Document 6BKwKwQmmwDrQL661XwLj12M4

ARa%6-- 1281 Telomer Research Program AScnontutaMlabReuproyr,tPoIf Activities for TRP Grant to University of Toronto; Projectyears: 1 September, 2001 to 1 September, 2002. Students/PostDocs currently active on the FTOH project: GPorsatddosctsu:denDtr.s:DaNvaiodmEillSist,ocDkr,. EJlolna Martin, Ye, Dr. Stella Melo, Undergrad Studens: Kerry Pratt, Fiona Lau, Ryan Sullivan, and Lisa Deelecbeck. Note: TRPfunds support the research of Dr. David Ellis while other funds support the rest of the team. SAicbaldeyem(iUcofCGou-eIlnpvhe)s,tiKgiatmorSst:roDnegr(eTkorMountior-P(hNyWsRiIc)s),,KTeiitmhBSuorlroomwon(TaonrodntPoa;ul Chemistry; NMR Facility), Ying Lei (Toronto; Chemistry; ANALEST). Project Coordination: During the initial year of the project the UofT research rteesaemarhcohstperodgTreRsPs,viasiptrsioirnitFiaells,s2et0t0i1ng(Leixberrec,isHeo,kWei,ntBeurc,k,20K0ai2s(eKra)ifsoerraangdeneGreaalrhart) safomrpflaimnilgiaarniazaltyisoenswainthd oaulrataenaslpyrtiincgal20t0ec2h`nuipqduaetse'fomreFetTiOnHg waiirth Libre, Hoke, aanndd vBaucpko.urFpurretshseurrtehemreeaswuerreemaetnltesastth2atcotnrfaenrsepinrceedcadlulrsicnognctehirsnipenrgiaoidr.saAmpling enxupmlboererroefsveiasricths pirniteorrestotsSeapntd, a2n0a0l1ytailcsaolotceccuhrnirqeudebso.thin Toronto and Guelph to `SAtpartiulstoofNNSSEERRCC.toStpruartseugeicadMdaittciohnianlgfFuunnddss:forAouprroFpoTsOaHl wwaorsk.subTmhiitstperdoipnosmaildhNaotsifMiacbautiroyn oafs sPulcacnesdsMiunitrh,isSigbrlaeny,t cayncdleSwoillolmloiknelaysbCeo-iInnvNeosvteigmabteorrs.. aSppepceinfdiicx)O:bjBeacsteidvoens ftohreTOcRtPobfeurn2d6s2f0o0r1Yemeaert1in(gftrhoamtitnhcelruedseedatrhcehMaabgruereyment L(Tiotrroen(tAot)o,fMinuei)rh(eNsWpeRcYif)icanwdoSrikbtloeybe(cGueolpnh)tanadindHnoekxtep,aenBudcedkd,foanrdtKheaiTsRePr f(Duingdpeodnt) and Jpeoolrltnoiwoivnngof:ih1ir)saponrafolnajeytctemtidciesaetlfeomrnfemoticthnuaostadiionollynoe.gairAen1sa:ol2ny)tteihncraveleimrspeoetnchimofeidncstawraiellalmsdaoinnridetcitonlrcyiflnoucdgueastnohdenf3u)rther optimizing oursamplingandGC-basedanalysis techniguesoffluoro-telomeralcohols 2 = 2 S92 58 2zg= n2 om = 4 primarily in airsamplesanddeveloping thebasicmethods utilizinglosis to determine ourhypothesizeddegradationproducts whichare the telomer-acids. Environmentalmonitoring willcompriseairsamplingat Toronto in an ongoing campaign andan intensiveairsamplingatselectedlocationsacross NorthAmerica. Initialsamplesfr telomerdegradationproducts willalsobe runfocusing on atmospheric particlesandmunicipaloutfalls. Ourmain objectiviens theenvironmentalfateareaare to determine degradationpathwaysand kinetic ratesforatmosphericpathoaysand furtherrefineourphysicalproperty measurements. Good progress has been made in eachof these areas and is reported below. A large air sampling study (FAMAS) conducted last November and an arctic sampling expedition this July, smog chamber experiments, initial experiments investigating biodegradation pathways, and further experiments focusing on physical property measurements of FTOHS and polyfluorinated alkyl chains, have taken up the bulk of effort during our inaugural year ofTRP funding. Environmental Monitoring 1. Fluorinated Telomer Alcohols in the North American Atmosphere (Stock, Martin, Lau) The presence of fluorinated telomer alcohols and other fluorinated compounds in the North American atmosphere was investigated using high-volume air samplers. In November 2001, samples were collected in six cities throughout North America, which were chosen as remote locations or for nearby presence of industrial sources (Winnipeg MB, Long Point ON, Reno NV, Cleves OH, Toronto ON, and Griffin GA). This study was given the acronym "FAMAS" for fluoroalcohol monitoriinng air samples. Both gaseous and particulate-bound fluoroorganics were collected on media consisting of XAD-2, polyurethane foam and quartz fiber filters. All samples were approximately 1000 m'. Due to the potential for contamination all sample preparations and subsequent extractions `were conducted in Class 100 clean room conditions. Briefly, these samples were extracted in large custom, glass columns by soaking