Document 103325dybgkKkwxY6ebppkJyE
RARE- 2697
19
|
#R3R6-2697 DuPont13202
TRADE SECRET
Study Title
i
J: Hydrolytic Stability of[
Jas a Function of pH
`TESTGUIDELINES: OECD Guideline 111
AutHOR: Bogdan Szostek, Ph.D.
STUDY COMPLETED ON: November 24, 2003
PERFORMING LABORATORY: EI. du Pont de Nemours and Company
Haskell Laboratory for Health and Environmental Sciences
--
Elkton Road, P.O. Box 50
Newark, Delaware 19714-0050
LABORATORYPROJECTID: DuPont-13202
`WORK REQUEST NUMBER: 14643
SERVICE CODE NUMBER: 392
`Company Sanitzed. Dosmsenomt contain TSCA CB. ARS
I[----J:
sapoenotgt
ors
GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT
`This study was conducted in compliance with U.S. EPA TSCA (40 CFR part 792) Good
Laboratory Practice Standards, which are consistent with the OECD Principles of Good
Laboratory Practice (as revised in 1997) published in ENV/MC/CHEM(98)17 and MAFF Japan
`Good Laboratory Practice Standards (59 NohSan Number 3850.
`The test substance was characterized by the sponsor prior to the initiation ofthis study, except the percent content of 8-2 TBA. The analysis ofpercent contentof 8-2 TBA in the test substance
was completed after this study completion. Although the characterization was not performed
iyunder Good Laboratory Practice Standards, the characterization was done by an ISO 9000
certified laboratory, and the accuracy of the data is considered sufficient for the purposesofthis
Api Spnc:aWLsingPoor.dbeNemos5n0d0Copy
-
stypesar_Boglee So
2B 4 V - 2002.
Ra Co `Bogdan Szostek, Ph.D.
Dae.
tnpom RT
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--_--
CompanSate. fTg=otonTOA!
tHydrolyic Stability o}f|
Js 2 Functionofpit
QUALITY ASSURANCE STATEMENT
Haskell Sample Number(s): 25707
Datesof Inspections: Protocol: Conduct:
Records, Reports:
July 25,2003 August 1, 2003 September 30, 2003; October 1-3,6, 2003
Dates Findings Reported to:
--
Study Director: October 15, 2003; November 20, 2003
Management: October 15, 2003; November 20,2003
DuPont 13202
Reported by:
Donda WK WoKnedla)KC 3 Ky Quality Assurance Auditor
28tal- 203 Date
5 -_-- Company Sanitized. Doss not contain TSCA CBI. AR226
1bye subi of
pss
Duron 13200
CERTIFICATION
`We, the undersigned, declare that this report provides an accurate evaluationofdata obtained from this study.
Approved by: e E__S_S. Va iAag s Roev=ogeey
estt y trougRhe
Sn Ea
24-wsv dees
~------.Sn--------
rHydrol Subily of| |
Jas Functionofpit
Dupont13202
TABLE OF CONTENTS
Page
GOOD LABORATORY PRACTICE COMPLIANCE STATEMENT c.rvsssnsnnn2
QUALITY ASSURANCE STATEMENT w.vvnssnssssssssmsssssssssssnsssonnn3
CERTIFICATION cosmid
LIST OF TABLEScravessss
LIST OF FIGURES crs
STUDY INFORMATION cvs]
Eg
A ----
INTRODUCTION css)
STUDYDESIGN.
dd
MATERIALS AND METHODS v.10
--~
A. M1aterTiealsst..S. ubstance.--..-------------------- ST wll
F 3. Equipment. E
n----
IunH
Be M1 oportelsimiunsatnrepys.agmnmmnn
eese----n----m----s----nrr--rn---- N1H2
23. pAlmneaaolfsteyutssraudibesemstmpaeenrncaerte...
IeII ------ n
45. CA alclaionOsF.BS 2TBA
eeeme--------------
oTen
RESULTS AND DISCUSSION crisis16
CONCLUSIONS wml
RECORDS AND SAMPLE STORAGE .cvvsnvsssnvssmsmmininessmmsssmmssisilnl
TABLES osm
-_--
`Company Saniized. Does not containTSCA CBI.
Aras
tHydrolyic Stability of|
Jas Functionofpt
Dupont 13202
LIST OF TABLES
Page
1. AnEalLytC ical EresultTs or aqDuemouwsestmabmilmityaomf|mnemsmsmensmspHmo12--,--37C,Days 0 (10-Sep-2003) 19
2. Aannadly3t0ic2a-lSreeps-ul2t0s0f3o)r.aqueoussibilityof
1,pH40, 50C,Days 0 (28-Aug-2003) --
3. aAnnadly$(t0ic2a-lSerpe-s2u0s03f)or.aqueous ability of
19H 7.0, 50,Draeysm0m(28p-Amuge-20n03m) --_y
4. aAnnadly$t(i0c8a-lSreeps-u2l0s03f)o.r aqueous stability of
1,pmH9m.0,iSs0Cm,Dsaymss0 (m03m-Seop-a20--03)----cl
5. Measuredconcentrationsof8:2 TBA for pH 12, 37C,Days 0(10-Sep-2003)and 5
(15- p-209). . . .23
6. Measuredconcentrationsof8:2 TBA for pH 4.0, 50C,Days 0(28-Aug-2003)and 5
(12-5p-20 3). . . . 24
7. Measured concentrationsof$:2 TBA for pH 7.0, S0C,Days 0 28-Aug-2003) and 5 (02-Sep-2009) 2
8. Measuredconcentrations of 82 TBAfor pH 9.0,50C,Days 0 (03-56-2003) and (08-Sep-2003. ..........26
9. Daily(cmperature adingsOfthe shaking WALEr
Bah..
