PFAS Update – Where We Are and Where We're Heading

EBC Rhode Island Emerging Contaminants Webinar

PFAS Update – Where We Are and Where We’re Heading

Environmental Business Council of New England

Energy Environment Economy

Welcome

Rick Mandile

Chair, EBC Rhode Island Chapter

Principal, Sage Environmental

Thank you to our Sponsor



Introduction

Steve LaRosa

Program Co-Chair & Moderator

Technical Leader

Weston & Sampson



PFAS: What Are They and Why Should We Care?

Karen Kinsella

Senior Technical Specialist

GZA GeoEnvironmental, Inc.

PFAS: What Are They and Why Should We Care?Karen Kinsella

GZA GeoEnvironmental, Providence, Rhode Island

Environmental Business CouncilRhode Island Emerging Contaminants

November 5, 2020 PFAS Update

EBC Rhode Island Emerging Contaminants Program • PFAS Update • November 5, 2020

Outline

2

• Overview• Uniqueness of the carbon-fluorine bond• Perfluoroalkyl vs. polyfluoroalkyl substances• Uses, sources• Non-polymers vs. polymers• Why so different?• Public perception• Risk communication


What are PFAS?

3

• A large family of organic compounds

• Man-made and widely used

• Persistent - don’t or slowly break down

• Accumulate over time

• Limited data on health effects in humans

EBC Rhode Island Emerging Contaminants Program • PFAS Update • November 5, 2020 4

Carbon-FluorineForms very strong bonds

Resulting PFAS PropertiesSurfactant, water- and oil-repellentStable in acids, caustics, oxidants, heatResistant to biodegradation

Unique Chemistry of Fluorine


Unique Chemistry = Usefulness

5

Organic fluorine special properties:Small atomic radius • High electronegativity • Low polarizability of the C–F bond

Many biologically relevant molecules Peptide/protein chemistry

Medicinal chemistryChemical biology

PharmacologyDrug discovery

Diagnostic and therapeutic applications

Ojima 2013. Journal of Organic Chemistry 78:6358.


Per- vs. Polyfluoroalkyl Substances

6

Perfluoroalkyl: all available carbons have fluorines instead of hydrogens

Polyfluoroalkyl: some carbons with fluorines, some with hydrogens

Fluorinated polymercoatings need to degrade or leach impurities to be

bioavailable

4:2 Fluorotelomer

Perfluorononanoic acid (PFNA)

Perfluorooctanesulfonic acid (PFOS)


Surfactants: non-polar tail, polar head

Surfactants

7Structures: comptox.epa.gov; pubchem.ncbi.nlm.nih.gov

Example of a surfactantthat is not fluorinated: sodium dodecyl sulfate (sodium lauryl sulfate)

PFAS: fluorinated surfactants

4:2 FtS

GenX

PFNA


Unique Chemistry: Specialty Surfactants

Fluorocarbon “Tail” = Hydrophobic and Oleophobic

Functional Group “Head” = Hydrophilic

Taryn McKnight, Eurofins-TestAmerica


• Aqueous Film Forming Foams (AFFF) – firefighting• Water/stain/oil/grease/heat/chemical resistant coatings• Textiles, leather, and clothing (including carpet and furniture)• Mist suppression for metal plating and anodizing• Chemical and heat-resistant seals• Fluoropolymer production• Fuel cell membranes• Cable and wiring• Lubricants• Pesticides

Unique Chemistry: Specialty Surfactants


PFAS Get Complicated Fast

10

PFOS is a PFSA

PFOA is a PFCA

Teflon™ is a PTFE


• Super-strong carbon-fluorine bond

• Thousands of different chemicals – dozens that can be identified in environmental samples – that interact differently with air/water/soil/sediment

• Typically, organic chemicals accumulate in lipids/fatty tissues – PFAS bind to proteins

Why are PFAS so Different?

