Document Yj6dadmxmZB10OM1QQJk5y21N

AR226-2704 26 AR226-2704 TORONTO WORKSHOP MATERIALS September 13-14,2004 Fluorotelomer Alcohol and Fluorotelomer-Based Polymer (Blo)degradatlon Bob Buck DuPont Chemical Solutions Enterprise, Wilmington, DE ?` Fluorotelomer-based Polymers Do polymers "degrade" to form fluorotelomer species that can transform, partition, migrate? Polymers: Route(s) to the Environment Soil Disposal of articles treated with polymer (i.e. landfill) STP sludge amended to soil A Incinerator ^ ^ ----------------------------- Municipal Waste disposal of articles treated with polymer STP (POTW) Laundering & cleaning activities No transformation expected, short residence time Majority settles in sludge which is amended to soil, remainder as particles in aqueous outflow go to sediment Sediment Aqueous outflow from STP -75% of Polymer remains on the article at disposal 3 Polymer "Degradation" - Where to Investigate ? Abiotic Transformation : Hydrolysis, Photolysis Industrial Use : Product Dispersion Consumer Use : Cleaning, washing, sunlight (hv), etc. a Disposal: Incineration Biotic Transforamtion : Sludge, Soil, Sediment Disposal Down-the-drain => POTW * Municipal waste => landfill or incineration I Polymer Hydrolytic Stability : OECD 111 - DuPont Fluorotelomer-based Acrylate and Urethane Polymers studied Reactions in water are one of the most common means of non-biological degradation of substances in the environment. Aqueous stability tests at environmentally and biologically relevant pH's and temperatures. . pH 4, 7, 9 at 50C ; pH 1.2 at 37C Four replicates : Analysis at 0 and 5 Days Study Conclusion N o change , Polymers are hydrolytically stable Fluorotelomer-Based Acrylic Polymer _______ Tnrinpratinn - DuPont------------- Experimental Approach Typical municipal waste incineration condition >1000C, 2 seconds University of Dayton Research Institute, Advanced Thermal Reactor System Article treated with Polymer and Polymer itself Studied Study Complete Manuscripts in preparation, To be presented at SETAC N.A. Nov. 2004 Study Conclusion The polymer is destroyed under typical municipal waste incineration conditions Municipal incineration is not a source of perfluorocarboxylic acids Polymer Biodegradation Studies - DuPont Acrylate and Urethane Polymers Sludge Ready Biodegradation (OECD 301 B/D) Inherent Biodegradation (OECD 302 B) Work complete, Analysis and reports in-progress Preliminary evaluation indicates no evidence that polymer is degrading Screening Studies (commenced September 2004) Soil: Aerobic; Sediment: Anaerobic For method development Then, commence longer-term studies ----------1 | Themiracleso fscience^ 7 Fluorotelomer Alcohols F(C F2C F 2)nC H 2C H 2OH "Telom er B Alcohol" Themiraclesof science] Telom er B Alcohol : Physical-Chemical Properties Water solubility ~150 mg*L4 (ppb) Vapor Pressure 3 pa at 21C (measured) Hydrolysis hydrolytically stable pH 4, 7, 9 at 50C, pH 1.2 at 37C for five days Photolysis does not absorb visible light Highly Sorptive to soils, sediments, sludge The miracles o f science] 9 CATABOL Biodegradation Prediction C8F17CH2CH2OH The sum o f the % values = 100 The model predicts this w ill be the pathway & distribution o f transformation products Chemical Standards To achieve unequivocal analytical quantitative accuracy and precision Isotopically - Labeled Standards M+5 : C7F1513CF2CD2CD2OH (internal standard) . M+2 : C6F1313CF213COOH C8F 1713CH213COOH C7F 15CF=13CH13COOH "Cold" Standards . C8F17CH2COOH C7F15CF=CHCOOH . C5Fn COOH Others are being synthesized for transformation products observed 8-2 Telom er B Alcohol : C8F17CH2CH2OH Biodegradability Screening Ready : emulate a POTW Inherent : favorable, forcing conditions Qualitative Identification & Analysis Enable analytical method development Biodegradation Studies 14C Radiolabeled Study Material Quantitative Identify stable transformation product(s) Themiraclesofsciencer] 28-Day Ready Biodegradation Modified OECD 301D of C7F1514CF2CH2CH2OH Sponsored by the Telomer Research Program Asahi Glass, Clariant, Daikin, DuPont Manuscript submitted to Environmental Science & Technolo, pm I Themmiracleso f sclena Results - Day 28 biodegradation sample LC/ARC analysis of 14C-labeled transformation products Themiraclesof science] 14 Ready Biodegradation PotentiaI Biotransformation Route 8-2 Telomer B Alcohol 56% 9 f (c f ,)714c f 2c h 2c h 2o h ....- I 27% r 2% C7F1514CH2CH2COOH ajor Transformation New, Previously Unidentified Transformation Product F(CF2)714CF=CHC00H 6% j9 F(CF2)714COOH 2% ! ;9 *t Other fluorinated substances ? F(CF2)714CF2COOH No C9 Acid Observe (Does A/oi include unidentified minor transformation products) I 15 Accelerated Biodegradation 90 Days Acclimated Sludge Themiraclesof science'] F(CF2)714CF2CH2CH2OH DuPont unpublished results ie Time Course of Biotransformation C7F1s14CF2CH2CH2OH____________ ......... F(CF2)714C00H T To be identified F(CF2)714CH2CH2CH2OH F(CF2)714CF=CHCOOH F(CF2)714CF2CH2COOH TM Unidentified metabolites F(CF2)714CF2CH2CH2OH parent 17 Inherent Biodegradation Potential Biotransformation Route 8-2 Telomer B Alcohol F(CF2)714CF2CH2CH2OH i 9 F(CF2)714CF2CH2COOH .... Undefined Pathway Defined Pathway h - C7F1514CH2CH2COOH 1 F(CF2)714CF=CHCOOH .... "s9 I 9 " F(CF2)714COOH IA T F(CF2)5COOH ^ F(CF2)714CF2COOH Not Observed Themiraclesof science] i 19 I Other fluorinated substances ? unpublished results 8 Time Course of CF3(CF2)4COOH Formation Test Vessels (Sludge culture +1160 ppb [3,14C]-8-2 TBA) O-- Abiotic Control (Killed Sludge culture + 0.5 mM NaCN + 1160 ppb [3,14C]-8-2 TBA) unpublished results SDike Recovery (%) Day 0 113 Day 7 102 Day 14 158 Day28 134 Day 56 177 Day 90 111 Days after the initiation Presence o f additional hydrocarbon co-metabolites accelerate formation ? 19 Inherent Biodegradation - 90 Day Study __________________ C7F1514CF2CH2CH2OH________________ Many Additional 14C containing transformation products h structural identification in-progress UC 0 2 observed C5F11COO' is a transformation product C7F15COO- is not formed rapidly or in great amount nor is it the primary transformation product No "C9" C8F17COO' observed Results indicate a transformation route or route(s) where more than one -CF2- group is "degraded" ! unpublished results Presentation Outline Telomer Alcohol Degradation Abiotic Hydrolytic Stability Biotic Catabol Sludge : 3M, UT, TRP, DD studies (9, 6) S o il: DD S 0 2 to COOH Fluorotelomer-Based Polymer Degradation Abiotic Incineration, Hydrolysis Biotic Zahn-Wellens, Sturm Tests Release, Fate and Effects Compartments Release to Ai r Themiracleso f science