bracing for a pfight: pfas sources, fate, impacts

Bracing for a PFIGHT: PFAS Sources, Fate, Impacts, Treatment & Regulation

Brian Yates, PEAndrea M. Salimbene, Esq.

Thursday, May 2, 2019

What you’re in for…

Per- and polyfluoroalkyl Substances (PFAS)What are they?Where are they found?Why are they bad?How do I treat for them?What should I be doing now?

Delaware News Journal

U.S. DoD Elsworth AFB

The Intercept

Per and Polyfluoroalkyl Substances (PFAS) - TerminologyOverview of PFAS

Over 5,000 exclusively anthropogenic compounds (only a handful can be analyzed commercially) Similar to PCBs in that they are a class of compounds with different structural configuration,

halogen substitution positions, and often found as mixtures of many different compounds (cf. PCB Aroclors)

Terminology PFAS is plural; “PFASs” is incorrect. S = Substances; “PFAS Compounds”, “PFAS Substances”, etc. is redundant The acronym PFC typically refers to PerFluorinated Compounds; it is not inclusive of all PFAS and

refers to compounds that are not PFAS. PFAS ≠ PFOS ≠ PFOA

Moiety

Each of two (or more) parts into which a thing can be divided

The chemical part of a specific PFAS that is fully fluorinated This is the “forever part” of PFAS

Perfluoroalkyl Moiety

PFAS Classification

Per and Polyfluoroalkyl Substances (PFAS)

Perfluoroalkyl Compounds (CnF2n+1-R)

Polyfluoroalkyl Compounds (CnF2n+1-R + Spacers)

ITRC, 2019

ITRC, 2019

Perfluorinated Compounds (CnF2n+1-R)

ITRC, 2019

Hydrophobic/Lipophobic Hydrophilic

University of Notre Dame

Per and Polyfluoroalkyl Substances (PFAS) - Terminology

Other distinctions Long Chain vs. Short Chain

8 or more carbons for perfluoroalkyl carboxylates

7 or more carbons for perfluoroalkane sulfonates

Acid vs. Anion Example: Perfluorooctanoate (anion

form) and perflurooctanoic acid (acid form) – Both use the same acronym!

Linear vs. Branched Linear compounds have a straight

carbon backbone (only one isomer) Branched compounds have at least

one carbon bonded to more than two carbons within the backbone (many isomers)

Xiao, 2017

Per and Polyfluoroalkyl Substances (PFAS) - Physical and Chemical Properties

Property Unit PFOS PFOA TCECAS Number - 1763-23-1 335-67-1 79-01-6Molecular Formula - C8HF17O3S C8HF15O2 C2HCl3Molecular weight g/mol 500 414 131Water Solubility mg/L at 25°C 680 9,500 1.1 × 103

Boiling Point °C 260 192 87Vapor Pressure mm Hg at 25°C 0.002 0.525 9.2 × 103

Log Organic Carbon Partitioning Coefficient (KOC)

- 2.57 2.06 1.93

Per and Polyfluoroalkyl Substances (PFAS) - Physical and Chemical Properties

Fluorine – most electronegative element in the periodic tableC-F bond – strongest covalent bond in organic chemistry

Resulting Chemical Properties:High thermal stability (400°C – 1,000°C)High chemical stability (low reactivity even with highly reactive free radicals) Strong acidity (pKa 1.0 – 3.0 ) Zwitterionic, amphoteric, lipophobic/proteinphilic, surfactant properties,

hydrophobicity depends on chain length and head groups. Long half-lives in the human body (5-8 years)

Per and Polyfluoroalkyl Substances (PFAS) -Production, History, Use, and Environmental Sources

Production and History Electrochemical Fluoridation

Developed in 1940s by 3M Produces a mixture of linear and branched-chain isomers

Telomerization (telo = end [Greek]) Developed in 1970s Produces exclusively linear PFAS with chain-length selectivity

