Document ZJJXYgLYRojK9xNDKoDDodoZ8
R EREEE iR A DR DRII
Provided - .
=
:
+o SMMO
Rd
TTEECCHHNNIICCAALL RREEPPOORRTT SSUUMMMMAARRYY
5/o1
TO: TECHNICAL COMMUNICATIONS CENTE--R 20126:12 CLOSED PPo<sPOe<rosaFed
{(Immnppoorrttaanntt=- IIff rreeppoorrtt 1tss ppurmntte,.d,doonnbbootthh ssklieess ooflppaappeer,r, sseennddttwwoo ccoop#)
e
| E-- nvir-- onmen-- tal -- Labor-- atory--(EEW-- PC) -- - 21-- -20-0-- 5 SE0P5135441983 Environmental Laboratory (EE&PC) - 21-2W-05
be..
fats.
SEP 1 1983
D~T. Num~
0535
Commercial Chemicals Division 70012600. Commercial Chemicals Division
Report Title
epor! Number
Environmental Aspects of pose t + _ Environmental Aspects of POSF ro
%.L. Rohon = Environmental Labortory - 21-26-05 Sept. 1, 1983 R. L. Bohon - Environmental Labortory - 21-2W-05
Period Covered or Date
Sept. 1,
Employ~ Num~t(s)
1983
8A, Re=iEnvniroe nmenrtal Laboratory = 21-24-05. ase E. A. Reiner - Environmental Laboratory - 21-2W-05
Notetlook Reference
47816
of Pages Including Cove~eet
None=SeeEnv. AssessI.ng. #82215 ~ 12 None - See Env. Assess, Inq, #82215
seoumrvh Dea i ance| "OR C ST y Sen SECURITY ~
~OIpCPonmRpeanpyorCf&onSfu=dmenmt aiorl]y
~ClosedRepor(-O~nSummary (Special Au t horization }
I
3MCHEMICAL REGISTRY
~CchaelRckubgoisxt~,lynFeowrcmhCeOmOic2aflos~meeproe~ptoalrl~needw.sUubsesClahnec,~,,.,-
uous KEYWORDS:
Lo predict the environmental properties of POSE I~_ ~I ,9~.......... a (Pu231685 "and evaluate its environmental Fisk. | Olher Keywords
~URRENT OBJECTIVE:
T~hhee oobbjjeeccttiivvee ooff tthhiiss rreeppoorrtt ((wwrriitttteenn iinn OJuul~yy,, 11998822))
~o pced~c~ the environmental properties of POSE
(FH-3168) and evaluate its environmental risk.
~waass
feL.o
EE TE Sr ET E, eon Ta or GW REPORT ABTRACT: This abs[roc! information is disltibu(e~ by the Technical Commun=calions Center to ale= I 3M'ets ~o
Company R&D. It is Company confide~l=al
705 (pertluorooctane sulfonyl fluoride) is not a POS (perfluorooctane sulfonyl fluoride) is not a Sion fcant environmental hazard becavse very little of significant environmental hazard because very little of Eh" 205F manufactured reaches the environment. the POSF manufactured reaches the environment.
Looms Lana
ee lEinvtiarvoantmeern,t. 1/4OF isthilso,st 1/t2o 1tshediatsmcohsaprhgeerde,witahnd 1/4 is -ee andtil ea, Some of the material which undergo Leis
a Cvontually land applied ith this sludge A -Ce {eoeee] aCtErlpeaaeettrmieaTntci.haza0raiinyfrtahotenewaatofsmtoesRpOhSteYrreea5.5tmeenxNtpoecdbtuiecodidnegginraadewaratasittoienowntaenardndvery Lo
AA rreevviieeww ooff tthhee mmaannuuffaaccttuurree aanndd pprroocceessssiinngg ooff PPCCSSFF sshhoowwss tthhaatt lleessss tthhaann 22%% oOff tthhaatt ssyynntthheessiizzeedd rreeaacchheess tthhee
environment. Of this, 1/2 is discharged with
wastewater, 1/4 is lost to the atmosphere, and i/4 is
lttarrneedaafttimmleenlntetd.ccoouullSddomebbe-eaofdadsstoohrerbbeemddabtebyryiawwlaassttweehictthrreeaauttnmmdeeennrttgo sslluuddggee
and eventually
ffrraaccttiioonn ooff tthhee
lassneedwweerraeepddpliPPeOOdSSFF
wiiitss h
aalltsshoois
llsiilkkueedllgyye.ttoo
Abbee
volatilized from waste treatment during aeration and
dispersed in the atmosphere. No biodegradation and very
little hydrolysis of POSF is expected in wastewater
treatment.