2]
10. pHmeasurorDeaym0nednDAtY5s.
inn 28
LIST OF FIGURES
Page 1. (LC)caclhirbroamtaitoongrstaamnsdoafrfdosuorfDay5,pH 12 replicaTsaempnlesm(An),i75m00pmye/Lm(m8),manmd e150r00rmgm/L------_-- 2. (LC)caclhirbroamtaitoongrstaamnsodafrfdosuorfDay , pH 4.0 replicate1samples (4)c, 75--00--mg/L. (B), and15000mg/L. 30 3. L(C)ccahlriobrmaattioongrsatmasndoaffrdosuorfDay 5, pH 7.0 replica)samples (A), 750i0 mng/sL (8o), --and--15--000--mg/rLr
4. (L)CcaclhirbormaatitoongrsatmasnodfarfdosuorfDay 5, pH 9.0 replicatePsaomprlesn(As),m75m00mmge/Lm(rB),--and 15000mg/L 3
5. RepresentativeLC chromatograms ofblanksamplesforDay 5,pH 1.2,8.0,7.0, 8090...
32
6. Reprecasliberatnioncturave tori82ve TBA.
wm
7. RteeprrnesaelnStaUtiRvAeTc.h.r.omatogorfa25m.s5 ug/L. 2 TBA calibratiosn sta-- ndard--and 5--20 g-- /L D-- -82 c TBA
8. RteeprrensaelnStaAtBivReIch.romartorgrramsforDay0, pH 4.0 hydrol-yticstabilitysampleand 5s20yrg/eLDm-8e2TmBA------
5. Representative chromatogramsforDay0, pH 4.0Bn
SABI. .
34
--_--
`CompanySanitized. DossnotcontainTSCA CBI.
AR228
0Hydrol Sabiltyo I
Jas: Functionofph
Dupont13202
STUDY INFORMATION
SubstanceTested: [
1
Synonyms/Codes: + H-25707
`Submilter's Notebook Number(s): E105186-11
HaskellNumber: 25707 Purity: 100% Fluorinated polymer
KnownImpurities: 0.016% 8-2 TelomeBr Alcohol (1H,1H,2H,2Hperfluorodecan-1-ol, CAS# 678-39-T)
Physical Characteristics: Off-white solid
Stability: The test substance appeared to be stable under the
conditions of the study; no evidence of instability was
_
observed.
`Sponsor: E.L du Pont de Nemoursand Company Wilmington, Delaware 19898 USA
`IStnuidtyiated/Completed: June 6, 2003/ (see report cover page) `Experimental StartCompletion: June 9, 2003 / September 15, 2003
ee `Company Sanitized. DARzoznsotscontsain TSCA CBl.
{Hydrolyic Sabi oJf|
Jas Function ofpH
STUDY PERSONNEL Study Director: Bogdan Szostek, Ph.D. Primary Technician:KeithB. Prickett, B.S. Management: S. Mark Kennedy, Ph.D.
Analytical Associate: Keith B. Prickett, B.S. Analytical Chemist: Bogdan Szostek, Ph.D.
Management: S. Mark Kennedy, Ph.D. `Toxicology Report Preparation:LisaG. Burchfield, A.A.
Management: Nancy S. Selzer, M.S.
DuPont 13202
Company Sanitized. DoeTssnotcontain TSCA CBI. R225
tm soy of
se inion opi
Dupe 132
SUMMARY
`The hydrolytic stability of[
1, fluorotelomer-based acrylate copolymer,
was tested in buffered aqueous solutions at pH 4.0, 7.0, 9.0 at 50C and pH 1.2 at 37C for five:
days. The [
1 was demonstrated to be hydrolytically stable under these test
conditions. The stability was demonstrated by the comparisonofthe percent recoveries of|
for Day 0 and Day 5 samples and analysisof chromatographic peak shape for Day 5 samples.
`The average percent recoveries for the Day 0 and Day 5, pH 1.2 replicate samples are
10141.2%and 101 1.0%, respectively. The average percent recoveries for the Day 0 and
Day 5, pH 4.0 replicatesamplesare 100+ 0.5% and 97 2.1%, respectively. The average
percent recoveries for the Day 0 and Day 5, pH 7.0 replicate samples arc 101 1.3% and
100 + 0.8%, respectively. The average percent recoveriesfor the Day 0 and Day 5, pH 9.0
replicatesamplesare 100 1.0% and 104 + 2.5%, respectively. The difference in percent
recoveries for Day 0 and Day 5 samples did not reach the critical level of 10% that would
indicate the hydrolysis of the test substance for anyof the investigated test conditions. The
observed increase of 8-2 TBA concentration is approximately two ordersofmagnitude lower
than the concentrationof 8-2 TBA expected if 10%ofthe test substance hydrolyzed. In addition,
the measured concentrations of 8-2 Telomer B Alcohol (8-2 TBA, C8F17CH;CH,OH) indicated
an increase of the 8-2 TBA concentration between Day 0 and Day 5. The increaseof the 8-2
TBA concentration can be accounted for by the presenceofthe residual 8-2 TBA raw material
-
present in the test substance.
E Company Sanitized. DossE not contin TSCA CBl. AR226
(Hydolyti Stability of:|
253 Functionofpt
DuPont 13202
INTRODUCTION
"The purpose of the study was to investigate the hydrolytic stability of[
Ja
fluorotelomer-based acrylate copolymer, in pH 1.2, 4.0, 7.0, and 9.0 aqueous buffer solutions.
