlidqeutiedrmicnhartoimoantboygraapshuyi,tableextarnaacltytiiocnal amnedthofdo.rmation of
it is i(m4p)orTteasntt ctoonmdaiitnitoanisn--(tihe) tTeemmpepreartautrueroef.tFheordeetxetrrmaipnoaltaitoinosn tpouraptolseeass,t
If0.t1he hCy.drAolnytaipcprboephraivaitoer coofnstthaentsubtsetmapnecreaitureunbiantohwsnh,oualpdrebleimeimnpalroyyeteds.t
at 50 C is required. For tests beyond this preliminary stage data for tem-
puheirrgeahmteeurnrtetseamitpnetrtwahoeturtraeenmsgp.eerI0an-tua4rn0eysCeivnaernteh,issotuhrgeahntdg.eetTeohrremyibnymataeixyotnrbsaepsoolhbaottuailiodnnebdferboydmomnteeharsea-et
temperatures differing from cach other by at least 10 C.
ried
(i) out
Light using
aannydsuoixtyagbleen.meAtllhoodf
ttoheavhoyiddroplhyostioslyrteiaccteifofnesctss.hoAullld
be carsuitable
omreaasrugroenstshhroouulgdh tbhee tsaoklevnenttofoerxc5lumdienuotxeysgbeenfo(rce.g.prbepyarbautbibolnionfg tnhietrsoogleun.
tion). *
test
s(h5o)ulPderbfeorpmearfnocremeodf
otnhethteesstu--b(st)anPcreelaitmSi0nar0y.1testC.
A at
preliminary each of pH
4.0, 7.0, and
5 days (ti
9.0.
>1
If less
year),
than 10 percent
the chemical is
of the reaction is observed after
considered hydrolytically stable
and ble
anto eandvdiirtoionnmaelnttaelsltiyngreislerveaqnutirteedm.pIefratthuerseusb,sttahneceprieslkimnionwarnytotebset
unstais not
required. The analytical method must be sufficiently precise and sensitive
to detect a reduction of 10 percent in the initial concentration.
as
de(fiii)neHdydbryoltyhesipsreolfimuinnsatrayblteests, utbhsetatnecstesp.roIcfetdhueresuibs sttoanbcee
is
as
unstable
follows:
The
the
buffered test solutions of the
selected temperatures. To test
fsourbsftiarnsct-eorsdheroubledhabveiotrheeramcohstartetacetdaiotn
11
000054
|
sooflustiixonspsahcoeudlddabtea apnoainltysz,ednoirnmatlilmye binettewrevaelns 2w0hipcehrcpernotviadned a70mipneircmeunmt
tohfreheyd(r4o,ly7s,is9)opfHt'hsatatteestacchheomfictahle.seTlheecterdeatcteimopnersahtouurleds
be examined at
with replication
at one of them (the middle temperature in the case of elevated temperature
determinations).
-
ble
c(oiimi)poHuydnrdolsyhsoiusldatalpsoHb1e.2c.aTrrhieedabouotveattepstHfo1r.2a,
hydrolytically employing a
unstasingle,
physiologically significant temperature (37 C).
tion
() of
Data first
aonrdderrepkionrettiincsg.--(T1h)eTdraetaat"mobetnatinoefdresshuolutlsd--(ib)e
Confirmaplotted at
Iogio C, versus t and the reaction rate constant kops calculated by regres-
sion analysis or from the slope:
:
Kove = 2.303 x slope
line,
(i) the
rIeancttioenrispnrotefotirfsatrtoersiduelort,sn.aIndf
the the
ddaattaamduostn-obet
faanlalloyzned
astraight by meth-
ds beyond the scopeofthis test principle.
(2) Test report. (i) The test report should include information on:
(A) Sample purity.
7
(B) stances.
Any
results
appropriate
to
the
procedure
employing
reference
sub-
for
(C) each
sDeettoafileexdpetresitmepnrtosc.edure
including
the
temperature,
pH
and,
buffer
ingde(tDa)ilDeedtmaileed atonafleyhxtitcroaalctmdieonthaonddruesceodvfeorrydtahetatiefstaendesxutbrsatcatnicoen, mienctlhuoddis used to separate the chemical from the aqueous phase.
serve(dEt)oAolrligcionnacteenatrnaotniloinn-etairmelodgactoancpeonitnrtastifoonr-rteiamcetipolonts. which were ob(F) Possibility of acid or base catalysis.
