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EBC Emerging Contaminants Program

Understanding the Science and Toxicity of PFAS

A Deeper Dive

Welcome

Frank Ricciardi

Chair, EBC PCB & Emerging Contaminants Subcommittee

Vice President

Weston & Sampson

Environmental Business Council of New England

Energy Environment Economy

Introduction, Program Purpose, and

What You Will Learn

Elizabeth Denly

Program Chair and Moderator

Program Director – PFAS Group

TRC



General Overview of PFAS



Elizabeth Denly

Program Director – PFAS Group

TRC

TRCcompanies.com |

General Overview of PFASMay 2, 2019

TRCcompanies.com6

PFAS in the News https://pfasproject.com

https://pfasproject.com/

TRCcompanies.com 7

Acronyms

• PFC = Per-fluorinated chemical

• PFAS = Per- and Poly-fluoroalkyl substances

Perfluoroalkyl Substances

• PFAA = Perfluoroalkyl acids

• PFOA = Perfluorooctanoic acid (perfluorooctanoate)

• PFOS = Perfluorooctane sulfonic acid (perfluorooctane sulfonate)

• PFCA = Perfluorocarboxylic acids

• PFSA = Perfluorosulfonic acids

PFCA

PFSA

PFAA

8

Quick Chemistry Lesson #1• Remember: PFAS are Per and Polyfluoroalkyl substances

C

F

F

F

F F

CC

F F

F

CC

F

F F

F

CC

F

F F

CSO3H

FF

(PFOS) SO3H = Head

PFAAs

• Perfluoroalkane sulfonates (or sulfonic acids): PFSAs

• Perfluoroalkane carboxylates (or carboxylic acids): PFCAs

• Per-fluoroalkyl substances: fully fluorinated alkyl tail

O

OHC

F F

F F

FF

F F

FF

F F

(PFOA)

F

F

FC

CC

CC

CC

COOH = Head

Alkyl tail, fully fluorinated

9

Quick Chemistry Lesson #2

• Remember: PFAS are Per and Polyfluoroalkyl substances

• Poly-fluoroalkyl substances: non-fluorine atom (typically hydrogen or oxygen) attached to at least one carbon atom in the alkane chain

Fluorotelomer Alcohol (8:2 FTOH)

CF

F F

CC

F F

F

CC

F

F F

F

CC

F

F F

C

FF

F F

CC

Non-fluorine atom on one or more carbons.

OH

H H

H H

Polyfluoroalkyl substances may also be degraded to perfluoroalkyl substances (e.g., PFOS or PFOA): PRECURSORS

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What Are PFAS?

• Poly- and per-fluoroalkyl substances

─ Generic family of chemicals

─ Manmade and do not occur naturally

─ Used since 1940 (Critical for the Manhattan Project)

─ Can be branched or linear

─ Used to make products that resist heat, oils, grease, stains, and water

• Most prevalent and researched: PFOA and PFOS

• PFAS: Acid or anion?

PFOS is present in the environment in the anionic form: perfluorooctane sulfonate.

Perfluorobutanoic acid Perfluorobutanoate (+ dissociated proton)

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CAS Numbers and PFAS State

PFAS State Structure CAS No.

PFOAAnion Perfluorooctanoate C7F15CO2

- 45285-51-6

Acid Perfluorooctanoic acid C7F15COOH 335-67-1

PFOS

Anion Perfluorooctane sulfonate C8F17SO3- 45298-90-6

Acid Perfluorooctane sulfonic acid C8F17SO3H 1763-23-1

Why is this important?

TRCcompanies.com 12

Chemical Properties of Perfluoroalkyl Substances

• C-F: Strong bond

• Chemically and thermally stable

• Water soluble and mobile in groundwater

• Surfactant properties

• Recalcitrant in environment

A PFAS Micelle

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Sources of PFAS and Potentially Affected Sites

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Where Are PFAS Used?

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What Types of Sites Can Be Sources of PFAS?

• Fire training facilities

• Fire stations

• Refineries

• DoD sites/Military bases

• Commercial and private airports

• Landfills (leaching from consumer products)

• Biosolids land application

• Rail yards

• Chemical facilities

• Plating facilities

• Textile/carpet manufacturers

• Residential areas with septic systems

TRCcompanies.com 16

Global Manufacture and Use of PFAS

PFAS Manufactured Globally

PFOA & PFOS No Longer

Produced: US, Europe, Japan

Class B AFFF with PFAS Banned:

South Australia

Prohibits Import, Manufacture,

Use & Sale of PFOS/PFOA: Canada

Banned Sale, Use and Import

of PFOA: European Union

Restrict Manufacture, Import, Export, and Use of

PFOS: Japan

Increased Production

of PFOA: China, India,

RussiaEtFOSA Produced on Industrial Scale: Brazil

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Replacement Chemistry

• GenX replaces PFOA

• ADONA replaces PFOA

• 6:2 Fluorotelomers replace PFOS in metals plating

• Telomers replace PFOS and PFHxS in AFFF

• Shorter chain PFAAs replace PFOA: PFBA, PFPeA

TRCcompanies.com 18

Plug for ITRC PFAS Team

• Includes >350 members: industry, academia, DOD, regulatory, consulting, analytical labs and vendors

• Seven PFAS Fact Sheets:

– AFFF Introduction

– History and Use

– Naming Conventions and Chemical Properties

– Regulations and Guidance

– Fate and Transport

– Site Characterization, Sampling, Lab Methods

– Remediation Technologies and Methods

• 2019/2020 – Technical Guidance Document

Questions?