in methanol and five aliquots of ethyl acetate. The aliquots were combined and an internal standard was added. The samples were rotovapped to ~ 5 mi, filtered using a nylon 0.2 Jim filter and subsequently reduced to ~200 iL. under pure nitrogen. Blank extraction samples were also run. Samples were separated using gas chromatography (either 30 or 60 m DB-35 column with 5 micron film) and detected using chemical ionization mass spectrometry (GC/CI-MS) (quadrupole instrument). Several fluorinated compounds -including fluorotelomer alcohols and perfluoro-sulfonamides - were detected at pgm concentrations in all locations (Table 1). Low concentrations of fluoroorganics were consistently detected in field blanks; however,this did not prevent confirmation or quantification of environmental concentrations. As the sample extraction 3 method lacked an adequate clean-up step, chromatography difficulties were unavoidable. This proved especially true forthe 10:2 FTOH where adequate chromatography was not achieved and thus no quantitative data are reported. Currently, a clean-up step is under development and samples will be cleaned-up and re-analyzed. In addition, the samples wil also be analyzed via gas chromatography coupled with tandem mass spectrometry (GC/ MS/MS) (iontrap instrumentation). We believe this will providae more robust analytical technique with the added value of MS/MS spectra for enhanced identification. Table1. Concentration of fluorotelomer alcohols (FTOHs) and perfluorooctane. Sulfonamidoethanols (FOSEs) in North American air samples. LOCATION | 6:(2gF/TmOH| 8:2FmT)OH ue 'NMepFhOeSE Giffn.GA |-- |1o7%71| 40:7 |3712309| [ofan ON]tei |pet [ead ld] 51:9 [Toronto,ON |62428|25:22| 38x46 | 3ix4 | chromatography difficulties 2. Fluorinated Telomer Alcohols in the Lake Ontario Ecosystem (Stock) In June 2002, Naomi Stock (PD student) participated in a 5-day research cruise, aboard the CGCS Limnos, of Lake Ontario. At eachofthree stations, water, sediment, zooplankion and phytoplankton samples were collected. Air samples, using high volume air samplers and polyurethane foar/XAD-2 sampling media (as previously described), were also collected for the durationof the cruise. Currently, methods are being developteod analyze these samples for a suite of fluorinated compounds including the fluorinated telomer alcohols and possible degradation products. Briefly, ar samples will be extracted and analyzed via gas chromatography coupled with mass spectromery as previously described. Water samples wil be concentrated onto XAD-7, extracted using a `method similartothat employed for air samples and analyzed via liquid chromatography coupled with tandem mass spectrometry. Sediment and biota samples will be extracted using an ion-pairing agent and also analyzed via liquid chromatography coupled with tandem mass spectrometry. 3. FTOUHssinignatddhietiAorncatlifcu?nd(iMnagrtprionv,iSdtedocbky)the Norther Contaminants Progam (NCP), Drs. Martin and Mabury traveled to Kuuijuarapik (Quebec) between the datesof July 11 and 17%, 2002, for collectionofmultiple environmental samples. Kuujjuarapik is located at the mouthofthe Great Whale iver on the eastern shoreofHudson Bay, just north of James Bay. This location is subarctic, and was chosenprimarilybecause it is an H ithneteCramneadidaitaendAirscttaincc.e TbhetewUeneinvetrhseihtiygohfpLoapvuallatailosno dheanssiatryeosfeatrhcehGcreenatterLaatkethsisrelgoicoantiaonnd (Centre D"Etudes Nordiques) which provided us with boats and other necessary sampling equipment To test the hypothesis that elomer alcohols (and 3M sulfonamidoethanols) can be transported to remote regions, an air sampler was installed in Kuuijuarapik to collect air ssaammpplleess,baylotnheg swiatmheamfeitehldodblaasnkM,abruttintheetasl.ampTleordiastsetiwlleinhsatvaellceodlalencdtewdeohnolypetwtootake. continuous samples if anytelomer alcohols are detected in the existing samples that have Yet to be extracted and analyzed. Its expected that air sample data will complement the Smog chamber work, allowing for abetter understandingof the long-range transport potential for telomer alcohols. `Water and biota