(ii) A suggested format for sample reporting form, which can be du-
plicated, is presented:
12
000055
oinnlymaiknincgaseupsutbhsetasnocleustiownist.h
The
low
wusaeteorf somliubxielditys.olTvhenetsamios urnetcoofmmseonlvdeendt
tshheouhlyddrboelysliesssprtohcaenss.| percent. and the solvent should not interfere with
studie(dC,) Gshloauslsdwarbee. sAtlerlilgilzaeds.swaSrteo,ppwehriecdh vmoulsutmebtericinerftlasinksth(enopHgrreaansgee)
should be used for carrying out the hydrolysis reactions. If the chemical
or buffer system is
temperatures, sealed
volatile, or if the
or septum-closed
test is being conducted
tubes are preferred and
at elevated
head space
should be avoided.
the n(a3t)urAenaolfyttihceaslumbesttahnocde.bTehienganteasltyetdi.caIlt mmeutshtobdewislulffbiecidenettleyrmsiennseidtibvye atinadn scpoencciefnitcrtaotiaolnlsowanddetmearyminwaetlilocnonosfitshteodfifsfoemreentcosmpbeciineastiaotnthoeftpesHt esloleuc-thriogdhes,prUeVs-svuirseiblleiqusipdectcrhorpohmoattomoegtrrayp,hyc,ondeuxcttriavcittiyo,n gaasndchrfoomramtaotgiroanphyo,f
derivative(s), and determination bya suitable analytical method.
(4) Test conditions--(i) Temperature. For extrapolation purposes,
it isimportanttomaintainthetemperatureofthedeterminationstoatleast
20.1
If the
C. An appropriate
hydrolytic behavior
constan
of the
t temperature
substance u
bath shoul
nknown, a
d be employ
preliminary
ed.
test
paetr5a0tureCsiinstrheequriarendg.eF0o-r40testCsabreeysoonudghtthi.sTphreeylimmainyarbyeosbttagaeindeadtba yfomretaesm--
urement at two temperatures in this range or by extrapolation from three
higher temperatures. In any event, the determinations should be done at
temperatures differing from each other by at least 10 C.
(ii) Light and oxygen. All of the hydrolysis reactions should be carried out using any suitable method to avoid photolytic effects. All suitable
omreaasrugroens tshhroouulgdh tbhee tsaoklevnenttofoerxc$lumdienuotxeysgbeenfo(ree.gp.rbepyarbautbibolnionfg tnhietrsoogfeun-
tion).
(5) Performance of the test--() Preliminary test. A preliminary
test should be performed on the substance at 50+0.1 C at each of pH
4.0, 7.0, and 9.0. If less than 10 percent of the reaction is observed after
5 days (tiz > 1 year), the chemical is considered hydrolytically stable
and
ble
anto eandvdiirtoionnmaelnttaelsltiyngreislerveaqnutirtede.mpIefratthuerseusb,sttahneceprieslkimnionwanrytotebset
unsta-
is not
required. The analytical method must be sufficiently precise and sensitive
to detect a reduction of 10 percent in the initial concentration.
as
de(fiii)neHdydbryoltyhesipsreolfimuinnsatrayblteests, utbhsetatnecstesp.roIcfetdhueresuibssttoanbcee
is
as
unstable
follows:
The buffered test solutions of the substance should be thermostattedat
the selected temperatures. To test for first-order behavior each reaction
un
000056
|
solution should be of six spaced data
analyzed in time points, normally
intervals between
2w0hipcehrcpernotviadned
a minimum 70 percent
of hydrolysis of that test chemical. The reaction should be examined at
three (4, 7, 9) pH's at each of the selected temperatures with replication
at one of them (the middle temperature in the case of elevated temperature
determinations).
