PFAS: What are they? &

What are we doing about them?

Brian PenttilaOctober 02, 2018

PPRC Regional Roundtable

PFAS Chemical Action Plan (CAP)

Persistent Bioaccumulative Toxic (PBT) Rule

• Identifies, characterizes, & evaluates uses & releases of a PBT.

• Recommends actions to protect human health & the environment.

• PBT list includes Perfluorooctane sulfonic acid (PFOS) & 4 salts

PFOS is a PFAS* (per- and polyfluorinated substances; a chemical class)

More Information

• PFAS CAP website: www.ezview.wa.gov/?alias=1962&pageid=37105

• Ecology’s PFAS webpage: http://bit.ly/prioritytoxics-pfas

2PBT Rule in WAC 173-333: http://apps.leg.wa.gov/Wac/default.aspx?cite=173-333

*Buck, Robert C., et al. "Perfluoroalkyl and polyfluoroalkyl substances in the environment: terminology, classification, and origins." IEA&M 7.4 (2011): 513-541.

PFAS from nowhere?

• Sinclair 2006 – 8 analytes

Influent

PrimaryEffluent

Treatment plant image from: Leonard G. at English Wikipedia

∆

Sinclair, E., & Kannan, K. (2006). Mass Loading and Fate of Perfluoroalkyl Surfactants in Wastewater Treatment Plants, ES&T, 40(5).

PFASs identified in arctic wildlife, but how?Physicochemical Properties - PFOS & PFOA

• Low vapor pressure (don’t evaporate)

• Soluble in water (likely to travel by water)

• Not a candidate for “Long-Range Transport”

Biomonitoring ca. 2004-2008

• Evidence of PFAAs and biomagnification in

animals of the Arctic

• “The transport pathway for these chemicals to

the Arctic remains unclear.”

• “Due to low volatility of PFCs, their atmospheric

transport to remote regions such as the Arctic

had been unexpected.”

Smithwick et al., 2005, “Circumpolar Study of Perfluoroalkyl Contaminants in Polar Bears (Ursus maritimus).”Environ. Sci. Technol., 39, 5517-5523.Dietz et al., 2008, “Increasing Perfluoroalkyl Contaminants in East Greenland Polar Bears (Ursus maritimus): A New Toxic Threat to the Arctic Bears,” Environ. Sci. Technol. 2008, 42, 2701–2707.Ellis et al., 2004, “Degradation of Fluorotelomer Alcohols: A Likely Atmospheric Source of Perfluorinated Carboxylic Acids,” Environ. Sci. Technol. 2004, 38, 3316-3321.

F

F

FF F

FFF F

FFF F

FF

O O–

H+

PFOA

PFOA ionized at normal pH

Per- and Polyfluorinated Alkyl Substances (PFASs)

• Precursors vs Intermediates vs Final Degradates

• FTOHs are volatile and travel long distances in

the atmosphere

8:2 Fluorotelomer alcohol (FTOH)(Precursor)

PFOA(Stable Degradate)

?(Intermediate Degradates)

5

Fluorotelomer-based products

6Content from FluoroCouncil presentation to CAP Advisory Committee, 11/01/17

Per- and Polyfluorinated Alkyl Substances (PFASs)

DiPAP used in paper treatment (now obsolete?)

PFBS - basis of new 3M chemistry

6:2 FTOH – currentworkhorse fluorotelomer

EtFOSA – abandoned

Varied chain lengths

Varied functional groupsVaried chain types

F-53B

*

ADONA (PFOA replacement)

?

7

Or not chains!

Na+

Chlorine

“Side-Chain” Evolution over Time

EtFOSA

6:2 FTOH

8:2 FTOH

8:2 FTOH

Image adapted from Dinglasan et al., 2006, “Significant Residual Fluorinated Alcohols Present in Various Fluorinated Materials.” ES&T, 40, 1447-1453

Weaker bonds susceptible to attack

8

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oly

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Ph

ased

ou

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ent

Side-chain Options

Long-Chain Manufacturing now in Asia+

Left figure based on 2014 FluoroCouncil submission to POPRC. FluoroCouncil members are not included in these data as they do not manufacture PFOS. Right figure reproduced from “Working towards a Global Emission Inventory of PFASs: Focus on PFCAs - Status Quo and the Way Forward,” © OECD, 2015, p. 39. 9

Over 100 companies could be involved in production of PFOS and derivative products globally, mostly abroad.

Projections of PFOA emissions suggest that PFOA use has not ended, but rather been replaced by use abroad.

What’s in Your Store?

