introduction to per-and polyfluoroalkyl substances … · pfaa, fts, fasa, fasaa, fase, precursors...

INTRODUCTIONTOPER- ANDPOLYFLUOROALKYLSUBSTANCES(PFASS)Jennifer Guelfo, PhDState Agencies Liaison, Brown SRPMay 8th-10th, 2017

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BrownUniversitySuperfundResearchProgram

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INTRODUCTION:ROLEOFRESEARCHTRANSLATION

Thegoalofthesurveyistoidentifykeysitecharacteristics associatedwithPFASsites,andtorecognizerealandperceivedchallengesto

managingsites.Wealsoseektoidentifystakeholders’knowledgeandexperienceswithtreatmentapproaches.

Survey link: goo.gl/zakRX3

Thank you!

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PRESENTATIONOUTLINE

PFAS Overview

Uses & Sources

Regulation, Sampling &

analysis

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PRESENTATIONOUTLINE

PFAS Overview

Uses & Sources


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

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Per=fullyfluorinatedalkyltail.

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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-



F

F

F

F

F

S

m

O

O

O-




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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-



F

F

F

F

F

S

m

O

O

O-




Polyfluroalkyl substancesthatcanundergotransformationtoformperfluoroalkylacids

Whatisaprecursor?

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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.


FigureadaptedfromRef.2

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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.


FigureadaptedfromRef.3

+-

Liquidhydrogenfluoride(HF)

H2

Organicrawmaterial

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

Cathode

2H++2e-èH2

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PFASOVERVIEW:MANUFACTURINGElectrochemicalfluorination4

+-


H2

Organicrawmaterial


AnodeCH4CH3

CH3F

CH2F2CHF3

CF4

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PFASOVERVIEW:MANUFACTURINGElectrochemicalfluorination4

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+-


H2

Organicrawmaterial


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

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Telemorization1,4PFASOVERVIEW:MANUFACTURING

F(CF2)nICF2=CF2Tetrafluoroethylene

n=desiredchainlength


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

+Perfluoroalkyl iodide

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PFASOVERVIEW:MANUFACTURINGTelemorization1,4

F(CF2)nICF2=CF2Tetrafluoroethylene

n=desiredchainlength


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

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PFASOVERVIEW:MANUFACTURINGTelemorization1,4

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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.

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C F𝛿+ 𝛿-

• Strongestcovalentbondinorganicchemistry

• Polarbond

FluorineProperty:highelectronegativity4,5

C CFF

F FF C

O

O


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.


Description:

FluorineProperty:lowpolarizability4,5

- -- -- - +++ +

+ +Polarizable

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• Weakintermolecularinteractions

• Ex:vanderWaals



--- -

-- +++ +

++

Notpolarizable

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• Ex:vanderWaals



• Hydrophobic&lipophobic


--- -

-- +++ +

++

Notpolarizable

C CFF

F FF F

Air

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• Ex:vanderWaals

C CFF

F FF C

O

O-



• Hydrophobic&lipophobic• Surfactant*


--- -

-- +++ +

++

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


• Chemicalstability

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PRESENTATIONOUTLINE

PFAS Overview

Uses & Sources


analysis

• Summaryofstateregulations• Typicalsampleprecautions• TargetmethodsandPFASs,statebystate• Overviewofstandardmethods&labs• Otheranalyticaltools

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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 SoilNewJersey 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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•SomeliteratureshowPFASoccurrenceincosmetics,sunscreens6,7

•Textbooks/literaturesupporthistoricaluseinotherrelevantproducts(butw/nosupportinganalysis)4

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

But…

Isitnecessary?

