Midwest Water Analysts Association Winter Expo 2020 PFAS ......Jan 24, 2020 · © TRC Companies,...

© TRC Companies, Inc. All rights reserved

Jeff Ramey

Midwest Water Analysts AssociationWinter Expo 2020

PFAS Update – Regulations, Analysis and More

January 24, 2020

1

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Analytical Methodology Update Drinking Water Non-Potable Water & Solids

Regulatory Updates Midwest States

WI MI IL MN

Federal TRC PFAS in Materials Study

Today’s Topics

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Analytical Methodology Update


Drinking Water Method Progression and PFAS Lists

EPA 537v1.1 – 14 PFAS

UCMR3 – 6 PFAS

2009

2013 -

2015

2018

2019

EPA 537.1 – 18 PFAS

EPA 533 – 25 PFAS

2023-

2025UCMR5 – TBD*

*Anticipating proposal summer 2020 and final rule late 2021 according to EPA presentation 7/16/2019. PFOS and PFOA on CCL4 but 537.1 and 533 compound lists are candidates.

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UCMR3 PFAS & MRLs

PFCAs

(C7) – PFHpA – 10 ng/L

(C8) – PFOA – 20 ng/L

(C9) – PFNA – 20 ng/L

PFSAs

(C4) – PFBS – 90 ng/L

(C6) – PFHxS – 30 ng/L

(C8) – PFOS – 40 ng/L


EPA 537v1.1 & EPA 537.1

MRLs for 537.1 slightly lower than 537v1.1 and in the single ppt range per PFAS


• Perfluoroether carboxylate surfactant

• Dupont/Chemours

• Is not Gen-Xone component of the Gen-X processing aid technology is a Gen-X chemical

• Shorter-chain PFAS: 6 carbons; 5 fluorinated

• Replacement for PFOA as a surfactant and polymerization aid in production of PTFE product

Hexafluoropropylene oxide dimer acid (HFPO-DA)

HFPO-DA


ADONA

• Polyfluoroethercarboxylate surfactant

• 3M/Dyneon

• Shorter-chain PFAS (7 carbons; 6 are fluorinated)

• Replacement for PFOA as a polymerization aid in production of PTFE product

ADONA


9

F-53B

9Cl-PF3ONSF-53B: major component

11Cl-PF3OUdSF53B: minor component

• Chlorinated polyfluorinated ether sulfonate• Used in metal plating as alternatives to PFOS for mist suppression• F-53 salts likely derived from fluorotelomer raw material• Used as mist suppressant in chrome plating industry for over 30 years in China• F-53 vs F-53B


Method 533 – Key Differences from 537.1

- Isotope Dilution for 16 labeled PFAS

- Addition of three isotope performance standards

- Solid Phase Extraction (SPE) cartridge containing weak anion exchange and mixed-mode polymeric sorbent (polymeric backbone and a diamino ligand)

- Multiple Reaction Monitoring (MRM)

- Sample volume 100 – 250 mL

- MRLs comparable


New PFAS in EPA Method 533

PFAS Analyte

3 Fluorotelomer sulfonates (4:2 FTS, 6:2 FTS, 8:2 FTS)PFMBA, PFMPA (used in manuf. of fluoropolymers)

NFDHA (food contact material)

PFEESA (replacement PFAS)

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PFAS Methods and Criteria Used for Non-Potable Matrices

Method Year Applicable Matrices # PFAS Analytes

EPA 537 “Modified” Current All 24+ analytes

ASTM D7979-17 2017 Water, Wastewater 21 analytes

ASTM D7968-17 2017 Soil 21 analytes

ISO 25101 2009 Aqueous PFOA/PFOS

ISO 21675 2019 Aqueous 30 analytes

SW-846 8327 2019 Aqueous 24 analytesCW1600/ SW-846

8328Internal

Validation Solid & Aqueous 25 analytes

DoD QSM 5.1 2017 Solid & Aqueous 24+ analytes

DoD QSM 5.2/5.3 2018/2019 Solid & Aqueous 24+ analytes

WI Criteria* 2019 All 36 analytes*Wisconsin PFAS Aqueous (Non-Potable Water) and Non-Aqueous Method Criteria


SW-846 Method 8327 – Screening Method?

- SW-846 Method

- Non-potable water and solid (soil, sediment, etc.)


