Measuring Poly/Perfluorinated Alkyl Substances (PFASs) in the - PowerPoint PPT Presentation

Measuring Poly/Perfluorinated Alkyl Substances (PFASs) in the Environment Marc A. Mills, Ph.D. Carolyn Acheson, Ph.D. Kavitha Dasu, Ph.D. * EPA Office of Research and Development Cincinnati, OH *National Research Council fellow Photo image area measures 2” H x 6.93” W and can be masked by a collage strip of one, two or three images. The photo image area is located 3.19” from left and 3.81” from top of page. Each image used in collage should be reduced or cropped to a maximum of 2” high, stroked with a 1.5 pt white frame and positioned edge-to-edge with accompanying images. photo: dupont.com Office of Research and Development National Risk Management Research Laboratory, Land Remediation and Pollution Control Division

Contaminants of Emerging Concern (CECs) • Includes physical, chemical, or biological pollutants • Limited information regarding: • Previously unknown human health effects • Exposures to humans and wildlife not widely documented • Effects of exposures not completely characterized • New materials whose environmental behavior, toxicity, and risk management are not fully understood • Generally, currently not included in routine monitoring programs • May be candidates for future regulation depending on information collected 2 (adapted from the EU NORMAN project: www.norman-network.com , Sept 2006)

Common CECs Categories

Emerging Contaminants enter the environment Sources Environment Risk Management WWTP t n e u l f f E d e t a e r T Pharmaceuticals, consumer products use/disposal Agricultural Other discharges B run off i o s o l i d Treated industrial discharge Trash and Landfill Land application of Biosolids debris direct use in the disposal Plant Uptake environment Photo Courtesy: USEPA, USGS, Artsyltech, West basin, Royer

PFASs Fate and transport • Environmental concerns • Ubiquitous - found world-wide • Residuals during production of fluoropolymers released directly • Preliminary research shows degradation of some fluorotelomers • urethanes and acrylates • kinetics subject of continued research • Fate and transport data is limited due to analytical limitations and minimum physical, chemical, and biological data on the wide range of PFASs in use and their degradation products 5

Effects and Fate • Bioaccumulative in wildlife and humans (rising blood levels) • Adverse effects in laboratory animals and wildlife • PFOS and PFOA shown developmental toxicity 1 • Highly persistent and bioaccumulative (t 1/2 PFOA ~4 yrs in humans) • Alter biosynthesis of gender-specific steroid hormones 1,2 • Decline in thyroid hormone levels 1,3 • Little data about presence in environment (soils, water, groundwater, biosolids, etc) • Environmental controls • Water - 0.4 µg/L for PFOA (US EPA OW, PHA) • Residential soil – 16 mg/kg (US EPA Reg 4, screening level) • PFOS, its salts and perfluorooctane sulfonyl fluoride have been listed under Annex B of the Stockholm Convention on POPs • EPA initiated 2010/2015 PFOA Stewardship Program with 8 global manufacturers - 95% reduction in direct emissions and residuals in products by 2010. Complete elimination by 2015 1 Lau et al., 2007; 2 Biegel et al., 1995 ; 3 Chang et al., 2009

PFASs F F F F F F F H 2 F C C X F H 2 F F F F F F F F x = carboxyl, sulfonyl x = halides, alcohol, olefin, ester Perfluorinated Compounds Polyfluorinated Compounds (Fluorotelomer) • Two primary types of chemistry • Even Numbered Chains • perfluoroalkylsulfonates (PFSA) • precursors • perfluoroalkylcarboxylate (PFCA) • residuals • Different production methods results in different mixtures of even and odd chains

Telomerization Process CF 2 =CF 2 (Taxogen) (Telogen) F(CF 2 CF 2 ) n I CH 2 = CH 2 F(CF 2 CF 2 ) n CH 2 CH 2 I (Telomer B) (FTOH) F(CF 2 CF 2 ) n CH 2 CH 2 OH F(CF 2 CF 2 ) n CH 2 CH 2 OCOR (Monomer) Polymer Products (Acrylates,, Stearate, Citrates, Urethane, etc) • Only even numbered products are formed • > 80% of the fluorotelomer compounds are used as polymers

Fluorotelomer polymer coatings 5 to 6.5 × 10 6 kg of fluorotelomer-based products produced annually U.S. EPA Public Docket AR226-1141, 2002

PFASs use and production • Uses • coatings for textile and apparel • fire fighting foams • manufactured in US or elsewhere • imported or processed to generate commercial goods • many industry segments including aerospace, automotive, building/construction, chemical processing, semiconductors, textiles • Production • PFSA – total production 1970 to 2002 ~100,000 tons • PFCA – world wide in 2006 ~ 10,000 tons 10