----
REAM
hr Pua? pacity Accteng
2{ko 28 Tonle Lo5P
(ost fo saver
Fooew proce
6 fetes
_
I3MMCCOONFNIFDIDEENNTTIIAALL
Des cotta.
Joh haul
Exhibit 1292
11229922..00000011
3MMA0AD00119933773388
-_-_-----.
A
EENNVVIIRROONNMMEENNTTAALL
ASPECTS
ASPECTS
OF
OF
POSE
POSF
Zear
I. sSuUmMmMeArRyY
pPoOsSFF
((ppeerrfflluuoorroooocsttaannee
sulfonyl
sulfonyl
fluoride)
1uoride)
is
is
not
not
a
a
ssiiggnniiffiiccaanntt
eennvviirroonnmmeennttaall
hazard
hazard
because
because
very
very
little
little
of
of
the OSP manufactured reaches the environment.
the POSF manufactured reaches the environment.
PPOoSsFE
iiss
nnoott
aa
pprroodduucctt..
IItt
is
is
an
an
intermediate
intermediate
used
used
in
in
the
the
manufacture of other fluorochemicals. POSE is made from
manufacture
05F (octane
of other
sulfonyl
fflluuoorriodceh)emiicnalesl.ectPrOoScFhemisicmaalde
from
OfSlFuor(ioncattaene ceslullsf.onylTheflucoerlildep)rodiuncteslecatrerocphuermiifciaeld by
fluorinate cells.
distillation and
theThediscetlilllpartoeduicstsreaarcetedpurtiofifeodrm
bya
dvviaasrrtiiieelttlyyatooiffonffllauunoodrrooccthhheeemmiidcciaaslltiliilnnattteeerrmmeeidsdiiarateteaescsteaadnndd topprroofddouurccmttssa..
A A
rreevviieeww
ooff
tthhee
mmaannuuffaaccttuurree
and
and
processing
processing
of
of
POSE
POSF
shows
shows
tthhaatt
lleessss
tthhaann
22%8
ooff
that
that
synthesized
synthesized
reaches
reaches
the
the
eennvviirroonnmmeenntt..
OOff
tthhiiss,,
11//22
iiss
ddiisscchhaarrggeedd
with
with
Jwaasstteewwaatteerr,,
11//44
iiss
lloosstt
ttoo
tthhee
atmosphere,
atmosphere,
and
and
1/4
1/4
is
is
llaannddffiilllleedd..
SSoommee
ooff
tthhee
mmaatteerriiaall
which
which
undergo
undergo
ttrreeaattmmeenntt
ccoouulldd
bbee
aaddssoorrbbeedd
bbyy
wwaassttee
treatment
treatment
sludge
sludge
aanndd
eevveennttuuaallllyy
llaanndd
applied
applied
with
with
this
this
sludge.
sludge.
A
A
ffrraaccttiioonn
ooff
tthhee
sseevweerreedd
PPOOSSEF
is
is
also
also
likely
likely
to
to
be
be
vvoollaattiilliizzeedd
ffrroomm
wwaassttee
ttrreeaattmmeenntt
during
during
aeration
aeration
and
and
adt~osppeerrsseedd iinn tthhee aattmmoosspphheerree..
No biodegradation and very
No blodegradation and very
lLiittttllee
hhyyddrroollyyssiiss
ooff
PPOOSSFT
is
is
expected
expected
in
in
wastewater
wastewater
treatment.
treatment.
II.
EENNVVIIRROONNMMEENNTTAALL
ENTRY
ENTRY
II.
AA.. MMaannuuffaaccttuu~rIinn@g.
3M CONFIDENTiAl.
1'1229922..00000022
3MMAA000011993773399
:
A A
rreevviieeww
ooff
tthhee
mmaannuuffaaccttuurriinngg
process
process
indicates
indicates
the
the
PPO0SSFE
wwiillll
eenntteerr
tthhee
eennvviirroonnmmeenntt
by
by
3
3
routes:
routes:
1)
i)
adiiasppoossaall
ooff
cceellll
tars;
tars;
2)
2)
maintenance
maintenance
of
of
cell
cell
celleeccttrroolliittee
ccoommppoossiittiioonn;;
and
and
3)
3)
distillation
distillation
of
of
cell
cell
products. Table 1 shows the maximum estinated
pernovdiurcotnsm.entTaalblreele1 assheoswsof thPeOSmFaxfirmoumm measntuif,a~cattuedre
eansvsiumrionngmenatnalannruealleaspersodoufctiPoOnSF1f,r0o0m0,m0a0n0uflabcstuorfe POSE
assuming an annual production 1,000,000 ibs of POSF
per year.