- Isotope Surrogates, not Isotope Dilution


CWA 1600/ SW-846 8328 Update

- SW-846 Method

- Non-potable water and solid (soil, sediment, biosolids, etc.)


- Isotope Dilution

- Drafted to meet DoD QSM 5.1 requirements


WI Criteria 36 PFAS Compounds

PFBA Perfluorobutanoic acid 375-22-4 PFBS Perfluorobutanesulfonic acid 375-73-5 PFOSA Perfluorooctanesulfonamide 754-91-6

PFPeA Perfluoropentanoic acid 2706-90-3 PFPeS Perfluoropentanesulfonic acid 2706-91-4 N-MeFOSA N-Methylperfluorooctanesulfonamide 31506-32-8

PFHxA Perfluorohexanoic acid 307-24-4 PFHxS Perfluorohexanesulfonic acid 355-46-4 N-EtFOSA N-Ethylperfluorooctanesulfonamide 4151-50-2

PFHpA Perfluoroheptanoic acid 375-85-9 PFHpS Perfluoroheptanesulfonic acid 375-92-8 N-MeFOSAA 2-(N-Methylperfluorooctanesulfonamido)acetic acid 2355-31-9

PFOA Perfluorooctanoic acid 335-67-1 PFOS Perfluorooctanesulfonic acid 1763-23-1 N-EtFOSAA 2-(N-Ethylperfluorooctanesulfonamido)acetic acid 2991-50-6

PFNA Perfluorononanoic acid 375-95-1 PFNS Perfluorononanesulfonic acid 68259-12-1 N-MeFOSE N-Methyl perfluorooctanesulfonamidoethanol 24448-09-7

PFDA Perfluorodecanoic acid 335-76-2 PFDS Perfluorodecanesulfonic acid 335-77-3 N-EtFOSE N-Ethyl perfluorooctanesulfonamidoethanol 1691-99-2

PFUnA Perfluoroundecanoic acid 2058-94-8 PFDoS Perfluorododecanesulfonic acid 79780-39-5

PFDoA Perfluorododecanoic acid 307-55-1 4:2 FTS 4:2 Fluorotelomer sulfonic acid 757124-72-4 GenX (parent acid) Perfluoro-2-methyl-3-oxahexanoic acid 13252-13-6

PFTriA Perfluorotridecanoic acid 72629-94-8 6:2 FTS 6:2 Fluorotelomer sulfonic acid 27619-97-2 ADONA (parent acid) 4,8-Dioxa-3H-perfluorononanoic acid 919005-14-4

PFTeDA Perfluorotetradecanoic acid 376-06-7 8:2 FTS 8:2 Fluorotelomer sulfonic acid 39108-34-4 F-53B Major Perfluoro(2-((6-chlorohexyl)oxy)ethanesulfonic acid) 756426-58-1

PFHxDA Perfluorohexadecanoic acid 67905-19-5 10:2 FTS 10:2 Fluorotelomer sulfonic acid 120226-60-0 F-53B Minor2-[(8-Chloro-1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8-

hexadecafluorooctyl)oxy]-1,1,2,2-tetrafluoroethanesulfonic acid

763051-92-9

PFODA Perfluorooctadecanoic acid 16517-11-6

7 Sulfonamides, Sulfomidoacetic acids, Sulfonamidoethanols

4 Replacement Chemicals

12 Sulfonic Acids13 Carboxylic Acids

WI Criteria established based on DoD QSM 5.2/5.3 and draft SW-846 8328


Precursor Transformations


Midwest States and Federal Regulatory Updates


WDNR & DATCP Order Website update for proper public communication Collaboration with municipalities and WWTPs for screening and source identification Expanded monitoring to fish and wildlife consumption Develop regulatory standards Modify VPLE to protect tax payers Assess NRD claims for compensation

Executive Order 40

Multi-Agency Order Create multi-agency PFAS action plan Protocol development – risk communication, source identification Identify PFAS sources, public health risks, natural resource impacts Academic collaboration Explore funding

Signed August 22, 2019


WisPAC Chartered approved with amendments on 1/16/20

Adopts the multi-agency goals listed in EO 40

Development of PFAS Action Plan no later than 6/30/20 Monthly meetings (four-phase plan

development) Plan expected to be a four year roadmap

Committee Engagement Opportunities: Local Government PFAS advisory group Citizen/ Public Policy PFAS advisory group

