Document mp7YNydN8gb7aoYGN1987V68B

State of Knowledge on Per- and Polyfluoroalkyl Substances (PFASs) at Military Sites Jennifer Field, Ph.D. Oregon State University US00007299 j^crc-or-us fM d O O D - E P A D O E Project Team ESTCP Dr. Jennifer A. Field, Oregon State University Environmental analytical chemist Dr. David L. Sedlak, UC Berkeley Advanced oxidation and contaminant fate expert Dr. Usa Alvarez-Cohen UC Berkeley Environmental microbiologist/engineer Dr. Markus Kleber, Oregon State University Soil scientist 2 US00007300 SERDP #E S T C P OUD * EPA DOE 11..... 11T" Technical Objectives Characterize per- and polyfluoroalkyl substances (PFAS) composition of aqueous film-forming foam (AFFF) formulations Characterize PFAS and precursor composition of AFFFcontaminated groundwater, sediment and soil Characterize PFAS biodegradation under aerobic and anaerobic conditions Characterize the sorption of the newly-identified anionic, cationic and zwitterionic PFASs 3 US00007301 ^SERDP I#ESTCP DUD * EPA DOE | wmmmu Unique Chemistry of PFASs C-F bond is the shortest & strongest in nature ^ hydrophobic & oleophobic1 ^ less predictable behavior in laboratory & environmental systems Few engineered/environmental degradation processes, stable in s heat s acid/base s oxidants s biological systems PFOS (periluorooctane sulfonate) 1Krafft and Riess 2015 Chemosphere 129:4-19 (perfluorooctanoate)4 US00007302 SERDP #E S T C P d u d * EPA DOE ^ " Tl ITlT'r " 11 11T" PFASs vs. PFAs = Per and polyfluoroalkyl substances Communicate accurately v contract laboratories, regulatory community, the public, internationally1 PFC = `Perfluorinated' = restrictive term FFFFFFFF s all carbons in aliphatic chain must be bonded only to F s no degradation in environment Polyfluorinated = not all carbons in chain bonded to F s C 2- linkages create `weakness' in molecule s susceptible to biodegradation, abiotic processes (oxidation) 6:2 FISA 1Buck et al. 2011 Integr Environ Assess Manag 7:513-541 US00007303 SERDP #E S T C P OUD * EPA DOE 11..... 11T" Why are PFASs Emerging Now Traditional analytical instruments (GC/MS) for priority pollutants are `blind' to non-volatile PFASs PFAS are measured by LC-MS/MS s Com m ercial L C -M S /M S < 15 yrs ago s Quality standards < 10 yrs ^ Standards for telom er sulfonates = 2015! Significance of field reports of foaming groundwater and soil overlooked Speculation: we associate foam with fun, not contamination 6 US00007304 SERDP #E S T C P d u d * EPA DOE ^ " Tl ITlT'r " 11 11T" PFOA & PFOS Toxicity Carcinogenicity Production workers1-3 and exposed community studies - 70,000 Ohio & W est Virginia residents (C8 Health Project)4 Immunotoxicity Negative associations with antibody levels in children5 and adults6 Many PFASs detected in human blood US, China, Germany (PFSAs, PFCAs, amides, acetic acids, telomer sulfonates, phosphinates, phosphates)1 Based on 3M (industrially-exposed) workers PFOA 2.3 yrs2-3.8 yrs3 ; PFOS 4.8-5.4 yrs3 PFHxS 7 .3 -8 .5 yrs3 (longest reported half life of PFASs) PFBS 25.8 days4 10 'Berg et al. 1987 J Occup M e d ;2 Deposition: Hearing before Leach et I vs. El DuPont de Nemours Company. Civil Action No 01-C-608, Circuit Court of Wood County, West VA, June 25, 2004; A lexander et al. 2003 Occup Environ Med; Lundin et al. 2009 Epidemiology; 4Steenland and Woskie, 2012, Am J Epidemiol; 5Grandjean et al 2012, JAMA; 6Granum et al. 2013 J Immunotox; 7Yeung et al. 2016 Env Chem; 8Bartell et al. 2010, Environ Health Perspec;9Olsen et al. 2007 Environ Health Perspect;10Olsen et al. 2009, Toxicol US00007305 1 Sources & Exposure Pathways Adapted from Oliaei 2013 Environ Pollut Res 20:1977-1992 8 US00007306 SERDP #E S T C P OUD * EPA DOE ^ " Tl ITlTir 11 11T" Total 3M PFAS Production and AFFF Only 3% of 3M's C8-based PFASs used in AFFF1 Military uses `lions share' of AFFF (75% of AFFF Military Other 1US EPA 2000; 2Moody et al. 2000 ES&T 34:3864-3870 US00007307 US00007308 SERDP #E S T C P OUD * EPA DOE 11..... 