samples were also collected for the purposes of our NCP project (Table 2) ic. analysisofperfluorinated acids) but will also be analyzed for fluorinated neexuttrraacltsio(ninacnldudainnaglytseilsoomfetrisasluceosh.olsW)atwehrensaamppplreospr(i4a0teL)mewtehroedcsolhlaevcetebdeeinn HduedvesloonpeBdayfor and in the Great Whale River by pumping water through XAD columns in the fild. Sampled biota included phytoplankton, zooplankton, and fish. Evenifairsamples reveal 10 traces of fluorinated neutrals (i. due to detection limits), biota may reveal traces because ofthe predictably high bioaccumulation potential for the longer chained telomer alcohols. "Table 2. Biotic and abiotic samples collected in Kuujjuacapik, Quebec. [Sample Thetis [Status 7] Fish Livers Pike (I), Whitefish (2), | Frozen Suckers (3), seulpin 2), Trout (1 [HuFrdesshonWaBtaeyrPZhoyotpolpalnakntkotnon|| 530l0ogcartaiomnss Mixed | ffrroozeenn | Copepods, chironomids, cladocera, diptera, rotifera, calanoida. Physical Properties 4. Vapour PressurebytheGCmethod (Le). The GC retention time method by Bidleman (1981) was chosen, because it allows the relatively rapid determination S of the temperature dependent vapor pressure of a large number of compounds. Small quantities of the substances are sufficient, and avery high purity is not required. Based on a comprehensive review Delle Site (1997) concluded that this `method "can be recommendedas one of the most suitable [methods] for the determination of the vapor pressure of low volatility compounds." Another recent study concluded that capillary GC is capable of providing vapor pressure data for non-polar and slightlypolar compounds with relative errors that "are either comparable with or lower than those resulting from more cumbersome direct experimental techniques" (Svoboda and Koutek, 2002). The method's success and reliability however is dependent on the availability of high quality vapor pressure data for some related compounds to serveas standard reference and calibration compounds. Isothermal gas chromatographic retention times at six temperatures within the range 30 to 80 C were determined. Super-cooled liquid vapor pressures Py. were obtained from these retention times following the procedure described by Bidleman (1981) and Hinckley et al. (1990). Specifically, for each analyte a vapor pressure Poc at 25 C was calculated using: In (PeciPa) = (AuseH / Aussi) - In (PuuiPa) + C 4) where Pu and AvssHe refer to the well-established liquid phase vapor pressure at25 C and the enthalpy of vaporization ofa standard reference compound. The enthalpies of vaporization are assumed to be constant over the temperature range from 25 C to the temperatures of the GC retention time measurements. The enthalpy ratio ratio AuseH / usHie and the constant C in eq (1) were obtained by linearly regressing the logarithm of the ratios of the measured isothermal GC retention times t/t at each temperature against the logarithm of the vapor pressure of the reference compound at that temperature using the relation (Bidleman, 1981), In (tare) = [1-(BvapH / SuasHed] In (PuioPa) - C @ Eq2 assumes that the infinite dilution activity coefficients in the stationary phase are the same for both the analyte and the reference compound (Hinckley etal., 1991). As thisis an approximation, Pccisnot always identical to the vapor pressure of the (super-cooled) liquid Pr, and acalibration of the method with closely related compounds is advisable (Bidleman, 1981, Hinckley et al, 1990). In the current study, hexachlorobenzene served as the standard reference compound. For the calibration we employed the following compounds with well established vapor pressure at 25 C: 12-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,23 richlorobenzene, 1,24-trichlorobenzene, 13,5trichlorobenzene, 1,2,34 tetrachlorobenzene,1,2,35-tetrachlorobenzene, 1,2.4,5tetrachlorobenzene, pentachlorobenzene, Pentafluorotoluene, Pentafluorophenol, 6 TCTFB, Octafluorophthalene, decafluorobiphenyl, a-HCH, v-HCH, 8-HCH, Aldrin, Heptachlor, Dieldrin, DDE, 0,/-DDT, z,DDT. `Table 3. Vapour pressure values for FTOHs obtained using the GC retention time `method. Log PGC PGC log PL PL PL PL 25C 42 FTOH 6:2 FTOH 8:2 FTOH 10:2 FTOH mean 2.401 2.161 1.662 1123 mean 252 1452 45.90 1327 mean 3.18 290 233 170 mean sudev RSD 15144 3214 24% 801.7 149.0 19% 12 34 16% 50 7 13% 5) Measurementof Vapor Pressure by Boiling Point Method (Deeleebeck, Ellis) The vapor pressure (Vp) of the liquids 4:2, 6:2, 8:2 and 10:2 telomer alcohols were `measured using the boiling point method. This method involved a 25 mL round bottom flask connected to a miniature thermometry adapter and condenser; 15 mL of the analyte was added to the round bottom flask. In the caseoffluorinated materials, they `were first de-gased by a procedure which involved cooling the mother liquotor -198C Table 4. Test Chemicals, Vp (Pa) [Compound [Exper[Liitermatuere[ndiftferaencle | [Cyclohexane [15720 +-3 13370) 6400 +-200 | 4910] 30%] [m-Xylene [2900 +2100 | 2250] 29%] (~li1q5uimdmNiyt)g.folFloolwleodwibnygwtahirsmtihnegptroesrsouoremotfemthpeersaytsutreemwwhialseraedvuacceuduamppwraosprmiaaitneltyaiannedd at atelmlpoewreadttuoreeqaunildibprraetes.suTrehereacnoarldyetde.wTahsistphrenocberdouurgehtwa(soirsepbeoaitleidngfoproidnetcraenadsitnhge values of p`pruemsps.ureT,owdheitcehrmwienreetahcehviaepvoerd pbryesrseumroevaitn2g5tdheegarierefsrcoemnttihgeraadpep,artahteunsawtiutrahlalovgac(Iunu) mof pressure in Pascal's was plotid against the temperature in Kelvin. The best lincar fit to the data points was used to extrapolate the boiling point of the chemical at 298 K, the vapor pressure at room temperature. `The method was first calibrated using cyclohexane, 72-xylene, and toluene and the vapor pressures measured were compared with typical literature values (n = 3, Table 4). The same method was then applied to the telomer alcohols, the results are presented in Table 5 (n=3). The telomer Vp's were compared with literature values for the corresponding hydrogenated versions, i.e. fluorine replaced with hydrogen. The increasein Vp associated with the incorporatioofn fluorine is seen clearly in Figure 1. The rate of decrease in Vp for the telomers as a function of increase in mass is much slower than would normallybe expected when compared with their hydrocarbon counterparts, resulting in the vapor pressure of the 8:2 being similar to that of octanol (Figure 2). "Table 5. Telomers, Vp (Pa) l[CzompounTd[Fuwn1 lRunw?a[lRunswwAverawgeo[staDo3v.)| lof z [gia ra aiselav laswm7a i 0] s20]) fT ez os taalc --tse8loao]]io] FEA em -- ys x 3FR 0 on IAFEf S si fomames | ( 4 | wii]47YodyFboggon I? I| B | | vserm| ' Figure 1. Change in vaporas a funocfttempieroamunre Figure 2. Change in Vapor Pressure a functionofmass. 6. Measurementofchain rigidity of perfluorinated fluorinated compounds by NMR (Pratt, Ellis, & Burrow) `dTehteerpmhiynseidca,ltporsopoemretiedse,grseuec,hbaystvhaepionrtepmreaslsmuoreleocrulKaour,goefomfeltuorryionfattehdemmoolleeccuullees.will be oIfnttehrasceticoonuopflitnheg cfolnuosrtiannetsniusclseifurnecsutlitoninof''tFhNe tMorRsiconoaulplainngglecobnesttawnetes.n aTdjhaecemnatgnCituFde moieties. The amountofenergyrequiredto allow fre rotation between two adjacent C F units is proportional to the "stiffness"of the alkyl chain, which in tum is relatedto the Vpofthe molecule. 1D "NMR is inadequate in the determination of long range coupling. ceosnosltvaentd ienxppeerrfilmueonrtoatlhkatylfacchialiintastedsutehetosespmeecatrsaulroevmeernlatps. foWr ewhhiacvheadneveexlaomppelde ai2sDhoJ-wn for perfluorobutanoic acid in Figures 3a & b. A) A| CFg ni i1 CF NA\ CFy nIA I 1 J / \ J TNT U UT LV JV[T AVAVAVI TAYY T _/RE \_ Tose wa ames ress som HR B) CF, ALA l WU | I| CF, ilHlI FYAMTRY AiIl CF, Aalliela FV Figure 3. AB)) 21DD. reFsoNlMvRedfNorMpRerfnlouowrosbhuotwainnoigccaocuipdliwnigthcosnpsetcatnratls ofvoerrallap and. fluorine atoms. "This method allowed for the assignment ofall fluorine coupling constants and furthermore indicted that at room temperature perfluorobutanoic and longer chain acids `have a rigid back bone str the CFs ~ CF; bond. This ucture between the molecular rigidity CF; units, facilitates with free rotation allowed around interpretationofthe underlying. omreiagsiunrsoemfentthse,high