per year.
rable 1 - Environmental Release of POSF Prom Manufacture
Table 1 - Environmental Release of POSF From Manufacture
Process Causing Release
Process Causin@ Release
PPOOSSFE
RReelleeaassee
(1bs/ye)
(ibs/yr)
RReemmoovviinngg
ttaarrss
from
from
cells
cells
trc<ea45satm((tteoontww)aasstteewwaatteerraUcnpdreosEseSbhfaerrladEmd
treatment)
dong
Cell electrolite maintenance <<22000000 ((ttoo llaannddffiillll))
Cell electrolite maintenance
CCeellll
pprroodduucctt
aistillation
distillation
<<990000
((ttoo
landfill)
landfill)
7500 (to wastewater
<7500 (to wastewater
treatment)
treatment)
<<22550000 ((ttoo aattmmoosspphheerree))
TToottaall rreelleeaassee
+% rreelleeaassee
< 13,000
a.
24- wu.
pr o5l2H0(a8
i1..
Disposal of Cell mars
Disposal of Cell Tars
MHiijshh
mmoolleeccuullaarr
vweeiigghhtt
tarry
tarry
materials
materials
that
that
accumulate in the electrochemical fluorination
accceelcllulsmsulaaarrteeewwaaissnhheetddhe fferrloomemctttrhhoeechcceeemllillcssalbbyyfhlhiuiggohhrinpparrteeissossnuurree
wwaatteerr
ssttrreeaammss
aanndd
sewered.
sewered.
Additional tars are
Additional tars are
sseevweerreedd
aafftteerr
rreemmoovvaall
by
by
bubbling
bubbling
steam
steam
through
through
tthhee
cceellllss
iinn
vwaatteerr
ffiilllleedd
boil-vats.
boil-vats.
Finally,
Finally,
3M CONFiDEHTIAL
11229922..00000033
MA00199740
3MA00193740
<
32
TL
ttaarrss wwhhiicchh ffaallll ooffff tthhee cceellllss iinn tthhee hhoouussiinngg
. nits (co11 totes) are severed, oF landilled units (cell .bodies) are sewered, or landfilled
when Laxge volumes axe present. when large volumes are present.
.
Cleaning of the cells is done spprosinately once Celveearnyin6gwoefekst,heancdellasppriosxdionnaetelayppr1o0x0i-m20a0telLybsonocfe
,
etvaesryav6eweSeikssp,oseadndatapeparcohximcalteealniyng1.00-T20a0zoIbasveof
ctsartsinaatreesditsopocsoendtaiatn e1a-c2h1 cFloesaPn.ingB.asedTarosn ahries
cessttiimsaatteed <5toIcbsontoafinF051F-2%entPOeSrF.theBaesnevdixoonnmethnits
eCshtriomuastteth<5isIbrsouotfe PeOvSeFryen6tewreskthse (e4n5virIoonsm/yeensts)
atnharoutghhe mtahijsorirotuyteofevtehriys v6ouwledeks0 {<t4o5vaIbsst/eyveaatre)r~
wreatnent. and the majority of this would go to wastewater
treatment.
2. Hofntenance of Cell Blectrolits composition
2. Maintenance of Cell Electrolite Composition
o
second manufacturing process routs of 103s
Aresseuclotnsd fmeaonnufmaacitnutreinnagnceproocfestsheroeulteectorfoliltoess
wrietsuhlitns thferomcelmlaai.ntenTaynpciecaolfly 2,the500 bs of electrolite
wciltehcitnroitiheteceilslsv.ihiTzyapuincalflryom2,t5h0e0cieblslsof3 tines
epsAleeperrpcrtwowreexoeeilkkmiattaaenenddlyiddsii6wss0itk8tiihliodlifreodaatwhnittsoofwrrroeeimccsoohvvtaeehzerrancHHFPe..lmlaster2iatlimes
|
(0) is rervenes Approximately 60% toof tthehiscewllist.hdraTwhne mraetmeirnidaelr
|
"(hHFi)ch isconrtetauirnneadpprtooxithmeatceellyls2.0 POThSe? isremainder
|
which contain approximately 2% POSF is
Jose to Tanafitied because of this cell llaannddffiilllleedd.. AApppprrooxxiimmaatteellyy 22,,000000 ilbbss ooff FFOOSSPF ppeerr
|
year is landfilled because of this cell
maintenance process.