Elizabeth Denly, ASQ CMQ/OEProgram Director – PFAS GroupP: (978) 656-3577 | E: [email protected]

Analytical Laboratory Considerations

for PFAS



Jim Occhialini

Vice President

Alpha Analytical

Analytical Laboratory Considerations

for PFAS

Jim Occhialini

Alpha Analytical

EBC Emerging Contaminants Program:

Understanding the Science and Toxicity of PFAS –

A Deeper Dive

Topics for Discussion

• Introduction

• PFAS Chemistry

• PFAS Methodologies

• Target Compound Lists

• Sampling Considerations

22

"What we find in the environment often depends on what we

look for and how hard we look" USGS website

Unregulated Contaminant Monitoring Rule

(UCMR)

1996 SDWA amendments

• UCMR 1 2001–2003 perchlorate, MTBE, explosives, pesticides

• UCMR 2 2008–2010 flame retardants, explosives, nitrosoamines

• UCMR 3 2013–2015 dioxane, PFAS, VOCs, metals, hormones

• UCMR 4 2018- 2020 (cyanotoxins, HAAs, pesticides)

• Some surprises…sources not considered…or sources not

considered significant

23

24

– Analytical methodologies

– What methods, are they applicable?

– Reference standard availability?

– Laboratory certifications

– Regulatory requirements– Requested target compound lists

– Compliance guidelines, required reporting limits

– What’s next?

MOVING TARGET

Carbon Chains; Isomers & Acids/Anions/Salts

• PFOA example

– "C8"

• Short chain vs long chain?

25

Source:(EPA PFAS Infographic)

26

Short Chain PFCAs Long Chain PFCAsC4 PFBA C5 PFHeA C6 PFHxA C7 PFHpA C8 PFOA C9 PFNA C10 PFDA C11 PFUnA

Short Chain PFSAs Long Chain PFSAsC4 PFBS C5 PFPeS C6 PFHxS C7 PFHpS C8 PFOS C9 PFNS C10 PFDS C11 PFUnS

November 2017

Isomers

• Straight (linear) or branched isomers?

• Isomers observed significantly based on manufacturing process

– Electrochemical fluorination (ECF): linear & branched, even number homologs,

1960 - 2002(?)

– Telomerization: (2 processes), linear *

27

Acids or Anions ?

Perfluorooctanesulfonate

28

Perflurooctanesulfonic acid

_

Perfluoroalkylcarboxylic Acids Carboxylates

Perfluoroalkylsulfonic Acids Sulfonates

CAS #s??

PFAS Analysis

• Primary methodology

– Method 537. Version 1.1 Determination of Selected Perfluorinated Alkyl

Acids in Drinking Water by Solid Phase Extraction and Liquid

Chromatography/Tandem Mass Spectrometry (LC/MS/MS) Sept, 2009

• Sample preparation

– Solid phase extraction (SPE)

• Analytical Instrumentation

– Liquid chromatography / tandem mass spectrometry (LC/MS/MS)

29

815-B-16-021, September 2016

• PFAS can exist as linear & branched isomers

– Method 537 addresses both for PFOS (2009)

• Standards not available at the time for PFOA

– Discrepancies in PFOA reporting

• Addressed in Tech Advisory32

New Drinking Water Method Under Development

34

Modified Method 537?

• Method 537

– “as specifically written”

– Is not amenable to expanded list of compounds or other sample

matrices without modification

• Other methodologies

– “Laboratory proprietary method”

• LC/MS/MS

• May use different or multiple SPE cartridges

– May use isotope dilution approach

35

Isotope Dilution Approach

• Addition of known amount of isotopically-enriched, compound-

specific internal standard

– PRIOR TO SAMPLE PREPARATION

– Matrix recovery correction

• Analysis-specific, analyte-specific concentration normalization

• Provides additional qualitative & quantitative certainty

36

38

DOD QSM Version 5.1 Table B -15

(pg 1 of 15)

2 New EPA SW-846 Methods in Process

• (1) SW-846 Method 8327 Public Comment Draft: Jan 2019

– Non-potable water

• Based on EPA Reg 5, Chicago Regional Lab, similar to ASTM D7979

• LC/MS/MS direct injection, external standard calibration

• 24 analytes

• (2) SW-846 Method 8328 Spring 2019

– Non-potable water plus soils, sediments & biosolids

• LC/MS/MS SPE, isotope dilution

• 24 analytes plus HFPO-DA

• Consistent with DoD QSM 5.1, Table B-15

40

"…plans to add additional analytes"

"SW-846 Methods will utilize 28 day holding times"

Sample matrices Other than Drinking Water?