"The study was conducted according to the protocol: Hydrolyic stability of
]coanscaenfturnacttiioonnoofftphHe"8,-w2hTieclhowmaesr pBatAtlecronhedoalft(e8r-2thTeBOAE)CwDasGumiodneiltionreed11t1o.)invAedsdtiitgiaotnealifly8,-2thTeBA
is released from the test substance during the test.
STUDY DESIGN
A preliminarytestwas performed on the test substance at 50 + 0.1Cateaocfthhe pH 4.0, 7.0, 9.0 and at 37 0.1C for pH 1.2. Ifless than 10%ofthe test substance hydrolysis is observed after 5 days, the test substance was considered hydrolytically stable and no additional testing was performed. In addition to the test substance determination during the preliminary test, the: samples were analyzed for 8-2 TBA.
e`Txhceepsttiuodny tdheastitghnecOomEpCliDesGuwiidtehltihnee f1o1l1lorweiqunigrteesstthgautidtehleinaemso:uOntEoCfDthGeuitedsetlsiunbes1ta1n1c?e wuistehd tishethe
-
smaller of 0.01 M orhalfthe saturation concentration in water. The test substance ([
1i insoluble in water and the analytical method does not allow detectionofthe test substance at
trace levels. Therefore, the study was conducted with an excessofundissolved test substance.
MATERIALS AND METHODS
A. Materials
I. TestSubstance
CNomapmoes:ition:
(100% Fluorinated Pol)ymer
`"TCeAstSSNuubmsbtearn:ce Chemisty: (|
1
)
Haskell umber: 2{{ 507 1 1
The test substance was characterized to determine the 8-2 TBA content, % fluorine, and polymer characterization parameters: Mn (number average), Mw (weight average),Mz (z average), and PDI (polydispersity index) with the following results:
--
Company Sanitizad. DAo2ss20not contain TSCA CBI.
tHydrolytie Stability of)
Jas a Funcion ofpi
- %8F2luoTrBinAe ((ww/ww)):: joMoe: MPiDL
016%
(0
11
{(
11
(
1
2. Preparation of buffer solutions
Duont 13202
"The following buffer solutions were prepareda described in the Annex to OECD
guideline 1117.
a pHI2
`STihgen0a.)2 iMn 2p5o0tamsLsoiufmwcahtleorr.idTeh(eKC0I.)2 wMashypdrreopcahrleodribcyadciisds(olHvCiIn)gw3a.7s3pg rofeKCpIbya(pduirrliutetyi9dn9g.10.%8,3 g of hydrochloric acid (36.5-38%, Sigma) in 250 mL water. The pH 1.2 buffer solution was pflraespkaraenddbbyripnlgaicnigngth1e2f5lamskLtoofv0o.l2uMmeKwCitlhawnadter1.61.T3hmeLpHoofaf0t.h2e bMufHfeCrlwsaosluatdijounstientdotao 51.020w-imtLh hydrochloric acid.
bo pH&
_ "The 0.1 M solutionofpotassium hydrogen phthalate was prepared by dissolving 10.21 g of spooltuatsisoinuwmahsydprreopgaernedphbtyhapllaatcei(npgur2itmyL99o+f%a,0.S1igMmas)odiniu5m00hymdLrooxfiwdaetseorl.utTiohneapnHd 245b0ufmfLerofa 0v.o1lMumepowtiatshsiwautmerh.ydTrhoegepnHpohfthtahleatbeusfofleurtwiaonsiandtjouast5e0dt0o-4m.L0fwlaistkhahnyddrborcihnlgoirnigctahceid.flask to o pHT:
p`Thhoesp0h.a1tMe, smoolnuotiboansoifcpo(tKaHs;sPiOuym, ppuhroistpyh9at9e.w5a%spSriegpmaar)eidnb5y00dimsLsoolfviwnagte6r..81 TghoefppoHta7sbsuifufmer tSohleu0t.i1onMwapsotparsespiaurmedphboyspphlaactiensgol1u4t8iomnLinotofaa 50.010M-mLsofdliauskmahnyddrborxiindgeinsgoltuhteifolnaaskndto2v5o0lmumLeof with water. The pH of the buffer was adjusted to 7.0 with sodium hydroxide.
a pH:
d`Tihseso0l.v1inMg 3b.o7r3icgaocifdK(CHI:B(pOusr)itsyo9lu9t.i0o%n,iSni0g.m1aM) apnodta3s.s0i9ugm ochflHoyriBdOe,(K(pCuIr)itwya9s9p.r5e%p,arSeidgmbay) in s5o0l0utmiLonoifnw0a.t1erM. KTChleapnHd 910b6u.f5femrLsooluatfi0o.n1waMs spordepiaurmehdybdyropxliadciensgol2u5t0iomnLintoofaa 50.010M-mLHyfBlaOs,k Saonddiburminhgyidnrgoxtihdee.flask to volume with water. The pHofthe buffer was adjusted t0 9.0 with
~
`puWraitfeircuastieodnfsoyrsbtuefmf.erTphreepawraatteironrewsaisstiovbittayiinse>d1f8r.o2mmaeBgaarcnhstmeeacdmN.AANlOlpbuufrfeersDoliuatimoonnsdwewraeter
`Companey Seaneitezeed.eDossenmot contain TSCA CB. ---- R226
Hdmi suiof
Liss ncionotit
Dare
sterilized prior to use by filtering through Corning Sterilization Filer systems with 0.22 ym cellulose acetate filters. The buffer solutions were storedatroom temperature.
