Typical analytical challenges in the analysis of perfluorinated alkylated substances. Pim de Voogt IBED-University of Amsterdam, The Netherlands

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1 Typical analytical challenges in the analysis of perfluorinated alkylated substances Pim de Voogt IBED-University of, The Netherlands 1

2 Contents A. PERFOOD Analytical Work B. PFAS analysis Typical analytical issues: ID confirmation, isomers impurities, contamination, solvent use and compatibility 2

EU project PERFOOD Project PERFOOD, 3y 5 M Start: August 2009

drinks and drinking water to the daily intake PFCs in EU >

3 EU project PERFOOD Project PERFOOD, 3y 5 M Start: August 2009 Coordination: Prof. Dr. Pim de Voogt (UvA) Finance: 3M FP7 Food, Agriculture and Fisheries Programme Aims > assess contributions from food, drinks and drinking water to the daily intake PFCs in EU > identify the sources of PFCs in our diet Partners SU(S), FI/BfR(D), NILU(N), UVA/VU/KWR(NL), UA(B), ISS(I), ICT(CZ) 3

4 PERFOOD analytical WPs Main Objectives WP 1 Development of fully validated, highly sensitive and easy-to-use methods for quantification of PFCs in single food and beverage items as well as in food composites Development and validation of sensitive methods for analysis of volatile PFC precursors in food items, beverages and food composites Main objectives WP2 Preparation of QA protocols for sampling, analysis, interlaboratory study and CRM production Validating methods developed in WP-1 (and transferred to the partners) in an interlaboratory validation framework Evaluation of performance of European food control laboratories by means of an interlaboratory study Production and certification in two food matrix CRMs 4

5 100 [C 3 F 7 ] Typical LC-ESI-MS spectra of PFAS Institute for Biodiversity Relative Abundance Relative Abundance Relative Abundance [C 3 F 7 ] CF C 7 F 15 COOH [M-H] PFOA CO m/z [FSO 3 ] CF CF C 11 F 23 COOH 2 -CF 2 -CF 2 PFOS PFDoA -CO 2 [M-H] CF m/z 499 C 8 F 17 S O 3 H [M -H ] m /z 5

6 6 Institute for Biodiversity

7 LC-MS/MS of PFsulfonates PFBS PFHxS PFOS PFOSA 6:2FTS 7 Institute for Biodiversity

8 Impurities present in a typical batch of the potassium salt of PFOS identified by using 19F-NMR analysis From Martin et al. ES&T 38, 2004, 248A 8

9 PFOA, PFOS, PFOSA isomers Environmental matrices isomer ratios change Reference standard Sea water Sediment / water Landfill effluent (water phase) Landfill effluent (particle phase) Isomers of PFOS Kallenborn & Berger 2004 PFOSA PFOS Isomers of PFOA PFOS milk fish dust serum PFOA tap water fish dust serum 9

10 Impurities in PFTeDA standard I. Presence of shorter chain congeners in standards 3 % P F D A ( C 1 0 F 1 9 O O H ) 3 % P F D o D A ( C 1 2 F 2 3 O O H ) 9 4 % P F T e D A ( C 1 4 F 2 7 O O H ) t R (m in) From Martin et al. ES&T 38, 2004, 248A II. Presence of 12 C compound in 13 C standards 10

11 Contamination: Contributions from water extraction procedure ng Sub-boiled water and blank extraction background PFBS PFHpA PFHxS 62FTS PFNA PFOS PFDA PFUnA PFODoA PFTeA PFOA PFOSA blank extraction sub-boiled extraction 11

12 Contamination due to instrument parts I. tubing/mixing chamber PTFE Stainless steel PTFE Contamination due to instrument: II. delay of instrument contribution through guard column prior to injection valve 12

13 Contamination due to instrument: PFOA 13 Institute for Biodiversity

14 Contamination due to instrument: 7H-PFHpA Institute for Biodiversity 7H-PFHpA: 345/181 7H-PFHpA: 345/131 14

15 PFOA in surface water samples 15 Institute for Biodiversity

16 Contamination due to filters: PFOA, PFNA PVDF: source of PFNA and PFOA PVDF: hydrophilic polyvinylidene fluoride membrane GHP: Hydrophilic polypropylene GH polypro membrane Housing: polypropylene Pore size: 0.2 µm 16

17 Preventing contamination of the MS/MS Switching valve to direct part of chromatogram to waist 17

18 ) g n ( Sorption of longer chain perfluorinated carboxylic acids to PP tube walls ph PFUnA PFODoA PFTeA sor pt i on t o wal l ) g n ( sor pt i on t o wat er ph PFUnA PFODoA PFTeA sor pt i on t o wal l 3.00 ) sor g pt i on n ( t o wat er PFUnA ph 8.80 sorption mechanism is related to the perfluorinated chain length PFODoA PFTeA Sorption to wall dissolved 18

19 Solvent problems Adsorption: depends strongly on solvent Increasing water content in sample vials leads to disappearance of (late eluting) (longer chain) acids Readjustment of vial solvent reintroduces wall-adsorbed longer chain acids into vial solution reappear in chromatograms 19

20 Solvent compatibility Institute for Biodiversity Mixture solution in MeOH:H 2 O injected in MeOH:H 2 O Mixture solution in pure ACN injected in MeOH:H 2 O Mixture solution in pure MeOH injected in MeOH:H 2 O 20

21 Conclusions PFAS contamination is omnipresent in laboratory environment and instrumentation Appropriate measures can be taken QA/QC is essential at an Interlaboratory level Check of 12 C and 13 C standards necessary 21

22 Acknowledgments Thanks to many colleagues at IBED and the following institutions for project collaboration or financial support: European Union (PERFORCE project NEST , PERFOOD project KBBE ) DuPont de Nemours, PlasticsEurope Flemish Government, Department of Environment, Nature and Energy...and the EU-project teams... Urs Berger 1, Wendy d Hollander 2, Stefan van Leeuwen 3 1 ItM-SU, Sweden 2 UA, Belgium, 3 VU, Netherlands 22

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