• Wastewater, "silty" ground water, SPLP, etc.

• All run by isotope dilution

– Samples pre-spiked with extraction internal standards

– Centrifuged if necessary and extracted.

• Particulate matter is included in the bottle rinse with the elution solvent

• Too much particulate could interfere with bottle rinse

– Centrifuging may not be possible with excessive particulate

• No other option - dilutions / decant, discussion

41

Soils & Biosolids

42

• All run by isotope dilution

– Samples pre-spiked with extraction

internal standards

– SPE clean up cartridge

• Biosolids?

Other Sample Matrices?

43

Plant tissueFish Oysters

44

Oxidative Conversion as a Means of Detecting

Precursors to Perfluoroalkyl Acids in Urban Runoff

Erika F. Houtz and David L. Sedlak*

Department of Civil and Environmental

Engineering, University of California at Berkeley, Berkeley,

California, 94720-1710

Environ. Sci. Technol. 2012, 46, 17, 9342-9349

TOP Assay

Total Oxidizable Precursors

https://pubs.acs.org/author/Houtz,+Erika+F

https://pubs.acs.org/author/Sedlak,+David+L

https://pubs.acs.org/doi/pdfplus/10.1021/es302274g#cor1

https://pubs.acs.org/action/showCitFormats?doi=10.1021/es302274g

TOP (Total Oxidizable Precursor) Assay

• Analysis of individual PFAS compounds using LC/MS/MS may underestimate

PFAS mass

– Precursors

• Polyfluoroalkyl substances that can undergo transformation to form perfluoroalkyl acids

• 2 aliquots

– Analyze 1 normally

– Treat other aliquot

• KS2O8 + NaOH / 85 °6 hrs

• Then analyze

• Total precursors = PFAStreated – PFASuntreated

45

So What Do You Analyze For?

• Industry

• AFFF

• Landfills

46

Application dependent

Regulatory oversight

Source

3 basic sources potentially have

different PFAS signatures

Application

site characterization, human

health / eco risk assessment,

remedial design

Methodology?

47

Current

MA

ORSG,

CT DWAL

𝟕𝟎 𝐩𝐩𝐭 𝐄𝐏𝐀 𝐇𝐀𝐋

20 ppt VT DW HAL

UCMR Compounds

48

NJ GWQC 13 PPT MCL

𝟕𝟎 𝐏𝐏𝐓 𝐄𝐏𝐀 𝐇𝐀𝐋

MassDEP Proposed Revisions to DW ORSG/MCL and

Establishment of GW-1 Clean Up Standard

PFDA perfluorodecanoic acid

Also looking at potentially testing residuals / biosolids

20 ppt

GW-1

.2 ppb

S-1/

GW-1

50

NYSDEC UPDATE

Oct 2017

For GW, SW, soils, &

sediments lab should

be directed to report all

calibrated PFAS cmpds.

Reported cmpds will

include at a minimum

(current Oct 2017)

ELAP offers DW cert for

PFOA / PFOS. No

certification for other

matrices but lab should

hold PFAS DW cert.

"modified" method 537

or ISO 25101

Expected PFOA /

PFOS RL 2 ng/L AQ,

3 ug/Kg soil

EPA Method 537 - List of 14 Compounds

51

Perfluorooctanoic acid (PFOA)

Perfluorooctane Sulfonate (PFOS)

Perfluorobutanesulfonic acid (PFBS)

Perfluoroheptanoic acid (PFHpA)

Perfluorohexane Sulfonate (PFHxS)

Perfluorononanoic acid (PFNA)

Perfluorohexanoic acid (PFHxA)

Perfluorodecanoic acid (PFDA)

Perfluoroundecanoic acid (PFUdA)

N-methyl perfluorooctanesulfonamidoacetic acid

(MeFOSAA)

Perfluorododecanoic acid (PFDoA)

N-ethyl perfluorooctanesulfonamidoacetic acid

(EtFOSAA)

Perfluorotridecanoic acid (PRTrDA)

Perfluorotetradecanoic acid (PFTeDA)

11/2018 UPDATE EPA Method 537.1 - Target Compound List

53

*

***

"Emerging" Contaminants of Emerging Concern

• Legacy and emerging perfluoroalkyl substances

– PFOA replacements

• GenX

• ADONA

– PFOS replacement

• F53B

54

PFOA Replacements

• ADONA

55

O O

F

F

FF F

F

F F

FF F

F F

O

O

_NH

4

Ammonium 4,8-dioxa-3H-perfluorononanate

PFOA Replacements

• GenX

– GenX is the trade name for the ammonium salt of hexafluoropropylene

oxide–dimer acid (HFPO-DA)