3. Equipment
pWaiteMretBear:th Atuuttocolmaavtei:c Pipers: BSoanliacnacteo:r: CVoorntteixfeurg:e: Glass Vis:
OWratieornbMaotdhe:lL2a5b0-LA.in Force Reciprocating Water Bath Shaker, Model 4682 AReMseSaCrcOhMPorode1l003,0213000, 5000; Eppendorft MBertatnlseornAMEo-d1e0l01210o Branson Model 5200 MSourlvail-luRbTe7vortexer, VWR f1o0ilmiT.hbeorvoislil,icfaotle,carnidmspepttoapwgelarses vaiuallosc(lSauvpeedlacto)12w1ithC 2f0om30mmTi/nbubteyf!orseeputsse.and aluminum
B. Methods 1. Preliminary test
`The preliminary test was performed on [
Jat 50C at eachofthe pH 4.0, 7.0,
9.0:and at 37C for pH 1.2. The same sample preparation procedure and study design was
followed for each of the pH levels tested. Approximately 100 mgofthe [
1
was weighed into each of sixteen 10-mL autoclaved glass vials and 3 mLofappropriate buffer
ol
solution was added. The vials were crimp capped with the bottom of the septum covered with
autoclaved aluminum foil. Eightofthe vials were processed for analysis as the Day 0 samples.
`The remaining eight samples were wrapped with the aluminum foil, submerged in the water bath,
and shaken at 100 rpm in the water bath for five days at the appropriate temperature. Eight vials
containing only 3mL ofappropriate buffer were prepared to serve as the blanks. Fourofthem
were used as the Day 0 blanks and the other four were wrapped in aluminum foil and placed in
the water bath to be the Day $ blanks. Additionally, six vials containing 3 mLofappropriate.
buffer were spiked with 8-2 TBA stock solution (4.5 uL of 1020 mg/L 8-2 TBA). The vials
`were crimp capped with the bottomofthe septum covered with autoclaved aluminum foil. Three
ooftthehre tvhiraelesvwiearlsewuesreed wasratphpeeqduailnitaylcuomnitrnoulm(fQoiCl)asnadmppllaecsefdoirn8t-h2eTwBatAerabnaaltyhstiosgoenthDearywi0t.h Teihgeht
ofthe test substance vials. These served a role ofQC samples for 8-2 TBA analysis on Day 5.
Fourofthe Day 0or four of the Day vials and two blank vials were processed forthe pH
measurement and the [
) determination. The other fourofthe Day 0 or
Day 5 vials, two blank vials, and 8-2 TBA QC vials were processed for the 8-2 TBA
determination.
2. pH measurement and temperature.
`The pH was measured on Day 0 and Day 5 in the vials containing the buffer and the test
substancethatwere designated for the
J analysis. The vials were
uncapped, the pH electrode was introduced to the vials and the pH reading was recorded. These
vials were further processed for [
Janalysis. The temperatureofthe water
a -_-- `Company Sanitzed. DAoRs26not containTSCA CBI.
(byte sai of
2 Fusionopt
Duron 3202
-
bath was monitored daily. The water bath temperature readings from the automatic temperature:
control were checked and recorded in the study records daily.
3. Analysisoftest substance
After the pH measurement, 0.3 mLofdiluted [ ) fluorosurfactant (H-24678) was added
0 each vial, the vials were recapped, vortexed for ten minutes, and centrifuged for fifteen
minutes at 3200 rpm. The addition ofthe [ | fluorosurfactant is necessary for wetting of
the [
Jand facilitates the pelletingof the material at the bottom of the vial
after centrifugation. After centrifugation the vials were uncapped and the supernatant was
discarded using a manual pipetter. The remaining solid material was dissolved by adding 10 mL
oftetrahydrofuran (THF) and sonication for 30 minutes. Approximately, 1 mL of the THF
solution was placed in aglass LC vial and subjected to LC-GPC analysis. The blank samples
were subjected to the same procedure except the pH measurement.
"The stock solutionofthe [
J was made by dissolving 0.15 g of[
Jin 10 mL ofTHF. Thirty minutesofsonication were required to completely dissolve the test
substance. Calibration standards for the [
J analysis weremadeby
a[ppropriate dilut1.ioFnroefshthcealstiobcrka.tioTnhsetacnadlairbdrastwioenrestparnedpaarrdesdrafonrgeedacfhrionmst3a0n0c0eotfoa1n5al0y0s0ism.g/L
Linear regressionofthe peak height vs. standard concentration was used to establish the.
calibration curves.
~~
Instrumeanndtcoandtitiioonsn:
CLoCluSmysnt:em: LFlCoSwoRavtea:: CRIolDuemtenctToermpTeermapteurraet:ure: DInajteactCioolnleVcotliounm:e:
SAtgyirlaegnetlHHPR.141,070.8wmitmh Agxi3l0en0tmRmef,raWcattievresI:ndex Detector (RID) T|emtmihmyidrnofuran (THF) 4305CC 0S.O15Lmin
4. Analysis of 8:2 TBA
tShaemvpilaelssdeepstiugmnautseidngfoarg8l-a2ssTsByArinagnea.lyNseisitwheerreDpraoyce0snsoerdbDyayi5njseactmipnlges6 wmeLreacuentocnaiptprieldebtehfrooruegh
acetonitrile injection `were vortexed for 15
to avoid minutes
any lossesof 8-2 TBA. on a multtube vortexer.
The vials containing injected acetonitrile Subsequently, the vials were uncapped
and 1mLofthe extract was transferred toa glass capped, and subjected to LC/MS analysis for 8-2
TLBCA.vial,
spiked
with
internal
standard,
crimp
aTsH,th1eHa,na2lHy,ti2cHa-lpsetrafnlduaorrdoodfec8a-n2-1T-B0Al.(971.D6,%1,DO,a2kDw,o2oDd, P3r-o1d3uCc-thse,pWtaedsetcaCfolluuomrboidae,cSanCo)lw(aMs+u5s)ed (thaebbarneavliyattiecadlasstDa-n8d-ar2dTaBnAd)thweasintuesrendalassttahnedairndtewmearlesptraenpdaarrde.d iSntomcekthsaonloultiaonnsd(w1e0r0e0smtgor/eLd) of - refrigerated. The calibration standards were prepared fresh for cach calibration in 50/50%
Company Sanitized. DTososnotcontain TSCA CBl. R228
tHeol Sabi of}
Jas Functionofptt.