Wis. PFAS Action Council (WisPAC)Proposed Focus Areas

1. Prevent Future Discharges and

Exposures

2. Minimizing Current PFAS Exposures

3. Addressing Historic or Legacy PFAS

Sources, Discharges and Exposures

4. Educating and Communicating About the Risks Associated

with PFAS


SS 089-19, SS 090-19, and SS-09-19 propose revisions:

NR 809 – Drinking water MCLs for PFAS including PFOS and PFOA NR 140 – Groundwater enforcement standards and preventive

action limit for groundwater polluting substances NR 105, NR 106, NR 219 – Adopt surface water quality standards,

analytical methodology and effluent limitations for PFAS including PFOS and PFOA

Public comments received and reviewed

Natural Resources Board (NRB) approved Scope Statements on 1/22/2020 starting 30-month rule-making process

Wisconsin Scope Statements

AFFF


Currently in the rule-making process for the first time in 10 years DNR requests groundwater recommendations from DHS

NR140: Groundwater Recommendations

CYCLE 10 (Spring 2018 – Fall 2021) 27 Compounds Requested 11 Revisions, 16 New Contaminant Requests 2 PFAS PFOS PFOA Scope statement approved on 8/27/19

CYCLE 11 (Spring 2019 – Fall 2023) 40 Compounds Requested 34 PFAS Remaining 34 of WI 36 Recommendations expected Fall 2020

ES - 20 ng/L PFOS + PFOAPAL – 2 ng/L PFOS + PFOA

TBD (not expecting recommendations for all 34 compounds)


Issued on 7/22/2019 to 125 (of 638) WWTPs:- 27 are authorized pretreatment programs that can

regulate their customers (over 5 MGD)- 87 were determined by keyword search for likely

historical industrial sources of PFAS.- 10 found by query of permit fact sheets- 1 community with PFAS in water supply

Monitor Influent and Effluent for 36 PFAS compounds and investigate industrial users if detected >20 ng/L PFOS+PFOA

Fate and Transport Study Participation Opportunity

DNR Request for Voluntary Testing


Industries listed as known PFAS sources (SIC Codes):- Platers/ metal finishers (3471, 3479)- Dairy processing facilities and cheesemakers where milk supply is sourced from livestock

grazing on fields that have received PFAS contaminated biosolids (0241)- Paper and packaging manufacturer (26)- Fire-fighting equipment manufactures (2899, 3999)- Tanneries and leather/ fabric/ carpet treaters (31, 23, 2273)- Military bases (9711)- Manufacturers of parts with PTFE (many)- Airports (4581)- Facilities that manufacturer or use coatings (many)- Household cleaning product manufacturers (284)- Centralized waste treaters (4953)

DNR Request for Voluntary Testing


9/16/19 – Lab certification program releases WI PFAS Aqueous (Non-Potable Water) and Non-Aqueous Matrices Method Criteria document for 3 week open comment period (FINAL on 12/16/19) Not a method Performance Criteria base on DoD QSM 5.2 Isotope Dilution Required LC/MS-MS Solid Phase Extraction (SPE)

Certification PFOS/PFOA or 36 Compounds Non-potable water or solids Posted ~ April 2020

NR 149: Lab Certification Program

533?537.1?


Starkweather Creek Peshtigo and St. Louis River Silver Creek and Suujak Sep Creek Mississippi River Menominee River Wisconsin River

DNR Surface Water Sampling - 2019

Wisconsin River Results3 sample rounds (ppt)

PFOA PFOSRhinelander 17 - 36 3.1 - 3.6Merrill 12 - 15 2.7 - 3.9Nekoosa 6.5 -11 2.5 - 5.6


Michigan PFAS Action Response Team (MPART) Rule 57 Promulgated surface water quality standards: PFOS – 11/ 12 ng/L PFOA – 420/ 12,000 ng/L MCL recommendations (final ~ 4/2020):

Potable Water Study (Phase 1 & 2) Industrial Pretreatment Program (IPP) source identification and elimination program

Michigan


Illinois

Draft Proposed Groundwater Standards (Dec. 2019):