3. biseitiaion of coll prosuets
3. Distillation of Cell Products
he tira rout of 205P anvirommantal entry in atThe tthheircdolirouptreodoufctsPOSdFisetnivlilraotnimoenntsatlep.entrFyOSFIsis aptuctihieedcelplripsraordiulcytsbydiastsiilnlgalteiopnlatsteep. POSF is psuiroieftiieidatiporni,marbiulsy sboymea insinEgrlaectpiloantaetly
distillation, but some is fractionally
3M CORFIDERTIAL
11229922..00000044
-- 3MA00193741
C-- e ----------------
-
oo
oo
-~
ddiissttiilllleedd.. MMaatteerriiaallss ddiissttiilllliinngg aatt hhiigghheerr oorr
-
lloowweerr tteemmppeerraattuurreess ccoonnttaaiinn ssoommee PPOOSSFF,, bbuutt tthhiiss
is consumed in the manufacture of other
is consumed in the manufacture of other
_
pprroodduuccttss..
=
TThhrreeee ppeerrcceenntt ooff tthhee cceellll pprroodduuccttss rreemmaaiinn aass
Ss
bboottttoommss aafftteerr ddiissttiillllaattiioonn.. TThheessee ccoonnssiisstt
mostly of very high boiling materials and have
mostly of very high boiling materials and have
lliitcttllee PPOOSSFE ((pprroobbaabbllyy <<33%8)).. AAssssuummiinngg tthhee
mmaannuuffaaccttuurree ooff 11,,000000,,000000 ilbbss ooff cceellll pprroodduuccttss,,
<<990000 i1bbsn ooff PPOOSSFE ppeerr yyeeaarr wwoouulldd bbee llaannddffiilllleedd
Wwiitthh tthheessee bboottttoomnss..
DDuurriinngg adiissttiillllaattiioonn 00..55--11%% ooff PPOOSSFE iiss lloosstt ttoo vvoollaattiilliizzaattiioonn.. BBaasseedd oonn eessttiimmaatteess tthhaatt tthhee ssccrruubbbbeerrss aarree 7755%% eeffffiicciieenntt,, 11220000--22550000 Ilbbss//yyeeaarr wWoouulldd bbee lloosstt ttoo tthhee aattmmoosspphheerree aanndd 33880000--77550000 1Ibbss//yyrr wwoouulldd bbee adiisscchhaarrggeedd wwiitthh ssccrruubbbbeerr wwaatteerr ttoo tthhee wwaasstteewwaatteerr ttrreeaattmmeenntt ssyysstteemm aass aa rreessuulltt ooff tthhee daiissttiillllaattiioonn pprroocceessss..
3. uUssaaggee
VVeerryy lliittttllee PPOOSSFF iiss wwaasstteedd aass aa rreessuulltt ooff iittss uussee iinn
tthhee ssyynntthheessiiss ooff ootthheerr fflluuoorroocchheemniiccaallss.. PPOOSSFE iiss tthhee
Rost expensive component in these synthesis
|
most expensive component in these synthesis
rreeaaccttiioonnss,, aanndd bbeeccaauussee ooff tthhiiss ccoosstt,, iitt iiss rreeaacctteedd
|
With excesses of other reactants. Also, tests are
with excesses of other reactants. Also, tests are
ffrreeqquueennttllyy mmaaddee ttoo mmaaxkee ssuurree tthhee PFOOSSFF iiss ccoommpplleetteellyy
consumed. It can be assumed that less than .5 of
consumed. It can be assumed that less than .5% of
PPOOSSFE i1sa lloosstt iinn uussaaggee..
33MM CCOONHFFIiDDEr'NflTTIIAALL
1'1229922..00000055
MA00199742
3MA00193742
ee
J
Pose is transported by pipeline within the plant.
POSF
hese
pis
ipterlainnsepsortaevde
bcyleapniepdelibnye pwuirtghiingn
tthheemplwaintth. Nz.
These
"hich
pfioprecleisnePsOSaFretoclreeatnuerdn
btyo
ptuhergitnagnkthoeFm rweiatchtorNs2,.
As a which refsourlcte,s PnOoSFPOtSoE riestunronrmatlolythelosttankfroorm within reactors.