11

Perfluorooctanesulfonic acid (PFOS)

Perfluorononanoic acid (PFNA)

Structures: comptox.epa.gov

4:2 Fluorotelomer sulfonate (4:2 FtS)Ammonium perfluoro-2-methyl-3-oxahexanoate (GenX)


PFAS partitioning between solids and water

PFAS are diverse – polarity alone is quite variable:

o Negatively charged (anions)

o Positively charged (cations)

o Both positive and negative charges (zwitterions)

o Neutral

Many of the useful fluorinated surfactants are anions:

o PFOS and replacements used in firefighting foams

o PFOA and replacements used to manufacture fluoropolymers

Soil/Sediment Groundwater/Surface Water


>

Partitioning to Soil and Sediment

13

Sorption depends on:

• PFAS chemistry: chain length, functional groups, branching, electrical charge, load of other pollutants

• Water chemistry: pH, ion concentration (e.g., salinity)

• Soil chemistry: organic carbon, iron oxides, surface charge of other minerals

Longer chain: more sorption: perfluorononanoicacid (PFNA) > perfluoropentanoic acid (PFPeA)

More organic carbon or iron oxides: more sorption

Sulfonic acids sorb more than carboxylic acids: PFOS > PFOA

Images: comptox.epa.gov; usgs.gov; pubchem.ncbi.nlm.nih.gov


How much is a part per trillion or a nanogram per liter?

• 1 grain of sugar in an Olympic sized pool

• 1 second in 320 centuries

• 30 gallons of water in Lake Michigan

14


Adapted from Marine Pollution Studies Laboratory at the Moss Landing Marine Laboratories

Non-Detect0Detected but not

QuantifiedQuantified

Quantified withStatistical Rigor

Method Detection Limit

Limit of Detection

Reporting Limit /Practical Quantitation

Limit

Contaminant Concentration

15

Know your limits – your accuracy depends on it!


Jump on the Band Wagon

What is driving the race to zero?

• Increased awareness? Public perception? Improved quantitation limits?

• Total PFAS appear to be going up as more lab standards become available and additional chemicals can be analyzed.

• States use different toxicological endpoints and conservative exposure factors.

• The recent trend in the States is to set Maximum Contaminant Levels (MCLs) for some PFAS to less than 20 ppt (PFOA, PFNA, PFHxS, PFOS), although PFAS like GenX, PFBS, PFHxA are generally set higher.

16


Risk Perception Challenges

17

According to the CDC, studies re possible relationships between levels of PFAS in blood and harmful health effects in people involve different

groups of people, different exposures, and different PFAS. The different studies reported a variety of health outcomes. Animal studies suggest a variety of ailments – but human and animal studies don’t match well.

What we do know is that some PFAS can bioaccumulate and have been associated with toxicity in some animal studies.

If the toxicological studies have not yet provided a clear definition of human risk, how do we explain why States are setting regulatory limits?

Agency for Toxic Substances and Disease Registry – Centers for Disease Control and Prevention https://www.atsdr.cdc.gov/pfas/health-effects/

https://www.atsdr.cdc.gov/pfas/health-effects/


Public Perception

18

High profile chemicals in the national and local media, leading to public fear.

Regulators must respond to their constituents.

Difficult to communicate risk when there is so much uncertainty.

Public health advisory concentrations and State DOH

regulations vary widely – this does not inspire public confidence!

Photo: Associated Press


Risks and Misperceptions

19

Important to put PFAS that are currently regulated in some states in the context of chemicals with known, well-

established risks to human health.

Misconception that PFAS compounds are as toxic or more toxic than other chemicals, which may or may not be true,

or which in some cases we know not to be true.

Avram Frankel https://waterwelljournal.com/pfas-roundtable/

https://waterwelljournal.com/pfas-roundtable/


Risks and Misperceptions: PFAS in Context

20

Agency for Toxic Substances and Disease Registry. https://www.atsdr.cdc.gov/ToxProfiles/ and https://www.atsdr.cdc.gov/mrls/mrllist.asp

Chemical ATSDR chronic oral minimal risk level (MRL)

EPA drinking water maximum contaminant level (MCL)

Dioxin (2,3,7,8-TCDD) 0.001 ng/kg/day 0.03 ng/L

PFOS 2 ng/kg/day (provisional)

No national MCL;EPA Health Advisory: 70 ng/L

PFHxS 20 ng/kg/day (provisional)

No national MCL;No EPA Health Advisory

PCB (Aroclor 1254) 20 ng/kg/day 500 ng/L

Trichloroethene (TCE) 500 ng/kg/day 5,000 ng/L

Arsenic 300 ng/kg/day 10,000 ng/L

https://www.atsdr.cdc.gov/ToxProfiles/

https://www.atsdr.cdc.gov/mrls/mrllist.asp


Why are PFAS Different?

21

• Persistent and mobile in air and water, due to their chemical stability and low volatility.

