advancing environmental solutions itrc pfas team...environmental protection kate emma schlosser, new...

8/3/20

1

Advancing Environmental Solutions

ITRC PFAS Team

US DOE ASP WORKSHOPAUGUST 11 – 13, 2020

ITRC PFAS Team Leaders:Bob Mueller, New Jersey Department of Environmental ProtectionKate Emma Schlosser, New Hampshire Department of Environmental Services

1

Welcome & Overview of ITRC Team

PFAS Background and Regulations

Richard Spiese, VT DEChttps://pfas-1.itrcweb.org

2

8/3/20

2

PFAS Team Subgroup Leaders

3

History& Use and Naming Conventions

Fate & Transport, Physical/Chemical Properties and Site Characterization

Regs, Toxicity and Risk Assessment

• Jeff Wenzel, MO • Sandra Goodrow, NJ • Brie Sterling, PA

• Jeff Hale, Parsons • Ryan Thomas, GHD • Linda Hall, GSI

Surface Water Quality Treatment Methods Risk Communication

• Alex MacDonald, CA • Cliff Shierk, MN • Kerry Kirk Pflugh, NJ

• Linda Logan • Scott Grieco, Jacobs • Mel Harclerode, CDM Smith

Sampling & Analysis AFFF Training• Kristi Herzer, VT • Richard Spiese, VT • Bob Mueller, NJ

• Janice Willey, US Navy • Shalene Thomas, Wood plc • Dora Chiang, CDM Smith

Stakeholders

• Peter Strauss, PM Strauss & Assoc.

3

What is ITRC?

u ITRC is a state-led coalition working to advance the use of innovative environmental technologies and approaches. ITRC’s work translates good science into better decision making.

u Since 1995, ITRC has grown into a national organization representing 50 states, D.C., and Puerto Rico.

4

4

8/3/20

3

How We Achieve Our Mission

5

Select Projects Form Team

Develop Documents, Training, and Other Tools

Conduct Training and

OutreachImplement Solutions

5

ITRC PFAS Team

6

PurposeState and federal environmental regulators and others need easily accessible information

to aid them in evaluating risks and selecting appropriate response actions at PFAS release sites

500+ PFAS experts from all sectors:

academics; state and local gov’t;

stakeholders; federal; industry and consulting

Producing concise technical resources for

project managers –regulators, consultants, responsible parties, and

stakeholders

2017-2018: Series of PFAS Fact Sheets

2018-2021: Web-based Technical and

Regulatory Guidance Document; Training

Workshops; Risk Communication Toolkit; Roundtable Webinars

6

8/3/20

4

PFAS Team Schedule – through December 2021

u Continue work on updating technical information and regulatory approaches in this rapidly evolving subjectu Fact sheet reconciling and republishing – 4-page versionsu New work on small updates and reference additions to the Tech Regu New content and major updates to the Tech Reg by the end of 2021

uNew surface water quality overview section – in progressu PFAS Roundtable webinars

u Groups of topics, next offering October 6u Physical & Chemical Properties, Site Characterization and Fate and Transport

7

7

Membership for 2020

u 2019 membership 630u 2020 membership 612

u Members = 329u Interested parties = 283

u We have state members and interested parties from 48 states & Washington DC

8

8

8/3/20

5

PFAS Technical and Regulatory Guidance Document Publishedu Final web document posted and announced 4/15/20

u https://pfas-1.itrcweb.orgu Seven Fact Sheet updates (April 2020) were reposted

u https://pfas-1.itrcweb.org/fact-sheets/u Spreadsheets

u PFAS Water and Soil Values Table updated regularly, current version June 2020u Basis for PFOA and PFOS values for drinking water in the US, current version March 2020

u Ten online video modules published on YouTubeu Accessible from the PFAS document home screen

u Risk Communication Toolkit published July 2020 u https://rct-1.itrcweb.org

9ITRC. 2020. PFAS Technical and Regulatory Guidance Document and Fact Sheets PFAS-1. Washington, D.C.. https://pfas-1.itrcweb.org/.

9

Technical and Regulatory Guidance Document

u https://pfas-1.itrcweb.org

10

What are PFAS?

• Introduction• History and use• Naming

conventions• PFAS releases to

the environment• Firefighting foams

How do they behave in the environment?

• Physical and chemical properties

• Fate and transport processes

• Media-specific occurrence

Why are we concerned about

PFAS?

• Human and ecological health effects

• Site risk assessment

• Regulations, guidance and advisories

How do we evaluate PFAS in the environment?

• Site Characterization

• Sampling and Analytical Methods

• Case Studies

How do we remediate PFAS?

