introduction to poly-and perfluoroalkyl substances (pfas) · 14.mcguire, meghan e., et al....

INTRODUCTIONTOPOLY- ANDPERFLUOROALKYLSUBSTANCES(PFAS)Jennifer Guelfo, PhDState Agencies Liaison, Brown SRPMay 8th-10th, 2017

1

BrownUniversitySuperfundResearchProgram

NewEnglandPFASdrinkingwaterissuesemerge

Effectivemanagementtoolsinplace

Stakeholderknowledgeneeded

ResearchTranslationtoStakeholders

Stakeholdersouline criticalchallenges

CompletePFASresearch

DevelopPFASresearchobjectives

INTRODUCTION:ROLEOFRESEARCHTRANSLATION

4

PRESENTATIONOUTLINE

PFAS Overview

Uses & Sources

Regulation, Sampling &

analysis

5

PRESENTATIONOUTLINE

PFAS Overview

Uses & Sources

Regulation, Sampling &

analysis

• Terminology• ManufacturingProcesses• Chemistry

61Buck, Robert C., et al. Integrated environmental assessment and management 7.4 (2011): 513-541.

PFASOVERVIEW:TERMINOLOGY&STRUCTURE1

PFASOVERVIEW:TERMINOLOGY&STRUCTURE

F

F

F

F

F

C

m

O

O-

Perfluoroalkyl carboxylates(PFCAs):

Examples:m=2PFBAm=4PFHxAm=6PFOA

F

F

F

F

F

S

m

O

O

O-

Perfluoroalkane sulfonates(PFSAs):

Examples:m=3PFBSm=5PFHxSm=7PFOS

7

Per=fullyfluorinatedalkyltail.

8

Polyfluoroalkyl substances:m=56:2FtSm=78:2FtSF

F

F

F

Fm

H

H2

S

O

O

O-

Poly=partiallyfluorinatedalkyltail.

F

F

F

F

F

C

m

O

O-

Perfluoroalkyl carboxylates(PFCAs):

Examples:m=2PFBAm=4PFHxAm=6PFOA

F

F

F

F

F

S

m

O

O

O-

Perfluoroalkane sulfonates(PFSAs):

Examples:m=3PFBSm=5PFHxSm=7PFOS

PFASOVERVIEW:TERMINOLOGY&STRUCTURE

9

Polyfluoroalkyl substances:m=56:2FtSm=78:2FtSF

F

F

F

Fm

H

H2

S

O

O

O-

Per + Poly =Per &polyfluoro alkylsubstances(PFAS)

F

F

F

F

F

C

m

O

O-

Perfluoroalkyl carboxylates(PFCAs):

Examples:m=2PFBAm=4PFHxAm=6PFOA

F

F

F

F

F

S

m

O

O

O-

Perfluoroalkane sulfonates(PFSAs):

Examples:m=3PFBSm=5PFHxSm=7PFOS

PFASOVERVIEW:TERMINOLOGY&STRUCTURE

Polyfluroalkyl substancesthatcanundergotransformationtoformperfluoroalkylacids

Whatisaprecursor?

10

8:2 FtTAoS(precursor)

8:2 FtS(intermediate)

PFOA(terminal endpoint)

2. Harding-Marjanovic, Katie C., et al. "Aerobic biotransformation of fluorotelomer thioether amido sulfonate (Lodyne) in AFFF-amended microcosms." Environmental science & technology 49.13 (2015): 7666-7674.

PFASOVERVIEW:TERMINOLOGY&STRUCTURE

FigureadaptedfromRef.2

11

3. Backe, Will J., Thomas C. Day, and Jennifer A. Field. "Zwitterionic, cationic, and anionic fluorinated chemicals in aqueous film forming foam formulations and groundwater from US military bases by nonaqueous large-volume injection HPLC-MS/MS." Environmental science & technology 47.10 (2013): 5226-5234.

