Document 70oRODQwko6OabdbZbXOOb0ne
AR2260365
OTHER AVAILABLE STUDY SUMMARIES FOR N-EtFOSE ALCOHOL TEST SUBSTANCE
Identity: N-ethylperfluorooctane sulfonamidoethanol; may also be referred to as
N1,-1E,t2,F2O,S3,E3,A4l.c4o,h5o,l5,o6r,6F,M7-.374,82,28.,8-(h1e-pOtcatdaenceafsluulofroon-aNm-i(d2-eh,ydNr-oextyheytlh-yl)-, CAS # 1691-99-2) Remarks: Material is an off-white, waxy solid of uncharacterized purity. The attached are overviews created from 1983 and before. Robust summaries are being submitted for many of the individual studies covered in these reviews. Others have not been summarized due to the fact new studies exist that supercede these, the original study cannot be found, or they are being repeated. OTHER Submitter: 3M Company, Environmental Laboratory, P.O. Box 33331, St. Paul, Minnesota, 55133 Last changed: 5/18/00
06470
Bo cree
TECHNICAL REPORT SUMMARY
Hp TECIGAL CORNICATINS ENTER - 0120 (Important 1 apo printed on both sidesofpage, end to copies 10 TCE)
(AL
Environmental Laboratory (EE PC Fate of Fluorochemicsls
0222 5970612643
Analytical Methodology
b. L. Bacon
A. vondel
on FM 3422
p SevEansll= ComRENT GRRCTIVE
LT
SSnen
FFElusrPoCc-hDeinvi.cal
Progress Report
Analytical
3.
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oR RSTRACT. FEo RoOhoeTo BmamaSars Seedy CoSo
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006471
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Vy InreowwTION hBTteifsvoarpseoraqtnuiaaolnnytsieotsaftetcdhoeublydrebpgeoarstcocwnhadrsuocmtcaeotdno,cgerrahnpoehwdyevew(riG,tCh) mautnsheyingavnaarelilyaetbciltcerasolnhacasadppettcuotrsebeodforteeFscMotliv3o4en2d.2. baenldowsomaendexdpeetraiimleendtailn otbheserevxapteiroinmsentnaeledesdectciloanr.ification. These are discussed DISCUSSION AND RESULTS TSghieennceesroallrveectnoetnettohfleirct.heoriaTcthueereforrestceuoxdviteerrsaychtoaifovneFMoifn34d2Fi2Mcab3t4ye2d2eesttfheryrolmewxaatctreeatracttewiaosntowebtaehsylsquupaaecnerttiiaottraet,iivne SFfoMrlou3nt4wi2oa2ntsecranoafbnedFMqfur3a4o2nm2twiatstabetorevdetoutphwihstiocchoatncsaellnettarsat(tsia1ol2n5t-op(upetm.g.t(,ercehg2ni5io0qnupepo)mf),wlaisngeaaavredidteryde;sproesnsespeeescFtiigvuerley.1). bwohowiyecorhndrietnhperceosniecnntetensgtrraa0tt.oi2ro5'nsngcarnaanbgbseeo.ludtieTl.hueteNdlaitmouirrtacloolfnyc,deentsteorclatutiteoidnonrwseassopfefcotFuiMnvde3l4y2t2o fhboeirg0ha.en0ra5loysrpipsm in the range of linearity. TFhiegugraes2.chrWohmialteogrtahpehiCc paattrer2nb0MfoocrolwFuMma3u42s2xedwasinextahimsinesdtubdryicrfelsyolvaensd itsheshporwonducitn iFMnto34t22hreientpoeatkhsr,eeotchoemrponceonltusms(1()s.g., 0V101, SES2, W982) may not all resolve
% TdheesisgonleudbialpiptayratoufsAMfor342c2ontiinnuwaotuesrlywassatudertaetrinnignewdatetor wbieth0.0h5ydrpoppmhoubsiicngoragarneiccently chemicals (2). CCiosonnccbeeennettnrrtaattiiooornnstohfactanFwMabet3e4r2c2onhdafsurcobmteeewdnatseurrcecmeo(svrseofdtuarplyrleyveivfoarupoosmrlayotrobgrya)nifcgoarvsmeoilnvgleownatnsreapczroevooetvrriiodepesed..watTehris . Sine observation was noted independently for another fluorine-containingcompound(3). * hIotlwdasFMal3s4o22neccoenstsaairnyintgosdameptleersinwehicthhewokuilndd obfe cgoenntearianteerds itnhastoilcoualndd baequautseidc ttoesting wshtiudliecsg.lassPlwaassticssatissucfhactasorypolaytetthhyele0n.e05 anpdpmpocloynccaernbtornaattieonweorfe FuMns3a4t2i2sfianctwoartye,r. These results are shown in Table IV. Shatyfadtbreiorlxiittdwyeenotafty-F5fN0o3u,r42ht2ohuirrtsot,yalpokenarllycienetwiagshotfaltpsheoercsFetMnutd3i4Fe2Md2.3h4y22dIrnorl2ey0m%zaeidnaeldcaofht(oeslreiecsTepaveobntlaehsoVs)ui.rusm aTnLdC nd IR studies of these products showed that FM 3422 was converted to FC-95 as expected. `1it1nedf3ao42br2iltiboitoyFdCeoogf1r2a8sdl(euNsd-,gpeetrh(febloaurcoetrteoirocicaat)lalnyts,osubilitofdomenigygrlha-tdNe-deetgFhMryald3ge4l2y2tcowianpseerfaollrsuooaroisoanclvtteasntteihgesaruteelodff.)o.namLifIdte
J waansalnyesciesssoafryFfto342s2h.ow Tthhiast wnaesiththeer ocfaset.hese materials interfered with the CC
006472
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3 \daidieoasctidveescrFiibe3d422els(elwahbeerleed inin.thtihse rRepogrrto.up) PwraeslimailnsaoryusTeLdCin(tbhiiond-elgaryaedration
hA"arcdcosonorurdtpiotniggorlnayp,thhyri)tonawanatsdogprsuaurpbihsfycqiuetedontbgyivaeuatocProMamdb3ii4on2ga2rt-ai1pg'hnCywohfroespvereeaplaaeurdtaottrihavedeisoaTgmLrCpalmeansdhtoowcebodeluoimnmepure. Spot only. Ditnhieca-catdahiyyflfesrtaeucndetiteastsectcoteixpotonraascoutfsrethfitrshoemrbetiphooerdstee.grdaideIan-taiwtoahnyi,s stisueflcaitneiyso,nweoorffe FthMreou34tr2ie2pnoeraltry,e edhxoiawsmecivunesersd,ed bC(yoppryTeLpCa(,r4a)wthiivacenhdTLGsChC)owseatdfudfiaoerssd.eecdoneIdnRousigpnhodtiocfianttehadidsdaitsfielocunoonrdtoocaceroxbmpopenocntesenpdteciFfeMosr3c4I2Ro2,m.pmlaesSxsecdaslppeeopcstsriobsl-y waimtmhoniaaniantdrogGeCn-rceovnetaaliendinognlycomFpMou3n4d2.2. MSThisshosweecdonFdM 3c4o2m2popnleunst wcaasrbnoontdifouxritdheerand characterized.
Awnaaslyhteivcoatledmettohotdrsy ttoo qduearnitviaftyizeFC-F9C5-95dirseocttlhyatartehenodterkinvoawtni.ve Scoomueldsbceoutainnalgyzteidm.e
Summarized below are methods which have failed.
Sduilsfpolnaacteemsentareofkntohwen chtolorfiodrom `tr: Fluoroncthanfeosnautle of
wciomtphletxhees swuiltfhonbaetnezyalnioins.othAicocuorredainhgyldyr,ochtlhoericdreysbtyalline the UV-absorbing benzyl isothiourea was synthesized
.
y
((4su1l4f3i3d4e9)o.dorsU)nfoarntduniattedliyd, notthislecnodmpiltesxelwfastonoatnasltyasbilsebyinHPaLqCueouussinsgolUuVtidoentection,
or by fluorescence (very weak fluorescence).
1cCo-u9l5d tchoeulpdhennoytlboestcearusbeed mtaoderebayctewsittehrif2i,c4a-tdiionnitrwoiftlhuoprhoebneonlz-ebnoeric(4a1c9i1d--2s5u)lfnuroirc fpheoisdph(o4r1u9s1-o3x3y)t.richFlCo-r9i5decouilndpynortidibneeco(n4v1e9r1t-e3d5)t.o the sulfonyl chlorid:e using
Pteherfplrueosreonoccetanoef sduilcfyocnliochexayclidcacrobuolddiinmoitdeb,e caapuosteednttowactoenrdenssceavweintgheran(i4l4i1n9e1-3i6n, 38).
LXPERIMENTAL (4)
.