• Treatment technologies

• Case studies

What are the major concerns and how do we share what

we know?• Stakeholder

perspectives• Risk

communication

10

https://pfas-1.itrcweb.org/


8/3/20

6

Document Information: External files

u Twelve external files for additional detailed informationu PFAS Water and Soil Values – updated regularly, includes US and some International valuesu Basis for PFOA and PFOS drinking water values in the USu Physical and chemical propertiesu Bioconcentration factors tablesu Ecological toxicity data summaryu Analytical methodsu Treatment technologiesu Water treatment case studies operation summariesu Toxicological effects in mammalian species for some PFASu Social Factors vision board

11

https://pfas-1.itrcweb.org

11

What Are Per- and Polyfluoroalkyl Substances (PFAS)?

u Large class of surfactants (>4000) with unique chemical & physical properties that make many of them extremely persistent and mobile in the environment

u Used since 1940s in wide range of consumer and industrial applications

Source: open access images – bing.com

12PFAS-1, Section 1 Introduction

12

8/3/20

7

Some PFAS Basics

u Per = fully fluorinatedu Poly = partially fluorinatedu Carbon – fluorine bond extremely strongu Length of carbon chain & functional group in large part

regulates the behavior of PFAS in the environmentu Longer chain and sulfonates – relatively less soluble, relatively better

sorbed, more likely to accumulate in animalsu Shorter chain and carboxylates – relatively more soluble, relatively less

well sorbed, more likely to accumulate in plants

13

TAIL HEAD

PFAS-1, Section 2.2 Chemistry, Terminology and Acronyms

13

PFAS Are Widespread in the Environment…

14

https://www.fws.gov/alaska/fisheries/mmm/polarbear/pbmain.htm

Source: Open source, Pixabay

Source: Open source, Pixabay

Source: Figure Courtesy of Geosyntec

PFAS-1, Section 6 Media-Specific Occurrence

14

8/3/20

8

…Leading to Concerns of Health and Ecological Risks

15

UCMR3: PFOS and PFOA Detections in Public Water Supplies

Detected < LHAExceeds LHA

US EPA Lifetime Health Advisory(LHA):70 parts per trillion (ppt) for PFOS + PFOA

Map data ©2016 Google

Figure used with permission from Andy Eaton, Eurofins-Eaton Analytical

ITRC PFAS Remediation writing subgroup call

15

16Figure by W. DiGuiseppi, Jacobs - used with permission. Data current as of August 3, 2020

0.07 0.07

24

300

0.29

0.56

0.035

2

0.07 0.07

0.02 0.02

PFOA

PFOS

0.070.07

0.070.07

0.010.01

0.070.07

0.667

0.667

0.070.07

0.010 0.040

0.015

NOT TO SCALE

0.008 0.016

0.013

Guidelines and Standards (µg/L)PFOA, PFOS

0.07 0.07

0.014

0.40 0.40

0.0150.012

0.07 0.07

0.070.07

0.02 0.02

NY – July 30, 2020

MI – August 3, 2020NH – July 24, 2020

NJ – June 1, 2020

16

8/3/20

9

IN

States with Values for Other PFAS(and year implemented)

17

2019

20162018

2017

2009

2015

2011MA: Sum of 6 PFAS <0.02 µg/L (Dec 2019)

MN: “TEQ-like” additivity for 5 PFAS

VT: Sum of 5 PFAS <0.02 µg/L (2018)

Figure by W. DiGuiseppi, Jacobs - used with permission. Data current as of June 2020

2016

2016

2019

2016

NH: PFNA (0.011 µg/L) and PFHxS (0.018 µg/L) (2020)

17

Representative Residential Soil Levels

0.0001720.00150.00060.017

0.350.0095

0.000720.0020.0017

1.261.261.22

0.50.2

1.560.320.24

61.7

0.3

1.316

1.3

0.0003780.025

0.00078

0.000220.021

0.0020.0070.003

1.261.261.22

1.50.1

1.563.2

0.0413.2

1.70.3

1.81.3

61.3

0 5 10 15 20

USEPA R SL (2018)TX 30-acre so urc e (2017)

NE (2018)NC (2016)MI (2016)

ME (2018)MA (2020)

FL (2020)AK (2017)

EPA RSL (2018)WI (2018)VT (2019)

TX (2017) 30-ac re sourc eNH (2019)NV (2017)NE (2018)

MN (2019)MI (2016)

ME (2018)MA (2020)

IA (2019)FL (2020)

DE (2016)AK (2017)

PFOS PFOA

Guidance and Screening Levels – Soil (mg/kg)

Health Canada (2019) 2.10.7

Protective of Human Direct Contact

Protection of Drinking Water or Groundwater

Australia (2018)0.0090.1

18Figure by W. DiGuiseppi, Jacobs - used with permission. Data current as of June 2020

35

18

8/3/20

10

Canada (0.6 µg/L)Maximum acceptable concentration

US EPA (0.07 µg/L)Health advisory level

UK (0.3 µg/L)Maximum acceptable concentration

Denmark (0.1 µg/L)Health-based criteria

Sweden (0.09 µg/L)(∑ 9 PFAS)Administrative level

Germany (0.1 µg/L)Administrative level

Netherlands (0.0053 µg/L)Administrative level

Australia (0.07 µg/L)Health-based guideline

How Other Countries are Addressing PFAS (example Drinking Water guidance and requirements for PFOS)