Fate and Transformation • Due to difficulty in quantitatively measuring these compounds, environmental data of fate and transport are limited and subject to significant uncertainties • Some species are volatile • fluorotelomer alcohols (FTOHs) • protonated PFOA • Aerobic reactions • complex reaction pathway • some compounds present as residuals in commercial products • must be able to distinguish degradation from transformation of process residuals • Anaerobic reactions - reports of reductive dehalogenation 11

Biodegradation Pathway of Fluorotelomer Derivatives Stable Stable R Stable Stable (Modified from Wang et al., 2009)

Transformation Pathway of Sulfonamide derivatives SO 2 N(R)CH 2 CH 2 OCOM SO 2 N(R)CH 2 CH 2 OH R = methyl, ethyl M = acrylate, methacrylate, urethane N-alkyl perfluoroalkyl sulfonamidoethanol N-alkyl perfluoroalkyl sulfonamido ester/urethane (RFOSE) monomer COO - SO 2 N(R)CH 2 Ester / Urethane Polymer N-alkyl perfluoroalkyl sulfonamidoacetic acid (RFOSAA) COO - SO 2 NHCH 2 Perfluoroalkyl sulfonamidoacetic acid (FOSAA) SO 2 NH 2 Perfluoroalkyl sulfonamide (FOSA)

Importance of precursors and pathways 1000 800 • Example: NP as a function of Time 600 • If only monitoring NP: NP • flat initially (mg/kg dry soil) • 40% increase between 400 70 and 170 days • decrease after 170 days 200 0 0 100 200 300 400 500 600 14 Time

Degradation of precursors to NP – “Created” NP Degradation pathway NP2EO NP 1000 NP1EO NP2EO NP1EO 800 NP 600 Conc • Accounting for the precursors and (mg/kg dry soil) their degradation pattern explains 400 observations • 240 mg of NP2EO converted to 200 mg of NP1EO 200 • eventually 300 mg additional of NP produced 0 0 100 200 300 400 500 600 15 • transformation rate and masses affect observation Time

All NPE Data graphed - molar basis Degradation pathway NP2EO NP 5 NP1EO NP2EO sum of NPEs NP1EO 4 NP 3 Conc • include all relevant (mmol/kg soil) precursors and metabolites in the pathway to track 2 transformation and removal • molar basis simplifies 1 quantitative tracking • molar sum of NPEs – unified variable 0 0 100 200 300 400 500 600 16 Time

Analytical Methods for PFASs • Compounds are chemically different than traditional contaminants • more hydrophilic • fluorocarbon chemistry • levels are typically very low and often in difficult matrices (e.g WWT residuals) • Typical analytical methods • extraction • solid phase • ASE (accelerated solvent extraction) • clean up • measurement using chromatography paired with MS/MS • QA/QC checks are critical to assuring data quality • Analysis of blanks to identify sample contamination • Accounting for ion suppression/enhancement • Surrogate recoveries • Matrix spikes 17

Measuring Selected Perfluorinated Alkyl Acids (PFAA) in biosolids and waste water by LC/MS/MS Shoji Nakayama (NIES, Japan), Kavitha Dasu (NRC/EPA) Marc Mills (USEPA, ORD) 513-569-7322 Example:PFOA - perfluorinated octanoic acid Warning: PFCs are present in most Teflon materials. Anything used in this sampling and analysis effort must be free of Teflon. So test tubes, pipets, glassware have to be non-Teflon and rinsed well with methanol before use. Blanks must be carried through sample and analysis processes to identify interferences. Sample preparation Weigh 0.5 g Biosolid 1 1. Add 2mL of KOH into 4.Shake sample for sample and vortex another 30 min 2. Add 5 mL MeOH and mix 5. Centrifuge the sample 3 . Sonicate sample 6. Collect the supernatant portion for 30 min 7. Add 45ml DI water to the supernatant 2 1 Draft method. Not endorsed by EPA. Please do not cite or quote.

3 2 SPE extraction and Clean up Measurement 15. Load onto LC/MS/MS 8. SPE cartridge : Condition a WAX and ENVI- Carb Cartridge 9. Sample Loading: Data Analysis/QC About 50 mL of sample was passed through the WAX Cartridge then followed by Elution through the ENVI –Carb cartridge. To Elute use 0.1% ammonia in MeOH 11.Concentrate the elute to about 1 mL 12.Add 100uL of IS Check spectra for ion suppression or enhancement. 13.Adjust sample volume to 1 mL with Check Surrogate recovery within 70 – 130%. MeOH Check calibration standards within 70 – 130% of true value. 14. Prep for Instrument Lab and solvent blanks should not contain targets Blank = 1: 1 of MeOH/ mobile phase ( 10mM (no peaks present). Formic Acid). Flag data as suspect if QC fails. Repeat analysis if Samples= 100uL of mobile phase with 100uL sufficient sample. of sample. For frequent violation ( > 10% samples), investigate problem, and repeat the sampling event. 3