:
TuhnidserwoErnkviriosnmreenctoarldedLabinornaottoerbyooRkesque4s1t4333,6454.1947, 44191, and 46269, and filed
wFiats 34o2f2f c(ollaobreleadndE7a8c8c,orCdGi7n4g5l-y2waasndsruebcleiimveedd (f6r0g/n<1D. mRnicHkge)r,toCogmimveercwihailteChseomliicdalwsh)ich
WTgaelsaagsesunstcpdlagtrienasdes,u(bE.seTqhMueierncn-ktl)awyoearrnkd cuphnlrlaoetmseastovgiirnsadupiahclyaitzewadatsiootnpheerwrfawsoirsmpeee.drfoonArLmLseidlsioaclcavceonrgtedslingucsoeatdtoewderoen
The "Hong" technique, described in notebook 4191-16, -17-20, -21, -22.
J
1Si3un1ptp3eo4pr2mt2orw(-acsporlugigannst-e0crh..r1o8maGCtxog5or.na1dp8imhtnei;donu6ssifnwogeortet:hxe 1CH/aP8rbMioondwcehalx0.S2007.41)3:cGoCliuwnmij,tehct6)itohneloMapododrietnl,g
3on380A 200C;
Getector, 300C; column isothermal, 170; argon/methane flow rate about 40 ml/min.
006473
-a-
} GAS GIROWATOGRAPHY OF FM 3422
Comparison of Nonsublimed with Sublimed FM 3422 (4194726; wmAaast1e0rgipaasplmcwshaorsloumtasithooognwrnaipnthoeldb-.eoctpauTnrhoeelr,aroefi.acF.pM,er3c4te2h2ne,tsncowrneusrdueelicamnoedmdpasrumebadltiemraeindadltrhweeasspescu9tb.il9vi4emlepydp,m, b1a70se;d ofninatlhetesmupbelriamteudrem,ate2r10igl abtei8gg/mi1n0. ppm. GC progran: initial temperature, Determination of Linear Range of Detection of FM 3422 by EC/GC At1h0e0sn-t',anidn5a0jr-e,dcte2s5do-l,uitnit2oo0n-,tohfeandG1C00100a-npdppmptmhoefsoRlEFuSMtPiO3oN4nS2s2E. w(aasFreiavd)eilwumatisecdrorletiocotregdrievdea.li2q50uT-oh,tes d1w2a5et-ra,e are given in TABLE I and illustrated in Figure 1.
TABLE 1
DETECTION LIMITS OF FM 3422
Standard Solution (ppm)
RESPONSE_(Area)
1000
y
250
125
100
0
25
20 10
. 18,534.,286 14,741,274
7,502,012 5,819,071 5,138,201 1,598,306
Area x 10
18.5
18.7
7.5
3.87
51
FE;
1.6
"Beyond signal response of integrator.
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006474
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7
N EXPLRIMENTS OV THE RECOVERY OF PM 3422
A. Recovery of FM 3422 from Ethyl Acetate: (41947-42
b2E5tyhywnleeeidgaehcdie.ntgate0A.05(50c0a0. pg.p1 mo)fstwaFanHsda3rs4dt2o2roefadndFoMdvie3l4ru22tainnhigyndreiottuhsytlosoatcdheeituammtaerskuwlaf(sa1t0ep0reaapln)dareuidsned
dD2iiplveuottltiuinsngogtriit5cmtloFlatoshfke.thmaerSkia.mbiolvaerlsyo,lutaio2n5 pipnmtosaolu1t0i0onmlwavsolpurmeeptraircedfblyask and
TVeovoalpmuoamrkeaettriisocunr,eFlat1sh0ka.tml thyl cetate and
tAohefslFtoMhwe34s225t2rpepsinms an aliquot vas
odgsrfatysannidcetathrrhryodolgmewanataoscgveratpasaipptheeuetsdtwe.eaddstnoCioontmtepovaalraopisotsr1o0abntyemloftheGC
Toosultsa with the original 25 ppa solution showed a recovery of 99.99 percent.
B. W( aRetcoevrery T of FMa 3422 fy rom Ethyl Acetate-Water and from Ethyl Acetate-Salt
beIitxotlwroaagscitciaaonlnticcoiofpmapFtoMende3n4t2ts2h,atf6r.oignm.,afquutfeuiorsueh,sexsmlpeueddrigiaem,eanntdssoiflir,novmoalmnvdeidnitgahectholeniktpea,rienfiientrgemnitgihatl
biTenoctroomtewootnheyrlceeassaoscnaesrt:yatet;ototuosienchersleapatsuerpartetevrdeanntssfoodtrihuemofpocthPelMnotr3ii4ad2le2 ef(m"rusolamsliatoq-nuoseuto"uwshitcmehechdnieiatqhuyel)
y
acetate appears to form with many biological ingredients.
AS25cocndonmirleudlmioncfghllwiyoaf,rttieydr2e,5, amvlnerdreossifpioennct2sto5ivp2ep5elmsypm.leFcMtoifE3v4se2wcl2hayt)eminrixtcenutodrhnyetlahiwenaaiscneegtssahptaeekcaetlnwiavseoifnpeitasphaystsltuetrpaeaacdtreeatdtiaontrteyo
TlFAuaByLeEr
wa(sf II.
analyizned
by
gas rchromatographya.
Tthe rresults ate shown in
;
006477
.
.
TABLE 11
3
RECOVERY OF FH 3422
Experiment Description
Vol. EtOAc Recov@e)red
INTEGoRCATOR RESPONSE AREA)
FM(pp3m4)22
1 25(ipnpEmtF0MA)3422 SStoalnudtairodn
4,337,111
25
@s wm)
2 25 ml FM 3422
23.5
4,363,283
25.15
+25 ml Water
3 25 mF 3422
2.5
4,325,514
24.93
++255mlmlSwaatt'edrNaCl
Neotthyelthaactetatthee atdodbietiosnepoafratseadltcwoamtpearredalltoowewadtearp,proi.xei.m,atetlhye 1FMsl34m22oreisof
ntoewchniinqu2e4s,)5 mtlheofFMet3h4y2l2 waacsetainte2w3h.5eremalsobfefeotrheyl (ancotetautsei.ng Tshailst-oeuxtplains
wNehvyertthheelreesssu,ltnoinleosxsperiismnenotted3 uissinsgligthhetlysallto-woeurtthtaenchntihqautei.n exApevroilmuemnet 2.
y
correction factor may be needed, however.
C. Recovery of FM 3422 from Water (41947-38, 39, 40)
bDeutrwienegnexlp-eorcitmaennotlsantod wdaetteerr,mintehetwheatedrispthraisbeutwiaosn csoeepfafgiactieedntandofqFuMant3i4t22atively *
tprreasnssufreer,red20tomam Hfgl)askt.o reImtowvaeswartoetra.ry Tehveaporreastieddue(wSa0s/twaakteenr wapspiinrataor
:
wkonrowen lvowoluimnediocfatiln-gocttahnaotlFMand342a2n waalsiqulootstwabsy gsausblcihmraotmiaotnogarnadp/hoerd.by Rsetseualmts
distillation.
AIcocaocrhdeidngiltyh, tahesmaallll agmloausnst-too-ftemfeltohnanolli.nin`gA simnaltlheporrottiaorny eovfaptohirsatolreawcahsing was gas chromatographed and the results showed the presence of FM 3422.
Feixntarlalcyt,edtwhietwhataersmcalolndeanmsoautnet, ofco1l-loeccttaendold,uriGnagsthcehrormoattaorgyraspthryippoifngt,hewas Saepppaerarastedthe1r-eocftoarneolthaetxtruancltessagaailln sthheowweadtetrheisprreesmeonvceed offroFmMFM342324,22-It wWTaihtlaeltrbsemiimxiltlouwarreisnprobFybMlea3mz4se22t.rwoeprieCconodsbiusslettraivtleildoanwtiitowhnithoortohbteyhrerafldwurooyrrikinengres-acgo(e3n)ntta,iinnridenisgcualtcteosdmpounds. Roefmosvoallvenotf,wastucehr bays aetzhcytlropaiccetadties,tilsloaltvieodn tohre bryecoevvearpyorpartoibolnemw.ith an.excess
006478
:
-9-
LCTERMINATION OF SOLUBILITY OF FM 3422 IN WATER
The Veith-Comstock technique (2) was used for this experiment.
G1l0a0ssmgbeoafdsFM(4ca2.230i0n ag,bou3tma5.00imnldioafmeatceert)onew,ereThaeddesdoltvoenta wsaoslutailolnoweodf cvaposate, thus depositing the fluorochemical on the beads, The beads
wteore
Spiatchkead 20inmtmo. alacyoelrumof(scai.lan25izmemd. gldiaas.s wxoo4l5,0 mfno.l)lowwheodsebyeand2w0asm.prelpaaycekredof sand.