Vp of polyfluorinated materials seen our vapour pressure: using vaTrhiaebelnettheamlppeyraotfufrreeeNrMoRta.tioAnocfotmhpearciasrobnonbbeatwcekebnontehoefetffheectacoifdcwhaaisnelsetnagbtlhisahnedd ptheenadmeonunttloofteonefrtghye r1e1quNirMeRd foforrfhreee rCoFtatgironouwpasanmdadweo. iFdiegnutircea4l CsFhowgsroautpesmpfeorratthuere. SpeCr6f0luCorwoh-iolcetaitnoisic anCd f-obuttahneooicctaacniodisc. aTcihde. cTohailsesicnedniccaetpeositnhtatfoarpbeurtfalnuooircocahcaiidnis seen d`libesentgcotrothmeedis.ncerneTearhsgeeest.riecsaullltys amosrset riingeidxpalsaainfiunngcttiheonmoifnicmhaailnclheannggteh ianndvaipsotrhupsrelsessusreea3ssilcyhain Temperature () Perfluorobutanoic Acid ; Tonswanescer CF CF, CF, - -- -- | To -- ~ ' Perfluorooctanoic Acid Figure 4. Temperature dependent 19F NMR for perfluorobutanoic and octanoic acids 7I.n cGollolbabaolraWtaiornmwiintgh PProotfe.ntKiiamlsSotfroFnlguo(rDienpaatretdmeTnetloofmPheyrsAilccso,hoUnlisv(eSrtsiotcyko&f TMoerloon)to), Drre.seSatreclhlagrMoeulpoi(sPionsttdhoecptroorcaelsFseolflomwe)asaunrdiDnagvtihde Babasrocrlpatyi(ounncdreorsgsrasedcutaitoenssotufdetnth)e, o4:u2,r6:2, 8:2.and 10:2 atmospheric FTOHs. window atThaersaengcreoosfstseemcpteiroantmueraessuarnedmepnretsssuarrees.obtOanicneedtihne the infrared absorption cross speocltyifolnuomreianastuerdemmaetnetisraalrse, caonmdplulettiemwateelcyacnalccaullcautleatae gtlhoebarladwiaatrimvie nfgorpcoitnegntfioarl tohfiseach fuorinated telomer alcohol once we have the accurate lifetime data from our smog cthheaymbmearyshtauvdieesex(tsreeembeellyowh)i.ghIrtasdinatoitveexfpoercctiendg tvhaaltuetshedFueTOtoHtShewillalrgheavneumhbigehroGfWCP-Fbut bonds (c.g. 21 in 10:2 FTOH), 10 Analytical Methodologies 8) Synthesis of isotopically labeled internal standards (Ells & Sullivan) "cTohnedusycnttehdesainsdofwialnl biesoctoonpivcearltleydltaobetlheed6:62:2 aallcdoehohlyd(eM(+M3)+a2ccmoorldeicnuglatrheiosnc)hheamseboeuetnlined in Figure 5 for use as internal standards in the analysisof these and related chemicals. CryCE +c==tcnococ cry(, cr --cmAcE HIO-- CO)CwH, pe crycr62aeAlmcohoclonon <2 Cr,(cry,Ci,"CHO (62 Aldehyde) Figure 5. Synthesis of labeled 6:2 aldehyde and alcohols. 9) Mass Spectroscopic Studies of Telomer Alcohols and Products (Ellis) A systematic mass spectrometry study of the telomer alcohols along with their oxidized pporsoidtuicvtes,chseatmuircaatledioannidzactr,ioBn-u(nNsCaItuarnadtePdC)f.luoTrohaecicdos,mpwoausncdosndiunvcetsetdiguastiendganreegsathiovwenanind Table 6. "Tabl6e. Chemical LD. and acronymns for the telomer based chemicals usedi the MS. sTteuldoym.er Alcohols Telomer Acids Telomer aB-Unsaturated Acids CF(CF),CF,CH,CH,0H CFy(CF),CF,CH;C(O)OH CF3(CF3),CFCHC(0)OH nn=-24 (@622)) nn-=4 (@62284)) nn==86 8(210)2 nn=-68 (8(:12042)4 + Acronyms are given for each in parenthesis. nn-=42 (86220UAA)) nn-=86 ((120U2UAA)) 1] In the case of the fluoroalcohols, NCI resulted in the productionofmore elaborate spectra cthoamnpltehxeaottihoenr ocfltahssiess.spMecoireesovweirt,h titheshpaorweendt tmhoeleicntuelrees(tFiingguprreo6d)uction of HF," and the oil Tw"r| oonn i HE oo A| HIRE] i w foam UL rei BLAU iy Figure 6. NCI mass spectrum for the 6:2 alcohol showing the production of HF Alteration ofthe functional group attached to fluoroalkyl moiety had a large impact upon athned farlaogmoennttahteiomnagcnhaintnuedles,ofwhfiracghmweentrepriodednutciefdi.ed (see, for example, Figures 12a and b) a)LP NS amgtoJnial roms af =ot wilt ~or = ga Ingea le. GF b) _gmrerento7n1 _guneIntrs |w JiT. oe] wor gaca--a |o if |= . germsit Figure 7. ma)odHyepoantdh,esbi)zferdagfmreangtmaetnitoantipoanttpeartntefronrtfohret6h:2e6t:e2lotmeelroamceirdalcohol in NCI 1% other reAselatrhcohuegrsh,tihnetehxeacctassetorufchtyurderooffltuhoersoecairnbtoenrsme,dhiaatveesirnevqoukireedsafusritxhmereminbveersteidgabtiaocnk, bfolunodrioncgartbraonnsiptoirotniosntattoe bsueptpwoeretntthheesheqyudernotciaalrbloonsspoorftHioFnoifn tshimeilcahraisnysatnedmsth(eNapoli er. amlo)l.ecPurleavriocuhsaixn-raadyopctrsysatarlildoggerdapzhiigczsatgugdieeosmesutgrgyeswtitthhatthetheenpderhfylduroorco-arpboorntisoenogfmetnhteof