19

Canada (0.6 µg/L)Maximum acceptable concentration

US EPA (0.07 µg/L)Health advisory level

UK (0.3 µg/L)Maximum acceptable concentration

Denmark (0.1 µg/L)Health-based criteria

Sweden (0.09 µg/L)(∑ 9 PFAS)Administrative level

Germany (0.1 µg/L)Administrative level

Netherlands (0.0053 µg/L)Administrative level

Australia (0.07 µg/L)Health-based guideline

Figure by W. DiGuiseppi, Jacobs - used with permission. Data current as of June 2020

Italy (0.03 µg/L)Health-based

19

PFAS Training Workshop

20

Eastern Time Tuesday August 11

1:00 PM 20 Min Welcome & Overview of ITRC TeamPFAS Background and Regulations Richard Spiese, VT DEC

1:20 PM 40 Min Naming Conventions, Physical and Chemical Properties, Sources Dora Chiang, CDM Smith

2:00 PM 15 Min Question & Answer2:15 PM 15 Min Break2:30 PM 50 Min Sampling and Analysis Janice Willey, US Navy3:20 PM 10 Min Question & Answer

Eastern Time Wednesday August 121:00 PM 25 Min Site Characterization Rula Deeb, Geosyntec1:25 PM 25 Min Risk Assessment Kevin Long, Terraphase1:50 PM 15 Min Question & Answer2:05 PM 15 Min Break

2:20 PM 50 Min Fate and Transport Chris Higgins, Colorado School of Mines

3:10 PM 20 Min Question & AnswerEastern Time Thursday August 13

1:00 PM 50 Min Treatment Technologies Bill DiGuiseppi, Jacobs1:50 PM 15 Min Question & Answer2:05 PM 15 Min Break2:20 PM 40 Min Risk Communication Kerry Kirk Pflugh, NJ DEP3:00 PM 30 Min Discussion, Question & Answer Bob Mueller, NJ DEP

20

8/3/20

11

Thank You!

Stay Updated on ITRC’s Activities:

@ITRCWEBfacebook.com/itrcweb linkedin.com/company/itrc

itrcweb.org

21

21

PFAS Naming Conventions, Physical and Chemical Properties,

Sources

Dora Chiang, Ph.D., P.E.CDM Smith


22

8/3/20

12

PFAS Technical and Regulatory Guidance Document Published

u Final web document PFAS-1: https://pfas-1.itrcweb.orgu Chemistry, Terminology and Acronyms, Section 2.2

u Figure 2-3 PFAS Family tree, available as a stand-alone PDF versionu PFAS Uses, Section 2.5

u Table 2-4 Sample historic and current uses of PFASu PFAS Releases to the Environment, Section 2.6u Physical and Chemical Properties, Section 4

u Table 4-1 physical and chemical properties, available as separate Excel file


23

Learning Objectives

u To understand the major classes of PFAS and those that you are most likely to encounter in your site work

u To understand the basic chemical structure and naming conventions for PFAAs and some PFAA precursors

u To understand the difference between PFAS anions and acids and why it matters

u To understand how PFAS have been produced, used and released into the environment

24

24



8/3/20

13

What Are Per- and Polyfluoroalkyl Substances (PFAS)?

u Large class of chemicals (>4,000) with unique chemical & physical properties that make many of them extremely persistent and mobile in the environment

u Used since 1940s in wide range of consumer and industrial applications

Source: open access images – bing.com

25PFAS-1, Section 1 Introduction

25

General Classification of Per- and Polyfluoroalkyl Substances (PFAS)

Perfluoroalkyl acids• Carboxylates (eg. PFOA)• Sulfonates (eg. PFOS) Fluorotelomers:

• Sulfonates• Carboxylates• Alcohols

Source: ITRC Naming Conventions and Physical Chemical Properties fact sheetPFAS-1, Figure 2-2, PFAS Family

• Fluoropolymers• Perfluoropolyethers

(PFPE)• Side-chain fluorinated

polymers

26

PFECAs

26

8/3/20

14

Basic PFAA Structure

uPerfluoroalkyl Acids (PFAAs)u Fully fluorinated chain (2 or more carbon “tail”)u Functional group (“head”)

uPFCAs: Carboxylate group (COO-)uPFSAs: Sulfonate group (SO3

-)

Source: open accessimage from bing.com

27PFAS-1, Figure 2-5, Tail and Head structure of PFOA and PFOA molecules

27

PFAA Naming System

u PFXYu PF = perfluorou X = number of carbons

u Same convention as hydrocarbonsu Includes C in the carboxylate group

u Y = functional groupu S = sulfonate (R-SO3-)u A = carboxylate (R-COO-)

u Example: u X: 8 carbons = “octa”u Y: S = sulfonate

Source: ITRC Naming Conventions and PhysicalChemical Properties fact sheet

4 B (buta-)5 Pe (penta-)6 Hx (hexa-)7 Hp (hepta-)8 O (octa-)9 N (nona-)…..

Perfluorooctane sulfonate (PFOS)

