PFAS (Per- and Polyfluoroalkyl Substances) Analytical Considerations and Application to Landfill Leachates

Transcription

1 PFAS (Per- and Polyfluoroalkyl Substances) Analytical Considerations and Application to Landfill Leachates Dr. Bob Symons National Technical Manager Eurofins mgt, 16 Mars Road, Lane Cove West, NSW 2066 Regional Contaminated Land Program PFAS for Councils Thursday, 22 February

2 Agenda NEMP and Landfills What are PFAS? Analysing PFAS Total Organofluorine - Combustion Ion Chromatography (TOFA- CIC) TOPA (Total Oxidisable Precursor) Analysis High-resolution Accurate Mass Quadrupole Time-of-Flight (Q-ToF) LC-MS Conclusions 2

3 PFAS National Environmental Management Plan (NEMP) Sent: Fri 16/02/2018 5:00 PM 3

4 PFAS National Environmental Management Plan (NEMP) 4

5 PFAS National Environmental Management Plan (NEMP) 5

6 Per- and Polyfluoroalkyl Substances What are they? PFAS are a large group of man-made chemicals that have been used since the 1950s. A wide range of household and industrial applications including fire fighting foams, stain resistant coatings in textiles & carpets plus food packaging, Teflon cookware, chrome plating and paints. Nominally a C8 aliphatic chain where all the H atoms have been replaced with F. Exceptionally stable and persistent in the environment. Bioaccumulates. Demonstrate moderate acute toxicity 6

7 Physical and Chemical Properties of PFOS and PFOA 3 Property PFOS (K Salt) PFOA (Free Acid) Chemical Abstracts Service (CAS) Number Physical Description (physical state at room temperature and atmospheric pressure) White powder Molecular weight (g/mol) Water solubility at 25 o C (mg/l) 550 to 570 (purified), 370 (fresh water), 25 (filtered sea water) Melting Point ( o C) > to 54 White powder/waxy white solid 9.5 X 10 3 (purified) Boiling point ( o C) Not measurable 188 to 192 Vapour pressure at 20 o C (mm Hg) 2.48 X Octanol-water partition coefficient (log K ow ) Not measurable Not measurable Organic-carbon partition coefficient (log K oc ) 2.57 (Value estimated based on anion and not the salt) Henry s law constant (atm-m 3 /mol) Not measurable Half-Life Atmospheric: 114 days Water: > 41 years (at 25ºC) 2.06 Atmospheric: 90 days 2 Water: > 92 years (at 25ºC) 1 Extrapolation from measurement. 2 The atmospheric half-life value identified for PFOA is estimated based on available data determined from short study periods 3 United States Environmental Protection Agency Solid Waste and EPA Emergency Response (5106P) 505-F March

8 PFAS in the Environment Most PFASs are extremely persistent. Low volatility but have been detected in the Arctic. Short-chain PFAS are more soluble. Long-chain PFAS are more bioaccumulative. Long-chain PFAS are more strongly bound to soil particles. Ionic strength and ph influence leachate methods 8

9 Per- and Polyfluoroalkyl Substances To develop information resources and processes to break down barriers to the use of technically sound innovative solutions for healthy communities, economy and environment. Presentation title: Emerging Contaminants PFASs EDR Document owner: Dr. R. Symons Last modified on: November

10 Per- and Polyfluoroalkyl Substances 10

11 Per- and Polyfluoroalkyl Substances PFAS Fact Sheets 1. Naming Conventions and Physical and Chemical Properties 2. Regulations, Guidance, and Advisories 3. History and Use 4. Environmental Fate and Transport (to be published February 2018) 5. Site Characterization Tools, Sampling Techniques, and Laboratory Analytical Methods (to be published February 2018) 6. Remediation Technologies and Methods. (to be published February 2018) 11

12 Per- and Polyfluoroalkyl Substances PFAS is made up of >3,000 compounds Replacement chemistries are currently in development viz GenX and ADONA. 12

13 Analysing Per- and Polyfluoroalkyl Substances (PFAS) US EPA Method 537, Version 1.1, is an LC-MS/MS method used to analyse selected PFASs in drinking water. SPE concentration using mixed mode WAX phase US EPA Method 821 Draft Procedure for Analysis of Perfluorinated Carboxylic Acids and Sulfonic Acids in Sewage Sludge and Biosolids by HPLC/MS/MS Alkaline digestion, solvent extraction and SPE clean-up United States of America s Department of Defense (DoD) Environmental Data Quality Workgroup (EDQW) and the Department of Energy (DOE) Consolidated Audit Program (DOECAP) Operations Team developed the Quality Systems Manual (QSM) for Environmental Laboratories aka QSM