– HFPO-DA is the target compound listed in Method 537.1

56

57

F

F

O

F

F

F

F

F F

F

F

F

O

O

H

HFPO-DA

Hexafluoropropylene oxide dimer (EPA Method 537.1)

2,3,3,3,-Tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)

Propanoic Acid

FRD-903

CAS No. 13252-13-6

F

F

O

F

F

F

F

F F

F

F

F

O

O

_NH4+

GenX

Ammonium salt HFPO dimer acid

2,3,3,3,-Tetrafluoro-2-(1,1,2,2,3,3,3-

heptafluoropropoxy)propanoate

FRD-902

CAS No. 62037-80-3

PFOS Replacement

• F53B

– chlorinated polyfluorinated ether sulfonate

58

Main

Minor

Acronym CAS No.

Sampling Recommendations"composite of multiple sources, refer to EPA, regulatory agencies"

"OK"

• Field Equipment – HDPE bottles, silicon tubing, loose

paper, aluminum clipboards, nitrile

gloves –

• Clothing / PPE– “Well laundered”, preferably cotton

• Personal care products– None, see “allowable” sun screens &

insect repellants

"NOT OK"

• Field Equipment– LDPE bottles, PTFE caps, PTFE tubing,

waterproof field books, plastic

clipboards/binders, "stickie notes", cold packs

• Clothing / PPE– No fabric softener, treated water repellent

fabrics, protective suits

• Personal care products– No cosmetics, moisturizers, etc. as part of

personal cleaning/showering routine on

morning of sampling

– Verify allowable sun screens / insect

– Food packaging

60

HDPE Tubing - LabBag Aluminum Foil

Note Pad

Suit

Polyethylene Bladder

HDPE Tubing: 1/8” OD3/8” OD

LDPE Tubing : 2 Manufacturers

Silastic Tubing PTFEBladder

PTFETubing

Passive Diffusion Bag Nitrile Gloves Bailer Line Field Book(cover & pages)

33rd Annual International Conference on Soils, Sediments, Water,

and Energy, October 16-19, 2017, Amherst, MA

Potential Contamination Study w/TRC

Waterproof Field Logbook

61

0.00

2.00

4.00

6.00

8.00

10.00

12.00

PFBS PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFTrDA PFTeA

Cover of Field Logbook (ng/L)

Book Cover A Book Cover B

C4 PFSA

C7 PFCA

0.00

0.50

1.00

1.50

2.00

2.50

PFBS PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFTrDA PFTeA

Pages in Field Logbook (ng/L)

Book Pages A Book Pages B

No PFSAs

PTFE Bladder/Bailer Line

62

0.00

2.00

4.00

6.00

8.00

10.00

12.00

14.00

16.00

18.00

20.00

8:2FTS PFPeA PFHxA PFHpA PFOA PFOS PFNA PFDA PFUnA PFTrDA PFTeA

Bailer Line (ng/L)

STRING 1 STRING 2

8:2 FTS

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

90.00

8:2 FTS PFPeA PFHxA PFHpA PFOA PFOS PFNA PFDA PFUnA PFTrDA PFTeA

PTFE Bladder in Bladder Pumps (ng/L)

Teflon Bladder A Teflon Bladder B

No PFSAsC5 PFCA

PFOA & PFOS

63

Wrap Up

Understand regulatory landscape, have dialog with lab

Methodology?

Compound List?

Potential for field contamination?

MOVING TARGET!

Jim Occhialini

[email protected]

PFAS: Toxicology, Health Effects,

and Risk Information



Karen Vetrano, Ph.D.

Risk Assessment & Toxicology Manager

TRC

TRCcompanies.com |

PFASToxicology, Health Effects, and Risk Information

Karen Vetrano, PhD | May 2, 2019

TRCcompanies.com

Presentation Overview

Toxicology

Exposure / Toxicokinetics

Mechanisms of Action

Toxicity Values

Health Effects

Rodent Studies

Epidemiology

National Initiatives

Risk Information

New England Approaches

Challenges

66

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➢ Ingestion of:

▪ contaminated drinking water

▪ contaminated food (landfarming, homegrown produce)

▪ fish/wildlife (biomagnification concerns)

➢ Contact with other impacted media (air, soil, sediment)

➢ Use of consumer products containing PFAS – generally low

▪ ScotchguardTM treated fabrics/carpets

▪ GoreTex®

▪ Non-stick cookware

▪ AFFF

▪ Personal care products – shampoos, dental products

Routes of Human Exposure to PFAS

67

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▪ Human half-life 2-10 years (up to 70 years for complete removal)

▪ Have a low affinity for lipids and preferentially bind to proteins

▪ Cross the placental barrier and are excreted into breast milk

Toxicokinetics of PFAS

Easily absorbed, slowly metabolized, widely distributed

Stored in liver, blood, kidney, and

muscle

Reabsorbed in kidney /

transported to bile

Slowly excreted in urine and feces

68

TRCcompanies.com

▪ Not fully understood

• PPAR-dependent effects

✓ Rodents have 10-times more PPAR than humans

✓ Overestimate human toxicity

• PPAR-independent effects

✓ More relevant to human toxicity

▪ Unanswered questions

• Which effects are caused by which mechanism?