PFOS – 14 ng/L PFOA – 21 ng/L Combined PFOS/PFOA – 21 ng/L

PFNA – 21 ng/L PFHxS – 140 ng/L PFBS – 140,000 ng/L

Open comment period ends 1/31/2020


Minnesota

Health-Based Values (HBVs) (not MCLs):

PFOS – 27 ng/L 15 ng/L PFOA – 35 ng/L PFBS – 2,000 ng/L PFHxS – 47 ng/L PFBA – 7,000 ng/L PFPeA – not established PFHxA – not established

3M groundwater Settlement - $850M

Per- and polyfluoroalkyl substances (PFAS)

Residential/Recreational

SRVmg/kg (µg/kg)

Commercial/Industrial

SRVmg/kg(µg/kg)

PFBS 5.7(5,700)

77(77,000)

PFBA 38(38,000)

520(520,000)

PFOS 0.041(41)

0.56(560)

PFOA 0.24(240)

3.2(3,200)

PFHxS 0.13(130)

1.7(1,700)


Vermont – PAL @ 20 ug/L ∑ of PFOS, PFOA, PFNA, PFHpA, PFHxS

New York – MCLs @ 10 ug/L PFOS, 10 ug/L PFOA

New Jersey – GWQS and MCLs @ 13 ug/L PFOS, 14 ug/L PFOA

Other Proposed State Rule-Making


Federal Regulatory Status – EPA

PFAS Action Plan released 2/14/19 with

end of year to decide to start MCL rule making

for PFOS and PFOS

Lifetime Health Advisory Level (HAL) established with multiple revisions for PFOS and PFOA in combination and individually (trending )

Draft Interim Guidance to Address Groundwater released on 4/25/19:- Screening 40 ng/L PFOS or PFOA- Preliminary Remediation Goal = HAL


Integrated Risk Information System (IRIS) assessment for five additional PFAS – PFDA, PFNA, PFHxA, PFHxS, PFBA

Regulatory determination in review for PFOS and PFOA Drinking Water MCLs

Analytical method development – EPA 533, 8327, 8328

Finalized groundwater screen levels and cleanup recommendations

ANPRM for Toxic Release Inventory (TRI) reporting

EPA PFAS Action Plan Recent Updates


Some NDAA 2020 PFAS Provisions

- EPCRA TRI Reporting Requirement

- DoD: AFFF and MRE Restrictions, GW Clean-Up

- USGS: Monitoring

- EPA: Disposal and Destruction Guidance

- EPA: Technical Assistance to States (DW)

- Long-Chain SNUR and Cooperative Agreements

NDAA and EPCRA Section 313 TRI Reporting

EPCRA TRI Requirement- Effective 1/1/2020 (report

due 7/1/2021)

- 100 lbs/yr. PBT threshold- PFOA (+salts)- PFOS (+salts)- HFPO-DA- PFNA- PFHxS

~160 PFAS on TSCA/ SNUR registries

Future PFAS listing evaluations (2-year) and threshold reviews

CERCLA

MCL


TRC PFAS in Sampling Materials Study


Due to sensitive detection limits and environmental presence of PFAS, special care is required to prevent cross contamination

Accomplished by exclusion of specific sampling equipment.

Include equipment and field blanks in sampling event

PFAS Sampling –High Risk of Cross-Contamination


PFAS Sampling Dos and Don’ts

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WHAT SHOULD I AVOID? USE INSTEADPassive diffusion bags (PDBs)

LDPE Hydrasleeves HDPE Hydrasleeves

Post-It notes during sample handling

Blue Ice® (chemical ice packs) Regular ice in Ziploc® bags

Waterproof field books, plastic clipboards and spiral bound notebooks

Field notes recorded on loose paper Field forms maintained in aluminum

or Masonite clipboards

Unnecessary handling of items with nitrile gloves

Personnel collecting and handling samples should wear nitrile gloves at all times while collecting and handling samples or sampling equipment



WHAT SHOULD I AVOID? USE INSTEADEquipment with Teflon® (e.g., bailers, tubing, parts in pump) during sample handling or mobilization/demobilization

High density polyethylene (HDPE) or silicone tubing/materials in lieu of Teflon®

Low-density polyethylene (LDPE) or glass sample containers or containers with Teflon-lined lids

HDPE or polypropylene containers for sample storage

HDPE or polypropylene caps

Tyvek® suits and waterproof boots Clothing made of cotton preferred Boots made with polyurethane and

polyvinyl chloride (PVC)