Uses Products: textile coatings, paper products, food packaging, cookware, aqueous

film-forming foams (AFFF) for firefighting Applications: aerospace, photographic imaging, semiconductor, automotive,

construction, electronics, aviation

Per and polyfluoroalkyl Substances (PFAS) - Production, History, Use, and Environmental Sources

Known direct emitters to the environment PFAS manufacturing facilities (e.g., 3M, DuPont/Chemours) Wastewater treatment plants (municipal/domestic and industrial) Wastewater biosolids Drinking water residuals Landfill leachate (municipal and hazardous) AFFF (especially at military and fire-fighting training grounds)

Per and polyfluoroalkyl Substances (PFAS) -Environmental Fate and Transport Extremely Persistent – No effective conventional treatment methods for

destruction/mineralization Essentially non-volatile at relevant environmental pH (anion form) Airborne sources are pure phase, or associated with aerosols or dust Longer chain PFAS tend to partition to soil organic (and mineral) phases,

shorter chain PFAS partition to aqueous phase Precursors are generally less mobile than transformation products and

can serve as on-going sources

Per and polyfluoroalkyl Substances (PFAS) - Human Exposure and Health Effects

What Happens After Exposure? PFAS are completely absorbed after oral exposure and

distribute primarily in the blood serum, liver, and kidney with a half-life of 5-8 years End products of degradation (e.g., PFOS and PFOA) are

chemically inert and not metabolized PFOS and PFOA are proteinphilic, and are not stored in fat PFAS are circulated in the kidneys and eventually excreted

through urine and feces over several years after chronic exposure PFAS look like fatty acids to our bodies and interfere with lipid

(fatty acid) metabolism in the liver (PPARα system)

Per and polyfluoroalkyl Substances (PFAS) - Human Exposure and Health Effects

C8 Science Panel (Parkersburg, WV) is the most comprehensive single source of data regarding negative health effects of PFASHealth Effects Correlated to PFAS Serum Concentrations (C8 Science

Panel) High Cholesterol Ulcerative Colitis Thyroid Disease Testicular Cancer Kidney Cancer Pregnancy-induced Hypertension (eclampsia, pre-eclampsia)

Sampling and Analysis EPA 537.1 released in 2018 includes 18 PFAS compounds measurable in drinking

water Modified EPA 537 includes other matrices such as soil and biosolids Other Methods

Particle-induced Gamma-ray Emission (PIGE) Total Oxidizable Precursor (TOP Assay) Total Organofluorine Methods

Analytical Method is LC MS/MS Restrictions on Sampling (develop a QAPP)

Clothing (boots, gloves, rain gear) Cosmetics Sunblock and Insect Repellant Food and Drink Detergent Sampling Bottles and Tubing Field Supplies

Almance County

The McCrone Group

Per and polyfluoroalkyl Substances (PFAS) - Treatment Options

Ineffective Conventional Treatment Processes Conventional and Advanced Oxidation (with some exceptions) Coagulation/Flocculation/Sedimentation (with some exceptions) Slow and Rapid Sand Filtration Dissolved Air Floatation (with some exceptions) Microfiltration/Ultrafiltration


Partially-effective Conventional Treatment Processes Activated Carbon (GAC/PAC) Ion Exchange (IX) Reverse Osmosis (R/O)


Emerging Treatment Processes Advanced Oxidation Processes (Oxidizing Free Radicals) Advanced Reduction Processes (Reducing Free Radicals) Sonolysis Plasma Treatment Next Generation Adsorbents (e.g., Carbon Nanotubes, Graphene, Polymeric

Adsorbents) Biodegradation?

Clarkson University Jurassic World, Legendary Entertainment

Adapted from Ross, et al., 2018

What you’re in for from Andrea …

Per- and polyfluoroalkyl Substances (PFAS)

What is US EPA doing?What is Congress doing?What are the states doing?What’s the legal landscape?How can PWSs prepare?

A Condensed History of EPA’s Approach

2002

2003

2004

2005

2006

2007

2008

2009

2010

2011

2012

2013

2014

2015

2016

2017

2018

2019

Voluntary Stewardship

Program


Program


Program

EPA added PFAS to UCMR3

to required water systems

to monitor.