As a
plant
result, no POSF
transportation.
is
Lniotrtmlaell(y<5l)ostPOSfEromis
wisthhiipnped
opflfantthetrapnlsapnotrtsaittieo.n. AlmLoistttleall(<5i%s) sPhOiSpFpedis isnhisptpeeedl
oafcfunstheinpeldantwitshiteb.lowA-lnmoolsdtedalplolyisethsyhliepnpee,d ainndstmeoeslt
drums lined
is sent vo
Mw'isth
Cbhleomwol-imtoeldepdlanpto.lyetDhuyeletnoe,itsandlomvost
Visiscsoesnittyt,o 3PMO'SsE Cchanemobleitneeaprllayntc.ompDlueeteltoy ritesmovleodw
viscosity, POSF
from the drums.
caTnhebePOnSeEarrleymaicnoimnpgletienlytheremdorvuemds
from
(app
the drums.
roximately
0.T28h)e
PiOsSFnorremmaalilnyindgestirnoytehde
dwriutmhs the
(approximately 0.2%) is norma!ly destroyed with the
=
ddrruummss iinn tthhee CChheemmoolliittee IInncciinneerraattoorr..
`
IIIIII.. EENNVVIIRROONNMMEENNTTAALL FFAATTEE
A. PPeerrssiisstteennccee
Under strongly basic conditions (pH >10) POSE will
Under
redct
sttorofnogrlmy tbhaesisculcfoonndiictiaocnisd
s(aplH t.>10)
POSF
will
react to form the sulfonic acid salt.
odor son mere sw
t Rf - S- F + KOH -----.-~ Rf SO3-K+ + HF
At neutral pi this reaction is very slow. For
Aetxamnpeluet,ralPOpSHE tchainsbereasctteiaomndiisstvielrlyedsloorw.storFeodr for
eexxatmepnldee,d PpOeSrFiodcsan ibne tsheteapmredsiesncteilloefdvoarterstowrietdhouftor
edxetteencdteadbleperdieogdrsadaitniotnh.e prNeesveenrcteheloefssw,atetrhewithout
podertfelcutoarbolseuldefgornaicdataicoind. anNdevietrsthsealletsss,viltlhebe the
_ peevrefnltuuosr)oshuyldfroonliycsisacipdroadnudctsitsofsaRlOtSFs,wialllthobeughthethe
3MM
CCOONNFFIIDDEENNTTIIAALl
eventual
,..c11c0
hofydrsoolsyrsimsayprbeoduwcetesks,ofmoPnOStFh,s, alotrhoeuvgehn
tyheears
halflife of DOSF may be weeks, months, or even years
11229922..00000066
amacoreares
3MA00193743
bbee lLoonnggeesstt uunnddeerr aacciiddiicc ccoonnddiittiioonnss.. Siosearadation is not expected to ose with ROSE. BLiaobdoergartaodraytitoenstiinsg no~thowesxpencotebdiodteoaozacdcautriownithof POiStFs. Lsaulbfoornaitcoryacitdeshtiyndgro:lbyoswes pnroodbuicotd.egraTdhaistiolnackofofits bsiuoldfeognricadaabciildithyydrioslypsreesdicptreodducsti.nceThaills lack of
biodegradability is predicted since all
1
ppeerrfflluuoorroocchheemmiiccaallss aarree rreessiisstteenntt ttoo bbiioo~deeggrraaddaattiioonn..
B. MMoobbiilliittyy
N%oo ddiirreecctt mmeeaassuurreemmeennttss ooff tthhee eennvviirroonnmmeennttaall mmoobbiilliittyy of POSE have been made. Tough estinates however can obfe mPaOdSeF hbaavseedboenenimtasdep.hysiRcoaulghcheesmtiicmaaltesprohpoewretviecrs can b(erambatdee 21b.ased on its physical chemical properties
(Table 2).
Table 2 - Physical Chemical Properties of 0ST
Table 2 - Physical Chemical Properties of POSF
: 2.5 an tg at 250 o
VVaappoorr pprreessssuurree
11..66 mmmm HHgg aatt 2200ocC
2.5 mm Hg at 25oc
rolecutar weight
soz
Molecular weight
502
soiiing
Boiling
rraannggee
1s4-ass0c
154-155oc
Specific aravity
Specific gravity
feat of vaporization
Heat of vaporization
Lox 1.838 20.3 eal/a
20.3 cal/g
Solubility fn water
Solubility in water
very lows
Very low*
"fo actual measurements of water solubility have
b*eNeoracstaudae.l meIatsuirsemkennotwsn otfo bweatevrerysollouvbilaindtyishave
beesetli,mamtaeded. toItbe isinkntohewnsatnoeb~ranvgeeryaslowtha~tndofisnect
eEsltuiomraotcehdentteoalbeliiqnuitdhse s(a1m-e10rapnpmg)e. as (tChaaltcuolfatiionnerst
fclounofriormcihnegmictahlislivqeuriydslow(i-sio0lupbpiml)i.ty a(rCealactutlaacthioends in
confirming this very low solubility are attached in
an appendix.)