Twahatettearct.hopedTobhfyetbhMaoeytontc'oo)fmygonf,tutpbhaeicnckgeodtlouwmitthhweastaop2a0ttimnalc,ehtedloabfyyeartou2fb-ilsniigtleartnhbirozoteutdglheglaafspiselrlwieodsotlwa,ilttwhiacs
pUpuipmpwpea,tr,dstoobnyethehtuhbneodptrutemodpnmoitulhtlrloieultgihtoerftshethoefcos2l-aultmiutreafrtoerdflaablsoikuq,tuidtTwhwoaeswweeawktiste.hrdrwaaBwsyn,vcoidlriuclmuuelttaertdiecdwith
oAT0nf'aea1t'lhiyoqlfuoataqcuweetaoastuesg.ass-aTcthhuerroamtcaeotdmobgsiranaletpd,heedxa.tnrdaTcehtxitsrwaascetxepddeirliu3mteetnditmetsowaws2i5tphemrlfao(rtvnooteladulmeeiotgfrhit2c1 tfmillmaessk.).
The results are reported in TABLE III.
TABLE 11 SOLUBILITY OF FM 3422 IN WATER*
Y
Experiment No.
1 2 3 4 5 6 7
8 Mean
pen FM 3422
0.050
0.045
0.061
.
v
0.042
0.040
0.062
0.050
0.048
0.04975
"Temp. = 20 Mean = 0.05
C. ppm;
Range
=
0.04-0.062
ppm;
Std.
Dev.
=
0.0084
RECOVERY STUDIES OF AQUEOUS FM 3422 SOLUTIONS IN VARIOUS CONTAINERS (44191-42)
cAtonstihdeerleodw osofluibnicloimtpyletleeverlecoofverFiMes342d2ueintowastoerrpti(o0n.05ofppFmM),34t22hebpyospsliabstiilcistyawnads/
Gr glass. Accordingly, the following study was made:
}
006479
i
-10-
Revised 12/27/77
J
one hundred milliliters on
Technique (2) as described
0.05 ppm
earlier)
wFaMs58a2d2dedin twoataenram(bbeyrthgelaVsesit-h-aCnodmsttoocak
pToolySettahndyleinneth- ecolnatbaoirnaetro,ryrefsoprecotnievewleye.k. ThTehecornetsapiencetrisvewecroentecnatpspedofantdheallowed
CCoonnttaaiinneeerrrsrwwaosarervitnrseeadnsdfweirtrheadqtwuqoeuomauinsltlisitoladititiuevmreslcyhlofotoriwadaetesreapndaorn1la9yt.ormylToofufntnheeetlh.yflunnTaehcleetawtaes.
ToShaeal coo2nf5temelntthsyvlolwueamrceeettraetixect.rafcltaTsehkde. acnodTmhbeitnheeadqoureogoraugnsaincipchaesxeetxrtarwcaatcstwraewsa-setxrdtairnlasucftteeerddrettdowiqctuheaenwtmiiattrhaktively
(ethyl acetate) and then gas chromatographed.
TTaohleiqeuarocethspoewfcastitvhgeeasncoocwnhtraoeimmnapettroygrwcaaopsnhteasdie.naleerdsE,xupsereridinmseeadnbtosvweitwwhearsethipasdedref1domrlm(epdoipfeitmn)etdhu1apnmlolilc,aotfeamnedatnhdaannol.
the results are indicated in TABLE IV.
TABLE IV
CONTAINER STUDIES WITH FM 3422
1F00M m3l422watienr TCootnatlainFeMr:342M2ethi-n TotRaeclovFeMre3d422
Experiment No. Container
[ors]
anol Rinse (ug) )
) : Grass oss
0.08
ss
2
Glass
a6
0.19
a8
3
Polyethylene
<3
1.88
<a.9
4
Polyethylene
<3
118
"2
Solubility of FM 3422 in water detemined as 0.05 ppm or ug/100 ml.
;
nIott apbepeaurssedthteoresftoorree tshoaltutigolnasssatcontthaeisenercsoncmaeyntrbaetiuosnesd;buottheprowliyseet,hylseenveermeust
losses of material are possible.
RN
006480
tie
Revised 12/27/77
3 ALKALINE HYDROLYSLS OF FM 3422 sTeeversatlabyielairtsy oargoiunnsdtearbilaiqtuyeouosf cFMond3i4t2i2ontso.wardBebcaasuesewatshisappmaarteenrtilayl ssttuedaimed "dtioswtairldlsbasaendibnecaalucsoeholofwaistsstluacdkiedofiwnatteher psroelsuebniltitwyo,rkthaes sftoallboiwlsi:ty of FM 3422 pSioxtasssaimpulmeshydcraocxhidoef awas25kemlptsionlaut50i ofnoil36b2atphpmfoofr FvMary3i42n2g ilnen2g0t%hsalocfohtoimlei.c cAonscaennplteratwaesd ntaikternicafatciedr t0o.5-t,he1p-,hen7-olpahndtha24l-einhrsi.n,diacnadtonreuetnrdalpioiznetd;witthhis ailnltoewrsfeprreecwiiptihtatthieonECo/fGCpoatnaaslsysieusm.nitGrCataenaalnydsimsinoifmitzhees awlactoehrolwhsioclhuttieonndsgatvoe the results in TABLE V.
TABLE V
HYDROLYSIS STUDIESOFFM 3422
Time (in hrs.)
0
0.5
1
7
2
3422 (in ppm)
62 380 362 256
28
nAeustirxatlhizseadmplaes waabsoveallanodwedfitloterreemdaitno rinemotvhee osiollidbsa.th Tfhoer 5f0ilhtrrsa/tSe0wasC. conIctenw-as } 4t6ra7t4e9d).to Adrycnoemspsariasnodnthoef trheesidRueevawalsueaOnfalytzheedrbeysiTdLuCe,wiatnhd tIRhatanodfMMaRuth(eRenqt.ic
wFaCs-95broskheonweddowtnheytoweFrCe-95theundseamrc.thesIeR acnodndNitMiRonsst.udies confirmed that the FM 3422
GAS_CHROMATOGRAPIY OF PERFLUOROOCTANE SULFONAMIDE AND FC-128 (41947-48)
v
`cloendirteitoennstiodnesctriimebedofeaFrMli3e4r2.2 waTso d2.e8temrimniunteewsheitshoetrhertmhaelabatove16s0ulfuosnianmgidteheand m1Cd-e128foprostehdeseastyaon miantteerrifaelrse.nceTteo sFMulf34o2n2a,middeiluctoeuldsobleuticohnrsoma(tiongrmaetphhaendoli)so-were cThhreormmaatlolgyraapthe2d00.0 T(hbeoruetfor3e.,3 mtihneuretesisrenotenitnitoenr)fewrheinlcee FpCr-o1b2l8em.could not be
TIN LAYER CHIROMATOGRAPIIY STUDIES OF FM 3422
okfadisoalmupbleelewdasFMspo34t2t2ed(o5)n waasplaetxeamwihniecdhbywasTLCthefnordepuvreiltoyp.ed Aibnouetthytlenamciectartoeg.ramsThe pIltatreevweaasleedxptohsatedthteo aFniX3-4r2a2y-,fCilmhadforthraebeoutimopnueriwteieeks,antdwothceompFoinlemntwassodfevgerleoapteedr. mRaytearnidalo,nenecaormlpyone1n.t7 gr,emwaaisnincgoluamtnthcehroormiagtiong.raphAeccdorodninsgillyi,cathgeelenbytircehlorraodfiooranctive lruadtiioognr.aphyA.boutPurfeortmyate1r5iamll wfarsactcioomnbsinewedrefocrolfluetcutreedstaunddiomso.nitoIrmepdurbeyFTMLC3-4a2u2tqyC. wis conbined and rechromatographed as above until cssentially all of the material 3 was rendered pure (6).
006481
"1 The visualization technique for nonradioactive fluorochemicals was described
TiLnCnoptlaetbeookis44s1p9r1a-y1e6d-1w7i,th 2c0h-2l2o,ropalndatiinnicTAGaci(d7).accBorrideifnlgy,totWheongdev(e8l).opedT,hedrdyry plate is then carefully sprayed with 1% aqueous starch solution until the plate
chamberfor about two minutes and examined, Fluorochemicals (and as it tums
against a dark purple background. This contrasting dark purple color will fade with time so that after about 1 hour, a faint pink-to-white spot will be noted
months and supersedes any visualization reagents to date, Between 0,1 and 1 microgram absolute of FM 3422 has been detected routinely.
106 STUDIES OF DIEU EERIE (SISTED)
Die-away studies on mixtures of FM 3422 with activated sludge-Alcanox()
eo a Sr (commercial surfactant) - YM broth-buffer-mixtures are detailed in another
report (E. A. Reiner). The final experiments were quantitatively extracted
evaluation for any materials not capable of being detected by GC (i.e., non-
volatile materials).