• What is the best animal model?

Mechanisms of Action – How PFAS Affect Cells

69

PPAR = Peroxisome Proliferator-Activated Receptor

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▪ With >3000 PFAS, very few have been studied for toxic effects

▪ Most toxicology studies have:

• Focused on PFOA/PFOS

• Used rodents as test animals

▪ Non-Cancer Chronic Oral Toxicity Value (EPA, 2016) for PFOA/PFOS

• 0.00002 mg/kg-day

‒ Similar toxicity to PCBs; 10-times more toxic than arsenic

▪ Cancer Oral Slope Factor for PFOA

• 0.07 (mg/kg-day)-1

‒ Possible human carcinogen

‒ 20-fold less potent than arsenic and PCBs

▪ Cancer endpoints occur at higher doses thannon-cancer

Toxicity Values – PFOA/PFOS

70

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▪ Linked to a number of possible adverse health effects including:

• Liver enlargement/altered liver function

• Immune effects (e.g., impaired response to antigens)

• Decreased mammary gland development

• Decreased pup weight, survival and altered locomotion

• Cancer *PFOA only (liver, testicular, pancreatic)

Health Effects – Rodents

71

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Health Effects - Epidemiology

High cholesterol

Pregnancy-induced

hypertension

Thyroid disease

Decreased antibody response

Decreased fertility/birth

weight

Cancer* (testicular,

kidney)

▪ Majority of US population exposed to PFAS (“background exposure”)

• Prevalent in blood and urine samples

• Blood levels have been declining since 2000

▪ C8 Health Project (2005-2006)

• Included 70,000 residents with drinking water exposure

• Linked blood PFOA concentrations to a variety of health outcomes

72*PFOA only

TRCcompanies.com

▪ July 2018 – ATSDR reviewed toxicity of 14 PFAS; published Draft Subchronic MRLs for 4 PFAS (PFOA, PFOS, PFHxS, PFNA)

• Awaiting final report

▪ Nov 2018 – EPA released draft toxicity assessments for Gen-X chemicals and PFBS

• Comment period closed Jan 22, 2019• Final values will replace PPRTVs for PFBS

▪ Dec 2018 – EPA announced 5 additional PFAS (PFNA, PFBA, PFHxA, PFHxS, PFDA) will be reviewed for toxicity as part of IRIS Program

• Public Comment Drafts anticipated 2020

Ongoing National Initiatives

73MRL = Minimal Risk Level

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▪ Feb 2019 – EPA published PFAS Action Plan outlining concrete steps to address PFAS and protect public health

• Moving forward to develop MCLs for PFOA/PFOS

▪ April 2019 – CDC/ATSDR announced intent to conduct multi-site study on human health affects associate with PFAS exposure

• Soliciting research applications from 6 communities

• Pease Health Study 2018 protocols to be used and all results will be integrated

Ongoing National Initiatives continued

74

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Ongoing National Initiatives continued

April 26, 2019 – EPA published “USEPA Draft Interim Recommendations to Address Groundwater Contaminated with Perfluorooctanoic Acid and Perfluorooctane Sulfonate”. Specifically, EPA recommends the following:

• Screening sites using a screening level set to a Hazard Quotient of 0.1 for PFOA or PFOS individually, which is currently 40 ng/L or parts per trillion (ppt);

• Using the PFOA and PFOS HAs of 70 ppt as the preliminary remediation goals for groundwater that is a current or potential source of drinking water, where no state or tribal maximum contaminant level or other ARARs exist; and

• In situations where groundwater is being used for drinking water, EPA expects that responsible parties will address levels of PFOA and/or PFOS over 70 ppt.

Stakeholders will have 45 days to comment upon publication of the draft guidance in the Federal Register.

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Drinking Water Guidelines – New England

▪ Maine and Rhode Island are currently aligned with EPA

• EPA 2016 Drinking Water Lifetime Health Advisory (HA)

• 70 ppt for PFOA/PFOS combined

76MMCL = Massachusetts Maximum Contaminant Level

▪ Connecticut and Massachusetts have gone one step further

• 70 ppt for PFOA/PFOS/PFHxS/PFHpA/PFNA combined

• “Precautionary approach” since the 5 PFAS have similar structures, half-lives, and likely exhibit similar toxicity

• Massachusetts has declared the intent to develop MMCL(s) for PFAS

• April 19, 2019 - MassDEP proposes GW-1 standard of 20 ppt for the sum of 6 PFAS (includes PFDA – perfluorodecanoic acid)

