Document o90Yzw6qBNOe6KXX7VagdXDBE

AR226-2704 26 AR226-2704 TORONTO WORKSHOP MATERIALS September 13-14,2004 Fluorotelomer Alcohol and Fluorotelomer-Based Polym (Bio)degradation Bob Buck DuPont Chemical Solutions Enterprise Wilmington, DE Fluorotelomer-based Polyme Do polymers "degrade" to form fluorotelomer species that can transform, partition, migrate? Route(s) to the Soil Disposal of articles treated with polymer (i.e. landfill) STP sludge amended to soil Incinerator Municipal Waste disposal of articles treated with polym STP . 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 sedime Sediment Aqueous outflow from STP Polymer "Degradation" - Where to Inves Abiotic Transformation : Hydrolysis, Ph Industrial Use : Product Dispersion Consumer Use : Cleaning, washing, sunlight ( Disposal: Incineration Biotic Transforamtion : Sludge, Soil, Se Disposal Down-the-drain => POTW e Municipal waste => landfill or incineration Polymer Hydrolytic Stability : OECD 111 - e Fluorotelomer-based Acrylate and Urethane Polym studied 9 Reactions in water are one of the most common me non-biological degradation of substances in the environment. 9 Aqueous stability tests at environmentally and biolo relevant pH's and temperatures. pH 4, 7, 9 at 50C ; pH 1.2 at 37C 9 Four replicates : Analysis at 0 and 5 Days 9 Study No change , Polymers are hydrolytically stable Fluorotelomer-Based Acrylic Polymer Tnnnfimtinn - DuPnnt e Experimental Approach Typical municipal waste incineration condition >1000C, 2 seconds a University of Dayton Research Institute, Advanced The System Article treated with Polymer and Polymer itself Studied 9 Study Complete 9 Manuscripts in preparation, To be presented at SETAC N The polymer is destroyed under typical municipal waste conditions a Municipal incineration is not a source ofperfluorocarbo Polymer Biodegradation Studies - D 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 po degrading Screening Studies (commenced Septem 2004) Soil: Aerobic; Sediment: Anaerobic For method development Then, commence longer-term studies Fluorotelomer Alcohols F(CF2CF2)nCH2CH20H "Telomer B Alcohol" '^s.i^ Telomer B Alcohol : Physical-Chemical P Water solubility ~150 mg*L"1 (ppb) Vapor Pressure 3 pa at 21 C (measured) Hydrolysis hydrolytically stable pH 4, 7, 9 at 50C, pH 1.2 at 37C for five Photolysis does not absorb visible light Highly Sorptive to soils, sediments, iiSfflaaasBiwasattiisiBil CATABOL Biodegradation Predic CgF^Ch^CHzOH 0.0% CgFpCH^CH^OH 75% CgF^C^COOH 6.8% "^ C7Fi5CF=CH 13.7% C^r ^cC^=CH.^ 1.2% C^F^C^COOH 3.3% C^F^CO The sum of the % values =100 The model predicts this will be the pathway & distribution of tran products ^w Chemical Standards To achieve unequivocal analytical quantitative accuracy and p Isotopically - Labeled Standards . M+5 : C7Fl513CF2CD2CD20H (internal standard) . M+2 : C^^CFa^COOH CgFi^CI^COOH C^FisCF^CHPCOOH "Cold" Standards . CgF^CHzCOOH C7Fi5CF=CHCOOH . CsFuCOOH Others are being synthesized for transformation prod observed 8-2 Telomer B Alcohol : CgF^CI-^ Biodegradability Screening Ready : emulate a POTW Inherent: favorable, forcing conditions * Qualitative Identification & Analysis 9 Enable analytical method development Biodegradation Studies ^C Radiolabeled Study Material Quantitative Identify stable transformation product(s) 28-Day Ready Biodegradatio Modified OECD 301D of ^F^CFzCh^CI^OH Sponsored by the Telomer Research Program Asahi Glass. Clariant. Daikin, DuPont Manuscript submitted to Environmental Science & Technolo. n i'<w7 Results - Day 28 biodegradation LC/ARC analysis of ^C-labeled transformation p xW2 Sample: E--61 DR-A . - -., ^,,, 3.7 , Vial: 1, lnj.# 1, Channel: ARC(CPM) .. ^ ^. -^ 5 paren 1.7 -0.3 0.00 20.00 - ^ L ^^ -^A^-J">?u-CA-~. -r^uAAf^l "i' -J L -1--1----1 ]"" I' I " 1 1 | ! i 40.00 60.00 Peaks 1,2, 3, &4are observed transformati products and peak 5 is the parent. Ready Biodegradation Potential Biotransformation Rout 8-2 Telomer B Alcohol 56% ^? i F(CF,),11CF,CH,CH,OH --'27% PiCP^CP^CH^COOH F(CF2)714CF=CHCOOH 6% V CyF^CI-^CH ^ New, Previousl Transformation ! -? v F(CF2)714COOH 2% 4? Other fluorinated substances ? F(CF2)714C No C9 (Does Not include unidentified minor transformation prod Accelerated Biodegradatio 90 Days Acclimated Sludge FtCFzl^CFsCHzCHzOH DuPont unpubli Time Course of Biotransformati C7F1,14CF,CH,CH,OH FtCFzl^COOH r To be identified FtCFaty^CHzCHzCHzOH ^ "^ ^" F(CF2)714CF=CHCOOH F(CFo)7 CFoCH^COOH Unidentified metaboli FtCFzly^CFzCHzCHaO 100 w w (0 80 (0 60 soP^ 40 20 The m/roctes ofsctence" Inherent Biodegradation Potential Biotransformation Route 8-2 Telomer B Alcohol F(CF2)714CF2CH2CH20H Undefin Define 9 F(CF2)714CF2CH2COOH s--""" F^F^CF^HCOOH -""l? C^^CI^CI-^C ? T F(CF2)714COOH F(CF2)sCOOH F(CF2)714C Not : : : : ^ f ; : T T T Other fluorinated substances ? unp .&m^&SWSs!sSSfS~.....-,~ Time Course of CF3(CF2)4COOHFor Test Vessels (Sludge culture + 1160 ppb P.'-O]^ TBA) Abiotic Control (Killed Sludge culture + 0.5 mM NaCN + 1160 ppb [3,"C]-8-2 TBA) 14 12 10 4 unp Spike Reco DayO Day 7 Day 14 Day28 Day 56 Day 90 0 20 40 60 80 100 Days after the initiation Presence of additional hydrocarbon co-metabolites accelerate form Inherent Biodegradation - 90 Day _______ CyF^CF^CH^CH^OH_____ e Many Additional ^C containing transformation pro structural identification in-progress 9 ^CO^ observed 9 C^F^ COO- is a transformation product 9 CyF^COO- is not formed rapidly or in great amoun the primary transformation product - No "C9" CsF^COO- observed OTO -Cfy fe unp ^3^5^' v^a^,-' Presentation Outline Telomer Alcohol Degradation Abiotic e Hydrolytic Stability Biotic 9 Catabol 9 Sludge : 3M, UT, TRP, DD studies (9, 6) Soil : DD @ S02 to COOH Fluorotelomer-Based Polymer Degradation a Abiotic Incineration, Hydrolysis a Biotic Zahn-Wellens, Sturm Tests Release, Fate and Effects Compartm