PFASOVERVIEW:TERMINOLOGY&STRUCTURE

FigureadaptedfromRef.3

+-

Liquidhydrogenfluoride(HF)

H2

Organicrawmaterial

4. Kissa, Erik, ed. Fluorinated surfactants and repellents. Vol. 97. CRC Press, 2001.

Cathode

2H++2e-èH2

12

PFASOVERVIEW:MANUFACTURINGElectrochemicalfluorination4

+-

Liquidhydrogenfluoride(HF)

H2

Organicrawmaterial

4. Kissa, Erik, ed. Fluorinated surfactants and repellents. Vol. 97. CRC Press, 2001.

AnodeCH4CH3

CH3F

CH2F2CHF3

CF4

13

PFASOVERVIEW:MANUFACTURINGElectrochemicalfluorination4

14

+-

Liquidhydrogenfluoride(HF)

H2

Organicrawmaterial

4. Kissa, Erik, ed. Fluorinated surfactants and repellents. Vol. 97. CRC Press, 2001.

C8F17SO2FOctanesulfonyl fluoride

C8H17SO2FPerfluorooctane sulfonyl

fluoride

C8F17SO2FPerfluorooctane sulfonyl

fluoride

C8F17SO2HPerfluorooctane sulfonic

acid(PFOS)

AnodeCH4CH3

CH3F

CH2F2CHF3

CF4

Electrochemicalfluorination4PFASOVERVIEW:MANUFACTURING

YZ +nA Y- (A)n - ZTelogen Taxogen Telomer

15

Telemorization1,4PFASOVERVIEW:MANUFACTURING

F(CF2)nICF2=CF2Tetrafluoroethylene

n=desiredchainlength

YZ +nA Y- (A)n - ZTelogen Taxogen Telomer

F(CF2)2IPerfluoroalkyl iodide,e.g.pentafluoroethyl iodide

+Perfluoroalkyl iodide

16

PFASOVERVIEW:MANUFACTURINGTelemorization1,4

F(CF2)nICF2=CF2Tetrafluoroethylene

n=desiredchainlength

YZ +nA Y- (A)n - ZTelogen Taxogen Telomer

F(CF2)2IPerfluoroalkyl iodide,e.g.pentafluoroethyl iodide

+

Perfluoroalkyl iodideF(CF2)nCH2CH2ICH2=CH2

Ethylene n:2Fluorotelomer iodideF(CF2)nI +Ex.1

Perfluoroalkyl iodideCF3(CF2)n-1CF2OOH+½I2Perfluoroalkyl carboxylicacid

F(CF2)nIEx.2 Oleum,heat,pressure

Perfluoroalkyl iodide

17

PFASOVERVIEW:MANUFACTURINGTelemorization1,4

18

PFASOVERVIEW:CHEMISTRY

C F𝛿+ 𝛿-

• Strongestcovalentbondinorganicchemistry

• Polarbond

FluorineProperty:highelectronegativity4,5

Description: Effects:

5. Banks, Ronald Eric, Bruce E. Smart, and J. C. Tatlow, eds. Organofluorine chemistry: principles and commercial applications. Springer Science & Business Media, 2013.

19

C F𝛿+ 𝛿-

• Strongestcovalentbondinorganicchemistry

• Polarbond

FluorineProperty:highelectronegativity4,5

C CFF

F FF C

O

O

Description: Effects:

ResultingPFASproperties:

H

+

-

• Strongacidity(lowpKa)*• Thermalstability• Chemicalstability

*Whenpairedwithanacidicfunctionalgroup

PFASOVERVIEW:CHEMISTRY4,5

5. Banks, Ronald Eric, Bruce E. Smart, and J. C. Tatlow, eds. Organofluorine chemistry: principles and commercial applications. Springer Science & Business Media, 2013.

PFASOVERVIEW:CHEMISTRY

Description:

FluorineProperty:lowpolarizability4,5

- -- -- - +++ +

+ +Polarizable

21

PFASOVERVIEW:CHEMISTRY

• Weakintermolecularinteractions

• Ex:vanderWaals

Description: Effects:

FluorineProperty:lowpolarizability4,5

--- -

-- +++ +

++

Notpolarizable

22

PFASOVERVIEW:CHEMISTRY

• Weakintermolecularinteractions

• Ex:vanderWaals

Description: Effects:

ResultingPFASproperties:

