Document NGw6rQEqL5gn7jembR3g9EqpR

AR226-3354 Soil-Water Partitioning of a Fluorotelomer Intermediate used to Manufacture Fluorotelomer-based Polymers Telomer Research Program - TRP: Asahi Glass Co. Clariant GmbH Daikin Industries DuPont Co. W.R. Berti, R.C. Buck, B. SzOStek, N. Wang - DuPont Co H. Iwai - Daikin Industries, Ltd. V. Koch - Clariant GmbH S. Shinya - Asahi Glass Co Abstract Fluorotelomer intermediates are used to manufacture fluorotelomer-based polymer products, which provide unique properties to a wide variety of consumer products. Four telomer manufacturers that are collectively sponsoring research on telomer compounds jointly sponsor the Telomer Research Program (TRP). The TRP program includes investigations on the environmental fate and effects properties of fluorotelomer intermediates. A soil-water partitioning study using a batch equilibrium method is being conducted on the fluorotelomer intermediate 8-2 Telomer B Alcohol [8-2 TBA; CF3(CF2)7CH2CH2OFI, CAS# 678-39-7]. Results of the study demonstrated that greater than 90% of 14C-labeled 8-2 TBA initially added to the test system partitioned to soil and sediment within three hours. The 8-2 TBA partitioned to activated sludge within one hour. Less than 2% remained in the aqueous phase at a 1:1 soihsolution ratio after 3 hours at 4C; total recovery of the compound was 95% and greater under these conditions. In one soil after a 24 h equilibration time and at room temperature, 50% or more of the 14C label added as 8-2 TBA was bound to the residual fraction, which was determined by combusting the soil after three washings with acetone, air-drying, and grinding. Freundlich adsorption constants characterize 8-2 TBA as a non-mobile (Koc > 4000) to slightly mobile (Koc 500 to 4000) substance under these conditions. TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Fluorotelomer intermediates Used to manufacture fluorotelomer-based polymers Provide unique properties in a wide variety of consumer products. 8-2 Telomer B Alcohol (8-2 TBA) focus of studies Primary fluorotelomeric intermediate F(CF2CF2)nCH2CH2OH, where n = 4 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 3 8-2 Telomer B Alcohol : Adsorption 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, DuPont Co. Page 4 8-2 Telomer B Alcohol: Adsorption Desorption Preliminary studies with 2 soils using "cold" 8-2 TBA Detailed studies based on: OECD 106: Adsorption - Desorption using a Batch Equilibrium Method - Radiolabeled [1,2-14C] 8-2 Telomer B Alcohol OPPTS 835.1110: Activated Sludge Sorption Isotherm - Radiolabeled [3-14C] 8-2 Telomer B Alcohol Work supported by the Telomer Research Program Asahi Glass Co., Ltd. (Japan), Clariant GmbH (Germany), Daikin Industries, Ltd. (Japan), DuPont Co. (USA) TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 5 ## 8-2 Telomer B Alcohol: 8-2 TBA - Radiolabeled [1,2-14C*] 8-2 Telomer B Alcohol - Radiolabeled [3-14C*] 8-2 Telomer B Alcohol TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 6 I Soil/Water Partitioning Studies: 8-2 TBA [F(CF2CF2)4CH2CH2OH] 200 8-2 TBA added at ~ 0.150 ug/mL 150 15 min 46 hours Keyport silt loam: -j f Sand 17%, Silt 62%, Clay 2 f 21%, pH 5.3, OM 4.0% White Clay Creek sand: m m< 4I| 1 v:Vfel100 mmmM mmm - Vv^ ! mV*' Sand 98%, Silt 2%, pH 7.2, # OM 0.4% 50 4 - :*JXK Control: 0.01M CaCI2 + vi 8-2 TBA only; no soil ? 1o 1 Keyport WhiteClay Control TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries,p&MRf&ticfeP- OECD 106: Adsorption/Desorption using a Batch Equilibrium Method TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 8 Study soils and characteristics Soils used in studies represent a broad range of characteristics Soil nam e OECD 106 pH (0.01 M O rg an ic carbon O rg an ic m a tte r C lay con ten t S o il T ex tu re soil type C a C I2) c o n te n t (%) c o n ten t (%) (%) (US DA) SK961089 2 7.6 4.6 7.9 34 Clay loam SK566696 Emperor Son's Lake 5 3 4.2 6 0.8 1.2 1.4 11 Sandy loam 2.1 17 Sandy loam SK179618 EUROSOIL 5 4 - 5.6 3.1 3.8 6.7 6.6 20 Clay loam 11.6 5 Loamy sand TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Recovery of 14C 8-2 TBA from Sealed Glass Vials: 4 Soils 14C 8-2 TBA applied through septum to attain 25 pg L'1 Samples centrifuged to separate phases 0.01M CaCI2 solution removed using syringe with SS piston through PTFE-coated rubber septum Cap removed, supernatant decanted, 14C by LSC Soil extracted 3 times with acetone Soil extracts analyzed separately by LSC and results combined Soil residue combusted Extracted soils dried, ground, combusted, 14C02 by LSC TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 10 Recoveries of applied radioactivity of 14C 8-2 TBA after 48 h equilibration time at 3 soihsolution ratios Supernatant Soil extract Residue Lid Wash 100 &> oCgO 1c3o OC 13 "q . <CL Soil: Solution 1:1 1:5 1:25 1:1 1:5 1:25 1:1 1:5 1:25 1:1 1:5 1:25 SK961089 SK566696 Emperor Son's Lake SK179618 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 11 'tZ & ggS ' OECD 106: Adsorption/Desorption using a Batch Equilibrium Method TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 12 Equilibration Time of 14C 8-2 TBA at 1:1 SoikSolution ratio, 25 Mg 8-2 TBA L 1 Equilibration time