28

28

8/3/20

15

PFAA Naming System

PFAS-1, Table 2-1, Basic naming structure 29

29

Wait…Which PFAA Are We Talking About?

u Acid or Anion?u PFAS may exists in various ionic states (acids, anions, cations, zwitterions)

u In the environment, most PFAS exist in the anionic state (sulfonate, carboxylate, etc.)u Acid form of the name often used interchangeably (sulfonic acid and carboxylic acid)u Different CAS numbers & very different chemical and physical properties

u What Is My Lab Really Testing For?u Some labs report some or all of their PFAAs in the acid formu Depends on the standards used, which may be acids or salts of PFAAs (typically Na+ or K+)u The lab performs a calculation to account for the mass of the cation

u For H+ in acids, this is essentially irrelevant in terms of the resultsu For salts, confirm the lab is accurately accounting for the cation mass (Section 7.2.3 of EPA Method 537.1)

30

30

8/3/20

16

Polyfluoroalkyl Substances

u Partially fluorinatedu Non-fluorine atom (usually H or O) attached to at least one, but

not all, of the carbons in the alkane chain

u Creates a “weak link” susceptible to biotic or abiotic degradationu Often named using a “n:x” prefix

un = number of fully fluorinated carbonsux = number of non-fully fluorinated carbons

31PFAS-1, Section 2.2.4 Polyfluoroalkyl Substances

31

PFAA Precursors (under environmental conditions)

u Some PFAS can degrade to PFAAs under environmental conditionsu Referred to as “PFAA precursors”u Resulting PFAAs sometimes referred to as “terminal PFAAs”

u Perfluoroalkane sulfonamides (FASAs)u May degrade to PFSAs and PFCAs

u Polyfluoroalkyl Substances u Fluorotelomers

u Fluorotelomer alcohols (FTOH)

u Fluorotelomer sulfonates (FTSA)

u Fluorotelomer carboxylates (FTCA)

u May degrade to PFCAs

u Perfluoroalkyl sulfonamido ethanols (FASE) & acetic acids (FASAA)• May degrade to PFCAs or PFSAs

32

As we learn more about transformation pathways, we maybe able to use that informationfor site characterization – to determine sources, age, history, etc.

32

8/3/20

17

Replacement Chemistry

u Short chain PFAS chemistries do not degrade to longer PFAAs

u New applications, but not necessarily new chemicalsu HFPO-DA (Hexafluoropropylene oxide dimer acid), a component of GenX processing aid technology (Shoemaker and Tettenhorst 2018)

u used for decades in fluoropolymer production

u For most replacement chemistries, limited information on toxicities, properties, fate and transport, and treatment optionsu USEPA released a draft toxicity assessment for GenX chemicals in November 2018

PFAS-1, Figures 2-7 and 2-11 Chemical structures 33

Chemical structure for ADONA Chemical structure for GenX Ammonium Salt

33

Learning Objectives- Chemical & Physical Properties

u To understand the key physical and chemical properties that affect PFAS behavior in the environment

u To be aware of the limitations of published values for PFAS physical and chemical properties.

34

34

8/3/20

18

Highlights of PFAS Properties

u C-F is the strongest covalent bond in chemistryu Small, highly electronegative fluorine atoms

“shield” the carbon from chemical reactions u No biotic or abiotic degradation of PFAA under

natural conditionsu PFAAs thermally degrade only at high temperatures

u The anion of the perfluoroalkyl acids (PFAAs) are negatively chargedu Interact and sorb on positively charged mineralsu Mediated by pH, chain length, and functional group

kJ/mol of bonds

C-F 485 C-H 436C-C 346C-Cl 339C-N 305C-Br 285C-S 272

High C-F Bond Energy

Source: open accessimage from bing.com

35PFAS-1, Section 4.3 Chemical Properties

35


u Chain length and functional group generally determine bioaccumulationu Longer chain and sulfonates tend to accumulate more than shorter chain and carboxylatesu PFHxS breaks this “rule” – longer half-life in humans than PFOSu Some PFAAs are “proteinphiles”, so bioaccumulation process may be more complicated than

for other environmental contaminants.

u Surfactant properties are importantu Partitioning to interfaces (air-water, soil-water, NAPL-water) and micelles

u Micelles are an aggregation of molecules that form a sphere that has the hydrophobic portion of the molecules on the inside

u PFAAs can be both hydrophobic and hydrophilic

36

36

8/3/20

19


u PFAAs may be linear or branched in formu May affect partitioning and/or bioaccumulation - not well understood yet

u PFAAs generally have low volatility, however…u Air transport may occur for PFAAs sorbed to particulates or dissolved in water dropletsu PFAAs may be formed from volatile precursors (e.g., FTOHs)

Source: ITRC Naming Conventions and Physical Chemical Properties fact sheet 37

37

Chemical and Physical Properties Control Environmental Distribution

38

Tm = melting pt.Tb = boiling pt.pKa = acid dissociation constantp = vapor pressureS = solubilityH = Henry’s law constantKd = soil/sed partitioning coefficientKoc = organic carbon partitioning coefficientBAF = bioaccumulation factor BSAF = biota-sediment accumulation factor