0, Shien, EE statics hu Shore mins Sabnioddey 6hd boSoe sete ne Ethyl acetate extracts of seven samples from die-away experiments (labeled
18AT; 3422 #2; 61AT, 3422 Day 0; G1ATC, #1; 61AT, 3422 #2; 25 SIAT, 3422 final;
} k3n4owSAnT,FM34324222 fiannadl;kno2w5nSIFACT-,95)34w2e2reDasypo0ttaendd oan roenfeerTeLnCceplcaotmep.ositIet wcaosntcaoinnfiinrgmed
by earlier GC studies that those samples labeled day 0 had sbout 500-600 ppm of
had considerably less (one-fifth or less) FM 3422 remaining. The TLC plate was
developed (ethyl acetate) and visualized in the usual manner. Extracts from
.
Se EL I a ee FM 3422, plus a new component whose Rg value (0.45) was just below that of
j
i dk A preparatively thin-layer chromatographed using five developments in chloroform
er a. Work up of the desired preparative layer by acetone extraction afforded about
5 mg of a semisolid which was found to be less readily soluble in methanol than
FM 3422. This semisolid was examined by IR (CRL Req. C47334, C47442) which
suggested a complex between FM 3422 and an unknown. Mass spectroscopy (Req. C 47585) indicated FM 3422, plus ammonia, plus carbon dioxide. GC of this complex
indicated FM 3422 only. Two nonrelated materials isolated in the course of this
preparative TLC study were glycerin and fatty acid, both of which probably arose
from biodegradation of the YM broth, an added nutrient for the sludge.
oi, and carbon dioxide. Accordingly, a mixture of urea and FM 3422 in methanol and
in acetonitrile was reflexed for several hours and examined by IR which suggested
ep ner wLeeinlbid (ard C
BEST COPY AVA0I0L6AB4L5E2
:
-13-
=
REFERENCES
(1) L. D. Winter (Comercisl Chemicals) commmication with A, Mendel. (2) G. D. Veith and V. M. Comstock, J. Fish Res. Board Can., 32, 1849 (1975). (3) C.D. Green (Commercial Chemicals) commmication with A. Mendel. (4) Uuch of the experimental work was performed by G. Vraspir and C. Schrandt. (5) Received from D, McCown (Commercial Chemicals). (6) Autoradiography and X-ray fils development was performed in the Agri-
pcehresmoincnaells iLsaboarcaktnoowrlieedsge(dC.ommercial Chemical). The help of Agrichem (7) 3 Technical Awareness Gazette (TAG), 6, No. 5, 3231 (1977). (8) F. F. Wong, J. Chromatography, 59, 448 (1971). (9) cJ.omJm.unMiccBartaidoyn w(iCtehntAr.alMeRnedseela.rch Laboratories, Molecular Spectroscopy)
)
A 006483
-- T ----rt S12 t--t--e --------------------------------------------
3m
Formarer iva
TECHNICAL REPORT SUMMARY
ow 1/17/79
TO: TECHNICAL COMMUNICATIONS CENTER -- 201-20N (important Ifrepioprirntted an both sidesofpaper, sind two copies to TCC.)
Environmental Laboratory (EE % PC)
Fate of Fluorochemicals
Analytical Methodology and Sunport
_-- D. L. Bacon ow Aerrthur Mendel
41947, 44191, 46269, 47703, 48277, 49400
secumitvh GO comamnin) (soi Runoraion)
K(eSvwaonromss.from a CURRENT OBJECTIVE:
ao
yo
Progress Report
| "here>
EFEluo&rPoCc-hDeimvi.cals
0535. 9970612643 008
rN 043939 oT T2E 2 Co Be Ee
T"ReEPSOoRaTrAsBtSaTaRAmCoT:s(2R0A0D..75}0 worCdosm)pTaineysSoorniaocetnnisasrreavteinosns ditrbuted oy he Techical Communications Cone
HinJ
006484
--2-
INTRODUCTION
Trheipsortrsepoorntbdioeasscsraiyb,esdsieu-papwoaryt,ingsoialnalaybtsiocrapltiowno-rdkesnoortptdieotna,iled in solubility, and the like on various fluorochemicals.
DISCUSSION AND RESULTS
wTahse nloostsedofpreFvMio3u4s2l2yon(1)rot, arayndeovnalpyoratteinonperocfenittsowfatFeMr3s42o2luwtaisons rInecoavneortehde;r seexepertihmeenetx,peraimweanttearlsosleucttiioonn ooff FtMhis342r2epwoarst faolrlodweetdaitlos. eofvapFoMra3t4e22,undeIrntearmebsiteinntglcyo,ndistiimoinlsarwiltohsseessseonftiPaClBl'ys cinompwlaetteer dluoess PtCoB'vsolaintiwliaztaetrioins wveerrye rsiempiolratredto(2)t.hatNootfeFMtha3t422the(asrooluunbdil1itpypmof wororkliesnsg).in Ian cotohle ecnasveiroonfmePnCtB'sa,ndvcoolvateirliinzgatsiaomnplewsaswimtihnimaizleadyerbyof hexane.
TwhheerediinstrtihbeutsioolnubicloietfyficoifenFtM f3o4r22 FMin 34w2a2terwaswasrenpootrtecdomepalretleileyr (3),
0d.e0f5inepdpm.butTbhiassedvaolnueewxapseribmaesnetdalonwowrakt,ertshooulguhttiontso bfeillteesrsedthtahnrough
vlairgihotusbeasimze(Tmyendmablrlaneesffeacntd).examIitniinsgkntohwen aqthuaetousmem[birlatnreatefiwlittehrsa
wcaotnetrainoriomtphuerriwtiixecs wchoincthamimanyatiinngterLfheerewatbyerr(e1m,o5v)i.ng Tahesubssotlruabtielitiyn
otfo
bFeM
03.40252
in water ppm, and
using the Veith technique (6) was calculated the distribution coefficient for FM 3422 is
Pth=u6s.3630x,001000.ppm
(in
n-octanol)
divided
by
0.05
ppm
(in
water) *
or
N-alkyl-substituted perfluorocctanesulfonamides have been shown ttoakeusndedragyos (a7l)k.alinAepialnodtasctiuddiyc ohnydrtohleysbiass;icheowtehvaenro,lystihse orfeaFcMtio3n422 aalnsdotchaotnfitrhemedsaltthatofthpiesrflsuuobsrtcroactteaneissulnfotonircapaicdliyd wdaesgrafdoerdmed(46(2i6n9f-r4a5r)ed aFnMd3T4L22C sutsuidniges1)0.% pAoctcaosrsdiiunmglhyy,droaxikdiedetiincasbtsuodlyutewasethcaonnodluct(etdo on eknisnuerteicscowmipltehtea sroalteuticoonn)s.tantTheKr=ea8ctxio10n7 zathre_gbeayneddafihrasltf olridfeerof seventy-seven hours.
Ifnoreatrhelieqruasnttuidtiaetsive(8)r,ecogvlearsys ocfontFaMin3e4r2s2 wferroem wshaotwenr itno btehespaatritssfacpteorry smiilmliiloanr a(qpupme)ousorsolleusstiocnosncoefntrFaCt-i9o5ncoruanlgde.be kIenpttheincpurorleynptropwyolrek,ne, bouft FnCo-t143incopuolldyetbheylkeenpet, inpolpyoclayrpbroonpaytlee,ne;orpogllaysest.hyleAnqeueoaunsd sgollaustsions wceormepoulnedsss (ssueietabelxep.erimTehnetsael)s.tudies were dome with radioactive
:
006485
.
-3-
BaansdedFC-on143s,tudwihiecshtohavdeateh,ighilty aippoenairzsabltehatgrocuopmspouanddhseresuctho gaslasFsC-95 p(lwahsitchicma(yhybderoccaornbsoinderoerdnotoniohnaivce sanurfiaocnei)c. surFfoarceq)uabnuttitamtotiveto cToenctoavienreiress. theOnn, thseuchothceormpohaunndd,s snohnopuolldarbecosmtpooruenddsi,nsupclhastaiscFM 3422, waoduhledrebe(ditshesolcvoen?t)ninteorpolfastcihcoicbeu.t noAtnottoherglarsast,ionaandlethienvollavtetserthe dciosetfrfiibcuiteinotn (ic.oee.f,licaireentv.erySalmipploepshilwihci)chwohuavled parehfiegrh dtoistardihbeurteion w(hdiilsesolsvaem?p)lestowhpilcahstihcavecomapalroewddtiostrgilbasustio(nsocoueseffigcliaessnt co(ni.tea.i,nerasr)e, pvlearystihcydr(ospohiulsiec)plawsotuilcd pcroenftearinetros)a.dhere to glass compared to
Tshueitaubslee ofconttheainperrosperfoarqusahriipapin(gglawsasteror spalmapslteisc)andandfisthhe bamcokst to tthoeBEinovniormoincsmenLtaabloraLtaobroyratpoerrysonJnoerl fbaerftohreer atnheaylysceosndwuacstedmadceriktniocwanl lliifneedstcaagpse, stuusdeidestoonseaFlC-9b5o,ttlFeCs-14c3o,ntaaindninFgM 3a4q2u2e.ousAsloulmuitniuomnsfooifltFhMat342m2i,ghtwerientaelrsfoereexwaimtihnedsubbesfeoqrueentuseGC foarnalpyossessi;blenocoinnttaemrifnearnetnsces were observed.