14 Per- and Polyfluoroalkyl Substances (PFAS) Perfluoroalkyl Acids (PFAA) Perfluoroalkyl carboxylic acids (PFCAs) n=11 Perfluorobutanoic acid (PFBA) Perfluoropentanoic acid (PFPeA) Perfluorohexanoic acid (PFHxA) Perfluoroheptanoic acid (PFHpA) Perfluorooctanoic acid (PFOA) Perfluorononanoic acid (PFNA) Perfluorodecanoic acid (PFDA) Perfluoroundecanoic acid (PFUnA) Perfluorododecanoic acid (PFDoA) Perfluorotridecanoic acid (PFTrDA) Perfluorotetradecanoic acid (PFTeDA) C n F 2n+1 COOH C 3 F 7 COOH C 4 F 9 COOH C 5 F 11 COOH C 6 F 13 COOH C 7 F 15 COOH C 8 F 17 COOH C 9 F 19 COOH C 10 F 21 COOH C 11 F 23 COOH C 12 F 25 COOH C 13 F 27 COOH Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment: Terminology, Classification, and Origins Robert C Buck, James Franklin, Urs Berger, Jason M Conder, Ian T Cousins, Pim de Voogt, Allan Astrup Jensen, Kurunthachalam Kannan, Scott A Mabury, and Stefan PJ van Leeuwen., Integrated Environmental Assessment and Management Volume 7, Number 4 pp , 2011 SETAC 14

15 Per- and Polyfluoroalkyl Substances (PFAS) Perfluoroalkyl Acids (PFAA) Perfluoroalkane sulfonic acids (PFSAs) Perfluorobutanesulfonic acid (PFBS) Perfluoropentane sulfonic acid (PFPeS) Perfluorohexane sulfonate (PFHxS) Perfluoroheptane sulfonate (PFHpS) Perfluorooctane sulfonate (PFOS) Perfluorodecanesulfonic acid (PFDS) C n F 2n+1 SO 3 H C 4 F 9 SO 3 H C 5 F 11 SO 3 H C 6 F 13 SO 3 H C 7 F 15 SO 3 H C 8 F 17 SO 3 H C 10 F 21 SO 3 H Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment: Terminology, Classification, and Origins Robert C Buck, James Franklin, Urs Berger, Jason M Conder, Ian T Cousins, Pim de Voogt, Allan Astrup Jensen, Kurunthachalam Kannan, Scott A Mabury, and Stefan PJ van Leeuwen., Integrated Environmental Assessment and Management Volume 7, Number 4 pp , 2011 SETAC 15

16 Per- and Polyfluoroalkyl Substances (PFAS) Perfluoroalkyl Substances Perfluoroalkane sulfonamides (FASAs), Perfluoroalkane sulfonamido ethanols (FASEs) and N-alkyl perfluoroalkane sulfonamido ethanols (MeFASEs, EtFASEs) Perfluoroalkane sulfonamido acetic acids (FASAAs) and N-alkyl perfluoroalkane sulfonamido acetic acids (MeFASAAs, EtFASAAs) n=7 C n F 2n+1 SO 2 NH(R ) where R =C m H 2m+1 (m=1,2,4) Perfluorooctane sulfonamide (FOSA) C 8 F 17 SO 2 NH 2 N-methylperfluoro-1-octane sulfonamide (N-MeFOSA) C 8 F 17 SO 2 NHCH 3 N-ethylperfluoro-1-octanesulfonamide (N-EtFOSA) C 8 F 17 SO 2 NHCH 2 CH 3 2-(N-methylperfluoro-1-octane sulfonamido)-ethanol (N-MeFOSE) 2-(N-ethylperfluoro-1-octane sulfonamido)-ethanol (N-EtFOSE) N-ethyl-perfluorooctanesulfonamidoacetic acid (N-EtFOSAA) N-methyl-perfluorooctanesulfonamidoacetic acid (N-MeFOSAA) C 8 F 17 SO 2 N(CH 3 )CH 2 CH 2 OH C 8 F 17 SO 2 N(C 2 H 5 )CH 2 CH 2 OH C 8 F 17 SO 2 N(C 2 H 5 )CH 2 CO 2 H C 8 F 17 SO 2 N(CH 3 )CH 2 CO 2 H Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment: Terminology, Classification, and Origins Robert C Buck, James Franklin, Urs Berger, Jason M Conder, Ian T Cousins, Pim de Voogt, Allan Astrup Jensen, Kurunthachalam Kannan, Scott A Mabury, and Stefan PJ van Leeuwen., Integrated Environmental Assessment and Management Volume 7, Number 4 pp , 2011 SETAC 16