Source: ITRC Naming Conventions and Physical Chemical Properties fact sheet

38

8/3/20

20

Published Physical & Chemical Values

u Most values reported in the literature are for PFAA acidsu PFAA acids not typically present in environment except at pH <3u Behavior of acids and anions are often VERY different

u PFOA acid: low solubility, volatile / PFOA anion: highly soluble, non-volatile

Sw = solubility in water Koc = org. carbon partition coefficient Y = data availablePo = vapor pressure BAF = bioaccumulation factor N = no data availableKh = Henry’s Law constant BCF = bioconcentration factor M = data may be available Kow = octanol/water partition coefficient E = estimated

Source: ITRC Naming Conventions and Physical Chemical Properties fact sheet 39

39

Physical and Chemical Properties and Associated Values- Overview

u The literature has varying levels of information on the physical and chemical properties of each of the PFAS compounds and may have wide ranges in final values.

u Review of the literature must include chemical speciation and relevant testing conditions.

u For a compilation of Koc values found in the literature, please see Table 4-1.

u For a more extensive compilation of chemical and physical properties, including solubilities, densities, and pKas, please see Table 4-1.

40

Tm = melting pt.Tb = boiling pt.pKa = acid dissociation constantp = vapor pressureS = solubilityH = Henry’s law constantKd = soil/sed partitioning coefficientKoc = organic carbon partitioning coefficientBAF = bioaccumulation factor BSAF = biota-sediment accumulation factor

PFAS-1, Table 4-1 Physical and Chemical Properties, Excel file

40

8/3/20

21

Learning Objectives- Sources

u Timeline of PFAS production and possible implications for site source identification

u PFAS usesu Sources of PFAS to the environment

41

41

A Brief History of PFAS Discovery and Manufactureu Two major production

processesu Electrochemical

fluorination (ECF)u ~70% linear and 30%

branched PFAS

u Fluorotelomerization u Primarily even

numbered, linear PFAS

42Source: ITRC History and Use PFAS fact sheet

42

8/3/20

22

Phase-Out of Long-Chain PFAS

u Potential health and environmental concerns, particularly for more bioaccumulative “long-chain” PFAS

u 2002-2008: 3M voluntarily phased out production of PFOS, PFHxS, PFOA, and related precursors

u 2010-2015: Most U.S. manufacturers eliminated production of PFOA and certain longer-chain PFCAs and related precursors

u Exemptions: USEPA SNURs allow continued, low-volume use in specific applications (semiconductor, etching, metal plating, aviation, and photographic/imaging)

u Long-chain production shifted to parts of Asia and Eastern Europe

PFAS-1, Table 2-2 Short-chain and long-chain PFCAs and PFSAs 43

43

Major Uses of PFAS

u Industrial (primary production and secondary manufacturing)u Surfactants, resins, molds, plasticsu Plating and etching (esp., chrome)u Coatings (textiles, leather, paper, carpets)

u Aqueous Film Forming Foam (AFFF) to fight fires involving flammable, combustible liquids and gases; petroleum greases, tars, oils and gasoline; and solvents and alcohols u Military installations and civil airportsu Petroleum refineries and chemical facilitiesu Fire fighting training and response areas

44PFAS-1, Section 2.6 PFAS Releases to the Environment

44

8/3/20

23

Sources of PFAS Releases to the EnvironmentAqueous Film Forming Foam (AFFF)

§ Military installations & civil airports§ Petroleum Refineries & Chemical Facilities§ Fire Fighting Training Areas and Response Areas

Industrial (primary production & secondary manufacturing)§ Surfactants, resins, molds, plastics§ Plating and etching (esp. chrome)§ Coatings (textiles, leather, paper, carpet, etc.)

Landfills§ Consumer products, industrial waste, demolition debris§ Biosolids from WWTP applied as cover

Waste Water Treatment Plants§ PFAS in influent (from industrial & domestic sources) may not be treated and end up in effluent§ Biosolids created in treatment process may contain PFAS

Source: open access images –bing.com

45*PFAS concentrations vary widely depending on the waste stream; not all landfills or WWTPs/biosolids are major sources

45

Questions?