Perfluoropolyether

8:2 FTOH

Image adapted from Dinglasan et al., 2006, “Significant Residual Fluorinated Alcohols Present in Various Fluorinated Materials.” ES&T, 40, 1447-1453

EtFOSA

8:2 FTOH

10

Still in imported products?

Are these alternatives

safe?

6:2 FTOH

SCP breakdown a long-term source of PFASs

Landfill burial a common end-of-life scenario

Washington & Jenkins, 2015, “Abiotic Hydrolysis of Fluorotelomer-Based Polymers as a Sourceof Perfluorocarboxylates at the Global Scale,” ES&T, 49, 14129-14135

Fluoro-telomerpolymer

atmosphere, OH-

FTOHlandfillhydrolysis

11

Emissions to date (mostly mfr. releases)

Future emissions from legacy products

PFOA will continue to build-up in the environment long after the products themselves are discontinued!

How many PFASs are there?

12

Can we detect & quantify them?Analytical capability

• Quantitative methods are very

limited (1 validated method)

• Qualitative and quantitative

methods are developing rapidly,

but are hampered by the lack of

standards

• The number of environmentally

relevant substances far outstrips our

analytical capability

• World-class labs quantify ~70

substances

13

Analytical Methods

Substances

KEMI. (2015). Occurrence and use of highly fluorinated substances and alternatives Report from a government assignment. Stockholm. Retrieved from https://www.kemi.se/global/rapporter/2015/report-7-15-occurrence-and-use-of-highly-fluorinated-substances-and-alternatives.pdfFrömel, 2016, “Investigations on the presence and behavior of precursors to perfluoroalkyl substances in the environment as a preparation of regulatory measures.” (UBA); Xiao, F. (2017). Emerging poly- and perfluoroalkyl substances in the aquatic environment: A review of current literature. Water Research, Volume 124, 1 November 2017, Pages 482-495.

5000

https://www.oecd.org/chemicalsafety/portal-perfluorinated-chemicals/

How many PFAS have

“robust” toxicology data sets?

14

Published Toxicology Data

on Short-Chain Substances

15

Substances with “Good” Data SetsSubstances with No Data

Based on data reported by FluoroCouncil members, in ECHA registrations, and in scientific literature.

>?00

6 to 10

Drinking Water

Whidbey NASFairchild AFB

Post-UCMR PFAS detections above 70 ppt

McChord Field and

Fort Lewis

Provided by Barb Morrissey (DOH)

PFAS tested vs. untested drinking water

17

PWS - sampled by UCMR80%

PWS not sampled

under UCMR

5%

Private wells15%

By % state population served… By number of drinking water systems…

~20% of WA residents are served

by wells that are untested for PFAS

WA population = 7.3 million

1% PWS tested for PFAS

PWS- Group A

PWS -Group B

PWS - tested

UCMR3 tested only 6 PFAS; larger suite of analytes in DOH testing.

We’re testing water for PFAS

so we’re safe, right?

18

Many environmental samples contain significant amounts

of precursors not identified by EPA Method 537

1) BeforeOxidation

React with OH- and heat

Oxidation treatment converts unknownprecursors to measurable PFAAs

2) AfterOxidation

AFFF impacted groundwater analysis presented by Arcadis, 2015

C6

C6

C8

C8

C6

Difference is large “unknown” mass converted to PFAAs

Gro

un

dw

ater

Sa

mp

le

Measure the sample twice

19

How does this apply to AFFF?

• Many AFFF concentrates contain precursors that can’t be quantified by standard methods

• The same is true of AFFF contaminated groundwater, aquifer solids, and soils

• Cutting-edge techniques have detected a large number of previously unknown classes of PFASs

20

Before TOP After TOP

Houtz et al., 2013, “Persistence of Perfluoroalkyl Acid Precursors in AFFF-Impacted Groundwater and Soil,” ES&T, 47, 8187-8195.

Interim CAP Report (April 2018)

• Health conducting expanded testing of drinking water– Developing health-based contaminant levels for PFAS

• EPA has only “advisory” levels for PFOS and PFOA (70 ppt)

– Develop guidance for water purveyors and the public

• Ecology working with Issaquah – Cleanup levels?

– Best practices for investigation and remediation?

• Implement new PFAS laws– Ban on use of PFAS-based AFFF for training & municipalities (RCW 70.75A)

– Ban on PFAS in food packaging pending alternatives assessment (may be application dependent) (RCW 70.95G)

21PFAS CAP Website: https://www.ezview.wa.gov/?alias=1962&pageid=37105

Why Fire-fighting Foam?