Saivnacileabales,imptlhee, mertahpyildenmeethbloude fporrocqeudaunrteitaftoironmetofhylFeCn-e95bliusestaicltlivenot sruabngsetanfcreosm 0(1M4BASt,o 0(.100)6) pwpamswaussednolteodquonantsietmaitleogFCp-a9p5e.r (AFilgiurneear1). Opfresceonutr,se,wilMlBASg,ivesucahpoassitliivneearintaelkryfleresnuclef.onates (detergents), if .
TlLaCbelaendd GFCC-9w5ereanadlsFoC-1p4e3r.formDeide-oanwaydies-aamwpalyesewxepreerimsepnottstewditdhirercatdliyoovnisEu.alMiezrecdkbysilaiuctaoragdeliogTrLaCphpyl.atesA wchoimcphariwseorne wtihtehn cdoenvterloolpsedshaonwded ncoontnrewolscowmeproeundmsetwheyrleatefdormaendd graesspecchtriovmealtyo.grapShamepdletso sienecluidfinagny new Cvaoslea.tilGeCmaotfertihaelssawmeprleesgpermieorratetdo bmuetthynloanteiownerealosobseirnvdeidcatinedeitthhaetr no new compounds were formed in each cuse.
Chiou and empirical
ecqou-awtoiroknersre(l9a)tipnugbleixspehreidmeanntaalrtinc-loectwahnioclh/wadteesrcridbiesdtrianbution
Tchoeeiffriccioernrteslattioona,uuwehouischsoclouvbeirlgidtimeosreofthamnanyeigohrtganoircdermsateorfiamlasg.nitude
idnisstorliubbuitliiotnyco(effrfoimci1e0nt t(ofro10m 10ppmt)o a1n0'g),sixmayordaelrlsowofanmaagsnsietsusdmeentin
ooff ldeissstritbhuantioonnecooredfefricioefntmagfnriotmudseo.lubiFluirttyherwmiotrhe,a tphreesdeictweodrkeerrsror
observed a correlation between the bioconcentration factors in
006486
2 EEN .
Figure 1. annette oF egg wit sein pie in
UH [AFTER qe
INI Doi
BT NC RE bhea
CoEii
oJnElNuHio E ihSHEPEAESE RRC L E 1
CN IN fLplah dfn
PE pi ib
ae
odao rm inn CE
P $ HE EI RERSENE ENHR RDI EE N AEE | AT Lo[Hhiall
CU Bp i e l
Cp HEE
1CR ONINGNGG N l le do
Gel]h
; Hil
iSE!O Ll
PONDFEd R Eon
a1 ll: NGL
Hh
ts h Tm i n ii LRiitEHNELE
PL Lon
| peli
LL ao il ] SjesetooPr avdeH
pl
id !
Hi
pool
oosasy |
ohn hey ar
Hl
ibe pdm Bo
1
Tod
0.2 wll rt 0.4
0.5
5 croamipnobuonwdst.routItawnads tohfe aiqnuteeroeusstsotloubaiplpilytietsheifroresmopmiericsatlableequaotrigoannsic tdoatasoloubbtialiinteyd, inbiotchoencEennvtirraotnimeonntaflactLoarb,oraatnodrydisontriFbMut3i4o2n2, cFoCe-f9f5i,cieanntd FC-143. Results are summarized in Figures 2 and 3 (11). Stooilofftehrin-alasiymeprlec,hroymetatorgerlaipabhlye,(somielthToLdC)ofofevpaelsutaitciindgesrelaaptpeiavres mbeoebnilidteysiginnatseodi.ls, Theevenadtvhaonutgahgesa uofnivseorilsalTLC"stianncdlaurdde" rsaopiildithya,s not reproducibility, and low equipment costs. IrnadithoelabcuerlreedntFMst3u4d2y2,, aFC-s9o5i,l-caonadteFdC-1T4L3C, plaantde twhaes asspcoetntdeidngwiwtahterdtheavtelnoopneed poflattehewassampvliessualaipzpeedarbytoamuitogrraadtieog(rRa,p=h0y).. SRoeislultTsLCshionw ltheeachdiensgceonfdinmgatedreivaellsopmtehnrtougmhodesowili.ll be done fo simulate the TFoM 3da4t2e2,. noItewvaisdenLcheouhgahst bteheant enoltcecdtrofcohremtihcealbioodxeidgartaidoantio(nvoolftammetry) miingdhitcatbeionsucocfestshfeule.aseIofrsod,iftfhieculptoytenotfiaolxidraetqiuoinredofwotuhlisd baelcoahnol tvooltthaemmeatlrdyehy(die.e.a,ndo/xoirdaatciido.n pFoutretnhteiramlo)rem,ighitt wbaes ahogpoeodd gtheanteral pIhnystihcisal-wcorhke,micFaMl3p42r2ediicntoarceotfontihterilbeiodweasgrandoattiooxnidoifzeda bcyandeildeactter.occhoenmdiictaiolnsp,rocne-dbuurteasnolusiwnags naotplaotxiidniuzmedeleccittrhoedre.(CRIU,ndReeqr. thBe342s4a7m)e. "Itoxiadpapteiaorns tphoattenttihails"meofthoadcaisndpirdoabteabloyrgannoitc.a good index for the
006488
Figure 2 SH Srmanie Compania
: 8 107
.
| & zas2asioe
=
x
DORs #.2.4.5.2,5"-pcB.
108)
;
~ CHoresprices
g
3
E2R
os > .
=E
"
-
3 a0}
5
"8 Methyl chioropyritos
|
~
4|
So parathion
a.
.
SN
:i10
-LaaA n NT.
7
re-95
NL
En
$ 10
.
1
Se sstteriie Acid
Benzene o
}
Prengiggerte
to $MM Phenoxyacetic AcSid oEY
822 107
10
107
1
10
10
10
10
Solubili`ty in water ( umoles/1), log scale
1077 14310]
3
Figare 3 RteolWaatitoenrshSioplubofiliBtiyocoonfceOnrtgraantiiconComFpaocutnodrs
4105
T88q
w
S10] Seexa.ch2i,o4r,o2b4en-czPeCnBe
.
&8
45810
a2
=
Biphenyl
g
Diphenyl Ether
ga t
P - DLoichlorobenz5enc
;
10
0? 107?
Loca4 2
1
10
10%
10%
10?
SOLUBILITY IN WATER uMOLES/1, log scale
006490
-8-
EXPERIMENTAL
Volatility Studies on FM 3422
A. Rotary Evaporation under Reduced Pressure (41947-38,-39,-40)
W4a2t6e6r9,-s1a7t),urawtaesduwsietdh fFoMr s3a4m2p2lecso,nduacntdeda 5inppamguarreifaere(nsceee of FiMndi3c42a2tedin thmeetwhaantoelr wtahsusaslsaoturparetpeadrehda.d aGC5 papnmalcysoenscentratVieointhoftecFhMni3q4u2e2 u(sneodtelattheart. thisThiiss hhiigghh, vbaalsueedmaoyn btehedue tloiqsuuipdsershaatduraatliaorngeaTnydn/doarllmiceeflfelcet,foramnadtitohne bseoclauutsieonsthweesere noont afirlottearreyd)e.vapAor2a5t-omrluwnadteerrwastaemrpleaspaibrovaetorwasprecsosnucreen.traTtheed Rreessuildtuse wsahsowetdaketnhatuponinlyoc0t.a5noplpmaonfd gFaMs 3c42h2romraetmoagirnaepdh.ed.A rreempaliinceadt.e eTxhpuesrimaebnotutinnidniectaytedpertcheanttoonflyth0i.s6 paplmcohoofl FwMas3422 10st due to volatilization.
B. Evaporation under Ambient Conditions (44191-43, -44; 46269-32)
AdetseartumrianteeddbyaqtuheeousVeistohluttieocnhniogfueFM (63;422seepre4p4a1r9e1d-43andand
0r.e0f5erpepnmc.es Ftohreretihne) ewvaasporsaiotwinontostuhdayv,e 1a00conmlcen(tvorla.tiopnipeotf)
ocfonttehnitsssoallultoiwoend wtaosevtarpaonrsafteerre(dca.to 1.A5bewaeekkesr).andThietsbeaker
waalsiquroitnsewdaswigtish 2chmrloma(tvoolg.rapphiepde.t) oRfesumletthsanionld,icaantdedatnhat
.
0.007 ppm of FM 3422 remained.