• Amphiphilic(hydrophobic&lipophobic

FluorineProperty:lowpolarizability4,5

--- -

-- +++ +

++

Notpolarizable

C CFF

F FF F

Air

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PFASOVERVIEW:CHEMISTRY

• Weakintermolecularinteractions

• Ex:vanderWaals

C CFF

F FF C

O

O-

Description: Effects:

ResultingPFASproperties:

• Amphiphilic(hydrophobic&lipophobic

• Surfactant*

FluorineProperty:lowpolarizability4,5

--- -

-- +++ +

++

Notpolarizable

*Whenpairedwithahydrophilicfunctionalgroup

Air Water

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CHEMISTRY3FluorineProperty:smallsize4,5

Description:9F17Cl35Br53I85At

• Atomicradius=0.72Å• Shieldscarbon

Effects:

CC

CC

R-

F

F

F

F

ResultingPFASproperties:

• Chemicalstability

25

PRESENTATIONOUTLINE

PFAS Overview

Uses & Sources

Regulation, Sampling &

analysis

• Summaryofstateregulations• TargetmethodsandPFASs,statebystate• Typicalsampleprecautions• Aretheyreallyneeded?

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PFASREGULATION,SAMPLING&ANALYSIS

State DrinkingWaterStandard OtherMatrices? Which?

Connecticut70ng/L∑PFOA,PFOS,PFNA,PFHxS,PFHpA Yes Soil,groundwater

Maine 70 ng/L∑PFOA,PFOS1 Yes1

Soil,sediment,groundwater,surfacewater,fish

Massachusetts 70ng/L∑PFOA,PFOS No NANewHampshire 70ng/L∑PFOA,PFOS Yes Soil

NewJersey 40 ng/LPFOA2 10 ng/LPFNA2 No NANewYork 70 ng/L∑PFOA,PFOS3 No NARhodeIsland 70ng/L∑PFOA,PFOS No NAVermont 20ng/L∑PFOA,PFOS Yes Soil1.Guidelines(notstandards)2.Standardunderreview3.OtherPFASsmaybeconsideredif∑PFOA,PFOSisslightlylessthan70ng/L

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State DrinkingWater SoilGround- andSurfacewater TargetPFAS

CT EPA537 ASTMD-7968-14 ASTMD7979-15 Nosetlist(moreisbetter)ME EPA537 EPA537 EPA537 26PFAS(listnotprovided)

MAEPA537orotherapprovedmethod NA NA UCMR3

NH

DoD/NELAPcertifiedlaborEPA537

DoD/NELAPcertifiedlab

DoD/NELAPcertifiedlab

PFBA,PFPeA,PFHxA,PFHpA,PFOA,PFNA,PFBS,PFHxS,PFOS

NJ EPA5371 NA NA

PFHxA,PFHpA,PFOA,PFNA,PFDA,PFUnA,PFDoA,PFTrDA,PFTA,PFBS,PFHxS,PFOS

NYEPA537(past)ISO25101(now) NA NA

UCMR3+othersdependingonlab

RI EPA537 NA NA SeeNewHampshire

VT EPA537 EPA537UCMR3required,12usuallyreported

DoD=DepartmentofDefenseNELAP=NationalEnvironmentalLaboratoryAccreditationProgram1.AtNJDEP-certifiedlabwithRL≤6ng/LforPFOAand≤10ng/LforallotherPFASs

PFASREGULATION,SAMPLING&ANALYSIS

28

PFASREGULATION,SAMPLING&ANALYSIS

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•SomeliteratureshowPFASoccurrenceincosmetics,sunscreens6,7

•Textbooks/literaturesupporthistoricaluseinotherrelevantproducts(butw/nosupportinganalysis)4

•Noliteraturedataabouttransferfromprohibiteditemsduringsampling•Unpublisheddatasuggestsnotransferfrommanyfieldmaterials(e.g.personalproducts,fieldnotebooks,etc.)

But…

?

Bottomline: Manyprecautionsmayproveunnecessarybutcurrentlythereislittledatatosupportwhichcanbeeliminated

PFASREGULATION,SAMPLING&ANALYSIS

6. Keawmanee, Sasipin, Suwanna Kitpati Boontanon, and Narin Boontanon. "Method development and initial results of testing for perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) in waterproof sunscreens." Environmental Engineering Research 20.2 (2015): 127-132.