17 Per- and Polyfluoroalkyl Substances (PFAS) Polyfluoroalkyl Substances n:2 Fluorotelomer sulfonic acids n=4 C n F 2n+1 CH 2 CH 2 SO 3 H 1H,1H,2H,2H-Perfluorohexanesulfonic Acid (4:2 FTS) 1H,1H,2H,2H-Perfluorooctanesulfonic Acid (6:2 FTS) C 4 F 9 CH 2 CH 2 SO 3 H C 6 F 13 CH 2 CH 2 SO 3 H 1H,1H,2H,2H-Perfluorodecanesulfonic Acid (8:2 FTS) C 8 F 17 CH 2 CH 2 SO 3 H 1H, 1H, 2H, 2H-perfluorododecane sulfonate (10:2 FTS) C 10 F 21 CH 2 CH 2 SO 3 H Perfluoroalkyl and Polyfluoroalkyl Substances in the Environment: Terminology, Classification, and Origins Robert C Buck, James Franklin, Urs Berger, Jason M Conder, Ian T Cousins, Pim de Voogt, Allan Astrup Jensen, Kurunthachalam Kannan, Scott A Mabury, and Stefan PJ van Leeuwen., Integrated Environmental Assessment and Management Volume 7, Number 4 pp , 2011 SETAC 17

18 PFAS National Environmental Management Plan (NEMP) Section 14 Landfill Disposal Landfill siting and design New sites Existing sites Landfill operation Leachate management practices Monitoring at landfills Closure considerations Landfill acceptance criteria PFOS 50 mg/kg ASLP Photo: ABC Goldfields-Esperance: Christien de Garis 18

19 Appendix B: Activities including PFAS Ski wax, outdoor clothing, carpets, outdoor textiles, water-resistant treatments. Tile coatings, stone coatings, paints, varnishes, sealants Fast food packaging pizza boxes. Popcorn bags Teflon: dental floss, non-stick bandages, cookware, plumbers tape 18

20 Consumer Products TOTAL FLUORINE Particle-induced γ-ray emission (PIGE) spectroscopy Combustion ion chromatography Fluorinated Compounds in U.S. Fast Food Packaging L.A. Schaider,* S. A. Balan, A. Blum, D.Q. Andrews, M.J. Strynar, M.E. Dickinson, D.M. Lunderberg, J.R. Lang, and G.F. Peaslee. Environ. Sci. Technol. Lett. 2017, 4,

21 PFAS Landfill Contamination Treatment PFAS have been used in a range of consumer products, such as carpets, clothes and paper, textiles, furniture and household products which at the end-of-life end up in landfills. PFAS are detected in leachate even after treatment for conventional contaminants. Adapted from Prof. Helena Solo-Gabriele and Oliaei et al. 2013) 21

22 Water acceptance criteria Table 1: Health-based guidance values for use in site investigations in Australia Exposure scenario PFOS + PFHxS PFOA Description Comments and source Health-based guidance values 0.07 μg/l 0.56 μg/l Drinking water 0.7 μg/l 5.6 μg/l Recreational water 0.02 μg/kg bw /d 0.16 μg/kg bw /d Tolerable daily intake (TDI) Australian Government Department of Health 2017 Food Standards Australia New Zealand (FSANZ) 2017a 22

