November 14, 2019

Toxics Use Reduction Institute Science Advisory Board Meeting Minutes

November 14^th, 2019

DEP, 1 Winter Street, Boston

12:30 PM

Members Present: Dave Williams (Chair), Robin Dodson (Vice Chair), Hilary Hackbart, Wendy Heiger-Bernays, Christy Foran, Amy Cannon, Christine Rioux,

Members not present: Ken Weinberg, Denise Kmetzo, Heather Lynch

Program staff present: Liz Harriman (TURI), Heather Tenney (TURI), Hayley Byra (TURI), John Raschko (OTA), Tsedash Zewdie (MassDEP), Tiffany Skogstrom (OTA)

Others present: Katherine Robertson (MCTA), Steve Rosario (ARS/ACC), Renee Lani (Fluorocouncil), Steve Korzeniowski (Fluorocouncil/ACC), Carol Holahan (Foley Hoag ACC), Trisha McCarthy (Coyne PC for ACC), Helen Poynton (UMass Boston), Rich Gurney (Simmons University)

Welcome and Introductions

Program Updates

• See TURA program update handout and TURI FY20 Grants handout
• Meetings will be held around the state in early December to gather input for the Halogenated Solvents Alternatives Assessment.
• The TURA category of C1-C4 Halogenated hydrocarbons/halocarbons not otherwise listed [C1-C4 NOL] should be tracked this year and first reported in June.
• The HF Fact sheet has been published.
• Discussed the Buffalo Wild Wings fatal chemical accident in Burlington and possible preventative responses. Members expressed the need for more janitorial cleaning training including in-house and job specific training.
• OTA has published the SE Shires case study.
• DRAFT PFAS Policy Analysis was summarized and will be posted on the LibGuide

MassDEP PFAS Update

• DEP has been reviewing information from ATSDR and other resources to establish a drinking water guideline. They noted concerns that long chain PFAS persisted in the environment and what information is available on toxicity and persistence in the body is similar to PFOS and PFOA.

• They decided that the EPA Health advisory numbers for PFOA and PFOS are not health protective and reduced the drinking water health number to 20 ng/L. This was achieved by applying an uncertainty factor of 3 to the EPA reference dose and driving a corresponding drinking water level by using the MassDEP updated RfD and exposure factors similar to that used by the EPA. Because of similarity in structure, persistence in the body, and toxicity (when data is available) MassDEP  is extending the EPA additivity approach as applied to EPA PFOA and PFOS health advisory to 4 other long chain PFAS (PFHpA, PFNA, PFDA and PFHxS).
• After receiving public comments and questions they did not find anything substantial and are continuing to propose an Office of Research and Standards Guideline (ORSG) for drinking water of 20 ng/L for the sum of six PFAS chemicals. The full document will be released soon. The value is also the basis for the Massachusetts Contingency Plan (MCP) method 1 standard for ground water that is or may be used for drinking water.

Approval of September Minutes

The minutes from the last meeting in September were reviewed and there was a vote to approve: 5 in favor, 2 abstaining. The members abstaining noted that their abstention was due to not being present at the last meeting.

 Perfluoroalkyl Phosphonic acids (PFPA) and Perfluoroalkyl Phosphinic acids (PFPIA)

Concerns were documented on the white board as follows (note that white board notes are very abbreviated, see discussion text below and EHS summary for more information):

Persistence:

• YES; PFPA persists and PFPiA degrades to PFPA

Bioaccumulation:

• Not the same [across category]. NICNAS (Chen 2016) zebrafish. C8 (Lee 2012) longer elimination half-life, high (> 5) BCF for PFPIA in different tissues

Mobility:

• Not a lot of data; biosamples 3 continents, multiple species.