Program

EPA issues provisional

drinking water health advisories (200 ng/L PFOS, 400 ng/L PFOA)


ProgramEPA promulgates TSCA SNUR


Program

EPA issues lifetime drinking water

health advisory (70 ng/L combined

PFOS and PFOA) and recommended

actions


Program

EPA hosts PFAS National

Leadership Summit


ProgramEPA issues PFAS Task Force and

Action Plan (Table 1)

Presenter

Presentation Notes

Voluntary Stewardship Program: EPA invited 8 leading PFAS industries to join program to commit to achieve 95% reductions in emissions, commit to elimination, baseline monitoring. Unregulated Contaminants Monitoring Rule (UCMR): SDWA requires EPA to issue list every 5 years no more than 30 unregulated contaminants to be monitored by PWSs. 2013-2015 min. reporting level PFOS .04 ug/L and PFOA .02 ug/L. Significant New Use Rule (SNUR): manufacturers/processors notify of new uses before commercialized to give EPA opportunity to block market re-entry. 2016 Health Advisory Level: accounts for non-DW sources of exposure like air, food, dust and consumer products. Recommended Actions: if sampling confirms exceedance, do more sampling; notify state and consult; provide customers information, i.e. risk to fetus and infants and identify options consumers can consider.

EPA Opened the PFAS National Leadership Summit (May 2018) by Announcing Action Items

1. Initiate steps to evaluate the need for a MCL2. Beginning the necessary steps to propose designating PFOS and PFOA as

hazardous substances through one of the available federal statutory mechanisms (i.e. CERCLA)

3. Develop groundwater cleanup recommendations4. Develop toxicity values (oral reference doses) for

Gen-X and PFBS

Presenter

Presentation Notes

To regulate contaminant under SDWA, EPA must find that 1) it may have adverse health effects 2) occurs frequently or a substantial likelihood that it occurs frequently at levels of public health concern and 3) there is a meaningful opportunity for health risk reduction for people served by PWS.

EPA PFAS Action Plan Unveiled Feb. 2019

EPA Priority Actions Announced at PFAS National Leadership Summit

Short-term Actions Understanding and Addressing PFAS Toxicity and

occurrence Identifying and addressing PFAS Exposures Risk Communication and Engagement

Long-term actions Listing PFAS on Toxic Release Inventory (EPCRA) Develop Ambient Water Quality Criteria for Human Health (CWA) Regulation of Industrial Sources’ through National ELGs (CWA NPDES) Nationwide Drinking Water Monitoring in next UCMR cycle Others

Presenter

Presentation Notes

Establishing clearinghouses for information; expanding analytical methods to test accurately; validate methods for testing in other media (soil, surface water, sediment, fish tissue, ambient air, etc.). Research into cost effective treatment and remediation methods; adding research info to publicly available databases; hold responsible parties accountable for releases with enforcement strategy using local and state government first and federal “as appropriate” where “responsible parties do not address PFAS voluntarily”; build database of sources and concentrations in environment Ensure coordinated communication; build materials to inform the public ARGUABLY SOFT APPROACH – explore, develop, evaluate, understand

What About the Legislative Branch?

Congressional PFAS Task Force Announced Jan. 2019 Bipartisan effort to more urgently address public health threat and protect

communities

PFAS Action Act of 2019 Introduced in Jan. by Rep. Debbie Dingell, D-MI To require EPA to designate PFAS as a CERCLA hazardous substance within 1 year

Presenter

Presentation Notes

Hold information events to educate Congress Craft legislation to address PFAS contamination Fight for robust funding through federal appropriations for cleanup Introduced in Jan. - In subcommittee 39 co-sponsors – none from OH – 2 Rs Legislation introduced to ensure veterans and families exposed to PFAS at military installations get health care services and benefits through the VA Legislation passed to fund health studies in National Defense Authorization Act from 2017