:
pbhlyesico(oilimoi)pgioHcuyandlrdloylssyhisoginuislfdiactaalnpstoHteb1me.p2ec.raTrarthiueerdeabo(ou3tv7eatCt)ep.stHfo1r.2a, heymdprolloyytiincgallay suinnsgtlae,-
tion
() of
Data first
aonrdderrepkionrettiicnsg.--(T1h)eTrdeataat'moebnttaionfedresshuolutlsd--(b)e
Confirmaplotted at
lsioognoanCalyvseirssuosr ftraonmdtthheeslroepaec:tion rate constant koss calculated by regres-
:
kos = 2.303 x slope.
line,t(hiei)reIanctteiropnriestantoitonfirosftorredseurl,tsa.ndIfthtehedadtaatmaudsot-nboetanfaalllyzoend abysmteratihgh-t `ods beyond the scopeofthis test principle.
(2) Test report. (i) The test report should include information on:
(A) Sample purity.
7'
stance(sB.) Any results appropriate to the procedure employing reference sub-
for
(C) each
Detailed test procedure set of experiments.
including
the
temperature,
pH
and,
buffer
ing de(tDa)ilDeedtmaieltehdodaonafleyxtitcraalctmieotnhaonddurseecdovfeorrytdhaetatiefstaend seuxbtsrtaacntcieo,n mientclhuodd-
is used to separate the chemical from the aqueous phase.
serve(dE)to Aolrligcionnacteenatrnaotniloinn-etairmelogdactoancpeonitnrtastifoorn-rteiamcetiploonts. which were ob(F) Possibilityofacid or base catalysis.
(il) plicated,
A is
suggested presented:
format
for
sample
reporting
form,
which
can
be
du-
12
000057
|
DATA SHEET FOR HYDROLYSIS STUDIES
Laboratory:
Date:
TestSubstamce:
Formula:
Name (IUPAC):
Test protocol
A. Preliminary test
:
YO ee.
: no_____
buffer systems used: _
pH4O___
TO
pHOO
.
-
-
7
Approximate ot saturation concentration
CI TT PH
Fe --
p--
B
000048
B. Determination
Separate runs at pH 4.0, 7.0, and 9.0 at the chosen temperature(s)
with replication at one of these (the middle temperature in the case of
determination
foreach pH.
at
elevated
temperature).
The
same
format
whould
be
used
Buffer solutionused______
Temperance,
Approximate saturation concentration,
tt
10
Hydrolysis at pH 1-2
Buffer solutionused_______ ~~
PH
000
`Temperature,
SE t--
Approximate saturation concentration,
tr
10
Final data
PH
|
EEE |=
heres! Co
stant, Kon
= | - ofcorrela-
14 000059
'
C. Report on test method
Provide detailed description of the experimental conditions, .g. for main-
tthaeintiensgt sstoelruitliitoyn;, teotc.av(oPildeapsheotuosleytsiecpaerfafteectssh;eettooefxcplaupedre.)oxygen; to prepare
Analytical combinations used
h
h
PH GIBCHOUES cer| rss
Uv-visible
`
High pressure liquid
Extraction and forma-
7
Details of the analytical performance: `Type of apparatus
Test conditions
`Was the accuracy of this result determined in any additional way ?
Particular incidents:
Comments:
15
000080
(f) References. The following references should be consulted for additional background material on this test guideline.
(1) Kolthoff, LM. and Laitinen, H.A. pH and Electro-Titrations, 20d
Ed., Wiley, pp 34-36 (1941).