Dupont13202
- TwaBtAe.r/acAetocnointsrtialne.t coTnhceenctarlaitbriaotnioonfsitntaenrdnaarldsstwaenrdaermdawdse iunsetdh:e r5a2n0geugf/rLomD2-5C8t-o22A5.50Thueg/L -2 "caTlBiAbraatnidonpecaukrvaerseawefroer icoonnstrmaocntietdourseidngfotrhDe-r8at-iToBoAf tahnedptehaekcaornecaenftorraftoinosnsm/ozf m-o2niTtBorAed for -2
Instrumeanndtcoandtitiioonsn:
MHPSLICnsnisuimreunmtent 2M0o.deMlic21r9o5m,asWsars
LCVoCilPuabmrnamPehtaesres: CInojlecutminonTVemepteraa:ture: Chum Switch
LAunma3r0 C18 @),20mmx2mm
G5am"dTeitmihean(orlin
Pn
o|
3E0y
a2`
Er00
3040C 5
Fudonin
Eunn
Flow 0(3nsmin)
1020
0033s5
10wo 00o33isss
- MloSniPzsatriaomnetmeordse::
[--
CCSooonpctuvaeytTveoomglpeea:rgaet:ure: 3T152o0vC
DDaetsaotAvcaqtuiosniTteimopneFruantcutrieo:n: 38:020T0BA: SIR"af463, 509,052mi3n
D8: THA: SIR of468,514,538mi0-6:min
* oaTFnhdecsseetoatntseanradedpldrouercsftenootrfmt8a.et2dTienpBhrAoeo(snmyastztee5d2mm3o)or,lieTgciuenlaatfironrogmo1fat8e-ant2dhaTrcBmtAeit(hvaod2dds4u6hc3tt)r,aefeofrfomoamoadbodeueccaStuysoseftoe8fmraTsnBAisl(mporvets5he0ens9ce,e Components he mobile pce,
5. Caleulations
"(TThaeblfeosll1o-w4i)ngFcoarlceuxlaamtpiolnes,wiefre0u.1s0e09dgtoodf[etermine the nominaJlwacosncweenitgrhaetidonisnoof the vial and ) snuobmsienqaulenctolnycednitsrsaotlivoendoifn11000.m9Lmgo/f0T.H01F Ld=u1r0i,ng09s0ammpgl/eL.proTcheesspienrgc,enthtisrewcoouvledryreisprceaslecnutlattheed by dividing the measured concentration by the nominal concentration, times 100%. "fTohlleoewxs:petchteed4.(5nokmLinoafl1)0c2o0ncmegnt/rLat8i-o2noTfB8A-2spTikBeAreipnrtehseenstpsi4k.e5d isaLmxpl1e0s2w0ansgc/aalLc=ul4at5e9d0ansg 8.2 _ TBA. Total volumeof extract is mL: 3 mL ofbuffer and 6 mi ofacetonitrile. The expected -- ee -- Company Sanhizd. GFor sos-- enot containe TSCA CB. -- e
bitiSubiiy of
Jas a Functionof ptt
Dupont13202
nominal concentration of 8-2 TBAintheextract is: 4590 ng/9 mL=510 ng/mL. The percent recovery is calculated by dividing the measured concentration by the nominal conceniration, times 100%
h`Tyhderoelxypezcetdecdacnobnceeensttriamtaitoendoifn8t-h2eTfBolAloiwnintghewaacye.tonTietrnipleerecxetnrtacotfif10100m%ogftohf[e [
]]
represents 10 mg. Taking into account that the test substance contain [
J fluorine and
assuming that all fluorine is present in the formofbound 8-2 TBA, the hydrolysisofthe 10 mg
Iotfthe
test
substance
would release: [ 15.56 mg 8-2
TBA.
This amount of 8-2 TBA would be contained in
1
9 mLsofextract. Therefore, expected concentration of 8-2 TBA would be: 5.56 mg/0.009 L=
618 mg/L.
The |
} contains residual raw material, 8-2 TBA. The expected, maximum
concentrationof 8-2 TBA derived from the 8-2 TBA present in the extract, assuming complete
extraction, is: 100 mg of[
1% (0.016%/100)/0.009 L= 1.78 mg/L
(1780 pil).
-
`Company Sanitized. DAoRs2s2n8ot contain TSCA CBl.
yoy sunnofy
Jos Function
Dupe
RESULTS AND DISCUSSION
Tables 1-4 present the results for measured concentrations of[
Jand percent
recoveries obiained for Day 0 and Day 5 replicate samples for pH 1.2, 4.0, 7.0, 9.0, respectively.
