Document QkQEXkZzqbo1Z0dzZ32KY2n06
State of Knowledge on Per- and Polyfluoroalkyl Substances (PFASs) at
Military Sites
Jennifer Field, Ph.D. Oregon State University
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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
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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
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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
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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
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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 C om m ercial LC-M S/M S < 15 yrs ago s Q uality 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
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PFOA & PFOS Toxicity
Carcinogenicity
Production w orkers1-3 and exposed community studies - 70,000 Ohio & West 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
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Sources & Exposure Pathways
Adapted from Oliaei 2013 Environ Pollut Res 20:1977-1992
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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
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AFFF History
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Proprietary mixtures
Complex mixtures with g/L PFASs
AFFFs (MilSpec) on Qualified Product List1
1965-1976 Light Water (3M) 1976 Ansulite (Ansul) and Aer-O-Water (National Foam) 1994 Tridol (Angus) After 2002 Chemguard (Chemguard), Buckeye (Buckeye),
Fireaide (Fire Service Plus)
Bottom line: Multiple AFFFs used at most sites Detection frequencies:2testing/maintenance >
hangars/buildings > emergency response Other: pipes, storage container areas, oil-water
separators, waste disposal sites
1Steve Fletcher, Fire Protection Engineer, NAVSEA HQ, SEA 05P5; 2Anderson et al. 2016 Chemosphere;Photo courtesy of John Farley, Director, CBD/ex-USS SHADWELL Fire Test Operations, Naval Research Laboratory, Washington DC
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AFFF: Equipment Testing & Training11
Test type C apacity2
N o z z le d is c h a rg e 2
Diluted A F F F (gal) 3,000
10
T ra in in g 3
20
C ra sh 4
50,000
AFFF (L) 341
1.1 2.3 5,678
Event/ yr 1
PFOS
/Ik S N I 3.2 1
PFOA (kg) 0.032
1
0 Qi
0.0011
La4 0.0084 .A 5.3
IP FA S (kg) 4.7
120 yr
/flS N f 93 ]
0.015 0-4-2.
o3i 2.5
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
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3M AFFF: Sole Source 1965-1975
89% PFSAs (e.g., PFOS) in 3M AFFF1'3 Only 1.6% PFCAs(e.g., PFOA) All contribute to total fluorine
PFSAs (C2-C10) PFCAs (C4-C12) :Other Anionic (-)
Zwittterionic (+/-) Other cationic (+)
1Place et al. 2012, ES&T 46:7120-7127;2Backe et al. 2012 ES&T 47:5226523;3Barzen-Hansen and Field 2015 ES&T Letters 2: 95-99
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Polyfluorinated forms in Fluorotelomei
n = 4, 6, 8
AFFFs1'2
,
rJ
none listed on UMCR3 & Method 537 lists
l\
FJn '
l/
tw- s 4 -- NH n =,4,,,6,,,8( i o j j )
note: long chain lengths!
all contribute to total F
-S - forms degrade to
FTSAs & short-chain
n = 5, 7, 9
PFCAs34
6:2 & 8:2 FTSAs =
major degradation
products in groundwater2 (only
F-- -C
n = 5,7, 9
trace levels in AFFF)
n = 6, 8
1Place et al. 2012, ES&T 46:7120-7127;2Backe et al. 2012 ES&T 47:52265234;3Weiner et al. 2013 Environ Chem 10:486-493; 4Harding-Marjanovic et al. 2015 ES&T 49:7666-7674
(biodegradation intermediate)
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Aerobic Biodegradation
Ansul precursor degrades to FTSAs & short-chain (< C6) PFCAs1'2
FTSAs precursors in site groundwater3
FTSAs stable under anoxic conditions ~ decade
-SO- and -S02intermediates in groundwater
|- :F IF
I FF r F |
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Ff : r | r
F-- Fi
FF F
IF |F I F
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- rF
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0s11- o ' n:2 FTSAs
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FI F
fY
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Xr1YtXr' IXo :
1Weiner et al. 2013 Environ Chem 10:486-493; 2HardingMarjanovic et al. 2015 ES&T 49:7666-7674;3Backe et al. 2012 ES&T 47:5226-5234
I'crlliiorohcxiLiutai. iPFHxAl
Pcr:1uoiopcit-inoasc iFFTcA i
PcnUu.whuiuniutc
IPF'B'A!
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PFASs in Groundwater at Military Bases
13 Air Force & Navy bases
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PFSAs and PFCAs not always
the most abundant
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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 ^ ^ ^ ^ ^ --> 34 567 Number of PFAS Classes Present...
6:2FTSA = 14 mg/L
1Schultz et al. 2004 ES&T 38:1828-1835
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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
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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;
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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
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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 21:46344642Res;9http://www.njspotlight.com/stories/15/04/06/drinking-water-panel-calls-for-stncter-standard-on-potentialcarcinogen/;10http://www.villageofhoosickfalls.com/news.html
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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
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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)
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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
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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
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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
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