Bottomline: Manyprecautionsmayproveunnecessarybutcurrentlythereislittledatatosupportwhichcanbeeliminated


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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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


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• PFAA=perfluoroalkyl acids• FASAA=perfluoroalkylsulfonamidoacetic acid

• n:3acid=n:3saturatedacid• FTUCA=fluorotelomer unsaturatedcarboxylicacid• FTCA=flurotelomer carboxylicacid

Method Name Method537 ASTMD7979-16 ASTMD7968-14

MatrixDrinkingwater

Water,influent/effluentwastewater,sludge Soil

CompoundClasses PFAA,FASAAPFAA,n:3acid,FTUCA,FTCA

PFAA,n:3acid,FTUCA,FTCA

Samplecontainer Polypropylene Polypropylene PolypropyleneSamplevolume 250mL 5mL 2g,adjustifneededExtraction SPE None 50:50H2O:MeOHFiltering None Polypropylene PolypropyleneReportingLimits 2.9-14ng/L 10-300ng/L 25-750ng/kgHoldingTimes 14days 28days 28days

Preservation5g/Lbuffer,cooled<10oC Cooled,<6oC Cooled,<6oC

Quantification Internal std. Externalcal.+recoveryof isotopelabeledPFAS

StandardmethodsforPFASs:PFASREGULATION,SAMPLING&ANALYSIS

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Laboratory Method Matrices Compound Classes Aqueous RL*

Axys Internal, TOP

Water, Solid, Air, Tissue, Serum, Urine

PFAA, FTS, FASA, FASAA, PAP, FTCA 1-80 ng/L

EurofinsEPA 537 ordirect injection

Water, Solid, Tissue, Products PFAA, FTS, FASAA 2-10 ng/L

Test America Mod EPA 537, TOP Water, Solid

PFAA, FTS, FASA, FASAA, FASE, precursors 2-100 ng/L

Vista Mod EPA 537Water, Solid, Tissue

PFAA, FTS, FASA, FASE, FASAA 1-40 ng/L

* Reporting limit (RL) range encompass all compound classes; RLs for all labs were below EPA HA levels for PFOS/PFOA

• PFAA=perfluoroalkyl acids• FTS=fluorotelomer sulfonates• PAP=polyfluoroalkyl phosphateesters• FASA=perfluroalkyl sulfonamides• FTCA=fluorotelomer carboxylicacid

• FASE=perfluoroalkyl sulfonamidoethanol• FASAA=perfluoroalkyl sulfonamidoacetic

acid• FTUCA=fluorotelomer unsaturated

carboxylicacid• TOP=totaloxidizable precursors

Commerciallabavailability:PFASREGULATION,SAMPLING&ANALYSIS

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Otheranalyticaltools:totaloxidizable precursor(TOP)assay:

PFCAs0 +PFSAsPrecursors

Add:60mM KS2O8125mM NaOH

React:6hrs850C

Heatedoxidativeconversion

TotalPrecursors=PFAAfinal – PFAA0

PFCAsfinal +PFSAs

• Bulk precursorquantification=totalamt.precursorspresent• Doesnot identifyindividualprecursorcompoundspresent


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PFASREGULATION,SAMPLING&ANALYSISOtheranalyticaltools:mobilelaboratorytechnology

PFASMobileLab:• CascadeEnvironmental• MobileLC-MS/MS• SPE&directinject• DoDQSMPFAS(24)

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PRESENTATIONOUTLINE

PFAS Overview

Uses & Sources

• PFASmanufacturing• AFFF• Othermanufacturing• Wastestreams


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

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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.

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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

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

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

• Solberg• Buckeye

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

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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)

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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)

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Othermanufacturing:MiscellaneousPFASUSES&SOURCES

Electroplating(NAICS332)• PFOSusedasmistsuppressant

ElectroplatingreplacementPFAS8

Paper• PFASusedasgrease/waterrepellant

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

Plusotherusestoonumeroustolist

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PFASUSES&SOURCESOthersources:WWTPs,biosolids,landfills

Consumer/industrialproducts

Biosolids23,24

Leachate19,20

Effluent21,22

Considerations• PFASoccurinindustrially- andmunicpally- sourcedwastestreams• TargetPFASwillvarybasedonwastereceived

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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

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Questions?

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ADDITIONALSTATEBYSTATEINFORMATIONConnecticut

NewHampshire

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ADDITIONALSTATEBYSTATEINFORMATIONNewYork

Moreinfo:http://www.dec.ny.gov/regulations/104968.html

Vermont

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Maine:

ADDITIONALSTATEBYSTATEINFORMATION

Information on screening levels in various media: https://www1.maine.gov/dep/ftp/RAGS-Background-Documents/PFC_ScreeninigLevels_060514.pdf