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Drinking Water Standards – New England

▪ Vermont uses “precautionary approach” and slightly different assumptions

• 20 ppt for PFOA/PFOS/PFHxS/PFHpA/PFNA combined

77

CriteriaWater Ingestion Rate (liters/day)

Exposed Population

EPA HA 3 Pregnant Female

VPGQS 1.75 0-1 Year-Old Child

VPGQS = Vermont Protection of Groundwater Quality Standard

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Drinking Water Standards – New England

▪ New Hampshire has a unique approach

• Adopted EPA HA of 70 ppt for PFOA/PFOS combined

• Proposed MCLs for PFOA (38 ppt), PFOS (70 ppt), PFHxS (85 ppt), and PFNA (23 ppt) based on DES-developed toxicity values and assumptions

78

CriteriaWater

Ingestion Rate (liters/day)

Exposed Population

Relative Source Contribution

EPA HA 3Pregnant Female

20%

NH MCL 4.4Lactating Female

40-50%

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▪ Rapidly changing information

• Always check for newly released information

▪ States continue to evaluate newly released information

• Criteria may be interim / subject to change

▪ Hundreds more PFAS out there, each with unique toxicity

• Understanding of toxicology is still in early stages

▪ PFAS are ubiquitous

• “Background exposure” is hard to define

Risk Assessment Challenges – Final Thoughts

79

PFAS

Questions?

Karen VetranoP: 860.298-6351 | E: [email protected]

PFAS Fate & Transport



Steven LaRosa

Technical Leader

Weston & Sampson

May 2, 2019

WESTON & SAMPSON ENGINEERS INC.

PFAS FATE & TRANSPORT

Important Concepts for PFAS Fate and Transport

➢ Release Mechanisms

➢ Source Material Makeup

➢ PFAS structural make up impacts reactivity and transport (Heads and Tails)

➢ Persistence in Environment

➢ Partitioning of PFAS is complicated

– Hydrophobic effects

– Lipophobic effects

– Interface interactions

– Multiple ionic species present

Release Mechanisms

• Use/Release of PFAS can result in impacts to:

– Air– atmospheric transport can result in large impacted areas,

– Surface Soils – air deposition, AFFF use, infiltration of runoff water

– Surface Water – via direct discharge, infiltration from soils, runoff

from soils, WWTF discharges

– Groundwater – via infiltration, wastewater disposal and soil

– Sediment – storm water infiltration, runoff of soils, groundwater

discharge

– Biota – via ingestion of impacted water, plants?, other biota

Source Type• AFFF Sources

– AFFF is a mixture of compounds - <5% PFAS

– There can be many PFAS (short and long) and precursors

– Hydrocarbons from fire source

– “Complex Mixture” in source area may effect advection, adsorption, precursor breakdown

• Manufacturing Sources

– Can have single PFAS source or complex PFAS mixture

– Additional compounds may be present

• Landfill Leachate

– “Complex Mixture” in source area may effect advection, adsorption, precursor breakdown

• Wastewater Treatment Facilities

– Multiple inputs may be present (industries, humans, surface water)

– Treatment may cause oxidation of precursors

– Concentration of PFAS in biosolids due to high TOC

– Biosolids drying, composting, spreading

Structural Makeup

Air

Water

PFOSPerfluorinated TAIL Anionic HEAD

PFAAs generally act as surfactants

with tail in the air and head in water

• Anionic Perfluorinated Alkyl Acids

– Negatively charged

– Low vapor pressure

– Water soluble

Structural Makeup• Anionic Perfluorinated Alkyl Acids

– PFSAs more strongly sorbed than PFCAs

– Sorption generally increases with C

– Short chains can have greater sorption

than expected.

– Retardation factors for anions can be

predicted as with other contaminants

(generally)

Analyte#

CarbonKoc

1 Rf

PFBA 4 76 5

PFPeA 5 23 1.4

PFHxA 6 20 1.1

PFHpA 7 43 3

PFOA 8 78 5

PFNA 9 229 14

PFDA 10 912 57

PFUnA 11 3,600 225

PFBS 4 62 4

PFHxS 6 112 7

PFOS 8 631 39

1 Koc data from Guelfo, J.L., Higgins, C.P. Subsurface transport potential of perfluoroalkyl acids at aqueous film-forming foam (AFFF)-impacted sites. Environ. Sci. Technol. 2013. 47, 4164–4171.

Porosity

densityBulk K1R df +=

Structural Makeup• Polyfluorinated Substance transport

– State of charge may dominate retardation

• Anions > Cations > Zwitterions

– Short Chains generally migrate faster

– Cation exchange onto soils may be significant….on par with organic carbon

– Transformation into Perfluorinated end products may occur with distance

from source.

