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Soil-Water Partitioning of Fluorotelomer Intermediat Manufacture Fluorotelome Polymers AR226-3354 Telomer Research Program - TRP: Asahi Glass Co. Clariant GmbH Daikin Industries Dupont Co- W.R. Berti, B. Szostek, N. Wang H. Iwai - Daikin In V. Koch - C S. Shinya - A 'eTMSSS%i^ ^ssy Abstract Fluorotelomer Intermediates are used to manufacture fluorotelomer-bas products, which provide unique properties to a wide variety of consume telomer manufacturers that are collectively sponsoring research on telo jointly sponsor the Telomer Research Program (TRP). The TRP progra investigations on the environmental fate and effects properties of fluoro intermediates. A soil-water partitioning study using a batch equilibrium conducted on the fluorotelomer intermediate 8-2 Telomer B Alcohol [8- ^(CF^CI-^CH^OH, CAS# 678-39-7]. Results of the study demonstra than 90% of ^C-labeled 8-2 TBA initially added to the test system parti sediment within three hours. The 8-2 TBA partitioned to activated sludg hour. Less than 2% remained in the aqueous phase at a 1:1 soihsolutio hours at 4C; total recovery of the compound was 95% and greater und conditions. In one soil after a 24 h equilibration time and at room tempe more of the ^C label added as 8-2 TBA was bound to the residual fract determined by combusting the soil after three washings with acetone, a grinding. Freundlich adsorption constants characterize 8-2 TBA as a no 4000) to slightly mobile (Koc 500 to 4000) substance under these cond TRP: Asahi Glass Co., Clahant GmbH, Daikin Industries, DuPon -^.agsK";^-? Fluorotelomer intermediates Used to manufacture fluorotelomer-based polymers Provide unique properties in a wide variety o consumer products. 8-2 Telomer B Alcohol (8-2 TBA) focus of studies Primary fluorotelomeric intermediate FCCFzCFz^CHzCHzOH, where n = 4 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon - ' ' 8-2 Telomer B Alcohol: Adsorpti Desorption Study Objective: Evaluation the mobility of the test substance in soil and sediment Determine the Freundlich adsorption constants TRP: Asahi Glass Co., Clariant GmbH,' Daikin Industries,' DuPon 8-2 Telomer B Alcohol: AdsorptionDesorption Preliminary studies with 2 soils using "cold" 8-2 Detailed studies based on: OECD 106: Adsorption - Desorption using a Batch Eq Method - Radiolabeled [l^-^C] 8-2 Telomer B Alcohol OPPTS 835.1110: Activated Sludge Sorption Isotherm - Radiolabeled [S-^C] 8-2 Telomer B Alcohol Work supported by the Telomer Research Prog Asahi Glass Co., Ltd. (Japan), Clariant GmbH (Germa Daikin Industries, Ltd. (Japan), DuPont Co. (USA) TRP: Asahi Glass Co,, Clariant GmbH,' Daikin Industries, DuPon ' ' 8-2 Telomer B Alcohol: 8-2 TBA Water solubility 150 w Vapor pressure 3 Pa a - Radiolabeled [l^-^C*] 8-2 Telomer B A - Radiolabeled [B-^C*] 8-2 Telomer B Alc TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries,' DuPon ' ' Soil/Water Partitioning Studies: 8-2 TBA [F(CF2CF2)4CH2CH20H] 200 8-2 TBA added at f\9 0,150 ug/mL 150 Keyport silt loam: Sand 17%, Silt 62%, Clay 21%, pH 5.3, OM 4.0% si 2 ^ 100 White Clay Creek sand: ^ Sand 98%, Silt 2%, pH 7.2, OM 0.4% 50 Control: 0.01M CaClz + 8-2 TBA only; no soil o Keyport White TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, ii^l^Bt OECD 106: Adsorption/Desorption usin Batch Equilibrium Method TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon Study soils and characteristics Soils used in studies represent a broad ra characteristics Soli name OECD 106 pH (0.01 R\H Organic carbon soil type CaCl2) conte nt (%) Organic matter Clay co conte nt (%) (% SK961089 2 7.6 4.6 7.9 34 SK566696 5 4.2 0.8 Emperor S(on's Lake 3 6 1.2 1.4 11 2.1 17 SK179618 4 5.6 3.8 EUROSOIL 5 3.1 6.7 6.6 20 11.6 5 TRP: Asa hi(31ass Co., Clanaint GmbH, Daikin Industries, DuPon ^ ^ ^ v:^:-:-:..;.