Comp(o2u)nMdasbeiyn,WWat.earnUdnMdiellr, ET.n,viCrriotnimceanltRaelvCioenwdiotfioHnysd.roJloyusrinsaolfoOfrgPahnyisc. ical Chemistry Reference Data 7:383-415 (1978). Revie(w3)s G29o:m1a7a1,(H19M69.).et al. Kinetics of Hydrolysis of Diazoxon. Residue
(4) OECD Document A80.30, Suminary of OECD-EEC Laboratory MInatyer1c9o8m0p.erison Testing Programme, Part 2, Umweltbundesamt, Berlin,
16
000061
SMEmbormerts Laboratory Report, W1868
A"BbtormdiinxaBt:io3nMoEfntvhierSotnambeilnittayol fLaWbooFoSEdMientAhqoudeEoTuSs-8B-u9f0f.e0rs Using Gas Chromatography with Atomic Emission Detection"
A0tMoet DCisnclotse r ProductPriaged
000062 ooNotCopy
3MENVIRONMENTALLABORATORY
MerHoD DETERMINATION OF THE STABILITY OF MEFOSEA IN AQUEOUS BUFFERS
USING GAS CHROMATOGRAPHY WITH ATOMIC EMISSION DETECTION
Method Number: ETS-8-90.0
Adoption date: 64 Jo | aq
Revision Date: NA
Author: Thomas Hatfield, Ph.D./Cleston Lange, Ph.D./Gregory MaisclJeanctte Wink
Approved by: 1
Laboratory Manager
</7/5 Date
Group Leader Sos I Technical Ristewer
a 6355 Date
l0ScoreavpApuicamin
1.1 This procedure defines the steps for preparation and analysisof2-(Vmhyedtrhoyllypseirsfibuyorgoaosctcahnrcosmualtfoognraamipdhoy)-wcitthhyaltoamcriyclaetmeis(sMieoFnOdSetEeAct)iofnr(oGmCa/qAuEeDo)u.s
1.2 Acceptable Matrices: Aqueous solutions at various buffered pHs.
Word 6.035
SabMoeftihMoedFlOESTySE.A8b5y00GC/AED
Page of13
GU053
1
2S 0 ummaRvoFTHEMETHOR 2.1 One milliliterofbuffered aqueous sample from the hydrolysis of MeFOSEA is
quenched with 0.5 mL isopropyl alcohol (IPA) and extracted with 10mLhexane. A portion (1-2 mL)ofthe separated hexane phase is dried through an anhydrous sodium sulfate column and then analyzed on a gas chromatograph with an atomic emission detector.
0Depwmons
00
3.1 Duplicate analyses. Analyses or measurementsofthe analyteofinterest performed identically on the same sample. The results from duplicate analysesareused to evaluate analytical or measurement precision but not precisionofsampling, preservation or storage intemal to the laboratory.
3.2 Sample duplicates. Two samples taken from and representativeofthe same sample. sourceandcarried through all stepsofthesamplingand analytical procedures in an iindecnltuidcianlgmsaanmnpelri.ngDuapnldicaanatleyssiasm.ples are used to assess varianceofthe total method,
3.3 Matrix spike. Prepared by adding a known mass oftarget analyte to specified amountof a sample matrix for which an independent estimateoftarget analyte concentration is available. Matrix spikes areusedto determine the effectofthe matrix on the methods recovery efficiency.
3.4 Solvent blank. A sampleofanalyte-free mediumtowhich all reagents are added in the same volumes or proportions as used in sample processing but is not carried through the complete sample preparation and analytical procedure.
35 Continuing Calibration Verification (CCV). A standard analyzed periodically during an analytical run to verify the continued accuracyofthe calibration curve. `This solution may be prepared from a different sourceoflot number than the calibration curve standards.
3.6 Limit of Quantitation (LOQ). The lowest concentration that can be reliably achieved within specified limitsof precision and accuracy during routine laboratory operating conditions. It may be nominally chosen within these guidelines to simplify Tdaotwaesrtepnoortni-nzge.roFsotranmdaanrdyiannatlhyetecsa,litbhreatLioOnQcuarnvael.ytSeacmopnlceenLtrOaQtisonariessheilgehcltyedmaatsrithxe. dependent.
SubiltyMoefMtheoFdEOTSSE-A8.b9y00GU/AED
Page20013
000054
4W 0 amNNgsanpCa00v0m 000o00n 000s0 41 Health and Safety Warnings:
4.11
Wearthe al times.
proper lab
attire
for al
partsofthese procedures.
Wear gloves
at
412 Handle all solvent in a hood for all partsofthe described sample preparation procedure.
413 Fshoeretpso,tepnatcikalinhg maateroziaflesaaacnhrdch3edMmiEcsnavliruosnemde,nrtefaelrLtaobomraatteorriya'lssCafheetmyidcaatla Hazard Review.