46

8/3/20

24

Thank You!



itrcweb.org

47

47

PFAS Sampling and Analysis

Janice Willey, US Navy


48

8/3/20

25

PFAS Technical and Regulatory Guidance Document Published

u Final web document PFAS-1: https://pfas-1.itrcweb.orgu Sampling and Analytical Methods, Section 11u Analytical methods Excel file

u Table 11-2, Published methods basicsu Table 11-3, Published methods specificsu Table 11-4, Analyte listsu Table 11-5, Draft published methods


49

Learning Objectives

u Understand why PFAS sampling is different than other sampling events

u Understand best practices for preparing for a PFAS sampling event

u Understand current state of PFAS analytical methods u Understand basics of compound-specific PFAS analysis u Understand alternative analytical techniques and how they

can be useful

50

50



8/3/20

26

PFAS Sampling

PFAS-1, Section 11.1 Sampling

51

Potential PFAS Sampling Media

Soil Groundwater Drinking Water Sediment Surface Water Treatment System

Pore Water Private Well Ambient Air Biological Tissues Vegetables Concrete

Images from MS Office ClipArt

52

52

8/3/20

27

Why is a PFAS sampling event different from other sampling events?u Unusually low screening/regulatory criteria for PFAS u Increased cross-contamination potentialu Sampling equipment and materials typically used for

sampling contain or may contain PFAS

Images from MS Office ClipArt53

53

Personal Protection Products

There is little published research on how certain materials may affect sample results. Therefore, a conservative approach is recommended during execution of the sampling plan

These materials are not of concern so long as they do not come into contact with the sample or sample container

Safe to use•Synthetic or natural fibers, well laundered, cotton coveralls, PVCTry to avoid•Water-repellent textiles, insect repellent and sun screenNeed verification•Non-brand name, water-resistant, waterproof, or stain-treated clothing•Tyvek suits and clothing that contains “Tyvek”

54PFAS-1, Section 11.1.2 Equipment and Supplies

54

8/3/20

28

Sampling Materials and Procedures

Good practice§Wash hands, wear powderless nitrile gloves and change them before every sample is collected§Only open sample container during sample collection and never set the sample container lid downTry to avoid§Any materials/supplies that will come into contact with the sample that are known to contain or are suspected to contain PFAS§Addition of sample processing steps (e.g., filtration) in the field that could be performed under the more controlled conditions of the laboratory

Need verification•Use of markers, which ones are acceptable and where ok to use

55

55

Filtering of Water Samples

u Evidence that PFAS may sorb onto various filters (e.g., glass fiber filters)

u Filtered/unfiltered data may be misinterpreted as PFAS sorbed to soil or sediment in the water sample when the reduction may actually reflect PFAS sorbed onto the glass fiber filter

u Consider use of low flow sampling or use of a centrifuge in the labu Laboratory centrifugation is a good alternative

56

56

8/3/20

29

Sampling Equipment

Do Not Use Acceptable Alternatives

Fluoropolymer bailers or pump bladders

Disposable EquipmentDedicated Equipment (no polytetrafluoroethylene (PTFE) parts)

Fluoropolymer tubing, valves and other parts in pumps

High-density polypropylene, high-density polyethylene (HDPE) and silicon materials (i.e. tubing)

LDPE HydraSleeves™ HDPE HydraSleeves™

Freezer packs or “blue” ice packs

“Wet” ice in double-sealed zipper bags or dry ice

57

57

What To Do If You Are Unsure If Item Contains PFAS Or Not?u Review the Safety Data Sheets and consult with the manufacturer of the itemu Consult:

u PFAS sampling guidance documentsu PFAS resources within your organization u An analytical chemist with PFAS experience

u Collect equipment blank(s) from a specific item in question or send a section or piece of the equipment (if practical) to the laboratory for a more vigorous leachate analysis

???

ERR ON THE SIDE OF BEING CAUTIOUS RATHER THAN BEING UNSURE AND RISK CROSS-CONTAMINATION

58

58

8/3/20

30

Laboratory Supplied Sampling Materials Sample containers (polypropylene or HDPE), solvents (such as methanol), and water used for blanks in the field and for final rinse of equipment should:

u be supplied by the lab performing the analysis, and

u be verified as being PFAS-free (as defined by the project) prior to use

59

If source water is used in the field for any blanks or

final rinse, a sample of this water should be sent

to the laboratory for analysis.

59

Sampling Event Preparation

Consider the overarching objectives of the project and conceptual site model will influence the fundamentals of any sampling and analysis program

• Site history (e.g., potential sources, quantities used) as an indicator of potential level of PFAS

• Project Action Levels

60

Develop a project-specific sampling and analysis plan (SAP) which addresses the

increased risk of contamination and project-

specific considerations

60

8/3/20

31

Planning Laboratory Analysis

u Project team must discuss with the laboratory: u the PFAS to be analyzed and project reporting levels,u the volume of sample required to achieve the lab reporting levels,u project sample preparation requirements, and u the number of bottles needed, including QC samples.

u Provide laboratory information on high concentration samplesu Request laboratory screen all samples prior to sample preparation

(additional containers will be needed for this)

61

61

QA/QC Sample Collection

Using blanks to evaluate composition or suitable nature of equipment/supplies for sampling, and to assess possibility of cross-contamination during sampling/transport/storageu Pre-investigation equipment blanks (decon water, methanol, new equipment, plastic bags as

sample containers, sun screen, insect repellents, anything you are unsure of)u Equipment blanks to assess adequacy of decontamination process and/or evaluate potential

contamination from equipment. u Field blanks to assess contamination from field conditions.

u Recommended frequency: one blank/day/matrix or one blank/20 samples/matrix, whichever more frequent.

u Field reagent blanks (USEPA Method 537.1) should originate from the laboratory for all drinking-water programs (minimum of 1/event).

u Trip blank to assess cross-contamination introduced from laboratory/during shipping procedures (1/cooler).