:
Reaction of FM 3422 with Alcoholic Potassium Hydroxide (48277-29, RS me ey eastfudiende
rAnounadl-cbohootltiocmepdotfalsusskium(choyndtraoixniidneg stowolutjiooinntsw,asonperepaared24/i4n0af5e0m0a-lmel ianngd atheteoftlhoenr-coaatcd10/m3a0gnefteimcalesgifrorreralbiaqru,otawnidthadnraawiarl-,cooalneddcocnotna-ind1e1n.6serg tofopp8e6d.2w%itphotaanssiAsucmarhiytderoxipdreote(c1t0iogn iftub1e0)0%byKOHd)issionlv20i0ngml, obfy aanbsoelxutetrenaallcoohilol.bathThifsorsotlhuetidounrawtiaosn thoefn tmheainetxpaeirniemdenatt 5(05-0453 hours).
Ovnoelummieltlriilcitpeirpetalitqhurootusghwetrhee wniotrhmdarllaywnclforosmedth$is10s/o30luteinotnrywiptorht.a Tfhliasskalcioqnutoatinwiansg qaubaounttit1a0timvleloyf atbrsaonlsufteerreadlcothoola, 2o5n-meldrvoopluomfetric pahciedn.olphTthhealpeuripnoss:oluwtasiontoansdtopthraeney dfruorptsherof rceoanctcieonntraatneddtonitnreiuctralize the base which proved to adversely affect the gas chromatographic
06491
9
tchoelummnarkusewdithsubasbesqouleunttelya.lcohTohle, voalndumeantriacliqfuloatskowfasthidsilustoeldutitoon PwaasckasrudbjeMcotdeeld 5to813gasgaschrcohmraotmoagtroagprhaipch uasnianlgysieslecontrotnhecHaeptwulreettdetection.
TFoM 3t4h2e2,aboavned ailmcmoehdoilaitcelyKOHthseorleuatfitoenr w(assoluatdidoend o4f0 mtgheofFMsu3b42l2imed
nraetqeudireads taibmoeutze1rom.inutAel)iquaot1s-lweraeliqrueomtovweadsawnidthadnraalwynzedandatdetsiimge-s
indicated in Table 1 and illustrated in reaction rate is shown by the following
kFiingeutriec4.treaAtmfeinrtst-(o12r)d:er
In(a-x) = -kt + 1n a
or
n1jg0(a-x) = 325.535053 + In1g0a
Since for any experiment, a is a constant, the above is an eIqnuyagtaiownillfyobre athsetrayigihntterlcineep.t (Wfhoeunndpltoottbieng2.2l)n(aw-ixt)h vtehersusslopt,e eqlfl to /2.303) and found to be -0.004.
Alkaline AlcToahbolleysi1s of FM 3422
t (hrs.) Cc (ppm)* In0C
01
117689
22..2225
17
176 165
2.24 2.22
.
v
a218
1135
22..0143
%
72
88
96
73
11..8964
168 216
4247..45
11.46a5
236346
207..33 01..8361
433824
0162
00..0748
501
hd
* Tdhuipslicnautmeb.er represents the average of two replicates done in ** Poor electronic integration - no results:
A plot of lnC) versus time gives a slope of -0.004;
Since kk == -22..330033 x(sl-o0p.e0)04t=hen9 x 10TMa hr half life=se t,=al. 1n 2 =- 03.:68933;=_ 77 hrs.
006492
mE em ee
|
EE
=
hei
J
S EEEREEE E E ee E S EE E fi e ee]
we
mfEetr e E ne e ee mee le e] Baa ees e omer
j= j= me & me
==
=
ee
Ee
ee
-11-
FM 3422 Sorption onto Soil (46269-50)
Saonrdpttihoen-rdeessuolrtpstiaorne sgoiivlenstiundiTeasblewer2.e conducted by S. K. Welsh,
Soil TLC (48277-30)
Vofari2o62usmtiycpreosn soifzesoiwlaswesraevedgrofuonrdTLaCndsstiuedvieeds, a(n4d266t9h-a4t2)f.ractAinon i(nstainmdyateloammi)xtuwritehof801m5l0 ogfowfat2e62r wmaiscrownellSizselurgrrieeednhoaunsdespsroielad o(ndteosig10nedx b2y0 Jc.m Wg.lasBselipsllaet,es A.usMienngdealn, ina-nhdouG.seGdutehsriigen)e.d sTphreeader tphleatebsotwteormewiatlhlowreaddiotolabaeilredd-ryF.C-95A,-pFlCa-t1e43w,asasnpd-oFtMted34222.cm Tfhreom Tshaemplpelsatewerweasthaoisre-dursieedd eaanrdlideervelfoorpewdat1e0r0 smomlufbriolmittyhesoturdiigeisn.al TsLpCotdeinvetlhoepinagscetnandkingpremvodieouwsliythewqautielribrinatead fwiilttherwaptaeprer-floirneodne day. Twhaes dtehveneloapumteonrtadiroegqruairpehdedme(a13r)l.y twToesuhlotusrsshaonwdedthethaalir-FdCr-i1e4d3 palnadte wFaMs3e42x2tredmiedlynotfailnetavefortheviosruiagiiinzat(iRdg=n0)b.ut Tahpepeasrpost,notduetotohavFeC-95, migrated either (Rg=0).
Preliminary Studies on Samples from Bionomics Labs
A. Examination of Foil-lined Caps for Interferences (46269-50)
bFootutrlefsoilc-olnitnaeidnincgapssawmhpilcehs BwieorneomsiccrseweLadbsontuosesfotuor scelaelan
wbeortetlemsechcaonnitcaailnliyngs2h5akemnl offord4eihoonuirzse,dawnadtetrh.e cTohmebinbeadttl1e0s0 ml .
owfaswactoenrcewnatsraetxetdraacntdedchwriotmhatoegtrhayplheadc.etatNeo. apTphairsentextirnatcetr-
:
wfietrhencFeM 3f4o2r2FMto 3c42o2nfwiarsm nnooteidn.terTfheirsenecxetraatctthweasrettheenntiosnpiked
time of FM 3422.
B. Examination of Standards and Controls Prepared at Bionomics Lab
PoefrsFoMnn3e4l22 frinomwaBtieorn,omitchsenLasbusbmpirtetpeadroende-sltiatnedrardsamspolleustioonfs
rtheesspeectsitvaendasradmspleanwdasconetxrtorlasctetod wuisthfoerthaynlalyasceest.ateThaend
the was
uosregdanitchenextfroarctGCwaasnalcyosnecse,ntraantdedtheto re10sulmlt.s
arAen
saluimqmuaortized
in Table 3 (Notebook 46269-50).
006494
Table 2
|
- umm om sr --- wo
1000 sme oso
asym ow oom 2mm 00
wBKA
umm 2/22/78 ow0.48; 0.51 iors 2/23/78 om0.044; om0.035 spars 2/24/78
!
g:2.32
;
Tate 3
|
Analyses for FU 3422 (in ppb) in Bionomics Samples
!
sample 10. soso
05) Theoretical Conc.
Decernized 0.8; 10.8
!| |
J
PM
10.8; 20.0
|
J
1
jo
30
102: 0.0 0; 10.1
seis wore
s s
5.3182 ssa
.
J
2s
25a
je
Cas
jo
12s
12s 1 @
s1s J
138 + onze 4
@ 01
620 saz
contre 8 sooivennt
wi wi
2g woz
sootvmente=
wi
% ase
"1s
137 1.00)
A5670
oneived
broken
in
shipment;1.(2b5)
replaces
original
sample1.s0;ASS1L.T6;(b)AS618
I-- -------------- tae
A--
C. EofxamFiCn-a1t4i3on(4o6f26W9a5t3e)r Samples for Possible Interferences AfsromdonBeionionmiPcasrtLBabsabowveer,e esexvternacstaemdplweisthofethwyaltera,cetraetcee,ived ftoolldoewteedrmibyne diifazotmheethwaanteermeatndhyltahteiovnariaonuds gacsontcahirnoemrastoghroalpdhiyng sFaCm-1p4l3e.s maAyllprseasmepnltes ianptpeerafreerdencfeosbeforfreteheofanailnytseirsfeorfences in the GC region for FC-143 analysis.