N EtFOSE PFOS

Precursor Transformation

• Branched and linear isomers

• Complex mixture• Cationic & zwitterionic• PFSAs (and some PFCAs)

as end products

Source: ITRC PFAS Fact Sheet – Fate and Transport 3/16/18

Precursor Transformation

• Built by 2’s• Fairly “clean” process

yielding predictable mixtures

• PFCAs only as end products

Source: ITRC PFAS Fact Sheet – Fate and Transport 3/16/18

What is Expected Where?PFAS plumes have varying complexity related to source type,

time since release and location relative to the source.

➢ Source Zone- complex chemistry

- multiple “families” of contaminants

- competing transport mechanisms

- “minimal” precursor breakdown (unless remediation has occurred)

➢ Transition Zone- separation of “families” via sorption/retardation/biodegradation

- precursor transformation seen (more PFAAs with distance?)

- separation of PFCAs/PFSAs and short chain/long chain via sorption/retardation

➢ Distal Zone- “simpler” chemistry

- terminal end products dominate

Transport in Air

• PFAS can be volatized by drying activities

(precursor alcohols)

• “Carried” in water vapor

• “Carried” on or as particulate

• Deposition via wet and dry methods

• Transported in all wind directions,

potentially miles

Industrial Airborne Release Bennington

• Industrial Plant operated in North Bennington from 1970 through 2002. During its operation

the facility primarily applied PTFE coatings to fiberglass fabrics by dip coating the fabrics in

a liquid bath of micron size PTFE particles and various additives (including PFOA) followed

by ovens to dry and melt the PTFE onto the fabric.

• Stack emissions with atmospheric transport yielded large impact area

• Limited number of PFAS apparently utilized in the manufacturing process

(PFOA dominates)

Landfill

1st Facility

Later Facility

WWTF

Transport in Vadose Zone• Chain length and organic content of soil dependent transport

dominant

• However, individual PFAS Koc, ionic state and the presence of

other contaminants may have significant impact

• Soil types will define advective transport via infiltration

• Adsorbed PFAS may act as “source” to groundwater for decades

• Air/Water Interface interactions likely results in retardation of

migration

• Formation of micelles and interactions with NAPL

Air

Water

PFOS

Transport in Groundwater

• Chain length and organic content of soil dependent transport

dominant

• However, individual PFAS Koc, ionic state and the presence

of other contaminants may have significant impact

• Soil types will define advective transport via infiltration

• Air/Water Interface interactions likely results in retardation of

migration

• Formation of micelles and interactions with NAPL

• Industrial Plant operated in Pownal from 1948 through 1986. During its operation the

facility primarily applied PTFE coatings to wire for the automotive industry.

• Surrounding area uses mix of public and private water supplies and wastewater treatment.

• Public Water Supply Well located 250 meters away

• Releases occurred primarily on surface and into subsurface

Wire Plant

Impacted Public Well

• Source zones may be complex: long-term discharge potential

– Non PFAS related contaminants can confound understanding of source area

– Investigation areas may be larger than you’re used to

• Perfluorinated PFAS:

– TERMINAL

– Mobility is chain-length dependent, affected by OC, pH, inorganic cations, etc.

• Polyfluorinated PFAS (precursors) are varying in their stability

– Much more variable in terms of transport

– Oxidizing remedial techniques (ISCO, air sparge, aerobic bioremediation) can

transform precursors to TEMRINAL PFAAs

• Surfactant properties may lead to increased concentrations at air/water

interface or at water/NAPL interface

Important Concepts for PFAS Fate and Transport

Questions?

PFAS Forensics: Chemical Signatures in

Surface Water and Groundwater



Andrew Cohen, Ph.D., PH

Principal Hydrogeologist

TRC

PRESENTATION NOT AVAILABLE

PFAS: A Legal Perspective



Robert D. Cox, Jr.

Managing Partner

Bowditch & Dewey, LLP

105 Boston Framingham Worcester BOWDITCH.COM

PFAS: A LEGAL PERSPECTIVEEBC EMERGING CONTAMINANTS PROGRAM: UNDERSTANDING THE SCIENCE AND TOXICITY OF PFAS – A DEEPER DIVE

ROBERT D. COX, JR.

MANAGING PARTNER, BOWDITCH & CHAIR, EBC

BOWDITCH & DEWEY, LLP | MAY 2, 2019


OVERVIEW

1. PFOS LEGAL LIABILITIES: 101

2. PFOS LITIGATION

3. REAL ESTATE TRANSACTION CONSIDERATIONS

4. WHAT’S AHEAD*

* (AND WHAT WE HAVE LEARNED FROM 29 YEARS OF SUPERFUND LAW.)


LEGAL LIABILITY: 101 –LAWS APPLICABLE TO EMERGING CONTAMINANTS

• CERCLA

• G.L. c. 21 E.