of 3, 6, 24 and 48 h 14C 8-2 TBA applied through septum Samples centrifuged to separate phases - 0.01M CaCI2 solution removed using syringe with SS piston through PTFEcoated rubber septum - Cap removed/ supernatant decanted, 14C by LSC Soil extracted 3 times with acetone - Soil extracts analyzed separately by LSC and results combined Soil residue combusted - Extracted soils dried, ground, combusted, 14C 02 by LSC Equilibration achieved within 3 hours TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 13 Adsorption graph for Soil A (SK961089) 100 -I 90 - 80 - 70 - 60 - e- o 50 - 40 - 30 - 20 - 0410 - 0 12 24 36 Adsorption Time (hours) -- -- Soil A 48 Adsorption graph for Soil C (Emperor Son's Lake) 80 70 60 for 50 40 30 - o4 o 12 24 36 Adsorption Time (hours) -- SoilC 48 TRP: Asahi Glass Co., Clariant GmbH, Adsorption graph for Soil B (SK566696) Adsorption Time (hours) ---- SoilB Adsorption graph for Soil D (SK179618) Daikin Industries, DuPont Co. Page 14 m Adsorption of 14C 8-2 TBA by Activated Sludge w % of Total Mass Adsorption of ^C -labeled 8-2 TBA (8/11/03) Sludge: POTW (Wilmington, DE), lyophilized and sterilized Test system: 4.5 g dry sludge L 1 plus 87 pg 14C 8-2 TBA L 1; Glass vial with aluminumlined cap 14C 8-2 TBA extracted and determined by LSC / TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 15 OECD 106: Adsorption/Desorption using a Batch Equilibrium Method Tier 1 Studies > Tier 2 Studies JT ie r3 j3 tu d ie ^ ^ ^ TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 16 14C 8-2 TBA Stability Studies 3 h equilibration time at 4C Soils sterilized by gamma irradiation TLC/LSC method used to determine 14C, 8-2 TBA -50:50 toluene: ethyl acetate mobile phase 8-2 TBA Stable under study conditions TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 17 Soil S K 961089 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 18 Emperor Son's Lake Sediment TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 19 EUROSOIL 5 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 20 OECD 106: Adsorption/Desorption using a Batch Equilibrium Method Tier 1 Studies Tier 2 Studies Tier 3 Studies TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 21 Adsorption and Desorption Studies Adsorption step 8-2 TBA at 5 concentrations in duplicate - 0.125, 0.100, 0.075, 0.050, 0.0125 pg 8-2 TBA/mL 1:1 soiksolution ratio, 3 hours, 4 C as used previously Samples centrifuged, liquid and soil phases separated, supernatant analyzed by LSC Desorption step Adsorption supernatant replaced by fresh 0.01M CaCI2 Mixed for 3 h, centrifuged, supernatant analyzed by LSC 0.125 pg 8-2 TBA/mL samples extracted 3 times with acetone, samples pooled, and analyzed by LSC Soil Samples air-dried, ground, combusted and analyzed by LCS TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 22 Radioactivity Recovery from 5 soils treated with 0.125 M9 8-2 TBA/mL Adsorption Supernatant Soil extract Desorption Supernatant Lid wash 100 Residue SK961089 SK566696 Emperor Son's Lake SK179618 Eurosoil 5 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 23 Adsorption and desorption chart for 8-2 TBA on Soil SK961089 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 24 _.. ' Adsorption and desorption chart for 8-2 TBA on Soil SK566696 -2.0 iI -------------1--------------- i--------------- i------------i - 4.1 -3.9 -3.7 -3.5 -3.3 i -3.1 log Ce, |ig/ml_ i I -2.9 -2.7 -2.5 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 25 Adsorption and desorption chart for 8-2 TBA on Emperor Son's Lake Sediment I log Ce, |ig/mL TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 26 Adsorption and desorption chart for 8-2 TBA on Soil SK179618 - 0.8 - 1.0 O) 1.2 t 3) I ' 14 O) o 1.6 - 1.8 - 2.0 - 4.1 -3.9 -3.7 -3.5 -3.3 -3.1 -2.9 -2.7 log Ce, [ig/mL -2.5 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 27 Hi Adsorption and desorption chart for 8-2 TBA on Eurosoil 5 # TRP: Asahi Glass Co., Clarlant GmbH, Daikin Industries, DuPont Co. Page 28 Freundlich adsorption and desorption constants and regression analysis for 8-2 TBA Soil Experimental Stage SK961089 Adsorption Step Desorption Step SK566696 Adsorption Step Desorption Step Emperor Son's Lake Sediment Adsorption Step Desorption Step SK179618 Adsorption Step Desorption Step EUROSOIL 5 f Adsorption Step Desorption Step Adsorption constants K Koc Korn 59 1293 753 37 812 473 34 4266 2438 50 6238 3564 1/n 0.9894 0.8602 0.9300 0.9693 R2 0.9736 0.9356 0.9950 0.9739 16 1348 770 0.8405 0.9864 17 1409 805 0.7820 0.9981 239 6302 3628 1.2120 0.9978 152 4000 2303 1.0994 0.9935 85 1264 730 1.0246 0.9746 63 940 543 0.9120 0.9688 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 29 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 soihsolution ratio 8-2 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 non-mobile (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 contamination at the national/regional scale. Pesticides in Soil and Water: Current Perspectives (A Walker Ed), BCPC Monograph 47, pp 169 to 174 TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 30 Acknowledgements Pat Folsom Mark Starr Lisa Sulecki Sharon Swales TRP: Asahi Glass Co., Clariant GmbH, Daikin Industries, DuPont Co. Page 31