• Resistant to direct oxidation, photolytic degradation, biodegradation and air stripping/vapor extraction, making their removal difficult.

• Animal toxicology studies indicate potential developmental, reproductive and systematic effects.

• After oral exposure, some PFAS accumulate and adsorb in the serum, kidney, and liver.

Emerging Contaminants: PFOS AND PFOA – Calgon Carbon


[email protected]

https://www.epa.gov/pfas

https://hero.epa.gov/hero/index.cfm/content/howto

https://www.secnav.navy.mil/eie/pages/pfc-pfas.aspx


https://www.ngwa.org/what-is-groundwater/groundwater-issues/Groundwater-and-PFAS

https://pfas-1.itrcweb.org/

Environmental Business CouncilRhode Island Emerging Contaminants

November 5, 2020 PFAS Update

mailto:[email protected]

https://www.epa.gov/pfas

https://hero.epa.gov/hero/index.cfm/content/howto

https://www.secnav.navy.mil/eie/pages/pfc-pfas.aspx


https://www.ngwa.org/what-is-groundwater/groundwater-issues/Groundwater-and-PFAS

https://pfas-1.itrcweb.org/



Burrillville Release – What Happened, What’s Been Done and What’s Next

Steve LaRosa

Technical Leader

Weston & Sampson

Rick Mandile

Principal

Sage Environmental

Nick Noons

Environmental Engineer

Rhode Island DEM

Oakland PFAS Contamination

Rhode Island Department of Environmental

Management

2017 Surveillance Monitoring Study

◼ Rhode Island Department of Health (RIDOH)

initiated a state-wide sampling effort of small

public water systems, license bottlers, and

licensed childcare facilities.

◼ Collaborative effort with RIDEM and Brown University Superfund Research

Program (Dr. Jennifer Guelfo)

DEM Involvement

◼ Potential source identification and mapping

❑ Water Resources, Waste Management, Emergency Response, Planning & Development

◼ In the event of an exceedance, DEM would be tasked with the subsequent source

investigation

❑ Contracted Weston & Sampson in advance via TAC

◼ Experience working with other New England States on response to PFAS contamination

❑ Bennington, VT

2017 Surveillance Monitoring Study

◼ Potential Sources and Information Considered

❑ Airports

❑ Fire Training Areas

❑ EPCRA Tier II

❑ Industrial Facilities with certain NAICS Codes

❑ DOD Facilities and NPL Sites

❑ Electroplating Operations

❑ Oil Terminals (Tank Farms)

❑ Wastewater Lagoons

❑ Emergency Response Incidents

❑ *Team from Brown University conducted separate geospatial analysis of potential impacts across

the State

Study Results

◼ < MRL: 26 water systems

◼ Detected < 35 ng/L (ppt): 8 water systems

❑ 4 - 24 ppt (Average and Median = 13 ppt)

◼ 35 – 70 ppt: 1 water system

❑ Raw 43.2 ppt, Treated (GAC) 11.0 ppt

❑ Ultimately connected to public water

◼ > 70 ppt: Oakland Water Association, Inc.

Brown University Geospatial Risk Evaluation

Initial Response

◼ Public meeting with community

◼ Over 1,000 gallons of bottled water

handed out to Oakland Water

Association Customers and those

within ¼ mile radius

◼ Burrillville Police and Emergency

Management

❑ Reverse 911

◼ Nearly all private wells within ¼ mile

radius sampled within first week

Regulatory Decision-Making/Challenges

◼ Key Factors

❑ Primary objective to control exposure

❑ Availability of public water

❑ Subsurface AFFF release

◼ No distinct “source area” in site soils

◼ Limited remedial alternatives

◼ Regulatory authority currently limited

to GA Groundwater Quality Standard

◼ Future regulation changes will

necessarily require reevaluation of the

site

❑ Potential State MCL

Case Study: Burrillville

Case Study: BurrillvilleGroundwater Quality Standard

PFOA & PFOS = 70ng/L (ppt)• http://www.dem.ri.gov/programs/benviron/water/quality/pdf/pfoa.pdf

RIDPH and Brown sampled 38 small public water systems

– Several between ND and 70 ppt

– Oakland Association public well impacted at >100 ppt

Immediate RIDEM Response– All Oakland Association users given spring water deliveries

– All private water supply wells in a ¼ mile radius of Oakland Association Well

– Public meeting to inform impacted customers and nearby private well users

– Feasibility for extension of neighboring public water system to affected residences evaluated

Case Study: BurrillvillePotential PFAS Source Identification

– Similar to Phase I Environmental Site Assessment Research

– Multiple Potential Sources Identified

Initial Private Drinking Water Well Data Plotted via GIS– Developed a Conceptual Site Model for PFAS makeup and distribution.