Acute Toxicity:

• LD₅₀ 50-300, On par with PFOS ( for butyl [phosphinic])

Corrosivity:

• Pretty strong acid pKa PFPA .9-3.9; PFPiA<1
• C4 low pKa<1.6 C4-C11 (Wang 2011)

Cancer:

• No data

Immunotoxicity:

• No data

Endocrine:

• Liu 2019 Thyroid mediated endocrine disruption
• High dose (mg/kg); has a potential for biological activity

Liver:

• Increased liver weight (Das 2011)
• Increased maternal liver weight (EPA, NICNAS – Tatum 2012)
• PPAR alpha activation (Das 2011)

Repro:

• Increase in maternal liver weight (Tatum 2012)

Breakdown:

• PFPiA to PFPA ( through metabolization) and 1-H perfluoroalkane to PFCA
• Bisnonafluorobutyl does not break down ( Wang 2016)

The board discussed whether to consider PFPA/PFPiA’s as a group of substances of varying chain length, as opposed to substances. . Bioaccumulation is variable across category. Even with fewer data available, this doesn’t mean the substances are less hazardous or there are fewer problems associated with these chemicals. There is a lack of funding for research. Studies aren’t available as they aren’t on the market in the U.S.

There was further conversation around the C4 chemical - persistence, LD50, acute toxicity are the only values for it. It was mentioned that the C4 shouldn’t be dismissed as it is included in the mix of commercial products. A visitor offered that surfactants typically contain mostly C6, C8, and C12 but the C4 can be present in the mix; especially using this specific chemical with the two C4 chains on both sides.

It was suggested to consider PFPA/PFPiA chemicals as a group because these chemicals are typically in a mixture and it is difficult to distinguish percentages or individual amounts of C6, C8, and C12 within the mixture, especially considering the lack of standards.

The data that we do have indicated that these chemicals have concerns including mobility, persistence, corrosivity/pKa, and similarities to each other and other PFAS.

Wang 2011 (page 240) contains information about C4 supporting the need to consider these chemicals as a group of perfluoralkyl phosphonic and phosphinic acids.

The PFAS we studied early on are data rich, now data is more limited.

A motion to recommend listing Perfluoroalkyl Phosphonic Acids and Phosphinic Acids based on mobility, persistence, corrosivity (pKa) with additional concerns based on evidence of liver toxicity and acute toxicity for some of the compounds. Additional evidence shows compounds are precursors to (can breakdown into) PFCAs (e.g. PFOA, previously recommended for listing). All seven members present voted in favor of the motion and the recommendation was unanimously approved.

PFAS: Precursors and Range of Substances

TURI summarized degradation and transformation examples that they have been gathering. Some were presented at the last meeting and some have been added since the last meeting. The goal is to cover a range of substances and possible breakdown/transformation pathways.

These breakdown pathways will be the focus of our discussion next time.

The examples were distributed, as well as a summary table showing for each example, which OECD sub-category the precursor fell into and the type of degradation/transformation pathway shown.  It was noted that both documents are still in draft form.  For the examples on pages 2-4, the general diagrams from the Jan 2019 Fluorocouncil webinar (Korzeniowski & Buck, 2019) are provided.  They are helpful in seeing how the specific examples given on those pages relate to the general degradation pathways.  References for each example are on the sheets, and some also have quoted explanatory text.

A visitor noted that the 6:2 fluorotelomer sulfonamide alkylbetaine (6:2 FTAB) precursor shown on page 3 is a major AFFF (Aqueous Film Forming Foam for firefighting) surfactant.  On page 3 it was noted that the “defluorinated and oxidized” arrow should go only from the 1-H Perfluoroalkanes to the PFCA.

TURI is still planning to add at least one thermal degradation example, and possibly one focused on degradation within landfills resulting in PFAS presence in landfill leachate.

Next Meeting

January 14^th

Handouts:

• TURI Program Update
• TURI Grant Projects
• Updated EHS Summary for PFPA/PFPiA
• Updated PFAS Degradation/Transformation Examples and Summary Spreadsheet