Waterproof labels for sample bottles Paper labels with clear tape

Sunscreens, insect repellants Products that are 100% natural, DEET

Sharpies Ballpoint pensAluminum foil ???? Thin HDPE sheeting



WHAT SHOULD I AVOID? USE INSTEADPersonal Care Products: cosmetics, moisturizers, deodorant, hand creams, shower gels, shampoos

Nothing

New clothing or recently laundered clothing Cotton materials that have been

washed at least 6 times since purchase

Food and drink in the sampling area Consume in designated areas

Conduct a study


To evaluate the potential for PFAS cross-contamination from commonly used products

Determine the relative concentrations of PFAS

Determine the types (classes) of PFAS

Purpose of Study


PFAS in Sampling Supplies: Fact or Fiction?

39

Polyethylene Tubing Re-sealable Plastic Storage Bags

Aluminum Foil Adhesive Notes

Level C Chemical-Resistant Clothing

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)

Sample Labels


40

PTFE Tubing

10.08

3.01 3.73 4.446.31 6.61

5.213.98 3.62 3.14 2.80

21.49

8.1810.17

9.02 9.968.71

6.61

3.50 3.06 2.26 0.000.00

5.00

10.00

15.00

20.00

25.00

PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFTrDA PFTeDA

PTFE Tubing(ng/L)

PTFE TUBING A PTFE TUBING B

C4 PFCANo PFSAs

ng/L


41

LDPE Tubing

0.0010.0020.0030.0040.0050.0060.0070.0080.0090.00

100.00


LDPE Tubing(ng/L)

LDPE 1 LDPE 2

C4 & C5 PFCA

No PFSAs

ng/L


42

Water Level Tapes

0

5

10

15

20

25

30

35

40


Water Level Tapes(ng/L)

Water Level Tape Model 1 Water Level Tape Model 3

No PFSAs

ng/L


43

Bailer Line

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

8:2FTS PFBA PFPeA PFHxA PFHpA PFOA PFOS PFNA PFDA PFUnA PFDoA PFTrDA PFTeDA

Bailer Line (ng/L)

Bailer Line 1 Bailer Line 2

PFOA & PFOS

8:2 FTSng/L


Field Book Pages vs Field Book Cover

0.00

5.00

10.00

PFBS PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFTrDA PFTeDA

Pages in Field Logbook(ng/L)

Book Pages A

C7 PFCANo PFSAs

0.00

100.00

PFBS PFBA PFPeA PFHxA PFHpA PFOA PFNA PFDA PFUnA PFDoA PFTrDA PFTeDA

Cover of Field Logbook(ng/L)

Book Cover A Book Cover B

C7 PFCA

C4 PFCA

ng/L

ng/L


PFCAs PFSAs Polyfluoroalkyl Substances

PTFE Tubing Bailer Line PTFE-lined TubingPTFE-lined Tubing Sample Labels Bailer LineLDPE Tubing Nitrile GlovesBailer Line Field Book CoverSample LabelsPizza BoxWater Level TapesSilastic TubingNitrile GlovesField Book PagesField Book CoverPTFE Bladder

PFCAs vs PFSAs vs Polyfluoroalkyl Substances


No PFAS Detected

Silicone Tubing Aluminum Foil

Polyethylene Bladder Adhesive Notes

Passive Diffusion Bag Resealable Plastic Storage Bags

Bubble Wrap Bentonite

Protein Bar Wrapper


Generally low levels of PFAS may leach off of specific sampling materials Study results were conservative Tubing stored in wells for extended period of time may be exception Forensic evaluation of sample data Equipment blanks must be collected

Published in Remediation:Per‐ and polyfluoroalkyl substances in environmental sampling products: Fact or fiction?https://onlinelibrary.wiley.com/doi/abs/10.1002/rem.21614

Some Conclusions of the Study

https://onlinelibrary.wiley.com/doi/abs/10.1002/rem.21614


Jeff RameySenior Project Manager/ Senior Chemist

[email protected]

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mailto:[email protected]

Midwest Water Analysts Association Winter Expo 2020 PFAS ......Jan 24, 2020 · © TRC Companies,...

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Transcript of Midwest Water Analysts Association Winter Expo 2020 PFAS ......Jan 24, 2020 · © TRC Companies,...