aM CONFIDENTIAL
|----------"-"""
11229922..00000077
aurea 3MA00193744
:
I---------------- 7
TThheessee
pphhyyssiiccaall
cchheemmiiccaall
properties
propertie3
suggest
suggest
that
that
vJoollaattiilliizzeedd
PPOOSSFE
wwoouulldd
tteenndd
ttoo
stay
stay
in
in
the
the
aattmmoosspphheerree,,
aanndd
wwoouulldd
not
not
be
be
removed
removed
at
at
a
a
ssiiggnniiffiiccaanntt
rraattee
bbyy
rain
rain
or
or
depositio(n1.)
deposition.(1)
POSE
POSF
would also tend to move from water into sediments or
would also tend
tthhee aattmmoosspphheerree,,
taondmowvoeuldfrotmenwdatteorbeintiommsoebdiilemenitns
and would tend to be immobile in
or
ssooiill..
w. EEFrFeEeCcTTSs
No actual environmental effects data exists on POSE.
No actual
Bbaasseedd oonn
ttehhenevillriiommniimtteeenddtattlooxxeiifccfooellcootggsyy
ddaattaa
data
eaxnidstosuronexPpOeSrFi.ences
and our experiences
with other non-water soluble perfluorochenicals, no
with other non-water
ssiiggnniiffiiccaanntt ttooxxiicciittyy
stoolutbelrerepsetrrfilaulorpolcahnetmsicoarlsa,qunaotic
to terrestrial plants or aquatic
oorrggaanniissmmss iiss eexxppeecctteedd..
While the material could
While the material could
bbiiccecoonncceennttrraattee,,
tthhiiss
iiss
uunnlliikkeellyy
to
to
be
be
of
of
significance
significance
since so little POSE enters the environment.
since so little POSF enters the environment.
i
33MM CCOONHFFIIiD)EEHRTTItPA,LL
1122922..00000088
MA0199745
3MA00193745
eee
:
3
AAppppeennddiixx -- CCaallccuullaatteedd SSoolluubblliittyy ooff PPOOSSFF
TThhee
ffoolllloowwiinngg
sshhoowwss
hhooww
tthhee
solubility
solubility
of
of
POSE
POSF
(CgP17S0F)
(CsF17SOF)
ccaann
bbee
ccaallccuullaatteedd
ffrroomm
tthhee
measured
measured
solubility
solubility
of
of
CCsaFFI177S5O027NN((CCHH2aCCHH33))CCHH2CCHHZ2OOHH
((EEtthhyyll
FFOOSSEE
Alcohol).
Alcohol).
TThhee
ssttrruuccttuurree
aaccttiivviittyy
rreellaattiioonnsshhiippss
uusseedd
here,
here,
hovever,
however,
may
may
nnoott
bbee
vvaalliidd
ffoorr
uussee
wwiitthh
ppeerrfflluuoorroocchheenmiiccaall
like
llke
POSE.
POSF.
The
The
pprroobbaabbllee
rreeaassoonn
ffoorr
tthhiiss
iiss
that
that
perfluorochemicals
perfluorochemicals
are
are
both
both
hhyyddrroopphhoobbiicc aanndd oolleeoopphhoobbiicc..
An example of this problem is
An example of this problem is
wwoorekk
ddoonnee
wwiitthh
ttrrii--ppeerrfflluuoorroohheexxyyllaamniinnee
wwhhiicchh
revealed
revealed
a
a
5
5
oorrddeerr
ooff
mmaaggnniittuuddee
ddiissccrreeppaannccyy
between
between
the
the
measured
measured
ppaarrttiittiioonn
ccooeeffffiicciieenntt
((KKooyw))
aanndd
that
that
calculated
calculated
from
from
its
its
wwaatteerr
ssoolluubbiilliittyy
ooff
00..7766
ma/l.
mg/l.
Its calculated Koy was 1.25
Its calculated Kow was 1.25
x X
110066
wwhhiillee
iittss
measured
measured
Koy
KOW
was
was
1.1
I.I
x
x
101.
I0I.
TThhee
wwaatteerr
ssoolluubbiilliittyy
ooff
EEtthhyyll
FFOOSSEE
Alcohol
Alcohol
has
has
been
been
measured
measured
22
ttiimmeess
wwiitthh
tthhee
ffoolllloowwiinngg
results:
results:
0.05 mg/l and 0.16
0.05 mg/l and 0.16
mmgg//ll..
TThhee
aavveerraaggee
vvaalluuee
ooff
00..11
mmgg//ll
wwiillll
be
be
used
used
in
in
this
this
ccaallccuullaattiioonn..