CERCLA: The SuperFUN Statute

WHEN: Where there is a release or threatened release of a hazardous substanceThat causes the incurrence of response costs

WHO: Owners/operators of facility where hazardous substances were disposedArrangers for transportation, treatment or disposalTransporters

LIABLE FOR: All costs of removal, remedial actions incurred by state or feds not inconsistent with NCPAny other necessary costs of response incurred by any other person consistent with the NCP NRDsCosts of health assessment or health effects studies

Presenter

Presentation Notes

Health assessments carried out by Agency for Toxic Substances and Disease Registry Section 107 Plaintiff brings action for costs voluntarily incurred. Joint and several unless Defendant can demonstrate divisibility of the harm/apportionment. Section 113 Plaintiff brings action for costs of reimbursement paid to another person pursuant to a legal judgment or settlement – a contribution action. Equitable allocation because it’s PRP against PRP. 107 Defendant can file 113 cross claim to blunt joint and several liability, but Defendant could still be liable for orphan shares. Any place where PFAS is disposed would become a Superfund Site. Any release above RQ has to be reported to National Response Center. RCRA = federal management of hazardous waste TSDs. CERCLA = response to abandoned, uncontrolled hazardous substance disposal

Presenter

Presentation Notes

Currently 22 states have implemented state PFAS rules – OH coming soon? OH convened Task Force and is drafting white paper on treatment technologies. Planning to focus on sources of PWS contamination Patchwork of growing regulations even beyond PFAS and beyond DW itself Michigan PFAS Action Response Team (MPART). R-Governor Snyder by EO. Renewed in Jan. 2019 by D-Gov. Whitner. Charged to ID impacted locations, assess sites and prepare response strategies, develop protocols, stakeholder education and outreach, ID funding, recommend changes in law and structure. Contrast with lame duck law, HB 4205, bans state agencies from creating new regulations stricter than the feds absent showing a clear and convincing need due to exceptional circumstances.

Toxic Tort/personal injury

Product liability/design defect/failure to warn

Citizen suits

Class actions

Takings/nuisance/ trespass Superfund litigation

Occupational injury/take-home injury

Evolving standards of care (worker training, PPE, product

safety)

Due diligence in transactionsSovereign immunity

Presenter

Presentation Notes

R 23 Certification 1) An adequate class definition – precise, unambiguous 2) Ascertainability – objective criteria/in or out 3) Numerosity – joinder impracticable 4) Commonality – law or fact 5) Typicality – claims and defenses 6) Adequacy – representative parties will fairly represent the class 7) Separate adjudications will create risk of inconsistent/dispositive decisions OR Declaratory/injunctive relief appropriate based on defendant’s acts with respect to class generally OR Common questions predominate and class action is superior to individual Establishment, maintenance, operation of a municipal corporation water supply system is Proprietary. Generally, liable for injury, death, or loss to person or property caused by negligent performance of acts by employees with respect to proprietary. RC 2744.02. Defenses: Conduct was authorized by law, other than negligence; resulted from exercise of judgment/discretion in determining whether to acquire or how to use equipment, supplies, materials, personnel, facilities or other resources, other than when malicious, reckless, in bad faith.

42 U.S.C. Section 300j-8 – Safe Drinking Water Act Citizen Suit

PERSONS SUBJECT TO CIVIL ACTION; JURISDICTION OF ENFORCEMENT PROCEEDINGS

Except as provided in subsection (b) of this section, any person may commence a civil action on his own behalf—(1) against any person (including (A) the United States, and (B) any other governmental instrumentality or agency to the extent permitted by the eleventh amendment to the Constitution) who is alleged to be in violation of any requirement prescribed by or under this subchapter;(2) against the Administrator where there is alleged a failure of the Administrator to perform any act or duty under this subchapter which is not discretionary with the Administrator;