Studies on FC-95: To Determine if FC-95 is Sorbed On/In Containers (47703-20, -32, -24) TthhreeeVe0it.h20-tmelchnsiaqmupeles(4o2f6694-c30)F)C-9w5er(eaqtureoaunssfseorlruetdiotnos sscaitnutrialtlaetdiobny vgginapllsestowwehreichlab15e-lmeld AC-q1u,asoC-l2X, waasndadCd-3e.d iTneneacmhillciaslei.tersTheosfethceontrol Ti4nCg FcCo-n9t5ainseartsu:ratebdolsyoplruotpiyolnenewas(PPt)r,anpsofleyrertehdylteoneeac(hPE)o,f ptohely-followcaanrdboanlaltoewed(PCt)o, satnnddglaatssroo(Gm).temEpaecrhatucroentafionreronewasweetki,ghtaltywhciacphped tciomnetaitnheersSowleurteionrsinwseerdetwtircaensfweitrhred2-mtlo wgaltaessr jaanrds.theThreinsveasrioaudsded tfoerrtheed rtreosmpecttheivejarjari.ntoBya psicpientt,ill0a.2tiomnl ovfialt.he Tshoilsutiwoans wraespeattreadnstawdodedtimteoseatochgsecnienrtatiellatthiroene sviaamlpleasndftrhoemneaccohuntjaerd. (13A)q.uasoTlhlesewasvials waebroevelwaabselerdinPsPe-d1,4 PfPi-r2s,t eatncd. a Esaecchondofttihmee wsiatvhed4cmolntaoifnemresthafnroolm, a1n'dmleaocfh threinsreeswpeactitvreansmeftehrarneodl foriansesepaabroavtee,wascletarnansvifaelr.r'edByto piepaecth, oTfhethsraemeplessciwnetriellaltaiboenledviaulssingcotnhteainnoitnagtioAnquaasboovle, abnudtthtehne cloeutntteerd. tfioorn,fires.tg.,riPnPsFe-1andinSdicfaotresthepolsyepcroonpdylreinnesecwoanstaiandedre,d ftoirstthemedthsaingonlaSTienceosnd5tmhetehanoflirsrtinssaempolfe,twhheilseecGoSn-d3saimnpdliec.atesThea grleassusltsconatraeinseur,m mcahroiizceedfoinllToawbeldeby1: polPyoeltyhpyrloepnyel.eno was the first containor of Studies on FC-143: T4o970D0e-t5e1r)mine if 1-143 is Sorted On/In Containers (4703-30, -37; Tthhies eexxcpepetriiomnentthawtas tpheerfpoorlmyecdarbeosnsaetnetiaclolnytailnikeers twhaetre fnoort FCi-n9v5e,swtiitghated. Vsaarmipoluess Cs-o1l,venCt-s2, aatntdackC-3p,olyascarwbelolnataes (teh.eg.5,00e-tphpyml 1g4oCetFaCt-e1)4.3 sCoolnuttriooln wgelraesstr(aGn)s-fcoenrtraeidnetros.polyEparchopycloennteain(ePPr)-w,ispotliyghettlhyylecnaeppe(dPE)a-n,d aanldlowed
006497
_15-
Table 4
Sorption Studies on FC-95 (Labeled)
Part 1: Scintillation Counting on Samples
sample dpm Cone. mg/l FC-95 ug absolute Ave. ug
c-1 15,163
c-2
16,058
228626
c-3
15,735
276
22686200
2750
2760
Pp-1 11,204
PP-2
10,523
119884
PP-3
11,585
203
22578700
2730
2840
PPEE--12 1111,,820788
219087
PE-3
11,994
210
22797000
2870
2940
pC-1 11,493
PC-2
11,558
220013
PC-3 11,138
195
28284100
2790
2730
6G--21
1111,285420
210987
6-3
11,760
206
22796100
2850
2880
Part 2: Scintillation Counting on Rinses
PPPPFF--12 1156..98
00..0066
PPF-3 7.22
0.02
00..2244
.9.19
.
0.08
.
PPPPSS--12 <Ba5c.kg8r0ound
00..0020
PPS-3 <Background
0.00
00..1000
0.03,
0.00
. Avg. Total 0.27
PPEEFF--21 6500..55 PEF-3 40.5 PPEESS--21 246..616 PES-3 31.0
00..2118 0.14 0.0.0092 0:11
00..8742
0.71
0.56
00..4150
0.37
0.55
Avg. Total 1.08
006498
eHitt sre fre
ES ---------------------------------------------------------------------- _16-
Table 4 (continued)
sample PPCCFF--21 PCF-3 PPCCsS--21 PCS-3
dpm 11886259 1958 227904..30 254.0
Cone. mg/l FC-95 66..5411 6.86 01..9053 0.82
g absolute 2265..26 27.4 45..7155 4.45 Avg. Total
Avg. ug 26.4
_ 4.78 31.18
GGFF--21
114400..69
GF-3
146.1
G6s8--21
111286..68
GS-3
125.5
00..4499 0.51
0.0.4442 0.44
211...099466 1.99
22..2100
2.17
2.20
Avg. Total 4.16
|
006499
-17-
stoolusttiaonnds awt erreoomtratnesmpfeerrarteudreto fogrlasosne jwaerse.k,
at which time the The various containers
wreersepecTtiinvseedjatrw.ice Dywitphipe2t,ml 0.o2f
wmlateofr
and the
the rinses added to the solution was transferred
tfirmoensthteo gjaerneriantteo tahrseceintsaimlpllaetsionfrvoimale.achThjiars. wasAquraespoelfatewdastwoadded
ettoc.eachEacvhialofantdhethseanvedcoucnotnetda.inerTshesferovmiaalbsovewerweas lraibnesleedd PaP-f1i,rstPP-2,
atondaasespeacroantde,timcelewanithvi4a-lml(inmetthhaenocla,seanfdoreatchhe rgilnasses wcaosntatirnaenrs,fer3rmeld
GrFa-t2hercontthaanine1d'ml1
omll
omfethrainnosle
was and
used GF-3
for had
the first transfer, to be eliminated).
thus By
ptiopeeta,ch1ofmltohfreethescirnetsiplelcattiivoenmevtihaalnsolconritnasieninagbovAequawsaosl fraanndstetrhermed
ecaorulniteerd.. TThhee sraemspulletss waerreegilvaebneleidn Twaibtlheth5.e nPootlatyipornopymleenntei,onetdhe
container of choice, was used in subsequent experiments.
Solubility of FC-95 in Water (47703-15)
TchoenduVecittehd tuescihnngiqruaedi(o6l)abefloerdsaFtC-u8r5atiansgdweastcerribweidthinoNrogtaneibcosokswas 2t8he710s3a-t5uraatnodr42a6t690-.301., 2,Thr4,ee6,0.2245,-nlandsam4p8lehsourwse.re wTihethdsraamwpnlesfrwoemre palnadcecdounitnsswceinrteiltlaikteniononvitahles NtuoclwehairchChi15camglo osfciAnqtuilalsaotliRonwascouadndteedr, (Agrichem). The solubility results are tabulated below:
Hr
mg/l C-95
01
226o
.
2a
228328
246
228002
18
291
Avg. (Hrs. 4-48) = 286
Quantitation of FC-95 by the Methylene Blue Method (47703-44)
aFCc-t9i5vewassubsqtuaanncteistataesddbeytaithleedmeinthSytleannedarbdlueMetmheotdhsod fofrortmheethEyxlaeminneatbilouneosfeeWabteleorw)anwderWeastaedwdaetderto(e10a)c.h oKfnofwinvecsoenpcaernattroartyionfsunnofelsFC-f9o5ll(o1w0e0d ml, bfyun2n5elsmlweorfemsehtahkyelneneforbluoene-rheaalgfentminauntde10andml thoef ccholnotreonftosrmw.ereThaellowed wtooolsepaanrdatceo.llecTtheed.desTihreedpoerrcgeanntic trpahanssemiwsassionwitofhdrtahwen ortgharnoiugch phgalsaess w(a6s52 dnemt)erwmiitnhedcahlfotreorfotrhme. SpeThcetrocnoincce2n0traitnisotnrumveenrtsuswasper[ciernstt ctraalnisb-rated mission is shown in Table 6 and illustrated in Figure 1.
:
006500
ie
Part 1:
Sample
c-1 cc-s2
PppPil-az1
PE-1 PE-2 PE-3
6c-z1
G-3
Part 2:
PpPpFr-21
PPF-3
PPS-1 PPS-2 PPS-3
Table 5
Sorption Studies cn FC-143 (Labeled)
Scintillation Counting on Samples
dpm
34,456 3434,,550201
Conc.
mg/l
534 S53365
FC-143
Bg absolute
5340 55335600
222444,,,185926090
333788515
555323953004
23,664
367
5138
24,078 23,409
373 362
5222 5068
3254.,394626
339867
s5541148
25,002
388
5432
Scintillation Counting on Rinses
370 084 3a 293
0.91
3.6
296
0.92
3.7
21.5 20.9
25.3
0.07 0.06 0.08
0.35 0.30 0.40
Avg. Total
Avg. pg 5350
sas
5143
546s
3.6
-,0.35 * 3.95
.
> .
PEF-1
PEF-2 PEF-3
PPEESs-1
PES-3
16,936 17,268 17,430
8s4s9o
802
52.5
210
53.5
.
214
213
54.0
'
216
22.67
1133.05
13.0
2.5
12.5
Avg. Total 226
rz GF-1
Gs-1 63 GS-2
133,451340
124 112269
11340.70 0.36 00..3490
s5a6.s0 1.9 22.00 Avg. Total )
55.4
1.0
57.4 006501
-19-
Table 6 FC-95 by Methylene Blue
Concentration of FC-95 (ppm)
% Transmission
0.0
100
0.068
76
0.12
56
0.20
40
0.40
17
:
Note that FC-95 can be quantitated in this range; however, the
lasimiatnaitoinoincssuarrefactthaanttsanyormoetthheyrlenseulbflouneic-acatciivdse
substances such will present a
positive interference.