-y Recovery of ^C 8-2 TBA from Sealed Glas 4 Soils ^C 8-2 TBA applied through septum to attain 25 Samples centrifuged to separate phases (L01M CaCI^ solution removed using syringe with SS through PTFE-coated rubber septum Cap removed, supernatant decanted, ^C by LSC Soil extracted 3 times with acetone Soil extracts analyzed separately by LSC and results c Soil residue combusted -r Extracted soils dried, ground, combusted, ^COz by L TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon ' ' ' Recoveries of applied radioactivity of ^C 8-2 TB 48 h equilibration time at 3 soihsolution ratios | Supernatant Soil extract II Residue D Lid Wa Emperor Son's Lake TRP: Asahi Glass Co.. Clariant GmbH, Daikin Industries. DuPon OECD 106: Adsorption/Desorption usin Batch Equilibrium Method TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon Equilibration Time of ^C 8-2 TBA at 1:1 SoihSo ratio, 25 |jg 8-2 TBA L1 Equilibration time of 3, 6, 24 and 48 h ^C 8-2 TBA applied through septum Samples centrifuged to separate phases - 0.01M CaCl2 solution removed using syringe with SS piston thr coated rubber septum - Cap removed, supernatant decanted/ ^C by LSC Soil extracted 3 times with acetone - Soil extracts analyzed separately by LSC and results combined Soil residue corn busted - Extracted soils dried, ground, combusted, ^CC^ by LSC Equilibration achieved within 3 hours TRP: Asahi Glass Co,, Clariant GmbH, Daikin Industries, DuPon -s ^ -0 H B 3r Qi s 0 0) w U) 0 0 0 fi -1 5" 3 i-+ 0 3 V I V 0 &. ^ 3' 5" a (A rt (5' y D c -0 0 3 ?+ 0 0 -0 (0 <D 3^: J l Percent adsorption to soil 0 Ci=>3SggS8 0 "D 0 ?-3 r 0 <: "8 0 03 3 M " > 00). 0 rtn^s s ^ ^^ ^^? s^" ^ 0) i 0 J. ^------' 3" 0 I 2. ^^" 0 8 ^00. " Percent adsorption to soil ^ 30000000000 c -^t\3C*3-p.cncn-^cotDO 0 1 >^J-l--i--l--i----------1----------i----------1--i------.--1 ~~~'---~--^ i5 > S 0 T| s g i 0 1 ------ y 0 c . S S - v^ ^ (^^^ -r' n -^ o 0" 3 (Q 5 D ^^9 31 - (x A 2. D -5) 5 ^1 (0 0> & 00 > 0.0w Percent adsorption to soil 3000000000 ^ -'tUG3^cnc7)-^fcotD "s "0 5' 3 (Q 5 D 1 ? mts'8 s -i 0) 1 i 2. I > 0) '5) 8 ^ (0 0) 0 00 s (0 Percent adsorption to soil vQ ^ , o O*.^O-.,IUO.--UO^CO--nOO--O>~O4--COOO--tDQO (-^ow- ^--~~~~~-----.r ^ "^ 1-1^ 5" 3 ^ (Q 5 -0 3 " y^ ^ ? T 3 K 9m ^f 0) I 0 ^^ CD ' 3 ^ cn w 0) w m CO 0> Adsorption of ^C 8-2 TBA by Activated Sludge Adsorption of1 ^-labeled 8-2 TBA (8/11/03) 100 \- w 80 w ec 60 i ^~ 40 % ^ 20 -- -Q^ -V- Sludge Aqueous Phase Test Vessel Wall Total Mass Balance 0- 0 -0 10 Time after the incubation (h) slud9e: POTW (Wilmin lyophilized an Test system: 4.5 g dry slud 87 |jg ^C 8-2 Glass vial with lined cap ^C 8-2 TBA extract determined by LS TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon OECD 106: Adsorption/Desorption usin Batch Equilibrium Method Prerequisite Studies Tier 1 Studiiees ^ -K Validate analytical method(s), check for radiochemical stability I Preliminary studies 1 Selection of optimal Check for adsorption to solid/solution ratio vessel Ef Tier 2 Studiiees ^ ~\^ Determination of equilibrium time Equilibrium plateau achieved? Tier 3 Studies ' Adsorption isotherms TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon ^C 8-2 TBA Stability Studies 3 h equilibration time at 4C Soils sterilized by gamma irradiation TLC/LSC method used to determine ^C, 8-2 TBA -50:50 toluene: ethyl acetate mobile phase 8-2 TBA Stable