– Identified area for field data collection based on CSM to isolate

source(s).

Targeted Site Investigation – Single Mobilization

– Collection of discrete interval soil and groundwater samples • (shallow, intermediate, atop bedrock)

– Installed permanent monitoring wells

– Data evaluation and reporting

Fire Station

Source Well

Case Study: Burrillville• PFAS identified characteristic of AFFF

• Multiple PFAS quantified on soils at very low concentrations

• Shallow and Bedrock aquifer plumes are centered around Fire Department

Building– AFFF stored on site

– Fire Department officials report no AFFF training on site

• Review of Fire Department construction plans indicate storm water infiltration

gallery collects floor drains and parking lot waters– Contaminated equipment washdown water and inadvertent spills enter the infiltration gallery

– The stormwater infiltration gallery has intermittent shallow groundwater table beneath it.

Infiltration waters directly enter bedrock when shallow groundwater is not present.

• More site characterization is needed to fully delineate impacts and determine

remediation actions.

THE FIRE DEPARTMENT SECURED THE 50+ 5-GALLON AFFF CONTAINERS IN A SECURE STORAGE UNIT WITH SECONDARY CONTAINMENT.

SAGE SITE VISIT PHOTOGRAPHS

JANUARY 6, 2020

ADDITIONAL VIEW OF FIRE DEPARTMENT CONTAINER STORAGE

Oakland Mapleville Water Line Extension Project

THE PROVIDENCE JOURNAL / BOB BREIDENBACH



Regulatory Status Update –Where Do We Stand Now and What’s Coming

Mark Dennen

Supervising Environmental Scientist

Office of Land Revitalization and

Sustainable Materials Management

Rhode Island

Amy Parmenter

Interim Chief, Supervising

Environmental Scientist

Center for Drinking Water Quality

Rhode Island DOH

RIDEM/ OFFICE OF LAND REVITALIZATION

& SUSTAINABLE MATERIALS MANAGEMENT

Mark Dennen, CPG


Materials Management Program

[email protected]

401-222-2797 ext. 7112

mailto:[email protected]

SOLID WASTE REGULATORY AMMENDMENTS

10/13/2020

• Solid Waste Regulations #1, 250-RICR-140-05-1, Solid Waste

Management Facilities

• Solid Waste Regulation #2, 250-RICR-140-2, “Solid Waste

Landfills”

• Solid Waste Regulation #7, 250-RICR-140-05-7, C&D Regulations

• Public comment period ended 10/25/2020- no comments were

received, regulations will be finalized as proposed.

Rule 2

• h.Upon notification by the Department, the owner or operator

must, within one hundred and eighty

(180) days, monitor groundwater for the full suite of Per- and

Polyfluoroalkyl Substances (PFAS) using a methodology

approved by the Department for at least

two (2) rounds. If exceedances of the Department's

groundwater standards are detected, the owner or operator

must revise the environmental monitoring plan to

address the exceedances and any impacts it may have.

PFAS TESTING

• Require 2 rounds of PFAS groundwater monitoring for PFAS (Per- and polyfluoroalkyl substances), specifically those PFAS included in the target analyte list for EPA Method 537.1

• Includes all currently regulated compounds (PFOA and PFOS

• Target analyte list for EPA Method 537.1 in both groundwater and drinking water

• Not very prescriptive in how testing will be done as regulatory changes often outpaced by science.

Why?

• Goal is to establish a baseline

• Too expensive at $300/sample to require quarterly

monitoring.

• Conducted Fiscal Analysis

Benefits

• PFAS has emerged as a significant concern in

drinking water only over the last several years.

• Rhode Island Department of Health is currently in

the process of promulgating drinking water

standards for these compounds

• Without PFAS baseline sampling data, it is not

possible to ascertain if any current or former landfills

are threatening public water supplies.

Cost

• Assume average landfill has 4 wells

• Estimated cost $300/sample

Breakdown of Costs

Ownership

Landfills

undergoing

monitoring

Estimate

d

number

of wells

cost/sam

ple

Number

of

rounds

of

sampling

Estimat

ed total

cost

Municipal 14 4 $300 2 $33,600

Private 5 4 $300 2 $12,000

RIRRC (state)

owned 1 39 $300 2 $23,400

Total cost $69,000

We Get Results- Now What?