41.4 Uusletrcavairoleewthleignhwtoarrekiprnegsewnitt.h GCAEDbecausehightemperaturesand
42 Cautions:
42.1 pRoisnssiebiwliittyhosfolCvoennttasmianlatgiloans.sware usedtopreparestandards to reduce the
S0 0 Iveme0 gmeNces000000 5.1 Caonnatlaysmiisnhaanrtdswianrseolmvaenytcsa,ruesaegeinnttesr,fgerleanscsews.arReo,uatnidnoetlhyearnsaalmyzpelelparboorcaetsosriynsgoolrvent
blanks to demonstrate that no interferences are present during the analysis.
60 Eovemenr
0000
6.1 Balance, capableofmeasuring to 0.1 mg.
62 Shaker, incubating, capableofholding at 50C + 3C.
63 pcoHmbmienteart,ioCnorelneicntgroMdoed(eplHl3r0e8feprHe/ncTee/mtpeemrpaetrautruereM)etoerreqwuiitvhal3e-nitn.-1 gel filled
6.4 (GAasEDC)hroormeaqtuoigvralaepnht,. HP 5890 Series I, with HP 592A1 Atomic Emission Detector
65
Column, J equivalent
&
W
Scientific
Incorporated,
DB-SMS,
30
m
x
.25
mm
x
.25
pm
or
SubiltyMoefthMoedFEOTSSE-A8.b9y0G0C/AED.
Page30r13
000055
!
6.6 Data Recording System, HP ChemStation Rev. A.05.04 with Windows NT software.
6.7 Autosampler, HP 7673 or equivalent. 68 Clock.
2s0 ureuesasoMavem 00w 00s 7.1 Autoviels, crimp top, 1.5 mL. 7.2 Vials, glass screw top, 40 mL, 1-CHEMorequivalent. 7.3 Labels, Avery 5160 or equivalent. 74 Graduatedpipettes, glass, disposable, various sizes. 7.5 Pasteur pipettes, glass, disposable.
7.6 Volumetric flasks, various sizes.
7.7 Beakers, glass, various sizes.
8R0 EAGENISANDSTANDARD 0 S 81 Buffer solutions
Prepare the buffer solutions in 1000 mL quantities. Adjust pH with NaOH or HCL UmesaesaurpeormteanbtlseopfHbumfefteersr.toSctaolriebrtahteebaulflfbeurfsfoelrustoilountsioinns.scaRleecdo1r0d0f0inmalLpfHlasks. Prepare buffers a follows:
8.11 pH1503 #) 250mLof0.1 MHC, b) 125 mLof02 MKC, Bring toa final volume of1L with ASTM Type I H,0.
`SubilityMoeftMhocdFEOTSSE.A8b9y00GUAED.
Page dof13
000066
|
8.1.2 pHS.003
a) Dissolve 3.57 g ammonium acetate in 200 mL ASTM Type I H,0. b) Add 230 mLof0.052 M acetic acid (3 mL glacial aceic acid into 1 L
ASTM Type 1H,0) Bring toa final volume of1L with ASTM Type IH,0.
813pH7.0+03
a) Dissolve 7.9 gTrizma-HCiln 200 mL ASTM Type I HO. b) Adjust pH to 7.0 with O.IN NaOH. Bring oafinalvoluomfe1 LwithASTypTeIHMO.
814 pH9.003
a) 46mLof0.1 NHCL b) 125 mL of0.1M borax (sodium borate, 10 hydrate). AdjustpH109.. d) Bring to.afinalvoluomfe1 Lwith ASTypTe IHMO.
215pH 11.003 a) 250mLof0.1 NNaOH. b) 2m5Lof00.1Mborax. AdjustpH1o 110. d) Bring to.afinalvoluomfe1 Lwith ASTypTe IHMO.