Presenter

Presentation Notes

Notice requirement Commenced and is diligently prosecuting civil action to require compliance Reasonable attorneys fees May still intervene R 24 RCRA, CERCLA, CWA

thedevilweknow.com

Presenter

Presentation Notes

DuPont began making Teflon in 1945 - 50 year cover up alleged in eco-doc debuted at 2018 Sundance Film Festival C8 = PFOA When Cincinnati lawyer Rob Bilott first received a call from a cattle farmer in Parkersburg, West Virginia, he almost didn’t pay attention. The farmer, Wilbur Tennant, told him chemical company DuPont had purchased land adjacent to his property to use as a non-hazardous landfill for its local factory, but something wasn’t right: the stream the cows drank from had white foam on its surface, and hundreds of cattle were either sick or dying. In the phone conversation, Tennant mentioned Bilott’s grandmother, who lived in a nearby West Virginia town. Bilott agreed to meet. “He brought his videotapes and photographs to Cincinnati,” Bilott says. “We took a look and we realized something really bad was happening.” In a legal fight that lasted nearly 20 years, Bilott represented 70,000 citizens whose drinking water had been contaminated. When he found C8 listed in DuPont’s landfill documents, Bilott researched the chemical in environmental libraries but found nothing. Through the legal discovery process, he asked DuPont for information about the chemical. After pushback from the company, Bilott began to receive internal records that showed the company had been documenting the chemical’s health effects since the 1950s. Not only was C8 in the West Virginia landfill, it was also being released into the air from manufacturing smokestacks and had been pumped into the Ohio River.

Coming to a Theater Near You … Dry Run

Dayton Daily News

Presenter

Presentation Notes

Mark Ruffalo, Anne Hathaway, Tim Robbins, Bill Pullman Media reported in 2018 DuPont settled over 3,550 C8 cases for nearly $671 million but continue to deny wrongdoing. Athens, Miegs and Washington County In 2018, DeWine sued DuPont for release from plant to Ohio River despite knowing risks it posed to Ohio’s citizens and natural resources

Wright-Patterson Air Force Base, Dayton, Ohio

Dayton Development Coalition

Presenter

Presentation Notes

Last year treated water from the Ottawa Water Treatment Plant measured 12.5 ppt in March and 7 ppt in April, 2018 – safe levels but present. Notices sent to 400,000 customers of trace amounts to Dayton and Montgomery County. Dayton has more than 180 wells and PFAS present in well field. Dayton filed lawsuit in October against makers of fire fighting foam to shoulder clean up cost – 3M Company, Minnesota Mining and Manufacturing Co, Buckeye Fire Equipment Company, Chemguard, Inc., Tyco Fire Products LP and National Foam Inc. DDN found most cities with issues are just shutting off wells rather than treating. Dayton stopped pulling water from Tait Hills and Huffman Dam well fields. Random exposure monitoring ongoing. OEPA sampled for chemicals near all bases from Sept. 2016 to April 2017 – Toledo Air National Guard Base had well impacts. OEPA says area homes have connected to PWS. DDN reports 5 known contamination sites in OH – DuPont/Chemours Washington Works Plant on the Ohio River; the Newport Volunteer Fire Department, the Dayton Fire Training Center, Wright-Patt, and the Toledo Air National Guard Base.

It’s Time to Huddle

How are you preparing to make these assessments and decisions?

What are you going to communicate?

When?

How?

To whom?With whom?

Presenter

Presentation Notes

The Feds are doing it. Are you? Social impacts cannot be underestimated. HAB. Flint. Lead and Copper notifications. CSO overflows to Lake Erie. Need technical, legal and PR together Need strategy - when to speak up on policy development and how. OAWWA has great voice. Been at statehouse with Todd Danielson. Tricky preparing strategy with public entity membership while creating public record. AOMWA discovery. ACP – mutual exchange of information and legal advice Work product doctrine Hoosick Falls, NY Bennington, VT Cape Fear River, NC

Brian Yates, [email protected] x 1416 (O)614-558-2689 (C)

Andrea M. Salimbene, [email protected] (O)614-804-5200 (C)

Questions or (PFAS) Concerns?

bracing for a pfight: pfas sources, fate, impacts

Documents