`The average percent recoveries for the Day 0 and Day $, pH 1.2 replicate samples are
101 1.2% and 101 1.0%, respectively. The average percent recoveries for the Da0y and
Day 5, pH 4.0 replicate samples are 100 + 0.5% and 97 2.1%, respectively. The average
percent recoveries for the Day 0 and Day 5, pH 7.0 replicatesamplesare 101 + 1.3% and
100+ 0.8%, respectively. The average percent recoveries for the Day 0 and Day 5, pH 9.0
replicate samples are 100 1.0% and 104 & 2.5%, respectively. The relative difference between
the Day 5 and Day 0 concentrationsofthe test substance was less than 10% for any of the.
investigated pHs. This indicates that the [
Jis hydrolytically stable at
investigated pH. Figures | to 4 compare the LC chromatograms of four replicates of Day 5
`samples with the chromatogramsoftwo calibration standards for pH 1.2, 4.0, 7.0, 9.0,
respectively. The shapeofthe chromatographic peak, eluting from 7 to 11 minutes, is indicative
of the molecular weight distributionofthe
1. The hydrolysis of[
J would result in changeofthe observed peak shape. Comparison of the peak shapeofthe
freshly made calibration standards of[
Jand the Day samples indicates
that no evident changeofthe peak shape for Day 5 samples was observed for any of the
investigated pHs. This further supports the conclusion of[
T hydrolytic
---
stability. Figure presents the LC chromatogramsofthe Day 5 blank samples for pH 1.2, 4.0,
7.0,and 9.0.
Additional evidence supporting the hydrolytic stability of[
J can be derived
from the measured concentration of 8-2 TBA. The hydrolysis of[
J would
result in the release of8-2 TBA and the increase of 8-2 TBA concentration in the test system.
Based on the charcterization data, the test substance contains 0.016% of residual 8-2 TBA.
Assuming that the buffer extracts all the 8-2 TBA during the time ofhydrolytic stability
experiment, the expected concentration of 8-2 TBA in the processed extract (3 mLbufferand
6mLacetonitrile) would be 1.78 mg/L (see B.S Calculations). Similasly, the expected
concentration of 8-2 TBA in the extract, if 10% of[
J was hydrolyzed, is
618 mg/L (see B.S Calculations). Tables 5-8 present the measured concentrationsof8-2 TBA in
the extracts for Day 0 and Day S replicate samples for pH 1.2,4.0, 7.0, 9.0, respectively. The
data shows a significant increaseof 8-2 TBA concentration in the Day 5 samples, when the
average concentration of 8-2 TBA for Day 0 and Day 5 samples are compared. However, the
concentrations reach only someofthe expected level of fully extracted 8-2 TBA (1780 pg/L) and
these are approximately two ordersof magnitude lower than the concentrations expected when
10%ofthe test substance would hydrolyze. The increaseofthe 8-2 TBA concentration between
the Day 0 and Day samples is simply a resultofextraction ofthe 8-2 TBA from [
during the hydrolytic stability experiment at elevated temperature (S0C or 37C). The percent
recovery results for 8-2 TBA (Tables 5-8) support the validityof the 8-2 TBA measurement in
the Day 0 and Day 5 samples for all investigated pHs. The Day $ sample percent recovery
results demonstrate thatno significant lossof 8-2 TBA occurred from the test system during the
_
hydrolytic stability experiment. Figure 6 shows representative calibration curve obtained for 8-2
--_--
`Company Sanitized. Doss not contain TSCA CBI.
R225
tHydrolytic Stability ofI
Las 2 FunctionofpH
DuPont-13202
-
TBA. Figures 7-9 show chromatograms for 8-2 TBA calibration standard, Day 0, pH 4.0 test
sample, and Day 0, pH 4.0 blank sample, respectively.
Table 9 summarizes the water bath temperature data for pH 1.2, 4.0, 7.0, and 9.0. In all cases, the water bath temperature was maintained at the specified level with deviation not exceeding 0.1C.
`Table 10 summarizes resultsofthe pH measurements for Day 0and Day $ samples for pH 1.2, 4.0,7.0,and 9.0. The measured pH for Day 0 and Day $ replicate samples for all of the investigated pHs was at the specified nominal level with the deviations not exceedin+g 0.1.
CONCLUSIONS
`The hydrolytic stability of{
1,a fluorotelomer-based acrylate copolymer,
was tested in buffered aqueous solutions at pH 4.0, 7.0,9.0 at 50C and pH 1.2 at 37C for five
days. The [
1 was demonstrated to be hydrolytically stable under these test
conditions. The stabilityofthe [
J was demonstrated by the comparison of
the percent recoveries of[
for Day 0and Day samples and analysis of
chromatographic peak shape for Day 5 samples. The difference in percent recoveries for Day 0
and Day 5 samples did not reach the critical level of 10% that would indicate the hydrolysis of
the test substance for anyof the investigated test conditions. In addition, the measured
---
concentrationsof 8-2 TBA indicated an increaseof the 8-2 TBA concentration between Day 0
and Day 5. The increase of the 8-2 TBA concentration can be accounted for by the presence of
the residual 8-2 TBA in the test substance. The increaseof 8-2 TBA concentration is
approximately two ordersofmagnitude lower than the concentration of 8-2 TBA expected if
10% of the test substance hydrolyzed
RECORDS AND SAMPLE STORAGE Specimens(ifapplicable), raw data, and the final report will be retained at Haskell Laboratory, Newark, Delaware, or at Iron Mountain Records Management, Wilmington, Delaware.
REFERENCES 1. Organisation for Economic Cooperation and Development (OECD). May 12, 1981. OECD
Guidelines for TestingofChemicals, Hydrolysis as a Functionof pH, OECD Guideline: No. 111.
-_--
`Company Sanitizad. Doss not contain TSCA CBI.
AR225
{Hydrolytc Stability ofI
Las Function ofpit
Dupont 13202
-
TABLES
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1yori subi ofJ:
Ja Function ofpi
- Table 1: Analytical results for aqueous stability of |
Days 0 (10-Sep-2003) and 5 (15-Sep-2003).
Duron 13202
1, pH 1.2, 37C,
Crrrr
[lol
ow TowTw]
[afolal wwTew wm |
fra lodsl wwTew Tm)
[oa Tola] ow TT iow Tw |
1
[Awe Tw]
[vom] ~ ome CC] [ -- --T -- [2TsThTew 1 ow 17 | [e we TowT Tw es mm Tows To [re lsTeT ww TT m w | 1
Company SaizI.TBioonnt continTSCA GBI.