23 Landfill acceptance criteria Landfill type Interim landfill acceptance criteria 6,7 Comments PFOS + PFHxS PFOA 6 Waste concentrations must be less than both the relevant leachable concentration and the total concentration values for the type of landfill. 7 Where significant PFAS are present beyond PFOS+PFHxS and PFOA, these solid PFAScontaminated materials may not be acceptable for landfill disposal. This should be discussed with the environmental regulator. Unlined ASLP leachable concentration (μg/l) Total concentration (mg/kg) 0.07 μg/l 0.56 μg/l 20 mg/kg 50 mg/kg Drinking water x 1 (Australian Government Department of Health 2017) Soil Human health industrial/commercial x1 Total concentration for PFOA of 50 mg/ kg (based on the low content limit) Clay/single composite lined ASLP leachable concentration (μg/l) Total concentration (mg/kg) 0.7 μg/l 5.6 μg/l 50 mg/kg 50 mg/kg Drinking water x 10 (Australian Government Department of Health 2017) Soil Human health industrial/commercial x10 Total concentration for PFOS + PFHxS and PFOA of 50 mg/kg (low content limit) Double composite lined ASLP leachable concentration (μg/l) Total concentration (mg/kg) 7 μg/l 56 μg/l 50 mg/kg 50 mg/kg Drinking water x 100 (Australian Government Department of Health 2017) Soil Human health industrial/commercial x100 Total concentration for PFOS + PFHxS and PFOA of 50 mg/kg (low content limit) 23

24 Concentration ng/l or PPT Landfill Data - USA Lang et. al Environ. Sci. Technol. 2017, 51,

25 8:2 10:2 4:2 6:2 N- N- N- N- N- N- FOSA PFBS PFDS PFHpS PFHxS PFOS PFPeS PFBA PFDA PFDoA PFHpA PFHxA PFNA PFOA PFPeA PFTeDA PFTrDA PFUnA Landfill acceptance criteria Landfill X 25

26 8:2 10:2 4:2 6:2 N- N- N- N- N- N- FOSA PFBS PFDS PFHpS PFHxS PFOS PFPeS PFBA PFDA PFDoA PFHpA PFHxA PFNA PFOA PFPeA PFTeDA PFTrDA PFUnA Landfill acceptance criteria 4000 Landfill Y

27 PFAS Distribution in the body 27

28 Total Organofluorine Analysis - Combustion Ion Chromatography (TOFA-CIC) 28

29 Total Organofluorine Analysis - Combustion Ion Chromatography (TOFA - CIC) from Imaging the atomic structure of activated carbon Peter J F Harris et al 2008 J. Phys.: Condens. Matter doi: / /20/36/ Source: Thermo Fisher Scientific Fact sheet BR71114-EN0614S, Combustion IC system Halogen and sulfur determinationspyrolysis of difficult samples,

30 Total Organofluorine Analysis - Combustion Ion Chromatography (TOFA-CIC) Weak anion-exchange interaction Reversed-phase interaction 30

31 Total Organofluorine - Combustion Ion Chromatography (TOF-CIC) 31

32 Aqueous Film Forming Foams (AFFF) 6:2 FTSAS has previously been reported to be present in AFFFs with product names F-500, Tridol S3%, Anslite 3% AFFF-DC-3, Niagara 1-3, and Ansul Ansulite ARC. 6:2 fluorotelomer thioether amido sulfonate (6:2 FTSAS) 6:2 FTAB has been reported to be present in Forafac 1157, F-500, Niagara 1-3, and Tridol S. 6:2 FTSAS = C15H17N1O4S2F13 = 1,000 mg/l 420 mg F/L MW 6:2 FTSAS = MW Fluoride = MW Fluoride in 6:2 FTSAS = amount F = / =

33 PFBS PFBA PFPeA PFHxA PFHxS PFHpA PFOS PFOA PFNA PFDA PFDoA PFUnA PFTrDA PFTeDA PFOSA 4:2 FTS 6:2 FTS 8:2 FTS NEtFOSAA NMeFOSAA Aqueous Film Forming Foams (AFFF) PFOS = 3,600 mg/l or 0.36% w/v Σ8PFAS = 4,729 mg/l Σ8PFAS = 3, mg F/L ΣTOF = 11,000 mg F /L ΣTOF 8,000 mg F /L MISSING! 33

34 PFBS PFBA PFPeA PFHxA PFHxS PFHpA PFOS PFOA PFNA PFDS PFDA PFDoA PFUnA PFTrDA PFTeDA PFOSA 4:2 FTS 6:2 FTS 8:2 FTS 10:2 FTS NEtFOSAA NMeFOSAA Aqueous Film Forming Foams (AFFF) PFHxA = 1.7 mg/l ΣPFAS = 3.2 mg/l ΣPFAS = 2.6 mg F/L ΣTOF = 14,000 mg F /L ΣTOF 14,000 mg F /L MISSING!!! 34