62PFAS-1, Table 11-1 Typical field QC Samples

62

8/3/20

32

Other PFAS Sampling Precautions

u Many PFAS sampling concerns are precautionary and have no scientific data to prove

u HDPE can sorb PFAS as well (evidence of strong 6:2 FtS sorption)u Laboratory should extract the entire sample in the sample container;

sub-sampling from the sample bottle must be avoidedu The empty bottle should be rinsed with extraction solvent to desorb any PFAS on the

sample bottle regardless bottle materialsu The rinsate should be included in the sample extract that is analyzed

63

63

Sample Holding Time

u Holding time may vary depending on the matrix, and individual laboratories should determine the holding time in their matrix

u Ask laboratory for a defined holding time for each matrix analyzed, document procedures for tracking sample holding time, and respond to any holding time issueu Samples must be chilled during shipment and must not exceed 10oC during the first 48 hours

after collection (EPA 537.1)u Water samples should be extracted within 14 days. Extracts should be stored at room

temperature and analyzed within 28 days after extraction (EPA 537.1)

64PFAS-1, Section 11.1.4 Sample Preservation, Shipping, Storage and Hold Times

64

8/3/20

33

Takeaway Messages

u PPE should be worn in all cases, regardless of any potential contamination

u Increased risk of contamination during sampling u Have a practical approach to contamination concerns u PFAS-specific sampling protocols are recommendedu Communication with the laboratory is essential

65

65

PFAS Analysis

PFAS-1, Section 11.2 Analytical Methods/Techniques

66

8/3/20

34

EPA PFAS Analytical Methods

u USEPA 537.1 u Finalized Method (Version 2.0 published 2020)u Compound-Specific Analyses (18 PFAS)u Drinking Wateru Laboratories allowed some modifications, but not:

§ Sample collection/preservation§ Extraction§ Quality control

u Multi-laboratory validated method

67

67


u USEPA Method 533u Finalized Method (published 2019)u Compound-Specific Analyses (25 PFAS)u Drinking Wateru Addresses compounds that were not included in Method 537.1 due to poor performance u Laboratories allowed some modifications, but not:

§ Sample collection/preservation§ Extraction§ Quality control

u Multi-laboratory validated method

Source: USEPA PFAS Research Webinar - Methods and Guidance for Sampling and Analyzing Environmental Media, November 28, 2018 68

68

8/3/20

35



u Analytes applicable to both Methods 537.1 and 533:

PFOA PFOS 11Cl-PF3OUdSPFDA PFDoA 9Cl-PF3ONSPFHxA PFUnA ADONAPFBS PFHpA HFPO-DAPFHxS PFNA

69



u Additional analytes applicable to Method 537.1 only:

NEtFOSAA NMeFOSAAPFTA PFTrDA

70

8/3/20

36



u Additional analytes applicable to Method 533 only:

4:2 FTS 6:2 FTS 8:2 FTSPFBA PFHpS PFPeSPFPeA PFMBA PFMPAPFEESA NFDHA

71

Other Published PFAS Analytical Methods

u ISO Method 25101 (ISO 2009)u Compound-Specific Analyses (2 PFAS)

§ PFOA§ PFOS

u Unfiltered Drinking Water, Ground Water, and Surface Wateru Multi-laboratory validated method

72

72

8/3/20

37

Other Published PFAS Analytical Methods

u ASTM D7979-19 (ASTM 2019)u Compound-Specific Analyses (21 PFAS)u Water, Sludge, Influent, Effluent, and Wastewateru Single laboratory validated method

u ASTM D7968-17a (ASTM 2017)u Compound-Specific Analyses (21 PFAS)u Soilu Single laboratory validated method

73

73

Draft PFAS Analytical Methods

u USEPA SW-846 Method 8327u Draft Method (published 2019)u Compound-Specific Analyses (targets 24 PFAS)u Non-potable aqueous samples u Multi-laboratory validated method

u ISO/CD 21675:2017 (E)u Draft Method (published 2017)u Compound-Specific Analyses (targets 27 PFAS)u Non-filtered waters containing < 2 g/L solid particulate materialu Multi-laboratory validated method


74

8/3/20

38

PFAS Analytical Methods Undergoing Validation

u Isotope dilution methoduCompound-Specific Analyses (targeting 40 PFAS) uGW, SW, WW, Leachate, Biosolid, Tissue, Sediment, SoiluWill be submitted to EPA OW for consideration as a 1600-

Series MethoduPossibly be published as SW-846 Method as well uSingle laboratory and multi-laboratory validated method


75

PFAS Analytical Methods Undergoing Validationu Method for the Determination of Specific Residual PFAS in AFFF and

AR-AFFFu Final Method to be published in 2020u Compound-Specific Analyses (33 PFAS)u AFFF and AR-AFFF samples u Single laboratory and multi-laboratory validated method

