Document M403Rgae4rn8Lp5R6poeb2j

Biotransformation of the ^C-labeled Fluorotelo Telomer B Alcohol* Wang N.1. Szostek B2, Folsom P.W.1, Capka V.2, Sulecki L.1, Berti W.R.1, Gannon J.T.1, and Buck R.C.3 1 DuPont Cent Development, Wilmington, DE, USA; 2 DuPont Haskell Laboratory, USA; 3 DuPont Chemical Solutions Enterp AR226-3350 8-2 Telomer B Alcohol: CgF^CH^CH^OH (8-2 TBA; CAS# 678-39-7) Background Information A key raw material used in the manufacture of sales products. May be a transformation product offluorotelomer based sales products. Key Questions Is it biotransformable? Under what conditions ? What are the major transformation products ? What are the likely biotransformation pathways ? Physical Properties and Purity of the Test Substance "A Difficult to Test Substance" ' Low solubility | ~ 150 ugL-1 I Vapor pressure | 3Paat21c| Adsorption to | surfaces I A Chromatogram ofHPLC Characterization ofRadiocbemical Purity of the Test Substance CPM i Virtually 100% purity Time (min) EXPE Modified OECD 301D Experimental System of test substance soluti serum bottles crimp-se Concentration of the mineral medium. Additional organic ca solvent). Inoculum: Fresh sludg 5 mL sludge L-1 test so Experimental Duratio EXPERIMENTAL METHODS (Continued) Analytical methods: Sample extraction: Acetonitrile for ^C-labeled parent and transformation products; alkaline lysis for fluoride ion. Parent (F(CF;)gCH2CH,OH) was quantified by GC/MS and fluoride ion by ion selective electrode. LC/ARC (On-line liquid chromatography/accurate radioisotope counting) was used for separation and quantification of "C-labeled parent and transformation products. Identification of the transformation products was conducted by Q-TOF-MS methodSpike recovery of "C-labeled parent and cold standard fluorinated acids from the sample matrices was analy2ed by liquid scintillation counting and LC/MS/MS, respectively. RESULTS Spike recovery of FCCF^CF^CH^CH^OH and other standard fluorinated acids from the sample matrices Substance spiked (dosed) % Recovery* FCCF^'-'CFzCHiCHzOH FCCF^CF^CHaCOOF(CF:,),CF=CHCOOFtCF^COOFCCF^COO- 92 7 100 20 8121 10414 12011 *: Average value for days 0,7,14 and 28. t This research was partially funded by the Telomer Research Program (TRP), participating companies include Asahi Glass, Clariant GmbH, Daikin Industries and E.I. duPont de Nemours & Company. LC/ARC Analysis % sy^^g*" | Day 28 b ai-^ Peaks 1,2,3, & 4 are obser <w^ Wieeyw&SSS Day 28 (Abiotic control - 5 mL a Biotransformation of the ^C-labeled Fluorot 8-2 Telpmer B Alcohol (Continued) Identification of Transformation Products 1 \ ; , LC/ARC Peak 1-415 in/; Parcnii CF^CF^fOO- | LC/ARC Peak 2-459 m/z Parent: CF,(CF^"CF=CHCOO- <,>.,,==.,,^^^^,^^^>.<, ' ; LC/ARC Peak 3 - 443 m/z : ParenI: C,H;t.',3-"CF,CHiCOO- : (Proposed nioleenlar formula) LC;ARCPck4-479; Farcnl: CF,(CFi)("CF,CHiCOO- C.T.BMalIlBrtMn.aiB^'t Daughter ion spectra of ions obtained for a ( ay-28 sample 1 y Q-TOP-MS 7 Accurate Mass Measurement for Observed Transformation Products Determined mass "C-labcled j traMformation ; products : Elemental comBOBlBon ^ Calculated | : mass ; : ; Error Inppm 478.9803 CF,(CTA"CF,- : ItC 9 14C H2 02 T17 i 4785816 ; -2.6 CH,COO- ; : : : 458.9764 CT,(CV^"Cf- ; 12C 914C H 02 F16 1 458.9753 ; +2.3 1 CHCOO- 1 : ; | ; 414.9771 CF,iCF,),"COO- ; 12C 714C 02 l?l5 | 414.9691 ! +193 ': \ 443.0837 ! C,iy?,3"CF,- ': 12C 914C H402F15 ': 443.0004 ; +7.4 ; CH,COO- : ; : ', 8 Time Course P Days after the initiation Mass Balance of Transformation Products at Day 28 Transformation Products % Total Peak 1 - F(CF;i),"'COO2 - FCCFzVCF'CHCOO3 - C7H2F|3"CF2CH2COO4 - F(CF:;)7"CF2CH;,COO5 - F(CF3),CF;,CH;,CH;;OH (parent) FCCFzVCF^CHaCrL.OH (parent) adsorbed by the test vessel surface Sum 2.0 5.9 2.3 26.6 16.1 ~ 40 93* : Estimated. *: Other unidentified minor transformation products together accounted for < 10% of mass balance, with each ofthem accounted for< 1% of mass balance. y 10 Potential Biotransformation Routes (Not include the unidentified minor transformation products) proposed F(CF,),"CF,CH,CH,OH j. i C^FU'-CF^CH^COO- \ F(CF,)7"CF,CH,COO- proposed : ; ------------ F(CF,),CF=CHCOO- +V- +2F- F(CF,)7"COO- + F- 4 (Other fluorinated substances ?) 11 Four biotransfonnatlon produc CrHaFja'^FaCH^COO", and F transformation products did no these are the ultimate produc The observed transformation p radioactivity in the test solutio indicated that biotransformatio point of the parent (itself) or P through F(CP,)7''1COO"(PPOA PFOA formation will not occur Although PFOA is one of the at day 28. Biotransformation ofF(CF^71 (13 nig L-') as a co-solvent.