Document rpZLn125DoadRQkKqdG25oy2v

AR226-3347 Analytical challenges in determination of Telomer 8-2 Jcohol and Telomer-derived fluorosurfactants and polymets4n biological and environmental matrices. Bogdan SzostekVl^eith B. Prickett1, S. Mark Kennedy1, Mary A. Kaiser2 1DuPont HaskellLaboratotvfotiiealth and Environmental Sciences^ew ai% <DE/ USA 2DuPont CentralResearch and Debflopment^Wilmington, DEf US/ SETAC Europe 13th Annual Meeting, Hamburg, Germany s for 8-2 Telomer B Alcohol Properties: - Structure: CF3-(CF2)7-CH2-CH2-OH - Water solubility: 150 pg/L - Melting point: 44C - Boiling point: 213C at 760 mm Fig - Vapor pressure: 3 Pa at 21C - UV: none for 225-400 nm 1. GC-FID P* 20- 5.1 pg/mL n H-*K 40 pg/mL15oo c/5 ' NJ O 10- H ^ ? 3446 V L .o- .1 3 2 4 6 8 rrin 2 ^ C -M S: sub je c^ p h liis presentation 1 iig/mL 8-2 TBA Ion: 523 WMW Basics of G Solvents MTBE Ethyl Acetate MeG|H IPA Chromatography 8-2 TBA^iieadspace losses from water E xperim en t I 10 m L g la ss via l; 10 m L w ater; 8 -2 TBA a t 150gg/L Environmental waters^-method validation and sample storage E xperim en t Results (% recovery st. dev.) 10 m l g la ss via l; 5 m l w ater; 8-2 TBA a t 150 va/L Water type 1 hr RT 1 week Frozen 1 week RT 1 week RT (No foil) 1 month 1 month Frozen RT Well 1026 Pond 982 985 916 6414 5712 Creek 996 865 536 Sea 962 865 929 354 302 298 298 1009 2416 1042 2615 1002 1514 992 8816 m/ Environmental validation and sample storage Results (% recovery r^st. dev.) 15 |ig/L 8-2 TBA Water type 1 hr RT 1 week Frozen 1 week RT 1 week RT (no foil) Well Pond 945 946 Creek 9 1 6 Sea 9 4 5 1084 -- -- --- 284 -- -- -- 144 -- -- -- example chromatogram 15 |ig/L 8-2 TBAlttsSea water Extraction: 2 g soil, spike 8-2 TBA; add 1 mL H20 ; extract with 6 mL hexane Clean-up: SPE: Si, 100 mg /10 mL (1ST) 1. 2 mL IPA and 2 mL Hexane 2. Load hexane extract 3. Wash with 6 mL hexane 4. Elute with 1 mL IPA Soil type Poiazzo (44% sand, 26% slit, 30% clay) Key Port (17% sand, 62% slit, 21% clay) Hildago (52% sand, 20% slit, 28% clay) White Clay (98% sand, 2% slit) Soil (/o Rec. st.dev) Soil extract (% Rec. st.dev) 87 4 981 8815 906 8111 876 927 941 - chromatograms Soil extracts Soils Abundance 1000 Poiazzo soil extract 900 am 800 700 am Ion 31 : 8-2 TBA 600 500 4B) 400 300 200 100 Poiazzo C9-iso: 4.61 min 8-2 TBA: 4.93 min 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 8.00 8.50 9.00 9.50 10.00 Ion 33 : D-8-2 TBA 1400 1300 1200 1100 1003 White Clay C9-iso: 4.61 min 8-2 TBA: 4.93 min I 1' ' 1I ' ' ' 111 1' 1I ' 111I 1 - ' ` I 1' ' - I ' 1' 1I ' ' 1 1I ' 1 1 I 40 45 / 50 55 60 65 70 75 80 85 90 95 t> ' ' ' I' ' ' 1I ' JL' ' ' ! ' ' ' ' I' 4.00 4.50 5.00 5.50 6.00 6.50 7.00 7.50 6.00 5.50 9.00 9.50 10.00 'Ort YX 8-2 TBA Fat a and tissues procedures Extraction: 0.3 g fat, (spike), dissolve in 6 mL heptane Clean-up: SPE: Si, 500 mg /10 mL (1ST) 1. 1 mL acetone and 2 mL heptane 2. Load heptane extract 3. Wash with 6 mL heptane 4. Elute with 1 mL IPA Extraction: 0.5 g tissue; (spike), add 2 mL water, 15 pL HC104; extract with 6 mL hexane; 15 min vortex; centrifuge Clean-up: SPE: Si, 500 mg /10 mL (1ST) 1. 1 mL IPA and 2 mL hexane 2. Load hexane extract 3. Wash with 6 mL hexane 4. Elute with 1 mL IPA Extraction: 0.25 mL plasma + 0.25 mL water +1 mL MTBE; x15 min vortex; centrifuge No Clean-up for plasma It ^ | '\YV***J!/^OS'VfOxV :'Oi! -ft 8-2 TBA - pla Fat: 190 ng/g spike and blank Sem?' 8-2 TBA isma and tissues results Matrix Fat Liver Kidney Plasma Spike Level 190 ng/g 950 ng/g 100 ng/g 200 ng/g 100 ng/g 100 ng/mL 200 ng/mL 8-2 TBA ( % Ree. st.dev) 631 1003 984 805 725 867 11311 C9-iso ( % Ree. st.dev) 6710 957 9715 799 7510 8215 10417 Estimated LOD 12 ng/g 6.0 ng/g 4.0 ng/g : :-OR . Summary 8-2 Telomer B alcohol is^Khallenging analyte because of its volatility and loW ^ater solubility; I low water solubility dictates the need fdKmethods developed at LOQ; extraction solvent choice is critical In achieving tequirei sensitivity, precision, and GC/MS system performance; volatility losses from water are rapid and significant; solvent exchange is not an option, limiting the choices f( sample concentration or/and clean-up; samples should be stored frozen; liP !'<A Summary demonstrated the analytiiaiprocedures for analysis of 8-2 Telomer B alcohol in environmental waters, soils, rat plasma, and tissues; - extracts derived from complex matrices (soit^tissues) require clean-up; - maintaining column performance is critical for re li^ le quantitation and maintaining GC/MS sensitivity; - use of internal standards (especially isotopically labeled^ is critical for accurate quantitation; - use of surrogates is important for accurate quantitation in' biological matrices;