Source: USEPA PFAS Research Webinar - Methods and Guidance for Sampling and Analyzing Environmental Media, November 28, 2018

76

76

8/3/20

39

Key Method Consistencies

u Utilize liquid chromatography tandem mass spectrometry (LC-MS/MS) u Do not address neutral/volatile PFAS (i.e., fluorotelomer alcohols and

derivatized PFCAs) u Standards must be analyzed in order to identify and quantify

individual PFASu Same equipment and supply concerns associated with field sampling

apply to sample preparation and analysis

77

77

Key Method Differences

u Method Scopeu Media u Limit of Detection & Quantitationu Analytes (individual and isomeric profile)

78

78

8/3/20

40

Branched & Linear PFAS

u PFAS from ECF chemistry: ~22 ± 1.2% branched and 78 ± 1.2% linear isomer1

u Branched and linear isomers of PFAS (including PFCAs) produced by ECF seen in consumer products, groundwater, sediment, soil, wastewater, landfills

u Observing branched isomers depends on chromatography

u Linear isomers have greater retention on C18 analytical columns - branched isomers are more compact (elute earlier)

u If ignoring the branched peak, concentrations will be low by ~ 25% u Telomer chemistry theoretically produces predominantly linear PFAS, however, final product may

contain branched isomers.

linear isomerbranched isomers-10 co-eluting in single peak

1 Giesy and Kannan, 2002; Schultz et al., 2003; Benskin et al. 2010; Riddell et al. 2009

Figure courtesy C. Higgins79

79


u Sample preparation processesu Whole sample vs Aliquotu Solid Phase Extraction vs solvent dilutionu Clean-up vs no clean-up

80

80

8/3/20

41


u Quantitation Schemeu External standard

u Surrogates added prior to sample preparationu Quantitation does not account for bias associated with sample preparation or

instrumentation u Data review must include evaluation of surrogate recoveries

u Internal standard u Surrogates added before sample preparation and internal standards added to

aliquot of extract prior to analysis u Quantitation does not account for bias associated with sample preparation but

DOES account for instrumentation bias u Internal standard recoveries matter

81

81


u Quantitation scheme mattersu Isotope standard quantitation

u Isotopically labeled standards added before sample preparationu Quantitation accounts for bias associated with sample preparation AND

instrumentation u Isotopically labeled standard recoveries matter

82

82

8/3/20

42

QC Requirements Guidance

u DoD/DOE Guidance: Table B-15 of DoD and DOE Quality Systems Manual (QSM) for Environmental Laboratories, Version 5.3, Final, 2020 (https://www.denix.osd.mil/edqw/index.html )

u Table B-15:u is NOT a method,u is a list of QC requirements,u is applicable to all media except drinking water, andu requirements can be modified to meet project needs.

83

83

Data Review and Validation

uPublished Data Review and Validation GuidelinesuDrinking Water Data Validation Guidance (Data Review and Validation

Guidelines for Perfluoralkyl Substances (PFASs) Analyzed Using EPA Method 537 (EPA 910-R-18-001, November 2018)

uData Review Guidance (USEPA Technical Brief “Per-and PolyfluoroalkylSubstances (PFAS): Reviewing Analytical Methods Data for Environmental Samples.” April 2019)

uDoD Validation Guidance (Data Validation Guidelines Module 3: Data Validation Procedure for Per- and Polyfluoroalkyl Substances Analysis by QSM Table B-15, May 1, 2020) (https://www.denix.osd.mil/edqw/index.html )

84

84

https://www.denix.osd.mil/edqw/index.html

https://www.denix.osd.mil/edqw/index.html

8/3/20

43

Data Review and Validation

u Currently there are no published EPA review and/or validation procedures to evaluate LC-MS/MS data for non-potable water or solid mediauPFAS data cannot be adequately evaluated using existing guidelines created

for other technologies (for example GC/MS)uReview and validation of PFAS data needs to be performed by someone with

a clear understanding of the technology utilized (LC-MS/MS)

85

85

Less-Standardized Analytical Techniques

u Particle-Induced Gamma Emission (PIGE) spectroscopy measures elemental fluorine from a sample isolated on a thin surface

u Precursor Analysis by Total Oxidizable Precursor (TOP) Assay measures PFAA precursors or polyfluorinated compounds that can be converted to PFAAs

u LC quadrupole time-of-flight mass spectrometry (LC-QToF-MS) tentatively identifies PFAS structures through library matches

u Extractable/Absorbable Organic Fluorine (EOF/AOF) measures fluorine in a sample as fluoride

86PFAS-1, Section 11.2.2 Qualitative

86

8/3/20

44

Takeaway Messages

u There are a number of PFAS analytical methods publishedu Significant differences between method need to be evaluated when

selecting a method in order to achieve project’s DQOs. u Additional analytical methods are currently in developmentu Less-standardized analytical techniques can be helpful as a

qualitative, or screening tool.

87

87

Questions?

88

8/3/20

45

Thank You!



itrcweb.org

89

89