11T" AFFF: Equipment Testing & Training*11 Test type Capacity2 Nozzle discharge2 Training3 Crash4 Annual equipment testing NFPA 412 stopped by Air Force in 2015 Most personnel training with `live' AFFFs (all formulas) stopped 1990s-2000s 1Kevin Matlock, Fire Emergency Services, AFCEC/CXF;2No fuel used, testing specified in National Fire Association (NFA) Standard 412, annual testing suspended by Air Force in 2015;3500-700 gallons fuel used & training varied by base, twice per year required, may have been quarterly depending on personnel training schedule 11 US00007309 ^S E R D P <>ESTCP ' " * D - EPA DOE ^ 3M AFFF: Sole Source 1965-1975 US00007310 Polyfluorinated forms in Fluorotel kWvi i US00007311 SERDP #E S T C P d u d * EPA DOE ^ " Tl ITlT'r " 11 11T" Aerobic Biodegradation 1Weiner Marjano ES&T 4 US00007312 SERDP #E S T C P OUD * EPA DOE ^ " Tl ITlTir 11 11T" PFASs in Groundwater at Military Bases 13 Air Force & Navy bases 6 PFSAs and PFCAs not always the most abundant 2 PFSAs & PFCAs concentrations EPA's FIAs No site has just PFSAs & COOH S03 FtSA Most Abundant PFAS at Site PFCAs Groundwater concentrations greater than any other aqueous media1 S PFOS = 1 mg/L PFOA = 6.6mg/L o1 ^ 3 ^ ^ ^ ^ --> 4567 Number of PFAS Classes Present... 6:2FTSA = 14 mg/L 1Schultz et al. 2004 ES&T 38:1828-1835 US00007313 SERDP #E S T C P OUD * EPA DOE ^ " Tl ITlTir 11 11T" Closing the Mass Balance: Why Care? Many PFASs used in AFFF & identified in groundwater, sediment/soil that won't be `lists' any time soon Selection of remedial treatments and treatment of drinking water sources requires knowledge of `targets' Increasing regulator and public awareness regarding presence of precursors and `other' PFASs Bottom line: Minimizing/preventing future liabilities 16 US00007314 SERDP #E S T C P OUD * EPA DOE ^ " Tl ITlTir 11 11T" Towards Mass Balance on Fluorine Additional analytical tools for closing the mass balance on fluorine: Total oxidizable precursor (TOP) assay s Quantifies precursor (total PFASs) in groundwater, sediment, soil1 s Closes mass balance in microcosm studies2 Total fluorine by PIGE3 s PFAS in groundwater sorbed onto media to create `target' s 10 nA of 3.4 MeV protons for 180 s s Quantitative, high-throughput ^ Inexpensive screening tool 1Houtz et al. 2013 ES&T 4 7 :93 42-934 9;2Harding-Marjanovic et al. 2015 ES&T 49:7666-7674;3Lunderberg et al. 2015 Fluoros, Golden, CO; US00007315 SERDP #E S T C P d u d * EPA DOE ^ " Tl ITlT'r " 11 11T" UCMR3 Data: Public Water Supply UCMR3: public water systems serving > 10,000 people 3 PFSAs & 3 PFCAs analyzed Positive hits (>MRL) for one or more PFASs (June 2015 database) Drinking water important source of short-chain PFASs1-3 1Gyllenhammar et al. 2015 Environ Res 140:673-683;2Eschauzier et al. 2013 Sci Tot Environ 458:477-485;3Weiss et al. 2012 Inti Hyg Environ Health 215:212-215 18 US00007316 SERDP #E S T C P OUD * EPA DOE ^ " Tl ITlTir 11 11T" Sources & Fingerprinting Landfill Leachate (municipal refuse/consumer products) ^ 2nd place (|ig/L)1'3 s short-chain PFCAs & fluorotelomer acids3 Municipal wastewater effluent 3rd place (< 0.1 ^g/L)445 Chromium electroplating (mist suppression)78 Industrial (plastics/polymer) manufacturing PFNA in NJ9& PFOA in NY10 Other: municipal airports & fire departments, oil refineries 1Allred et al. 2014 J Chrom A 1359: 202-211 ;2Allred et al. 2015 ES&T 49:7648-7656;3Benskins et al. 2012 ES&T 46:11532-11540; 