• May require additional monitoring based on results.

• May look more closely at potentially impacted

drinking water.

• Treatment of aquifers not realistic

• Hydraulic controls

• Capping

Composting and PFAS

• Biosolids most likely contain PFAS.

• Testing difficult as the EPA-approved laboratory

procedures in use are those for drinking water.

• Most commercial labs are using their own “modified

Method 537” making comparisons difficult.

• At this time, no reasonable way to reduce PFAS in

compost other than control of input.

Questions?

RIDOH PFAS in Drinking Water Update

November 5, 2020

PFAS Webinar

Environmental Business Council of NE, Inc.

PFAS Vulnerability Study 2017-2019

• Major Partners:

• RI Dept. of Environmental Management

• Brown University – Dr. Robert Hurt

• Texas Tech University – Dr. Jennifer Guelfo

• RI Dept. of Children, Youth, & Families


• Potentially Vulnerable Water Systems:

• Large PWS (UCMR3)

• Communities, water bottlers, food

processors, licensed child cares w/DW

source:

• w/in 1 mile of potential PFAS facility

• w/in ½ mile of fire station

• Schools w/own public wells


• Airports

• Fire academy

• EPCRA Tier II

• Industrial Facilities –certain NAICS codes

• High, Medium, Low Priority

• St. Gobain Plastics

• CERCLIS and CERCLIS NPL

• Wastewater Lagoons

• Military Sites

• Chrome Platers

• Large ASTs

• Fire foam used in emerg. response

• Facilities ID’d by Brown University

In bold are those within 1 mile of priority public wells

Potential PFAS Facilities:


• Potential PFAS Facilities (cont.):

• Fire Stations

• Schools


• # Sampled (analyzed 9-14 PFAS):

• 82 PWS

• 5 child cares

• Percentage PWS Sampled:

• 87% of Rhode Islanders’ drinking water

• 97% of RI’ers on public water

• 100% serving >10,000 people

• 49% Community water systems

• 100% schools with their own public wells


• Analysis conducted on LC-MS/MS utilizing

isotope dilution

• DoD / ISO / ASTM methods

Technical Advisory Group

• RIDOH Drinking Water Tech. Advisory Group

• RI Dept. of Environmental Management

• URI STEEP – Sources, Transport, Exposure & Effects of PFAS

• Dr. Rainer Lohmann, Alicyn McCann, Dr. Angela Slitt

• Brown University – Dr. David Savitz

• Texas Tech University – Dr. Jennifer Guelfo

• Cumberland Water/RIWWA – Chris Champi

• Suez Water/AWWA – Carol Walczyk

• Westerly Water – Bill Beauregard, Ed Giron


0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%

Detection of any PFAS*

5 PFAS > 20 ppt*

PFOA+PFOS > 35 ppt*

PFOA+PFOS > 70 ppt*

PFAS Results (out of 87 water systems sampled)

% of PWS Sampled

* In one or more dw sources. Not necessarily representative of levels reaching consumers.


0

5

10

15

20

25

30

35

0

20

40

60

80

100

120

# o

f W

ater

Sys

tem

s

pp

t

Occurrence and Highest Concentration in Sampled Water Systems

Highest Concentration (ppt) Frequency of Occurrence (#)

RI Process for Establishing Regulations

We must follow a process defined by the

federal Safe Drinking Water Act:

1. Determine whether there is a need

2. Determine a drinking water concentration that

fully protects human health

3. Examine the feasibility, benefits, and costs of

the health-based approach and any alternatives

4. Determine an approach, that in the opinion of

the Director, best balances the costs and

benefits

14

Cost-Benefit Analysis

• Costs

• State & water system implementation costs:

• Northeast Water Solutions, Inc. (NWSI)

• Determined costs based on:

• Individual PWS results from 2017-2019 study

• MCL of 70 ppt, 35 ppt, 20 ppt, 10 ppt, or 2 ppt

• PWS annual water volume & flow rate

• GAC

• Safety factor: with & without (PFAS conc &

costs)

Other Costs

• Other costs

• PWS sampling & analysis

• RIDOH Lab equipment & standards upgrades

• RIDOH database compliance add-on (IT contract)

• RIDOH staff

• Rule/compliance management

• Engineering review & approval/SRF review

• Bottled water

• Contract: community outreach workshops

Exposure Assessment

• Which PFAS are of concern?