7. Fujii, Yukiko, Kouji H. Harada, and Akio Koizumi. "Occurrence of perfluorinated carboxylic acids (PFCAs) in personal care products and compounding agents." Chemosphere 93.3 (2013): 538-544.

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PRESENTATIONOUTLINE

PFAS Overview

Uses & Sources

• PFASmanufacturing• AFFF• Othermanufacturing• Wastestreams

Regulation, Sampling &

analysis

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PFASUSES&SOURCESPFASManufacturing(NAICS325)8,9PFASmanufacturers• Arkema• Asahi• BASF/Ciba• Clariant

• Daikin• 3M/Dyneon• DuPont/Chemours• SolvaySolexis

Currentmanufacturingfocus:• 3M:noAFFForfoodwrappers,currentfocuson‘shortchain’(PFCA<8,PFSA<6),Ex:PFBS-basedproducts,ADONA

• DuPont:GenX (aperfluropolyether)• Daikin:6:2fluorotelomer products• Solvay:perfluoropolyethers• Asahi:perfluoropolyethers

8. Wang, Zhanyun, et al. "Fluorinated alternatives to long-chain perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkanesulfonic acids (PFSAs) and their potential precursors." Environment international 60 (2013): 242-248.

9. http://www.3m.com/3M/en_US/sustainability-us/policies-reports/3m-and-fluorochemicals/

• Dynax

32

PFASUSES&SOURCESPFASManufacturing(NAICS325)

Sourcezoneexamples:10,11• 3M,MN• 3M,AL• Daikin,AL

10. Yingling, Virginia. "Perfluorochemicals: How Groundwater-Surface Water Interactions Helped Create a Megaplume." 2014 NGWA Groundwater Summit. Ngwa, 2014.

11. Oliaei, Fardin, et al. "PFOS and PFC releases and associated pollution from a PFC production plant in Minnesota (USA)." Environmental Science and Pollution Research 20.4 (2013): 1977-1992.

33

AFFFandPFAS:13• 3M,1980’s-2000:

• ~7-13g/LPFCAs+PFSAs• 4.9-11.4g/LPFOS• 0.5-1.4g/LPFHxS• Negligibleprecursors

• 3M,NationalFoam,Buckeye,Chemguard,Ansul,2000’s-present:

• NegligiblePFCAs+PFSAs• Primarilyprecursors

H2O + AFFF

Liquid hydrocarbon

PFAS (fluorocarbon surfactant)Hydrocarbon surfactant

AqueousFilmFormingFoams(AFFF,NAICS325)PFASUSES&SOURCES

12.Moody, Cheryl A., and Jennifer A. Field. "Perfluorinated surfactants and the environmental implications of their use in fire-fighting foams." Environmental science & technology 34.18 (2000): 3864-3870.

13.Houtz, Erika F., et al. "Persistence of perfluoroalkyl acid precursors in AFFF-impacted groundwater and soil." Environmental science & technology 47.15 (2013): 8187-8195.

Adapted from ref. 12

34

PFASUSES&SOURCESAFFFmanufacturers:• 3Mbefore2002• Chemguard• Ansul• NationalFoam• Angus

AFFFendusers:• DepartmentofDefense• Airports• Firestations• Firetrainingareas• Petroleum(NAICS324)

• Solberg

Sourcezoneexamples:14-16• EllsworthAFB,SD• Wurtsmith AFB,SD

14. McGuire, Meghan E., et al. "Evidence of remediation-induced alteration of subsurface poly-and perfluoroalkyl substance (PFAS) distribution at a former firefighter training area." (2014).

15.Moody, Cheryl A., et al. "Occurrence and persistence of perfluorooctanesulfonate and other perfluorinated surfactants in groundwater at a fire-training area at Wurtsmith Air Force Base, Michigan, USA." Journal of Environmental Monitoring 5.2 (2003): 341-345.

16.Schultz, Melissa M., et al. "Quantitative determination of fluorotelomer sulfonates in groundwater by LC MS/MS." Environmental science & technology 38.6 (2004): 1828-1835.