22

Aqueous film-forming foam (AFFF)

2018 Law Restricts AFFF Makeup & Use• Beginning July 1, 2018, the use of PFAS-containing Class B firefighting

foam is prohibited for training (no exemptions)

– Training uses are likely responsible for all of the areas identified in Washington

state above the PFOA/PFOS lifetime health advisory

• Beginning July 1, 2018, manufacturers and sellers must notify on use of

PFAS in personal protective equipment (PPE)

• Beginning July 1, 2020, the manufacture, sale, and distribution of PFAS-

containing Class B firefighting foam will be prohibited

– Certain airports, refineries, terminals, and chemical plants are exempt

23

https://ecology.wa.gov/Waste-Toxics/Reducing-toxic-chemicals/Addressing-priority-toxic-chemicals/PFAS/Toxics-in-firefighting

Why Food Packaging?

24

Why Food Packaging?

25

Some Potential Food-related PFAS Exposure Routes• Food via PFAS in food-contact materials• Food/packaging to compost/biosolids to food

o Beneficial reuse of manufacturing wasteo Home recycling (e.g., Seattle), composting

• Releases from manufacturing operations…

Not addressed

by FDA approvals.

PFAS accumulate in plants

Alternatives to PFAS in Food Packaging• Beginning January 1, 2020, no manufacturing, sale, or distribution of food

packaging with intentionally added PFAS. The ban takes effect when:– Ecology identifies safer alternatives

– An external peer review supports the safer alternative determination

– Ecology publishes its findings in the Washington State Register

• RCW 70.95G includes definitions and additional criteria that must be met. Safer alternatives must:– Meet improved hazard and exposure considerations.

– Be practicably and economically substituted.

– Be readily available in sufficient quantity and at a comparable cost.

– Perform as well as or better than PFAS in a packaging application.

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Packages containing metals and toxic chemicals: http://app.leg.wa.gov/rcw/default.aspx?cite=70.95G

Ongoing CAP Work

• Request and review EPA and FDA data

• Research PFAS in industrial, commercial, & consumer

products to reduce exposures

– Test for long-chain PFAS in imported products

• Evaluate & promote use of safer alternatives for legacy PFAS

in consumer products

• Promote best management practices for reducing human &

environmental exposures to PFAS

27

28

Other Manufacturing Sources

Legacy applications of PFOS/PFOA• Surfactants for wetting, spreading,

and leveling• Adhesives, paints, floor treatments,

sealers• Water/Oil/Soil repellants• AFFF

Exempt PFOS/PFOA Uses• Metal plating (mist suppressants)• Semiconductors• Photolithography• Specialty plastic

Exposure not only to groundwater and surface water, but also via aerial emissions!

Are you acting on concerns about PFAS?

29

What’s in your garage?

30

Legacy Product SourcesHistoric applications of PFOS/PFOA• Surfactants for wetting, spreading, and leveling• Adhesives, paints, floor treatments, sealers• Water/Oil/Soil repellants

PFAS CAP TimelineWe are here

Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec

4

Oct 2018CAP Meeting

Recommendations

Draft CAP

Oct 2019CAP Comments

May/Jun 2019Publish Draft CAP

Dec 2019Publish Final CAP

2018 2019

Final CAP

Develop Draft CAP Final CAP

Public Review and Meeting(s)

Recommendations

Mar 2019 Cost Webinar

Some Possible Federal Actions

• EPA (dates from EPA website)

– Propose PFOA/PFOS as “hazardous substances” under CERCLA 102

– Develop groundwater cleanup recommendations for PFOA/PFOS

(Sept 2018)

– Developing human health toxicity values for GenX and PFBS

(Summer 2018)

• Congress - FAA Reauthorization

– House: Passed, removes requirement for fluorinated foams

– Senate: still in process

32https://www.epa.gov/pfas/epa-actions-address-pfas

Summary

• There are hundreds or thousands of overlooked PFASs

– Due to weak disclosure, technology gaps, & regulatory failings

• Gaps in our knowledge of product nature/composition

– Ecology product testing program partially addressing this

• Vast gap in analytical methods & data on fate properties

(not to mention toxicology)

• PFASs generate degradates with very high persistence

– Product impacts will remain long after production ends

– Opportunity for Green Chemistry & Safer Alternatives

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Questions? Discussion?

Thanks!

Manufacturing

2007 carpet/upholstery protector concentratePercent of Each Isomer Typein Commercial PFOS Samples

Isomer profile based on Jiang et al., 2015, Chemosphere 127 (2015) 180–187Carpet product based on Liu et al. 2012, EPA/ 600/R-12/585, August 2012

Example of ECF branched isomer

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1) Electrochemical fluorination (ECF) 2) Telomerization