• Which PFAS found in RI?

• Consider them individually or combined? Do

they do the same thing? Have the same effects?

• What health effects do they cause?

• What’s an acceptable level of exposure? (RfD)

• Who is most at risk?

• What percent of exposure can come from

drinking water vs. other sources?

• How much PFAS can be in drinking water

without exceeding RfD?17

Predicted Health Benefits

Reducing PFAS in drinking water will

improve health:

• Better immune function

• Slightly larger babies

• Slightly lower cholesterol

Other benefits are also expected, but

are less measurable or less

significant

18

Benefits in RI

• Use RI data with each potential MCL – actual

PFAS found in drinking water, population

served, amount of change in PFAS level if lower

to below the MCL

• Affects on health of newborns

• Risk of death from ischemic heart disease

• Economic impact of the health benefits

19

Regulation Development

• Hired temporary employee March – July

• Unpaid legal student scholar

• Reviewed other states, compared w/SOC

framework

• Massachusetts

• Michigan

• New Hampshire

• New Jersey

• New York

• Vermont

INITIAL MONITORINGRHODE ISLAND: Four consecutive quarterly samples

MASSACHUSETTSCollected first month of each quarter

PWS serving > 50,000 - April 1, 2020; < 50,000 - October 1, 2020; < 10,000- October 1, 2021May request to use previously obtained sampling data and substitute for equal quarters

MICHIGANBased on 2018 / 2019 PFAS Survey

-PWS with one or more sample > 50% MCL → sample each point beginning first full quarter

-PWS with no detection or < 50% MCL → sample within six months

-PWS with no survey data → sample each point beginning first full quarter

NEW JERSEYPFNA: Groundwater CWS serving < 10,000 and NTNC - begin sampling first quarter of 2019

Surface water PWS and groundwater CWS serving > 10,000 - begin sampling first quarter of 2020

PFOA and PFOS: All systems begin monitoring first quarter of 2021

VERMONTOne sample per year at each sampling point (R)

Monitoring for maximum number of detectable PFAS by all CWS and NTNC on or before December 1, 2019 (A)

Example sub-part review of the current RI SOC regulations compared with how other states addressed (or considered addressing) this sub-part for PFAS

Meetings w/Governor’s Office

• Draft regulations

• Cost-benefit analysis

• Proposed RIDOH supplemental budget

Amy B. Parmenter

Interim Chief


Center for Drinking Water Quality

Rhode Island Department of Health

[email protected]



Analytical Methods Update

Jim Occhialini

Vice President

Alpha Analytical

PFAS Analytical Methods Update

Jim Occhialini

Alpha Analytical

EBC Rhode Island Emerging Contaminants Webinar: PFAS Update – Where We Are and Where We’re Heading

11/05/2020

1

LOOKING AHEAD

INDUSTRY develops

new cmpds

REGULATORS

take interest

NEW COMPOUNDS added to PFAS

lists

NO lab method,

NO ref std

/

Lack of standardized methods

Lack of reference standards

Multiple compound lists

Differing state specific

requirements

2

Make, process

or use > 45

kG / yr

Need to report

to EPA's Toxic

Release

Inventory

172 PFAS

Added to

Toxic

Release

Inventory

3

Honeywell, Chemours Among PFAS Makers on EPA Chemicals List March 11, 2020, 10:26 AM; Updated: March 11, 2020, 2:53 PM Bloomberg Law, Pat Rizzuto

Bloomberg Law FOIA - 630 PFAS compounds in U.S. commerce between 2006 - 2016

Topics for Discussion

Drinking water methods

Other method options

In the Beginning…

• 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)

EPA Method 537.1 - Target Compound List

7

*

***

8

F

F

O

F

F

F

F

F F

F

F

F

O

O

H

HFPO-DA

CAS No. 13252-13-6

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

heptafluoropropoxy) propanoic Acid

Perfluoro-2-propoxypropionic acid

FRD-903

C3-dimer acid

F

F

O

F

F

F

F

F F

F

F

F

O

O

_NH4+

GenX

CAS No. 62037-80-3

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

heptafluoropropoxy)propanoate

Ammonium 2,3,3,3-tetrafluoro-2-

(heptafluoropropoxy)propanoate

FRD-902

C3-dimer salt

F

F

O

F

F

F

F

F F

F

F

F

O

O

_

WATER WATER

• Uses extracted internal standard isotope dilution approach– ratio of peak area of the native analyte to that of an isotopically labeled analogue