under study condition TRP: Asahi Glass Co., Clariant GmbH,' Daikin Industries, DuPon - SoiS SK961089 40 [mm] [mm] TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon Emperor Son's Lake Sediment [mm] [mm] TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon EUROSOIL 5 150 100 [mm] TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon OECD 106: Adsorption/Desorption usin Batch Equilibrium Method TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon Adsorption and Desorption Studies Adsorption step 8-2 TBA at 5 concentrations in duplicate - 0.125, 0.100, 0.075, 0.050, 0.0125 [ig 8-2 TBA/mL 1:1 soihsolution ratio, 3 hours, 4 C as used previously Samples centrifuged, liquid and soil phases separated, sup analyzed by LSC Desorption step Adsorption supernatant replaced by fresh 0.01M CaC12 Mixed for 3 h, centrifuged, supernatant analyzed by LSC 0.125 |jg 8-2 TBA/mL samples extracted 3 times with aceto samples pooled, and analyzed by LSC Soil Samples air-dried, ground, combusted and analyzed by TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon ' ' ' Radioactivity Recovery from 5 soils treated with 0.125Mg8-2TBA/mL Adsorption Supernatant Soil extract Desorption Supernatant Lid wash D Residue SK961089 SK566696 Emperor Son's Lake SK179618 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon Adsorption and desorption chart for 8-2 TBA on Soil SK961089 -4.1 -3.9 -3.7 -3.5 -3.3 -3.1 -2.9 log Ce, ug/mL TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon Adsorption and desorption chart for 8-2 TBA on Soil SK566696 -4.1 -3.9 -3.7 -3.5 -3.3 -3.1 -2.9 log Ce, |jg/mL TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon Adsorption and desorption chart for 8-2 TBA on Emperor Son's Lake Sediment -4.1 -3.9 -3.7 -3.5 -3.3 -3.1 -2.9 log Ce, ug/mL TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon Adsorption and desorption chart for 8-2 TBA on Soil SK179618 -4.1 -3.9 -3.7 -3.5 -3.3 -3.1 -2.9 log Ce, ug/mL TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPon Adsorption and desorption chart for 8-2 TBA on Eurosoil 5 -4.1 -3.9 -3.7 -3.5 -3.3 -3.1 -2.9 log Ce, ug/mL TRP: Asahi Glass Co., Clahant GmbH, Daikin Industries, DuPon Freundlich adsorption and desorption constant regression analysis for 8-2 TBA Soil SK961089 SK566696 Emperor Son's Lake Sediment SK179618 EUROSOIL 5 Experimental Stage Adsorption Step Desorption Step Adsorption Step Desorption Step Adsorption Step Desorption Step Adsorption Step Desorption Step Adsorption Step Desorption Step Adsorption conistants K Koc Kom 59 1293 753 0.9 37 812 473 0.8 34 4266 2438 0.9 50 6238 3564 0.9 16 1348 770 0.8 17 1409 805 0.7 239 6302 3628 1. 152 4000 2303 1. 85 1264 730 1. 63 940 543 0.9 TRP: Asahi Glass Co., Clariant GmbI4, Daikin Indusltries, Du Pon Summary >90% radiolabel recoveries in 4 of 5 soils at 1:1 ratio Fifth soil 86% recovery Predominately recovered from soil extracts and residue Recovered 88 to 99% sorbed to soil at 1:1 soil solution rat 82 TBA reaches equilibrium in less that 3 hours Less than 1 h in freeze-dried, activated sludge Freundlich adsorption constants characterize 8-2 TBA as no (Koc > 4000) to slightly mobile (Koc 500 to 4000) Based on classification by Hollis 1991 Hollis, J M (1991). Mapping the vulnerability of aquifers and surface water to pesticide contamin national/regional scale. Pesticides in Soil and Water: Current Perspectives (A Walker Ed), BCPC 169 to 174 TRP: Asahl Glass Co., Clariant GmbH,' Daikin Industries, DuPon - ' Acknowledgements Pat Folsom Mark Starr Lisa Sulecki Sharon Swales TRP^ Asahi Glass Co., Clariant GmbH,' Daikin Industries, DuPon ' '