(Hydrol Sabi of)
250 Funcionofpit
-
Table 2: ADnaaylsyt0ic(a2l8-rAesuugl-t2s0f0o3r)aaqnudeo5u(s02st-aSbeipl-i2ty00o3)f|.
Dupont13202
1, pH 4.0, 50C,
NomiotConcnrnin| Mesure Concent
rr =r r Tr
feo poPl mw 1 01
[eoToba] vowTowTw]
[ro Toll ow TwTw]
frolols] vow 1 ww Tw |
1
[pee Tw]
[SmbrdboiminTos]
[ --T -- ----1
[ooTsToThem 1 sw 1
Foo Tsa m0 1 o 79}
[eo TsTomoTow 10}
[eo IsTT ow Tw TT 5
1]
--
[te T]
[soti| pe5 mn]s
i -------- Gompa-- ny Sanhi-- zed. Dforss-- yno cont-- ainTSCA-- CBI. ------
0Hydrolyic Stability of}
Jas a Function ofpit
Table 3: Analytical results for aqueous stability of[ Days 0 (28-Aug-2003) and (02-Sep-2003).
DuPont13202 1,PH 7.0, 50C,
rr rr r rr
[roToT] ow ] ow Tw [roTol] om 1 ow 1 ww] [rooT w 1owl wT s w ]| [ro Tole om 1 ow 10
-- 11 IS TR
rr1
FeTePv] wwe Tew 7] we]
[ro TsTal om TwTw]
[roTsls] om 1 owTw
frolsTs] ww J wo | 1
1
-
[me To
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(Hydrolyti Stability oXf
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Table 4: Analytical results for aqueous stability of | Days 0 (03-Sep-2003) and 5 (08-Sep-2003).
DuPont.13202 1, pH 9.0, 50C,
rr
-- rr
PooJobo ww 1 ow Tw 1
[ooTolal ow | vow Tm
[ooTols] ow T ww J wo 1
[ooJofe] ow J ww J 1
11
[meeTw
[Fommtmeie 01
[1 --
[ooTTT wow 1] ww J wm]
[roTsl=1 om T wow | ww
[ooT5ToTom 7 iow Tos |
[ooTsTol ow 1 vwTo |
[1
Pa
[reeTw]
a
EE
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Duron 5202
and 5 (15-Sep-2003).
Tom [| Rep|Concentration(191)|_Concemraton (pl)
rrrT
[oa fof
1wT
[eo =
[elo
1
[eels
Tw 11
1 1 1 1
[TT1 wwe Tw [1]
[1 1 1 swtperiwn J =
TT 1
rrr rT
[a soo Ts eT ] w |
[2Toteal so 1 ss 1 we |
[loessTov Tw |
TT
CT awe Tw]
--
[| swaiboisn| as |
rr
1
11
[fe Tw 1
La stew 1]
[ess
Tw
-
1
[1 1
C awe T eT
--]
|
1
[esTeal wn Tw Tw |
[a seal soTa[i 7 |
[aTsJeal so1 we Tw |
TT
TT
ewe
7% |
C1 T seston| 55 |
Ee eee Be
[--
Joa Fanconi
pr
Table 6:
Measured concentrationsof 8-2 TBA for pH 4.0, 50C, Days 0 (28-Aug-2003)
and 5 (02-Sep-2003).
en em | Concentration (ug/L). Concentration(up/L)*
[eo]
[| mw 1
[oT
[eo Tops
1
[oo 1% 1
rT
TT mew Ts
CT swipes| 6
1 TT
Feel
Lo Lo]
[eo] [so ww)
[oo [oTeo 0Tw Tw
rT
TT ew 9
--
LT
Sebwibevision | 25 |
rT TT
[eo TT weT 1
[eo oT
Tw 1
Cee [eo]
[wT
rT TT
TT eeTw
[I [ owtiboiien | 0
rr TT
[eo [seal 0Tw Ta
[oo[sda 0Ta|
[5Teel seTw Tw |
rr rT
LT Rew wn |
CT Sete [a1]
EE mE=
--
bnsomesaand --
sn
le em - Table 7: Manedas5u(r0e2d-Sceopn-c2e0n0t3r)a.tions of8-2 TBA for pH 7.0, 50C, Days 0 (28-Aug-2003)
Caveats Oa)
rT 1
[oo on 1%
[ooTole pw
[oe Tels Tw 177
[ro Tolel
1 wo 177
rr
71
LT wee| T TT 7
[|| swtioisin | 5
17]
11 1
1
[oo [oeal m0 15 T0 w |
[oo [odealTM sw 17
Tw |
[oo [odea 50 17 Tw |
rrr1 1T
CTeT we 5 |
_
TT soutooinin| 27 |
rrr rT
[oeTso]
1 wo T77
[oo Toll Two 1771
[eo [5STTw T
Lee [sla Tw 1--]
(1 11
[TT1 meme Tw 7
[soT tiooin| 0 T1
11TT
[ro [lea] 01
Tw |
[ro [stealsTw Tw
[ro [steal ooTw Tw
rrr 71
TT ewe [wn
CT sotaiooioin[5]
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aa Fantonoft
Duron 15702
`Table 8: Measured concentrations of 8-2 TBA for pH 9.0, 50C, Days 0 (03-Sep-2003)
and 5 (08-Sep-2003).