– added to the original sample in a known amount and carried through the entire

analytical procedure

• 16 isotopically labeled extraction internal standards

– Matrix recovery correction

– Analyte-specific sample concentration normalization

• Provides additional qualitative & quantitative certainty

10

Method 533 Procedural Differences from Method 537.1

Other Method 533 Procedural Differences from Method 537.1

• Solid Phase Extraction (SPE)

– Uses WAX SPE cartridge

• Weak anion exchange

– More amenable to shorter chain PFAS

– Versus SDVB for Method 537.1

• Styrene divinylbenzene

• 533 uses ammonium acetate rather than Trizma® as a preservative

• 533 uses a 28 day holding time to extraction

– Versus 14 day holding time for Method 537.111

12

Method 533 shifts focus to

shorter chain PFAS

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

Method 533: 25 compounds*

Method 537.1: 18 compounds

* Method 533 does not include

all 18 537.1 compounds

29 PFAS compounds total if

you ran both methods

"New" Method 533 PFAS Compounds

• Nonafluoro-3,6-dioxaheptanoic acid (NFDHA)

• Perfluoro(2-ethoxyethane)sulfonic acid (PFEESA)

• Perfluoro-4-methoxybutanoic acid (PFMBA)

• Perfluoro-3-methoxypropanoic acid (PFMPA )

National Center for Biotechnology Information.

PubChem Database. CID=2782393,

https://pubchem.ncbi.nlm.nih.gov/compound/Perfl

uoro-3_6-dioxaheptanoic-acid (accessed on July

15, 2020)

NFDHA

National Center for Biotechnology Information.

PubChem Database. CID=12498036,

https://pubchem.ncbi.nlm.nih.gov/compound/1249

8036 (accessed on July 15, 2020)

PFMBA

Non- Drinking Water EPA PFAS Method?

• Validated Test Method 8327: Per-and Polyfluoroalkyl Substances (PFAS) Using

External Standard Calibration and Multiple Reaction Monitoring (MRM) Liquid

Chromatography/Tandem Mass Spectrometry (LC/MS/MS)

– Applicable to other aqueous media beyond drinking water

• Based on EPA Region 5, Chicago Regional Lab method

– similar to ASTM D7979

• LC/MS/MS, direct injection, not SPE, external standard calibration

The DoD considers Method 8327 a “screening method” (Alyssa G. Wingard, Senior Chemist,

NAVSEA 04X6 Laboratory Quality and Accreditation Office (LQAO); July 2019, email

correspondence, DENIX).

Additional EPA Methods?

• SW-846 Method 8328 Target date??

– 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

• EPA 1600 series method?

– EPA working with DoD

• ~ 40 compounds?

Reporting Linear & Branched PFAS Isomers

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Perfluorooctanoic acid (PFOA)

Method 537.1 / 533 Limitations

• Written for clean drinking water sample matrix

– SO WHAT IF YOU HAVE…

• Silty groundwater? Wastewater?

• Soils, biosolids…tissues?

• 537.1 - 18 specific PFAS ; 533 -25 specific PFAS

– SO WHAT IF YOU NEED…

• Other compounds and/or longer or different list?

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Other Matrices

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

– Need a specific SOP • Additional sample prep

– Filtering??

• Soils, sediments, biosolids

• Tissues, food products

• Other

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Landfill Waste Stream Study

22

photo courtesy Sanborn, Head & Associates, Inc.

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Anything else?

- TOP, SPLP, other method sources?

Moving target, stay current

Wrap Up

Alpha AnalyticalJim Occhialini

[email protected]

Moderated Discussion

Moderator: Ed Summerly, Program Co-Chair, GZA

Panelists:

• Terry Gray, Deputy Director, RI DEM

• Mark Dennen, RI DEM

• Karen Kinsella, GZA GeoEnvironmental, Inc.

• Steve LaRosa, Weston & Sampson

• Rick Mandile, Sage Environmental

• Nick Noons, RI DEM

• Jim Occhialini, Alpha Analytical

• Amy Parmenter, RI DOH

PFAS Update – Where We Are and Where We're Heading

Documents

Transcript of PFAS Update – Where We Are and Where We're Heading