GC Calibration and Recovery Studies on FC-143 (46269-34, -54)
The purpose of this work was to FC-143 and to evaluate recovery
prepare absolute standards of from water. An internal standard
of perfluorodecanoic prepared by weighing
acid (obtained and dissolving
from 0.100
Dr. g
Jon Belisle, of this acid
CRL) into
was 100
ml
of hexane (1000 ppm). made by weighing and
A standard of dissolving 0.100
1000 g of
ppm of FC-143
FC-143 in 100
(lot ml
83) of
was
methanol. For acidification of aqueous solutions, 1 sulfonic acid (PTSA) in 100 ml of methanol (10% ppm)
g of p-toluene was prepared,
and 2-3 drops of this solutior was diazomethane methylation. Samples
added to prepared
extractants prior to for GC was as follows:
In a 20-ml vial was placed 5 ml benzene and in a second vial was
p20lacuegdof5
mtlhe
ofFC-1101%3
etahnderwiitnh
hexane. 20 ul
Each of Lhe
vial was internal
spiked with standard. Three
5 *
drops of methane.
PTSA were After 15
maidnduetdestoofeacrheacvtiialon ftoilmleo,weedxcbeyssethdeiraezaolmetdhiaanzeo-was
removed (Np purge) and the samples were diluted to 10 ml.(volumetric
Task) folfowed ether-hexane as
by GC. Results showed that benzene was a solvent (larger integrator response).
superior to Furthermore,
tdhieffeelreencttrofnromcaptthuarte torestpheonspeerftlouoFrCo-d1e4c3an(oaisc thaecimdet(haysl tehestemre)thywlas
ewsetreer)m.ade,Accfoorldlionwgeldy,by vmaeritohuyslatcioonncenatnrdatgiaosnschorfomabottohgratphheys.e
acids An
satvaenrdaagredsreosfponFsCe-11f3acwteorrewapsreptahursedobitnaiwnaetde.r.
Hen, The
0.1 and 1 ppm water sample,
con-
taining trated,
tahceidiifntieerdna(lPTSsAt)a,ndaarnddmaectihdy,lawtaesd
benzene in the
extracted, concenusual manner. GC
of the samples showed recoveries solution and 90.9% and 99.4% for
of 93% and 100.4% for the 1 ppm solution.
the
0.1
ppm
:
006502
--20-
TFLMC3O4F22Bi(o4d77e0g3r;ada6t-i1on42,S1t,u2di5e-s2o7n,R-3a5d;io3a9c-t4i3v,e 4F6C-)9~ 5, FC-1~ 43, and
Details FM 3422,
of the biodegradation studies and controls are described in
on E.
labeled FC-95, FC-143, A. Reiner's report (14).
Ianndtehtehyplresaecnettatweorke,xtrtahcetsningeetneeernatseadmpflreosm
each from sludge, water, biodegradation studies
were gel).
applied directly The plates were
to plates (20x20 cm, developed in ethyl
E. Merck GF acetate then
254 silica examined
faiurtsotradbyiogurlatprhayv.ioleTthe lpilgahttes(lwoenrge aenxdpossheodrt twoavKeoldeankgtxh-)rayandfilthmenfobry
woinethweceokn,troalndsatmheplefsilminwdaiscattehdennodesvieglnoipfeidcaanntd
examined. Comparison differences.
In a second part extract from the
of this various
experiment, samples was
a portion of the ethyl acetate methylated with diazomethane
ttohe cuonnvmeertthylaanytednonavnodlamteitlheylactomepdosneanmtpslestoweGrCe vtohleantilaenaslpyezceidesb.y
Both gas
chromatography. No differences were samples. GC conditions are detailed
noted between these and in Notebook 47703-43.
control
Determination of the Solubility of N-Methyl FOSE Alcohol FM 3925
About 20 g homogeneous
of FM 3925 sample.
Lot The
505 was cooled,
melted (steam solid material,
bath) 200
to mg,
obtain a was dis-
solved in was added
about 200 ml of to precleaned 2
reagent grade acetone, and this solution mm diameter solid glass beads contained
in a beaker. chloroform,
Beads acetone,
were precleaned successively with heptane, water, methanol, and then air dried. The
FaMnd 3s9u25ppocroatteeddbyglalsasssbeawdosolwe(rpereptlraecaetedd iwnitah gGllaassstrceoaltugTMn)..(3T5h0ex18endmm)
rubber stoppers were connected to Bev-Line pump.was used to circulate deionized water
VX tubing and & peristaltic through the column. The
weanltkir-einseetnuvpirownasmenctoanlducrtoeodm
in thg dark in a temperature-controlled (18+1). Prior to the start of this
etxhpiesriwmaetnetr, wawsatedriswcaasrdepdu.mpedThefoprur5pohsoeursof tthhriosughwasthetoserteumpo,ve anadny
impurities that FM 3925. Fresh
would water
be as soluble as, or was then placed: into
more soluble than, the system and at intervals
(see Table 3), 100 ml (volumetric the main 2-liter storage chamber.
pipet) of water was Each of the 100 ml
withdrawn from samples was
qsuaatnutriattaetdivaeqluyeoutsranssofdeirurmedchltooriadesepwaasrataodrdyed fufnonlello,wedanbdy 1015mlmlofof
ethyl phase
acetate. The mixture was extracted was quantitatively transferred to a
and the separated organic 10-ml volumetric flask.
The the
aqueous organic
phase phase
was was
reextracted with 4 added to the 10-ml
ml of ethyl acetate, and volumetric flask whose
volume was aliquot was
fuisnaeldlyJobrroguagshtchrtoomattheogrmaaprhkywiutshingethaynl
acetate. electron
An capture
detector apd run at 180.
aTsheix-rfeosoutlts(1.a8re merteeprosr)tedcoliunmnTabofleCa3.rbowax
CW20M
006503
--2i-
Table 3 Solubility of Ff 3925 in Water
Time of Water Circulation (hrs.) 21 a 68 24
FM 3925 (ppm) 11..7920; 11..8827 2.10] 2.17 22..3313]; 22.03350 2.17; 2.14
Avg. (Hrs. 4-24) = 2.3 ppm
TThhee the
sreotleunbtiilointytoifme FoMf39T2M539i2s5 fiosrtyc-lsosiex ttiometshatthaoft gas chromatographic patterns (see Figure 2 in
oTfM F34M223,422a,nd reference 1)
are essentially tho same.
REFERENCES
(1) r"eApnoarltytitcoalD. MLe.thoBdacoolno,gydoantedFM113/41252/,7"7,A. p.Men8.del's progress
(2) D(.197B7.).Easty and B. A. Wabers, Analytical Letters, 10, 857
v
(3) MFIaMnrtce3hr4o222f6.f,"ice1T9h7c6eo,rdreiensstptiorntidlbeuentdcieo"nGaosfcoCGe.hfrfoiA.mciaetVnortgarsapipishridcteofiADnn.eadlyL.saessBatcohoefn,
s;
prhaatsieo otfo tthhee ccoonncceennttrraattiioonn ooff aclolmpsopuencdiessoluibnlethein anq-uoecotuasnol
phase at a given pH (usually 7).
(4) A. Otsuki and K. Fuwa, Talanta, 24, 584 (1977).
(5) EG.nviTr.onW.allSaecie., 'iJcra.l,th,I.AS1.2 4F9l3etc(h1e9r7,7).and R. A. Duce, J.
(6) 3G2., D.18V49eit(h197a5n)d. V. M. Comstock, J. Fish. Res. Board Can.,
(7) RB. F. Heine and R. R. Burford, C. G. Klaus, J. D. LaZerte,
J. W. Sargent. (Unpublished)
(8) NA.ov.Men1d5,el 19r7e7p.ort on Fate of Fluorochemicals to D. L. Bacon, (9) EE C.nvn iT.rovnCmheiinout,arlSV.o cSciiHen .ennccFm ereaeaendnd,dn TTDe.ect chhWn.noaollSoocglghyym,,edd111i1,,ng47a5nd(1R.977L).. Kohnert,
006504
-22-
(10) "Standard Methods for the Examination of Water and Wastewater," M. C. Rand, A. E. Greenberg, and M. J. Taras, Eds., Washington, DC, 14th Edition, 1976, pp. 600-603.
(11)
TCahkeemnicaflrsompeA.rsoN.nneWle,ltOecrt'.s
oral presentation 23, 1978; minutes
to of
Commercial meeting,
Oct. 31, 1978.
(12) C. F. Prutton and S. H. Maron, "Fundamental Principles of Physical Chemistry," Macmillan, 1951, Chapter 19.
(13) Agrichem Laboratory personnel are acknowledged for their help in autoradiography and scintillation studies.
(14) E. A. Reiner, "Biodegradation Studies of Fluorocarbons III," July 19, 1978.
AM/cen
:
006505