PNET Concentration(ug/L)| Concentration (sgl) *
rr rT 1
[oo[oP
me
[oeTole
1
0 17
[ooTol
1
wa
17
[oe oe
7]
rrr TT
[TT1 ewe | 17
[1 1 1 somwoeviin| 0
1 7]
rr TT 1
[ooToTeal 0Tw TT 7}
[oo Toteal soTm TT 5 |
[oo Joleal so 1
T7
rrr T
[TNeT we |o|
_
[sud| o 07 |
rrr7 T
[ooIs TT TT
[oeIseTw 1
[oeIss
1wT
[ooTsPel
1 wo TT 77
rrr
rT
hee
[TT |samtwivoision [00
|
rrrT
[ooIsTea] 0Tw Tw |
[ooIsTeal soTm 17%
[oo[seo m0 Tw Tw
Lee [1
| Ae Tw
CTTSeT sion| 56]
_-- mmmm z
[--
1 Function ofpit
Dwroni3202
Table 9: Daily temperature readings of the shaking water bath.
E EE N Ee om
--
r o[r o we |oi
Co o e iwse e owne]]
Tr o Te woseee| [i]]
C1 o [oe|m ne]
a oo me [|n |0oo]]
C I o Ta meEo wT [wn]
s se e ommewen [|0wo]]
~
rr
ee| wo
o oe e oommen [[wi|]
o ee m ospen[[we|]
---- 0[-- as[-- -- ewen]
{ ov o em [m [ow||
C o o 0 T oomeeo mn wwmn]|
CT 0Toommeens Taw]]
- JL...Sa
Htcsiof
saFactor
Table 10: pH measurements for Day 0 and Day 5.
Durem
on Toe Tom|m scaari eapu
-- rr
ee
a
as
se ae |
Te as
------ rr 7 1
Ce|
Te Te|
se|
a
---- or
ew ae
ee Tae
es Tae
ew Tae
------ | -- 1
Ls
we
ae |
ee
ae |
ss se ae
-
sss an
--mr 7
oe es |
ow
[Co
he
es |
Ce es
rr 1
ee|
Te|
se Te]
= | 1% Tw|
---- rr TT
Toes
ee Toe |
ee Toes |
Te Tes |
| --r------/T
= Te Tw |
=Te Tw|
ss Te |
CsTT 1a]
--
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Duront13202
_
FIGURES
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--
roe sitoyf
J--------
Duro 13202
-
Figure 1: LanCdc1h5r0o0m0amtgo/gLra(mCs) ocfalfioburratDiaoyn s5,tpaHnd1.a2rordefpslicate samples (4), 75I00 mg/L (B),
-
c
"
[SSoVnR
m
8] \
-
/a
I =
~
\
==
:
ama
[
Figure 2: LC chromatograms of four Day 5, pH 4.0 replicate samples (A), 7500 mg/L (B),
and 15000 mg/L (C) calibration standards of|
3 BEE
a
c., |
ANY
|
B JAN
\ -
\
-
/ \CA
:
reel
CompanySantaDwooenotconanTSCA Bl.
Hype subi of
Jas Function of ptt.
Dupont13202
-
Figare3: LC chromatograms of four Day 5, pH 7.0 replicate samples (A), 7500 mg/L (B),
and 15000 mg/L (C) calibration standards of |
I
|
c
-
a ~~
ol
\
|
-
\ \A4 |
.
|7
Ar]
=
Figured: LC chromatograms of four Day 5, pH 9.0 replicate samples (A), 7500 mg/L (B),
and 15000 mg/L (C) calibration standards of|
1
| ~ -
c
-
A
SMa
he
B
\
=
/\
/
\
i
! _------
----------Co--mpan--y Sak--ize. oAs------n-- t contin TSCA CBL
!
i
\
7
fe i
tHydrolytc Stability ofJ|
852 Function ofpi.
Durant13202
-
Figure 5: Representative LC chromatograms of blank samples for Day 5, pH 1.2, 4.0,
7.0, and 9.0.
- IEEE ESET 1
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rHydrolyic Sabiiy ofl
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- Figure 6: Representative calibration curve for 8-2 TBA.
Sarpleatnodn craomsoBfZ1iAc09i98o87n1, 2 = 0907343 Ruaorrsaetppioeo:nn Lspciuneoree:a:rn, 1Otr1ian3:Sr5dE5m(xxR3cauedf5le20,)1W.5eA 7ig2hi*nr(g1:5C1a onAcd.s1r5anAs:raN)one.
08s:
Dupont.13202 x
[Respense-
> 0 pi) 600 | iso Zao onoot)
a Figure 7: Raenpdre5s2e0nptagt/iLvDe-c8h-r2oTmBatAoginrtaemrsnoalfs2t5a.n5daurgd/.L 8-2 TBA calibration standard
[062803515 Smoot 13) 100
% 297
052o803015 Smoohn 1) 100,
*
e22meA 4a2s1e9 1s3882378A s7te0s
SR 4 chann6e3l.s5255405301003
50 Sol channemli5sn. 750i3e0s.4050235
Tah ak abo shh ah min
-_--
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(Hydrolyic Stability oIf|
Jas. Function ofpt
Dupont 13202
Figure: Representative chromatograms for Day 0, pH 4.0 hydrolytic stability sample and 520 pg/L D-8-2 TBA internal standard.
[G8280341 Smoohtin 15) hae
*
0[032603041 Smoot 13) 100
*
o
Tho 3b
z3e53n _ 71150426885
Sold chann4e6l3s,5253152100005
SIRfd channels m5i-n
seaa2m
886d8es0,1050238
104057.083
hab sho ehomin
Figure 9: Representative chromatograms for Day 0, pH 4.0 blank sample.
[06280305 Smo 15) wo *
SROs chomeen5E2S.0 2
062o203205Smo 13) 3 *
SRot4chome ESm-o sssnte.i5c2nz0
o
Ta ak ak shain
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