82 Acetone, spectroscopy grade or equivalent.
83 IPA, spectroscopy grade or equivalent.
84 Hinejxeactnieo,n 8so5l%vennt-Hweasxhaens, fsopretchteroGsCc/oApyEDgr.adPeroerpaerqeuiavaolneentL. hUesxeanheexsaonluetiinonpost-
containing blanks
10
mLof
IPA
(hexane-1%
IPA)
to
use
for
extraction
and
for
solvent
SubiltMyeotfMhEoFdOESTSE-A8b9y00GU/AED
000057
Pagesort3
8:5 MEFOSEA, prepared in acetone, approximately 10,000 ppm. Weigh 0.1 g of MeFOSEA and dissolve in 10 mL acetone. Use this solution for calibration standards, test analyte samples and spikes.
8:6 Sodium sulfate, anhydrous, 60 mesh, reagent grade.
9.0 SAMPLE HANDLING 9.1 Handle all samanpdsltanedarsds in a well-ventilated arca. Wear gloves when
handling solutions. 9.2 Prepare hydrolysis sample prep worksheetsforeach sample set. (Attachment A.)
Prepare a tracking schedule for sample extraction. 9.3 Analyze all samples assoon as posasferiextbracltioen.Ifsamples cannot be
analyzed immediately, store in refrigerator at approximately 4C.
100QuauryConreor,
101 Solvent blank. Prepare solvent blanks (hexane-1% IPA). Thisservesas an instrumental checkforany analyte carryover.
102 Duplicates. Preapsamaplreaend aduplicate. Perform two injectionsofcach. 10.3 Mthaetrstiuxdys.piPkeersf.oPrrmetpawroeianjpeocstti-ohnysodrfoclaycsihs mspaitkrei.x spike for cachofthe pHs used in 104 CCV. Runa CCV every 15 or fewer injections.
11.0 CALIBRATION AND STANDARDIZATION. 11.1 Sfrtoamndaaprpdropxriempaatrealtyio1.n6.toPr3e2paprpemsairxecsaulgibgreasttieodn.standards of MeFOSEA. Standards 11.2 Calibration standards. Analyze calibration standards at the beginning ofthe run. 11.3 CoefficientofDetermination. The acceptable coefficientofdetermination (7) is
0pa.r9t9i0cuolrarglryeaftoerr.acCcuurravceysosfhoquualndtbiteaetixoanmaitntehdechliogshelaynfdorloliwneeanrdistoy fatnhdeinctuerrvcee,pt,
SuabiliMyeotfhMoedFEOTSSE-8A.b9y00GU/AED
Page6or13
000058
LoPeocgpuee
0000000
12.1 Sample preparation.
12.11 Establish time points for sample analysis. Typical time points are at days 0,1,2,7,14,21 and 28.
12.12 ForcachpH tobetested,setupthe 40mL I-Chemvialstoallowfora sample,a duplicate and a spike for the durationofthe experiment, Each time point has 3samplesperpHand five pHs faototralof15 vials per time point.
12.13 Create labels andaffixto vials. Label information should include date, a sample number; the pH; whether the vial contains sample, duplicate or spike; the time point; and the initialsofthe analyst. An example using June 15, 1999 is: 61599-MeFOSEA-002 PH1S Duplicate Day 0 ccL
12.14 Remove vial cap. With apipette, add 1mL ofbuffetro the bottomofeach vial, taking care to avoid the wallsofthe vial. Always replace cap immediately after any addition to minimize evaporation.
1215 Using a 25 uL gas-tight syringe, add 104LofMeFOSEA test analyte solution toeachvial with buffer, exceptfor those markedDay 0. Tilt the vial50thebuffer runs tooneside ofthebottomofthevial. Addthetest analyte solution on the opposite sideofthe vial, away from the buffer.
12.1.6 Prepare time zero samples when adequate time is available to immediately `wqiutehnchh tehe sxampalIePs.nAbSeeetfour-peseta1acthi%snagmpalneotihnedrivtiodgueatllay.trEuxetrtaicmteczaecrho one:
12.0.7 Fill out hydrolysis sample prep worksheets (Attachment A) for each sample set.
12.1.8 Ptilmaec,edtahtee,saamnpdlteesimpnertahteuSr0eoCniwnocrukbsahteore.ts.Set for 100rpm shaking. Note.
12.19
At the specified time point, remove samples 10 room temperature for 15 minutes
from
the
incubator.