• Strict, joint and several liability

• Responsible parties

• Owner/Operator

• Arranger/Generators

• Transporters

• G.L. c. 21E, § 5(a)(5)


COMMON LAW CLAIMS

TRESPASS

• Negligence

• Nuisance

• Strict Liability

PRODUCT LIABILITY

• Defective Design

• Failure to Warn


PARTIES AND PFOS LOCATIONS

• OWNERS/OPERATORS

• MUNICIPALITIES

• AFFF SITES

• Airports

• DOD Sites

• Firefighter Training and Equipment Test Areas

• Crash Sites

• MANUFACTURING FACILITIES

• LANDFILLS


PFOS LEGAL CLAIM ISSUES

CAUSATION

• CERCLA – release or threatened release of a hazardous substance from a facility which caused the plaintiff to incur response costs

• G.L. c. 21E – “Regarding the release or threat of release of [OHM]”

• Dedham Water Co. v. Cumberland Farms Dairy, Inc., 889 F.2d 1146, 1154 (1st Cir. 1989), on remand, 770 F. Supp. 41 (D. Mass. 1991).


PFOS LEGAL CLAIM ISSUES (CONT’D)

IS PFOS A “HAZARDOUS SUBSTANCE?” A “HAZARDOUS MATERIAL”?

• CERCLA - No. But, …

• EPA Action Plan

• Proposed Legislation –PFAS Action Act of 2019

G.L. C. 21E - Yes. But, …

• PFOS not on MOHML and no PFOS RQ/RC

• See 310 CMR 40.0006 (definition of “Hazardous Material”)


PFOS AS C. 21E/MCP “HAZARDOUS MATERIAL” (CONT’D)



• 2 HOUR NOTIFICATION

• See 310 CMR 40.0311(7)

• Even if not reportable, response actions are required for releases of OHM that “pose a significant risk” to H, S, PW, or E. See 310 CMR 40.0370


PFOS LEGAL CLAIMS (CONT’D)

• PROOF OF SOURCES

•Multiple Sources

• and at PPT . . . ?

• Ubiquitous

• EXPERT TESTIMONY


PFOS LEGAL CLAIMS ISSUES (CONT’D)

• STATUTE OF LIMITATIONS

• CERCLA - 42 USC § 9613(g)

• 3/6 years

• G.L. c. 21E, § 11A

• Private Parties - 3 years

• Government - 5 years


PFOS LEGAL CLAIMS (CONT’D)

• DAMAGES

• Response Action Costs – G.L. c. 21E, § 4 (Section 4A)

• Damage to Real or Personal Property – G.L. c. 21E, § 5

• Personal Injury

• Medical Monitoring


PFOS LITIGATION

• IN RE: E. I. DU PONT DE NEMOURS AND COMPANY C-8 PERSONAL INJURY,MDL DOCKET NO. 2433

• approximately $670 million settlement3,500 individuals injured from drinking PFAS-contaminated water

• MINNESOTA AG’S SETTLEMENT WITH 3M COMPANY

• $850 million.

• HARDWICK V. 3M COMPANY, NO. 2:18-CV-1185 (S.D. OHIO OCT. 4, 2018)

• Class Action

• IN RE AQUEOUS FILM-FORMING FOAMS (AFFF) PRODUCTS LIABILITY LITIGATION, MDL DOCKET NO. 2873 (DEC. 17, 2018)

• 70 cases


PFOS SITES

• DOD

• PFOS in excess of limit in more than 560 private or public drinking water supplies around 50 bases.

• MASSACHUSETTS SITES

• Ayer

• Barnstable

• Hudson

• Mashpee

• Westfield


MASSACHUSETTS PFOS LITIGATION

• TOWN OF BARNSTABLE V. BARNSTABLE COUNTY –BARNSTABLE SUPERIOR COURT

• BARNSTABLE COUNTY V. 3M COMPANY ET AL, TOWN OF BARNSTABLE V. 3M COMPANY ET AL, CITY OF WESTFIELDV. 3M COMPANY(D. MASS.)

ALL TRANSFERRED TO MDL


REAL ESTATE TRANSACTION CONSIDERATIONS

• CERCLA DEFENSE - ALL APPROPRIATE INQUIRIES (AAI) RULE - 40 CFR § 312

• Coextensive with ASTM E1527 - 13

• PFOA NOT CERCLA “HAZARDOUS SUBSTANCE”

• AAI = “GOOD COMMERCIAL AND CUSTOMARY STANDARDS AND PRACTICES”


WHAT’S AHEAD?

• NPDES PERMITTING

• POTWS/STORMWATER/SEWER LINES

• TSCA

• BIOSOLIDS

• LANDFILLS

• INSURANCE COVERAGE

• NGO’S

• GENX COMPOUNDS

• WHAT’S SAFE


QUESTIONS?

BOB COX

[email protected]

(508) 926-3409

Moderated Discussion

Moderator: Elizabeth Denly, TRC

Panelists:• Andrew Cohen, TRC

• Robert Cox, Bowditch & Dewey, LLP

• Steven LaRosa, Weston & Sampson

• Jim Occhialini, Alpha Analytical

• Karen Vetrano, TRC



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