TThhiiss
iiss
eeqquuiivvaalleenntt
ttoo
a
a
molar
molar
solubility
solubility
(S)
(S)
ooff 00..1188 uu mmoolleess//ll..
Using the regression equation of
Using the regression equation of
BBaanneerrjjeeee
eett
aall..((22))
aanndd
iittss
mmeellttiinngg
ppooiinntt
of
of
approximately
approximately
4455o0Cc,,
oonnse
ccaann
ccaallccuullaattee
tthhee
lloogg
ooccttaannooll
wwaatteerr
partition
partition
ccooeeffffiicciieenntt ((lloogg KKoowy)) ffoorr EEtthhyyll FFOOSSEE AAllccoohhooll..
l1o0g9 KKoouw == 66..55 -- 00..8899 lloogg S -= 00..001155 (Mx)
l1o0gg KKooww == 66..55 =- 00..8899 ((--..7744)) =- 00..001155 ((4455))
Jog Kow = 7.2
Mm CONFIDENTIAL
|
11229922..00000099
MA0019746
3MA00193746
-- ss
costticients, (3) one can calculate the log Koy for (POSP)
coefficients, (3) one can calculate the log Kow for (POSF)
from the 10g Koy of Ethyl FOSE Alcohol
from the log KOW of Ethyl FOSE Alcohol
- s05 = pose
R - SO2F = POSF
R --- SONA, SO2"~Ci(ACHCH2H2C2CCHHH2330N == BEtehhy)l FPOOSSEE AAllcccooohhhooo!ll
he fragnent constant for ~S02F (sone) When attached to Tahreomaftriacgsmenits c0o.3n0s.tantItsforfra-gSn0e2nFt (cfoSnO2sFt)antwhetno aanttaaclhiepdhattioc is
aromatics is 0.30. Its fragment constant to an aliphatic is
nnoott lliisstteedd ((33)) bbuutt aalliipphhaattiicc ffrraaggmmeenntt ccoonnssttaannttss ffoorr ffrraaggmneennttss wwiitthhoouutt ccaarrbboonn oorr hhyyddrrooggeenn aarree aallwvaayyss lloowweerr.. OOnn aann aavveerraaggee tthheeyy aarree lloowweerr bbyy ..8877.. TThhiiss ccaallccuullaattiioonn aassssuummeess that the aliphatic fragaent constant for-s0zF is 0.30-0.87 =
that the aliphatic fragment constant for-SO2F is 0.30-0.87 =
-"00..5577..
he xaqnent. constant for ~s0pn< Sz, 00 is calculated The fragment constant for -SO2N~/CCHH22_CCH~2-OH is calculated
frroomn tthhee ssuumm ooff iittss ffrraaggmmeenntt ccoonnssttaannttss I{ff)) aanndd bbiinnddiinngg aanndd bbrraanncchhiinngg afaccttoorrss ((FF)) aass ffoolllloowwss..
hThee ffaaccttoorr ffoorr SSOO2NN == hhaass oonnllyy bbeeeenn mmeeaassuurreedd ffoorr aarroommaattiiccss aacssons-2t2.a.00n99t.. foArAggaaaiilnniphttahhtiisiscsccaallasccuull(aa-tt2ii.oo0nn8 a-assss0uu.mm87ee)ss =tthhee~2.ff9rr6aaggmm=eennfttsopNe
constant for aliphatics as (-2.09 - 0.87) = -2.96 = fSO2N=
hThee bboonnddiinngg ffaaccttoorr FFBp iiss ccaallccuullaatteedd bbyy mmuullttiippllyyiinngg tthhee
nnuummbbeerr ooff bboonngdss,, nnoott ccoouunnttiinngg tthhoossee ffrroomm hhyyddrrooggeenn oorr wwiitthhiinn
fErraaggmneennttss,, mmiinnuuss 11 ((nn--i1 == 44)) ttiimneess tthhee bboorndd ffaaccttoorr.. HHeerree,,
aass ddeessccrriibbeedd iinn tthhee mmeetthhoodd,, aa bboonndd ffaaccttoorr ooff --00..2200 iiss uusseedd
ssiinnccee 33 hhyyddrroopphhoobbiicc cchhaaiinnss rraaddiiaattee ffrroomm aa tteettrraahheeddrraall aattoomm
((tthhae NN)y.. TThheerreeffoorree FFBp == 44((--00..2200)) == --..8800.. AAnnootthheerr ffaaccttoorr
ffoorr bbrraanncchhiinngg FFpB;r iiss ccaallccuullaatteedd bbyy mmuullttiippllyyiinngg tthhee nnuummbbeerr ooff
bbrraanncchheess ttiimneess --00..1133..