tEhrekocch).ainItfohladsinaglsboabcekeonnshtoopwonf tthhaatttfhleuroeriisnaetveiddpeonrcteiofnor(tWhaencgleaanvdagOebeorf,thEerkCoFc; a~ndCHy bond within the molecule suggesting there is unusually high stabilityofthis bond which could be explained by a Ho---F bridging interaction. Such intramolecular interaction in the caseoftelomer alcohols in the liquid phase tishastupfpluoorrtiendatbiyonthine tshteudBiepsocsiotnidouncttoeda bCyHV;oOnHWgerronueprhaadndaWmraarckkemdeyefefre.ctTohnetyheshCoweNdMR cahsesimginceadltsohitfhtewhhyipleerhcaonvjiunggaltiitvlee eifnfteecrtacutpioonnotfhethce:lCoHne,paainreofffeelcetcwthriocnhsohfasthbeeefnluorine at tshhaotwceadrbtohna.t eIlnecltatreornsdteundsiietsyVaotnthWeeomxyegrenanids iWnrcarceaksmeedyaesroablsseorevemdpltohyreodug"h 0theNoMxRygaennd shielding effect. associated with Thisstrongly suggests thatthe terminal the fluorocarbon potionof the molecule. ethanolic group We believe i is is closely this association, and with it changes in electron density distributions, that lead to the favoured c`oCmFp.lCeHxa,tCiHo;nOsHoafndF"tahndusHFth;is mFoultehceurlmeorweo,ulthdisexahsisboictiadtiifofnerweoncuelsdinnoitt ophcycsuircainl tahnedcase of reactive properties relative(0 the Telomer alcohols. Detailed analysis and comparisonsof the mass spectral data obtained collectively ftrhoemrmaolldyannaalmyitcesphaylsliocwaeldpcreorptearitniecsonacnldusfiroonms tthoisbehydproatwhnesceosnccaenmibnegmtahdeeirtoward eannvditrhoenmreesnutlatlanftateef.feFcortheixsaimmpplaer,tsthuepuonniqthueepgheysoimcealiepsropaesrstoiceisatmeadywiltehadthteo cnoovmeploaunndds ithnattertehsetitneglcohmeemrisatlrcioehsolisn mtaheyahtamvoespahecrloiscegaasssopchiaastei.on,Foarneaxsasmopcilaet,iotnhetsheatreosnueltwsosuulgdgensott efxrpoemctthefiorr aulnciovheorlssa,l waistsohctiraotpioosnpwhietrhic chaanrdgeHdF;s'p.ecCioemspalnedx/aotripoonlawristphegcaisespahsaseevisdpeenciceesd esfufcehctasthesiurldpihsasteem,ionrateivoenn. wiAtthmonsopnh-ecrhiacrgleidfeptoilmeasr,mfoolreecxualmesplseucrheaacstiwoantreartvesapwoirt,hmay tcroomppolsepxhaetriiocnsc,leaalnlsoiwnignrgelaognegntesr-sruacnhgeastrhanysdprorotx.y radicals may also be effected by such It would appear from the fragmentation that occurs that the lowest energy pinatthhewapyrofdourctthieondeogfrsadaabtlieonpoolfytfhloeuraolmcoehtoalbso,lietietsh,erwbhiioctihcailnlytuomr ambiigothitcablelye,xwpoecutleddrteosublet edennvsiirtoynmdeisnttrailbluytipoenrsaisssteoncti.ateFdrwoimththseuscehruesnuilqtu,e isttcraunctburealpogsetoumleattredietshawtiltlheimelpeaccttron Pehxypseicctaeldpfrropoemrtliienscasrupcrhedaisctviaopnosrbparseesdsuurpeso,n(te.hge. mvoalpeocrulpersesssiuzreesanwdilflubncetgiroenaatlegrrtohuapns) 1) `which is indeed experimentally observed to be the case. The unique differences in molecules such as Ko and hence bioaccumulation. This postulation is supported by the recent observation that bioaccumulation potential increases ten fold for every additional CF, unit within the alkyl chain for perfluoroacids (Martin er al). Ss ean Erne Eo Fate Pathways "The telomer alcohols are proposed to degrade in the atmosphere following a mechanism outlined in Figure 8. , a. , LD5 \ SI e NN AXE F(RE3, woe TET pa rT ey pel JETT E|. PEE,SE#fS, --- - SP! irs ss" Figure 8. Proposed atmospheric degradationof Telomer alcohols, 6:2 alcohol is used as an illustrative example. 3 "aTlhcioshhoylpwotahsesiinstrwoadusceteds1t0edtuhseisnygsate1m0amlonargtiwfiictihalcyactlmoohsepxhearniec(asmreofgercehnacmebceorm.poTuhned)6:,2 bNlOacgkalsi,ghatnsdainsdopsraomppylieniatliitqeuo(tasn winedrieretcatkseonuarncde oafnaOlHy)z.edTahseasfyusntcetmiownaosfitrirmea.diaRteeadlutsiimneg rNeOac,tiaonnds.0S,acmopnlceesntwreartieocnoslwleecrteedmoinnirteoalretdimien boyrdSerPoMEelainmdinaantaelpyozsesdibulseinsgecGoCn/daMrSy.loss cSoanmdpelnessatwieornebaulbsboletrask,enanudsibnygpXaAssDinagngdasNas;amCpOlsesdetnhurdoeurgsh, DloNwPtHemSpPerEatcuarrterigdagsesphfaosre XfuArtDhercoaantaleydsifsi.erCsownthiincuhowuesraercfollloewctferdomantdheancahlaymzbeedrfowrapsarptaiscsueladtethfroorumgahtinoynl.onPoasntd chamber"Tahneatleylsoemsewrearlecochoonldduocetsednoutsiunngde"rFgoNMphRo,tolLyCsi/sMaSt/tMheSwaanvdelGeCn/gMtShs.oflight