Let
cool
12.110 Avidald5100itkmLioxfetshweiMthebFufOfSerE.A spike solutiontothe bottomofeach spike.
SabiltyMoefMtheoFdOESTSE-A8.b9y0G0U/AED.
Page of 13
000059
12.1.11 Add 0.5 mLof IPA to all vials. Swirlto mix.
12.1.12 Add 10 mLofthe hexane-1% IPAto vials. Recap vials and shake
vigorously for 10-15 seconds. Let settle for | minute. The water phase is on the bottom;the hexane phase is on the top.
121.13 With a pipette, pull ofaf portion (1-2 mL)of the top phase. Dispense the
NheexianSeOonitnosaPacsotleuurmnpicpoetntsei,stiAnlgloofwaptporohxeixmaanteeelxyt1racitncioh hleoiwghrt oofugh the
column intoa prelabeled autovial. Use two autovials per sample. Cap the `vials. Storeonesetofvialsin the freezer at approximately -20C. Place the other setofvials in the autosampler for analysis. Ifsamples cannot be immediately analyzed, store in refrigerator at approximately 4C.
122 Solvent blanks.
122.1 To 40mL I-Chem vials, add 10 mLofhexane-IP1A%. Analyze in the
`same manner as the samples.
12.3 Sample analysis.
12.3.1 Install the analytical column and establish instrument conditions. Allow
the system to equilibrate for 30 minutes before starting the analysis.
TABLE 1. SUGGESTED GC CONDITIONSFORSAMPLE ANALYSES
[ PAmamETeR
TT SUGGESTEDVALUE |
I I ---- Te -- [OP I ven ro --gr LC-- a ----m]|
I I -- -- ET --
I -- LL ----
SubMoefdaePaEOTSSEn89oy0S0 AD
resorts
000070
12.3.2 Set head pressure for a linear velocity through column between 28-32 cm/sec.
TABLE 2. SUGGESTED AED CONDITIONS FOR SAMPLE ANALYSIS
[__ Pamamemer
[Coie
TTTSaTuocCGGESTEDVALUE|
EETE -- -- LL --
I I -- --
[OFt [3sommm im e--
spoons
JsCwarebon 193, Sulfur 181, Nitrogen 174
12:33 TOARBSLEASI.LSEUGAGRESATTEDEAUTOSAMPLERConorTIONs
[P uato e ecm on eSm om] a]
E [SampT lewashes: -- 1----
[iI njectionvolume: -- TEoTp ----
EI T CS --
PPoosstt Iinnjjeeccttiioonn SSoolv AB wwaasshheess:: [[( 44(hexr ane) ear)71]]
VPiisncgoenrtsydpeelady:
faose
|
12.3.4 Enter the standard and sample information into the sequence table.
Analyze calibration standards first, then a sample set of 15or fewer
er he highest clbation sandud and afteor15 1 four injections, followed by either the continuing calibration verification
standard or by the full setofcalibration standards. Run a solvent blank
injections to check for any analyte carryover.
Sub[oroMrAOSEA oy GOAED
Peoria
000071
12.35 Placethe standards, samples and QC (duplicates, matrix spikes, and blanks) into the autosampler tray according to the order they are listed in the sequence tableofthe HP ChemStation.
12.3.6 Start the sequence.
BoDamaAvays 00s 0 13.1 Matrix spike recoveries. Calculate spike recoveries using the formula below:
recovery = e (spiked sample rese ul--tsamplereal) 100 actaspiked amount
13.2 MEFOSEA concentrations. Calculate the concentrationofMeFOSEA in the hexaneextractby extemal method using the calibration curve.
13.3 Data plot. Obtain a plot ofMeFOSEA concentration in the hexane extract as a functionoftime for each pH. Use these data for degradation rate determinations.