3M CORFFiDEETXTEIAL
3M ~f~.~~'~
The Erament constant for-S0;N(CHZCH3)CHICH;0H Ls thus
The fragment constant for-SO2N(CH2CH3)CH2CH2OH is thus
1~229922..0000~100
amco16a747
3MA00193747
:
|
70
fIfcCuHy3
++
33fcCH,2
+
+
EsopNe
fSO2N=
+ +
ff-oOnH
+ +
FFpB
++
FFBorr
=
=
0.89
0.89
+
+
33((00..6666))
--
22..9966
- =
11..6644
=-
..8800
--
..1133
-= 2-2..6666
The log Koy for POSE is then calculated as:
The log Kow for POSF is then calculated as:
!10ogg KKoowu == lloogg KKoowy ffoorr EEtthhyyll FFOOSSEE AAllccoohhooll --
fSO52N(0CH, 2CCHHN2))CC(HH2CCCHHo2H0OHH ++ f5S0O527F
L10ogg KKooww == 77..22 -= ((-<22..6666}) ++ ((<-00..5577))
l1o0g9 KKoouw == 99..2299
TThhee ssoolluubbiilliittyy ooff PPOOSSFF ccaann bbee ccaallccuullaatteedd bbyy uussiinngg tthhee rreeggrreessssiioonn eeqquuaattiioonn ooff BBaanneerrjjeeee eett aall.. ((22))
lloogg S == 77..33 -- 11..1122 lloogg KKooww =- 00..017 (MP)
SSiinnccee POOSSEF iiss aa lliiqquuiidd,, 2255o9cC iiss uusseedd iinnsstteeaadd ooff tthhee aaccttuuaall mmeellttiinngg ppooiinntt..
== 77..33 -= 11.1122 ({99..2299)) -- 00..002177 ((2255))
lloogg Ss == --33..55
SS == ..00000033 uu mmoolleess/[ll
SS == .1155 uugg//lL
TThhiiss iiss aann eexxttrreemmeellyy llooww wwaatteerr ssoolluubbiilliittyy..
Due
Due
to
to
the
the
llaacckk
ooff eexxppeerriieennccee iinn aappppllyyiinngg tthheessee mmeetthhooddss ttoo
ppeerrfflluuoorroocchheenmiiccaallss aanndd tthhee nnuummbbeerr ooff aassssuummppttiioonnss mmaaddee tthhee
rreelliiaabbiilliittyy ooff tthhiiss ccaallccuullaattiioonn iiss lloovw.. TThhee ccaallccuullaattiioonn,,
hhoowweevveerr,, ddooeess ccoonnffiirrmm tthhee llooww ssoolluubbiilliittyy ooff PPOOSSEF..
3M
11229922..00001111
aMAOD103748
3MA00193748
-- ee -- ee-- e ------
i"
RReErFeERReEnNCcEeSs
1.
CCcuuppiitttt,, LLaarrrryy TT..
Fate of Toxic and Hazardous Yaterials
Fate of Tozic and Hazardous Materials
iinn tthhee AAiirr EEnnvviirroonnmmeenntt..
EPA 600/3-80-084, Augast
EPA 600/3-80-084, August
((11998800)),,
NNTTIISS
PBBO-221948.
~PB80-221948.
2.
RReeff::
BBaanneerrjjeeee,,
SS..,,
YYaallkkoowwsskkyy,,
S.
S.
H.,
H.,
and
and
Valvani,
Valvani,
S.
S.
CC..|y
wWaatteerr
SSoolluubbiilliittyy
aanndd
Octanol-ater
0ctanol-Water
Partition
Partition
CCooeeffffiicciieennttss ooff OOrrggaanniiccss..
Limitations of the
Limitations of the
SSoolluubbiilliittyy--PPaarrttiittiioonn
CCooeeffffiicciieenntt
Correlation.
Correlation.
EEnnvviirroonnmmeennttaall
SScciieennccee
aanndd
TTeecchhnnoollooggyy
Vol.
Vol.
14(10)
14(10)
2.
p.
11222277--11222299 ((11998800))..
3. Hansch, C. and A. Leo, Substitutent Constants for
Hansch, C.
Correlation
and A.
Analy
Leo,
sis in
SuCbhsetmiitsuttreyntanCdonBsitolaongtys,
foJro
h
n
WCiolrreeylatiSoonns,Ana1l9y7s9i.s in Chemistry and Biology, John
Wiley & Sons, 1979.
3M CONFIDENaTIAL
1122922..00001122
MA0019749
3MA00193749