used caonnddiittidoonessunsoetd.unTdehreggoassipgnhiafsiecacnotnwdaelnlsarteaecotiboinasi,neodr wfirtohmNthOe,samnodgOcyhaunmdbeerrtahtelow NteMmRp.eratTuhreer(e-s7u8ltaCn)tbsypebcutrbab,liancgqutihreedaiovtehrroau2g4h-ahcoeutronpeerwiaodscalneaalrlyyzeidnddiicraetcetdlythuesing "F apsrseisgennecdeoafstfhleuo6ri:d2e.alcNoohoolthaerafnlsueocrdionnadtedfliunotreirnmaetdediastpeesciweesrethaotbsweervheadv,epotsenstiabtliyvedluye to NthMe Rlowexcpoenrciemnetnrta.tioGnCs/oMfSflaunoarliynsaitsedofinstaemrpmeldeisataecsqucioruepdlbeyd pwiatshsitnhgeslmoowgsecnhsaitmibveitryoaifr the othrtohuegvholaantiXliAtyoDfbtehdehparvoepotsheusd fianrtoenrlmeydiinadtiecsaittewdatsherperceosgenniczeedofthsitsamrtaiyngbmeatreersiuallt.ofDpuoeor dreanpupdienrgsetfhfaitciheanvcey. Lgarregaetrervcoalpuamceistoyffoarrsuhcahvemabteereinalpsa.ssTehdeisoewsempprle-ecsoaatreedcXurAreDntly being analyzed. c"Tyhcelophseexuadnoefiirsstshorodwenr ikninFeitgiucrsef9o.rthe reaction of the 6:2 telomer with OH relative to "oH Dograofd6t2Tiooomenr sol * i] I i sepcica oan racemes Figure 0. Relative ates of reaction fo cyclohexane with 6:2 telomer 1S cUyscilnoahgexraatneecroenssutlatnetdoifna7c.a4l9cuxl1a0te"dmroalteeccuolnestcamn't f5oratthe296:82Ktfeolrotmheerraelaccothioolnooff2O.8H+w0i.t1h bmuotlaencoulleisc8m.'24s2"0(.n8=42)x.10T"hemorlepeocrutleedclmit'ersa*tuwrehivcahluiefs oartehxepecOtHedignriteiaatteerdtdheagnratdhaetion of t`hmiesasrautreedisvgarleuaetefrorthtahne w6:o2ultdelboemeprreadliccotheodl udsuiengtothteheKewffoekctaonfdlAutokriinnastoinonm.etHhoowdevoefr, eprtehdaincotliiocn.subWsteitbueelnitevweitthhatthtehifsluiosrainraetseudlttoaifl osfetchoendmaorlye,ctuhlreo,uahghypsoptahceesiinstetrhaacttiiosnof the lsiutpeproatrutreeddbeyalMinSg wdiattha soibmtialianredco(mdeptoauilnsdosf.wThhicehpraroedupcrtespeenrtfelduoirnoahbeoxvaen)oiacnadcifdrowmasthe rpeolsaittiivveeltyo itdheensttiafriteidn(gnm-a3t)erbiyalL~C/itMdSo/esMSno(tFaipgupreear1(00) baendthies cmuarjroerntrloyutbeeifnogr dqeugarnatdiaftiieodn. FOvTeOraHlldwegerahdaavteiohnadprsoidguncitfsi.canFtordififnisctualntcieeswien'ivseoloantlinygoabinadiindeedntsipfoyriandgictheevbiudleknocfetfhoer the `inmiatyialinadledeedhyidndeivcaitaeGtCh/aMtShea`nudnzwieppdinog'obrsoeurtveeifsltuhoeriddoemiinnastoemefasteamppaltehsw.ayThfeosrethreesults oFfTprOoHdsuc(tssceaFnidgc8o)n.fiArmgionogdtdheeadleogfrafduartthieornwpoarthkwmauy.st be done obiaining a mass balance | ES t | ha Figure 10. LC/MS/MS indicating the productionofperfluorohexanoic Acid the forTmhaetipornoofppoesrefdliunotreorhmeexdiaantoeicaladnedhyldoengaenrdcahcaiidns (Section 5) that acids (Figure $) potentially lead to were synthesized by the methods outlined in Figure 8 for the use as standards for the identificationof these intermediates. le craymCsr5p0c9uycnon----2M0cp cr,cnycon crcrcaion MoO opcr, cD r--cntfon w-s579 i crcrcncon--D--es2sMEarEtin wm crycrcncn CFy(CF3U)CSH,SCHG, OH--CE HyCCCly CFyR(CEF,Ornb Figure 11. Synthesisoffluoro aldehyde and acid standards. is an imApufruirttyhecroinntnereesdtiwnigtohbisnertvheatmiaonnuifs athcattu1rHe,d1H6:2,e2lHo,r2sHrpe1rfolutoroobdseecryvleido 1dided,egwrhaidceh uncdehr thleosnegceornHdiotpioosnsp,hethrueslifnediicmaet.ing greatly reduced reactivity with OH and ultimately 11) Biodegradation of FTOHs (Ye & Dinglasan) denied to dae rom this mined cular = Ralsonia 5. nd andhobacte Range finding experiments have been initiated on the suite ofFTOHs with initial experiments focused on the fateof the 6:2 FTOH in a mixed cultureofmicrobes. Mixed enrichment aerobic degrading cultures were obtained from a 1, 2 DCA site in LA, U.S. `and subsequently maintained on either 1,2 DCA or ethanol. Two isolates have been "These experiments have clearly shown that the 6:2fluorotelomeralcohol is efficiently oxidized to the 6:2 telomer acid (see Fig 12) which then either hydrolyzes or further metabolizes to the 6:2 o,f acid. Low but clearly measurable quantitiesof the CpFeiorcnfudlsoueogdraoodanactiodepntPieFmixHzpxionAgnaearnneatloybwtsiiectrahlvpemdaettnohoobudsisldtfouomproeniniottnoherchraselearccvtoiimonnpgovteuhsnsdeelssv.oafnnWtoterciektsecturrmdreuedrniitanlgtyetishse P{oe.teo6a2dmaegephoyndteewxhpietihmnhatsspwoielml dsoysnebetseveidd.rbiTeolseecluraelwyidehttonm6i2nesthhiechreyadteion aaccihd,.alWpehaw-bieltathaocnidc,oamnpdaPrFHthXeAreilnatoirvdeeurstoeoabptbailnirsateosf ahned4p:2atthrwaoyugihnf[o0r:m2atFiTonOHonS and confirm whether the degradation pathway is similar across the varied chain length. 