PFOS • TyndallAFB,FL

35

Emulsionpolymerization

EmulsionpolymerizationandPFASs• PFOAhistoricallyforPTFEandothers• PFNAhistoricallyforpolyvinylidene fluoride(PVDF)• Usedas‘polymerizationaids’inemulsionpolymerization• Solubilizemonomers• Generatesfinepowderanddispersedfluoropolymers• Usedprimarilyincoatings(e.g.metals,plastics,fabrics)

Tetrafluoroethylene (TFE) Polytetrafluoroethylene (PTFE)

PFASUSES&SOURCESOthermanufacturing:fluoropolymer(NAICS325,326)

36

PFASUSES&SOURCES

Sourcezoneexamples:17,18• DuPont,Parkersburg,WV• St.Gobain,NY,VT

Examplereplacementpolymerizationaids:8

17. Davis, Katherine L., et al. "Transport of ammoniumperfluorooctanoate in environmental media near a fluoropolymermanufacturing facility." Chemosphere 67.10 (2007): 2011-2019.

18.Shin, Hyeong-Moo, et al. "Environmental fate and transport modeling for perfluorooctanoic acid emitted from the Washington Works Facility in West Virginia." Environmental science & technology 45.4 (2011): 1435-1442.

Othermanufacturing:fluoropolymer(NAICS325,326)

37

Othermanufacturing:MiscellaneousPFASUSES&SOURCES

Electroplating(NAICS332)• PFOSusedasmistsuppressant

ElectroplatingreplacementPFAS8

Paper• PFASusedasgrease/waterrepellant

Textiles(NAICS313),carpets(NAICS314,561),furnishings(NAICS423)• Stain-resistantcoatings• Textilessourcezone:Amherst,NH(NHDES)

Plusotherusestoonumeroustolist

38

PFASUSES&SOURCESOthersources:WWTPs,biosolids,landfills

Consumer/industrialproducts

Biosolids23,24

Leachate19,20

Effluent21,22

Considerations• PFASoccurinindustrially- andmunicpally- sourcedwastestreams• TargetPFASwillvarybasedonwastereceived

39

Othersources:WWTPs,biosolids,landfills

PFASUSES&SOURCES

19. Benskin, Jonathan P., et al. "Per-and polyfluoroalkyl substances in landfill leachate: patterns, time trends, and sources." Environmental science & technology 46.21 (2012): 11532-11540.

20. Huset, Carin A., et al. "Quantitative determination of fluorochemicals in municipal landfill leachates." Chemosphere 82.10 (2011): 1380-1386.

21. Loganathan, Bommanna G., et al. "Perfluoroalkyl sulfonates and perfluorocarboxylates in two wastewater treatment facilities in Kentucky and Georgia." Water Research 41.20 (2007): 4611-4620.

22. Schultz, Melissa M., et al. "Fluorochemical mass flows in a municipal wastewater treatment facility." Environmental science & technology 40.23 (2006): 7350.

23. Yoo, Hoon, et al. "Analysis of perfluorinated chemicals in sludge: Method development and initial results." Journal of Chromatography A 1216.45 (2009): 7831-7839.

24. Sepulvado, Jennifer G., et al. "Occurrence and fate of perfluorochemicals in soil following the land application of municipal biosolids." Environmental science & technology 45.19 (2011): 8106-8112.

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PFASUSES&SOURCESPotentialPFASsources,RI

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41.2

41.4

41.6

41.8

42.0

−71.8 −71.6 −71.4 −71.2Longitude

Latit

ude

FacilityType

●

●

●

●

●

airport

fire station

fire training

landfill

manufacturing facility

Futureworkandresources:• FrameworkforgeospatialIDof

potentialPFASsourcezones(Brown)•NIEHSwebinar(6/17):https://www.niehs.nih.gov/research/supported/centers/srp/events/riskelearning/analytical/index.cfm

• PFASFactSheets(ITRC)•History&Use(8/17)•Nomenclature(8/17)•RegulatorySummary(8/17)•Fate&Transport(12/17)•SiteCharacterization(12/17)•Remediation(12/17)•Reviewedby:EPA,DOD,DOE,industry,stakeholder,academic