35 PFAS Precursors AFFF formulations are vastly unknown because of proprietary non-disclosures. Electrochemical fluorination technique is a dirty chemistry creating many side products. Target products are just the tip of the iceberg. Abiotic and biological transformation of precursors is now seen as an important consideration for ecological and human health risk assessments. NEMP states sampling and analysis quality plan should investigate whether precursors and their transformation products have migrated along identified pathways and to receptor sites. 35

36 TOP (Total Oxidisable Precursor) Analysis Samples are treated via hydroxyl radical oxidation using an activated agent with overnight heating (85 o C) which converts precursors to PFAA viz PFCA and PFSA. Mass-labelled fluorotelomers are added prior to the cooking procedure to validate the oxidation process. PFCA and PFSA are not altered by this process. PFAS determined by isotope dilution LC-MS/MS before and after TOPA. Mass balance of PFAA to Total PFAS calculated. 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB) 36

37 TOP (Total Oxidisable Precursor) Analysis 4,200%!!! Control TOP 10 80% ΣPFASs increased by ~70% 37

38 Quality Assurance Ensuring the quality of analytical data in the laboratory is essential to ensure ongoing customer confidence in any laboratory s work and this is the purpose of quality assurance (QA) Results you can Trust Metrological Traceability Certified Reference Materials (CRMs) ISO Guide 34 accredited standards Participation in proficiency studies 38 38

39 Quality Assurance Ensuring the quality of analytical data in the laboratory is essential to ensure ongoing customer confidence in any laboratory s work and this is the purpose of quality assurance (QA) Results you can Trust Metrological Traceability Certified Reference Materials (CRMs) ISO Guide 34 accredited standards Participation in proficiency studies 39 39

40 Quality Assurance 40 40

41 Conclusions PFAS are a complex mixture of potentially thousands of compounds. Analysis strategies should include a multidimensional approach TOFA - CIC TOPA LC-MS/MS QToF LC-MS or Orbitrap LC-MS 41

42 Questions Dr. Bob Symons

43 High-resolution Accurate Mass Quadrupole Time-of-Flight (Q-TOF) LC-MS Negative mode Positive mode 43

44 High-resolution Accurate Mass Quadrupole Time-of-Flight (Q-TOF) LC-MS F F F F F F F F F F F F F S O O H 3 C NH OH S CH 3 O 6:2 Fluorotelomer Thioether Amido Sulfonate (6:2 FTAS) 44

45 Lodyne (Fluorotelomer Thioether Amido Sulfonate) 6:2 Fluorotelomer Thioether Amido Sulfonate (6:2 FTAS) 6:2 FTS 6:2 FtUCA 5:3 FtCA PFHxA PFBA PFPeA Adapted from Aerobic Biotransformation of Fluorotelomer Thioether Amido Sulfonate (Lodyne) in AFFF-Amended Microcosms Katie C. Harding-Marjanovic, Erika F. Houtz, Shan Yi, Jennifer A. Field, David L. Sedlak and Lisa Alvarez-Cohen, Environ. Sci. Technol. 2015, 49, Presentation title: Emerging Contaminants PFASs EDR Document owner: Dr. R. Symons Last modified on: February

46 Forafac :2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB) Metabolite M1 Metabolite M2 Metabolite M4 Metabolite M3 Metabolite M5 6:2 fluorotelomer sulfonamide Adapted from The structure of the fire fighting foam surfactant Forafac 1157 and its biological and photolytic transformation products, Morten K. Moe, Sandra Huber, Johan Svenson, An Hagenaars, Martial Pabon, Monika Trümper, Urs Berger, Dries Knapen, Dorte Herzke Chemosphere 89 (2012) Presentation title: Emerging Contaminants PFASs EDR Document owner: Dr. R. Symons Last modified on: February

47 Acknowledgements Thanks to Prof. Jochen Mueller at Queensland Alliance for Environmental Health Sciences (QAEHS) incorporates the former National Research Centre for Environmental Toxicology (Entox) for access to the Quadrupole Time-of-Flight (Q-TOF) LC-MS for high-resolution accurate mass experiments. 47