1 carton, RFRFRFCHiCHOH Fe FOF ECF RF 1 c'anumieF- 0 rf CH CH . Ceres =P% o oot n = 61rd F[EF om 2Hr Ir P.XEF en " ni F } RFRF dFgOAon crap fp OF FF[ F A ? others? Figure 12. Proposed biodegradation pathway of 6:2 FTOH with intermediates so far confirmed appears to by LC/MS/MS. follow the build We are unclear up slowly after specifically where PFHXA arises high concentrationsof the 6:2 a; but it B acid are formed. References Bidieman, T. . Estimation of Vapour Pressures for Nonpalar Organic Compounds by Capillary Gas Chromatography. Anal. Chem. 1984, 56, 2490-2496. DelleR1S9ei9vt7ei,,eA2w.6,oTf1h5Me7e-Vt1ah9po3odrs ParnedssDuirteaofatEnAvmibrioennmtenTteamlpleyraStigunrief.icJa.ntPhOyrsg.anCihcenCh.emRiecfa.lsD:atAa ErkSoaned Erkoc E. J, Mol. Sruc-Theochem. 2001; 49: 289 Hinckley, D. A; Bidleman, T. F; Foreman, W. T.; Tuschall, J. R. Determination of VCahpioormatPoregsrsauprhees RfeotrenNtoionnpoDlaatr. Ja.ndCheSme.miEpnogl,arDaOtraga1nic93C5o9,m2p30o2u-2n,3d1s, from Gas \3 Martin, J. W.; Muir, D. C. G.; Solomon, K. R; Moody, C. A; Ellis, D. A; Kwan, W.; Mabury, S. A. Anal. Chem. 2001, 74, 584-590. MartinD,isJ.t,ribuAt.ioMnaobfurPyer,fKl.uSo.rinSaotleodmAocni,dDs.iCn.GR.aiMnubior.w T2r0o0u2t (BiOonccoonrcheynntcrahtuisonmyaknidssTissue Environ. Tox. Chem. Accepted. MartinP,er1f,luSo.rAi.naMtaebduArcyi,dKs.Si.n RSaoilnobmoown,TrDo.uCt.G(.OnMcuoirr.hy2n0c0h2usDimeytkiasrsy.AEcncvuimruolna.tTiooxn.of Chem. Accepted. Napoli M, Krotz L, Conte L, Seraglia R, Traldi P. Rapid Commun. Mass Sp. 1993; 7: 1012. Svobovdaap,orVi.zatCi;onKforuotmekg,asB.chrDoetmeartmoignraatpihoynreotfenstaitounradtaetad. vCahpeomripcrkeessLuirsetsy 2a0n0d2,he9a6t,s1o0-f 18. Von Wemer K and WrackmeyeBr. J. Fluorine Chem. 1981; 19: 163. `Von Wemer K and Wrackmeyer B. J. Fluorine Chem. 1986; 31: 196. WangJ and Ober CK. Lig. Cryst. 1999; 26: 637 Presentations S.A.`MBaarbcuerloyn,a,"EEsnpvainrao,nmAeungtuaslt,an2d002A.nalIyntviictaeldSCpheeamkiesr,tyOrogfanFliuzoersinoafttehdeSsuersfsaicotnanotsn"."NDeIwOXPOIPNS2"0.02, Published Short Paper in "Xenobiotics". 5A. `MCahbemuircya,l"SFolcuieotryi,naMtiendneCahpeomliicsa,lMsNi,n tJhueneE,n2v0i0r2.onmIenvnitte~dRpeldaetffoirnmi.ng Persistence?" GLRM.American Martoifn,FlJuWo,rinMautierd,ODr.gCaGn,icSCtoonctka.mNi.n,aMnotosdiyn,ACt.mAo.s,Eplhlesr,icD.SAa.mpKlwesanb,yGW.CC/.,CIM/abMuIrSy",. SI.nAt.er"nDateitoencatlion `AssociationofGreat Lakes Research 45th Annual Conference, Winnipeg, May, 2002. Platform Presentation. A. 2M00a2b.urTyo,ro"nRteod,efOiNn.ingMaPye,rs2i0s0t2e.nceIn~viFtleudoKreiynnaotteed.Chemicals in the Environment". Environalysis S.A. `MCaalbiufroryn,ia"-FDlaivgihst.s MofayFa,n2c0y02~. FIlnuvoirtiendatSeedmiCnhaerm.icals in the Environment". University of S.A `MAambeurricya,n"CPheermfliucoarlinSaotceiedtSyu,rEfnacvtiarnotnsmienntEanlviCrhoenmmiesnttraylDSiavmispiloens. ~ApArniall,y2s0i0s2.byILnvCi/tMedS/PlMaStf.o"rm.2234 S.A 2M2aFbbur,y2,00"21,9SFhNanMgRri-iLnaAnHaoltyetli,cMalanCihleam,iPshtirlyip"p,inAessi.a-PIancviiftiecdCKoenyfenroetnecSepoenakAenralytical Science, 19- S.A. `MCahbemuirsyt,ry,"AUnnailvyetrisciatlyaonfdthEenvPihriolnimpeinntesa-lLCohseBmainsotsr,yFoefb,Fl2u0o02r.inIantveidtePdolSleumtiannatrs.", Department of S.A. oMfatbhuerPyh,il"iCpapribnoens-aDtieliRmaadni,caFleba,nd200t2h.e PIhnvoittoeFdaSteemiTnesatr.System. InstituteofChemistry, University SA.`MInasbtiutrutye,, U"nAivNereswitCyloafssthoef PPohlilluitpapnitne~s-FDliuloirmianna,teFdebC,o2m0p02o.unIndvsi"t,edNSaetmuirnaalr.Science Research S.A CMhaebmuirsyt,ry""FlSutoarnifnoartdedUnCivheresimtyi,ciNanotvl.hse30E,n2vi0r1o.nmIennvtit.edAnSaelmyitniacra.l and Environmental S.A. Mabury. "Toronto "What Makes a Lecture Series in Chemicaal Markham", POocltloutbaenrt'3,. 2I00n1a.uguIrnavlitsepdeaplkaetrfoirnmt.he "University of 20