1M 40ETHODPERFORMANCE 14.1 Solvent blanks. The measured value for the solvent blank should be less than half
the LOQofthe method. 14.2 Sample duplicates. The warming limits are the average * twice the relative percent
difference. The control limits are the average three times the relative percent difference. Ifthe lower valueofthe waning or control limit calculates to be less: than zero, usezeroasthelow limit. 14.3 Mthaetsrtiaxndsapridkedse.viTahteiorne.coTvheeryrewcaomviernygcloinmtirtoslalriemitthseaarveetrhaegeavsepriakgeerespciokveerryecovtewriyce+ threetimes the standard deviation 144 CCV. Analyze a mid-range calibration standard and a solvent blank after 15 or afmewoeurntsaomfpmleeaisnujreectdioannsalayntde aetxtcheeedesnd+o2ft5h%eofrtunh. e Itftrhuevpaleurec,enrteldaitfifveerteonctehefoirnitthiael sactcaenpdtaarbdlceucravlei,brsattoiponthcehreucnk. sUtasnedaorndl.y tRheoasneaslyazmeptlheseraenmaaliynzeidngbesfaomrpeltehsewliatsth a new calibration curve.
SabilyMoeftMhoedFEOTSSE.Ab3y00GUAED
000072
Page 100f13
14.5 Coeflicient of Determination. The coefficientof determination () should be
0.990 or greater. The curves should be examined closely for linearity and intercept, particularly for accuracyof quantitation at the low and high endsof the curve.
14.6 LOQ. The LOQ is equal to the lowest standard in the calibration curve.
1W 5.0PA OLLUS TIONPT REVEE NTIOM NANDANAGEMENT 15.1 Disposeofsample waste according to acceptable laboratory practice. Refer to the
3M Waste Stream procedure for further information.
l0 6ORecoros 0000 16.1 Print out hard copies ofall graphics and data analysis summaries for archiving. 16.2Signanddateallgraphiacnsdlabelwith instrumeInDt.
16.3 RWoerckosrhdesetasmp(lAettwaecihgmhetnstaAn)d.extraction information on the hydrolysis sample prep
16.4 Print out the sample sequence table, reduce the size with photocopying and tape the `phiontottheoincstroumepntly og.Keepalltheoriginal copiesintherawdatafiles package.
16.5 Print chromatogramsandintemal standard reports for all analyses. 16.6 Print calibration tables and curve information and storein raw data file.
16.7 Store hydrolysis sample prep worksheets in the raw data file.
16.8 Enter all standard preparation information in the standards preparation logbook. 16.9 Backup all electronic data to appropriate media.
17.0 TABLES, DIAGRAMS,FLOWCHARTS,AND VAUIDATIONDATA
17.1 Method validation has not been performed for this method.
SabilyMoefdMeaFEOTSSEA89by00GCIAED.
Page tharts 000073
I0 sORe0 remen0 ces 0000000000 18.1 FPaetset,icTirdaenssapnodrtTaonxdicTrSuabnsstfaonrcmeast.io(nOTPeTsSt)G.ui8d3e5l.i2ne1s1,0.OfHfyidcreoolfysPirsevaesnatiFounn,ction of
pHand Temperature. EPA. 712-C-98-057. January 1998.
18.2 PFaetset,icTirdaenssapnodrtTaonxidcTrSaunbsstfaonrcmeast.io(nOPTPesTtS)Gu.i8d3el5i.n2e1s3,0.OfHfyidcreoolfyPsriesvaesntaiFounn,ction of `pH and Temperature. EPA. 712-C-96-09. April 1996.
18.3
HandbookofChemical through 7-48.
Property
Estimation
Methods.
RateofHydrolysis.
pp.
7-1
184
COpReCratHiaonndabloDoefkionfitCihoenmsiosftprHy.a"ndRPohbyesritcsC,.
15 Student Edition. Weast, Ph.D. 1988,
"Buffer Solutions p. D-87.
1A 90 precreoDocume0s00t 00s 0 19.1 None
20.0 Revisions
Rev number Revision reason
Revdate
SubiliMyeotfhMoEdFEOTSSE-8A.b9y00GU/AED
Page 120613 000074
Fluorochemical Degradation (Hydrolysis) Analysis
ours
tees
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Tm-- = EE BREETSay O urrAimeD
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