4Schultz et al. 2006 ES&T 40:289-295l;5Sinclair and Kannan 2006 ES&T 40:1408-1414 ;6Logananthan et al 2007 Water Res 41:4611-4620;7EPA Region 5 PFOS Chromium Electroplater Study, 2009; 8Yang et al. 2014 Env Sci Pollut 21:46344 6 4 2 R e s ;9h ttp ://w w w .n js p o tlig h t.c o m /s to rie s /1 5 /0 4 /0 6 /d rin k in g -w a te r-p a n e l-c a lls -fo r-s tn c te r-s ta n d a rd -o n -p o te n tia lc a rc in o g e n /;10h ttp ://w w w .villa g e o fh o o s ic k fa lls .c o m /n e w s .h tm l 19 US00007317 SERDP #E S T C P OUD * EPA DOE ^ " Tl ITlTir 11 11T" Transport Generalizations Transport related to chemical structure & charge/ionization ^ For anions, shorter chain lengths generally migrate faster (less retardation, lower Koc)1"3 likely to impact surface waters challenging to remove by GAC4 s Transport potential: anions > zwitterions > cations ^ For many polyfluorinated forms, transport will depend on pH and molecule's charged state (ionic or neutral), ionic strength, ion exchange capacity Cationic forms potentially cation exchanged onto source-zone sediments ^ Mobile or immobile under what conditions? ^ Caution when applying oxidants to source-zone sediments, potential to liberate PFASs as water soluble, short-chain forms5"9 that are most difficult to remove 1Higgins et al. 2006 ES&T,40:7251 -7256;2Higgins and Luthy, 2007 ES&T 41:3254-3261 ;3Guelfo and Higgins 2013 ES&T 47:4164-4171 ;4Appleman etal. 2014 Wat Res 51:246-255;5Houtz and Sedlak, 2012 ES&T 46: 9342-9349;6Houtz and Sedlak, 2013 ES&T 47: 8187-8195;7Yang et al. 2014, Environ Sci Pollut 21: 4634-4642;8Fang et al. 2015 Environ Tox Chem 34: 2625-2628;9Park et al. 2016 Chemosphere 145: 376-383 US00007318 SERDP #E S T C P d u d * EPA DOE ^ " Tl ITlT'r " 11 11T" New SERDP/ESTCP Projects . ESTCP Project ER-201574-T2 "Catalyzing Rapid Information Transfer Among Key Stakeholders on Per- and Polyfluoroalkyl Substances (PFASs) at Contaminated Military Sites" OSU lead (J. Field) . SERDP Project ER-2627 "Advancing the Understanding of the Ecological Risk of Per- and Polyfluoroalkyl Substances" Townson University lead (C, Salice) . ESTCP Project ER-201633 "Characterization of the Nature and Extent of Per- and Polyfluoroalkyl Substance (PFASs) in Environmental Media at DoD Sites for Informed Decision-Making" Navy lead (J. Kornuc) 21 US00007319 SERDP #E S T C P OUD * EPA DOE ^ " Tl ITlTir 11 11T" Conclusions PFOS and PFOA are important but not the only major PFASs at AFFF-contaminated sites Fluorotelomer-based substances partially biodegrade to metastable intermediates, including short-chain PFCAs, but not to PFOS Mobility in groundwater anions > zwitterions > cations Anion mobility depends on chain length Mobility of many substances influenced by sediment, soil and water geochemistry 22 US00007320 .......................... <^SERDP I <^>ESTCP ' " * DUD - bPA DOE | " Benefits of Future SERDP/ESTCP Projects to DoD Hundreds of fire/crash testing (mixed waste) sites Full characterization of PFAS contamination v More accurate conceptual site models v Identify remedial approaches that decrease time and cost v Optimized monitoring v Fingerprinting to differentiate AFFF from other sources s Source zone identification s Accurate predictions of transport s Indicators of in situ biotransformation Groundwater contaminated by PFAS used as drinking water source is a potential exposure pathway for humans and wildlife * Attention to short-chain PFAS highly mobile, difficult to remove from water 23 US00007321 Fora isit https://www.serdp-estcp.org/Program- Areas/Environmental-Restoration/Contaminated- Groundwater/Emerging-lssues/ER-2128 Speaker Contact Information Jennifer.Field@Oregonstate.edu 541-737-2265 US00007322