PFAS AND WASTE WHAT TO DO WITH IT?Bharat Chandramouli, Ph. D.Product Manager and Senior Scientist - SGS AXYS

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PFAS 101

n Per-and Poly Fluoro Alkyl Substancesn Introduced as early as 1948 (Teflon, or

PFTE polymer) with a great increase in use in the late 1960s and 1970s.

n C-F bond very strongn PFAS are surfactants that repel oil and

water, reduce wear or surface adhesionn Diverse and complex chemistries based on

product usen “Precursors” FTS, PAP (Polyfluorinated

Alkyl Phosphate Esters), PFPA (Polyfluorinated phosphonic acid), FTOH and other polyfluorinated precursors can all degrade to PFOA and other carboxylates

PFCAs incl. PFOA PFSA incl. PFOS

FTS

PAP, DiPAPFTOH

FOSAM

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WASTE: CONSUMER PRODUCTS

n Carpet, furniture and upholstery - stain-resistantcoatings such as Scotchgard™

n Waterproof clothing, boots, tents

n Food containers/wrappers, microwave popcorn bags

n Non-stick cookware such as Teflon™ coated pots/pans

n Personal care products such as shampoo, dental floss,and cosmetics (nail polish, eye makeup)

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WASTE: INDUSTRIAL PRODUCTS

n Aqueous film forming foams (AFFF)

n Polymer manufacture

n Textile manufacturing

n Paints, varnishes and sealants

n Adhesives, aviation hydraulic fluids, cleaning products

n Paper, water and grease-proofing

n Chrome plating

n Tannery waste, water proofing

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WASTE FROM REMEDIATION/TREATMENT

n Contaminated wastewater

n Contaminated groundwater

n Biosolids

n Contaminated absorbent and resins used in remediation process (Granular Activated Carbon, Ion exchange (IX) or polymer media used to remove PFAS from water)

n Contaminated soil and sediment

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MANY POINTS OF ENTRY

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PERSISTENCE IS THE BIG ISSUE

Image Courtesy Dr. Ian Ross, Arcadis

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METHODS

Most PFAS measurement by LC-MS/MS, but details matter!

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BEST PRACTICE ATTRIBUTES

n Multi-matrix EPA 1600 series approach: Data comparability

n Use of suite of isotopically labeled standards for quantitation and recovery correction (Isotope dilution)

n Identification using retention time and surrogate, multiple transitions

n Transition ratios to check for interferences

n Assessment of all isomers linear and branched

n Use of entire aqueous bottle, and plenty of rinsing

Extraction• Solids:, Sequential basic/acidic extraction • Aqueous: pH Adjustment• Tissue: Sequential/extended basic

extraction

Cleanup: Weak Anion Exchange + Carbon

LC-MS/MS Analysis with Isotope Dilution/Surrogate Standard Quantitation

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USE OF CONFIRMING TRANSITIONS

n Prominent peak in primary transition

n Secondary transition shows no peak

n Use ratios to rule out detects

PFBS – 399 ->80 in sample Interference?

Surrogate Standard 18O2-PFHxS in sample

PFBS – 399 ->99 in sample

PFBS – 399 ->80 in standard

Surrogate Standard 18O2-PFHxS in standard

Surrogate Standard 18O2-PFHxS in sample

11© SGS SA 2016 ALL RIGHTS RESERVED 11© SGS SA 2016 ALL RIGHTS RESERVED

§ Eleven known isomers of PFOS in ECF process

§ 499>80 and 499>99 transitions have different relative response factors for the linear and the branched isomers.

§ Quantitative biases possible depending on standard type and MRM transitions used for quantitation

§ Distribution/half lives in tissue are different between linear and branched

§ Speciation is more important in research applications.

§ SGS AXYS Follows DOD QSM 5.1 guidelines for quantitation of isomers

LINEAR VS. BRANCHED ISOMERS

BranchedPFOS~30%

Linear PFOS~70%

Linear PFOS~70%

Riddell, N. et. al, Environ Sci. Technol. 2009 (43) 7902-7908.

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TARGETS

Family Targets

PFCA - Perfluoroalkyl carboxylates (11) C4 (PFBA) - C14 (PFTetrDA) including PFOA

PFSA - Perfluoroalkyl sulfonates (8) C4 (PFBS) – C10 (PFDS) including PFOS, PFDoS

FTS - Fluorotelomer sulfonates (3) 4:2, 6:2 and 8:2 FTS

Perfluorooctane sulfonamides (3) PFOSA, N-MeFOSA and N-EtFOSA

Perfluorooctane sulfonamide acetic acids (2) N-MeFOSAA and N-EtFOSAA

Perfluorooctane sulfonamide ethanols (2) N-MeFOSE and N-EtFOSE

Ether Carboxylates and sulfonates (4) HFPO-DA, ADONA, F-53B components

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PFAS REFERENCE METHODS

Method Who Matrix Targets Attributes Status Weak Anion Exchange

EPA 537.1 EPA Drinking Water

19, excludes PFBA and PFPeA

No isotope dilution, drinking water only, no transition ratio requirements

Active No

EPA 8327 EPA NPW 24 No isotope dilution, screening method

Comments No

EPA Isotope dilution method

EPA NPW, solids, biosolids, tissue

TBD, will becomprehensive

Isotope dilution, ratio requirements, DoD compliant

In preparation – Expected 2019

Yes

EPA 533 EPA Drinking water

TBD – More short chains and ethers than 537.1

TBD In preparation TBD

ASTM D7968/7979

ASTM 32? Isotope dilution optional, transition ratios guidelines

Active No

ISO 25101 ISO Water 2 (PFOS, PFOA) Isotope dilutionISO 21675 ISO Water,

solids30+ Still in validation Validation Yes

US DoD QSM 5.2 Table B15

US DoD

Any Not a method, but QA/QC for PFAS methods

Isotope dilution, transition ratio requirements

Active Yes

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PFAS IN WASTE

Options are limited and persistence is a pain

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TREATMENT OPTIONS LIMITED

Drinking water Carbon filtration or resin ion exchange/membrane

Contaminated ground/surface water

Isolate the plume, cap and monitor?, pump and treat?

WWTP effluent/leachate Carbon filter/ion exchange?Contaminated soils Excavate and landfillContaminated soils Cap, cover and monitor, use

adsorption aids?Contaminated soils IncinerateHazardous waste IncinerateHazardous waste LandfillAir emissions ??

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LANDFILLS

n Waste containing PFAS§ Consumer Products§ Industrial Waste§ Carpet and upholstery§ Food waste§ Biosolids§ Hazardous waste

n Landfill fires when foam is used

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LANDFILL PROVIDE PARTIAL CONTAINMENT

n Since 1990, lined landfills with leachate collection mandated. However, sanitary landfills prior to 1990 may still be active.

n Direct re-entry into environment from unlined landfills/leaks

n Indirect re-entry from leachate via WWTP

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CARPET EXAMPLE

n Half of all floor coverings in U.S. homes and workplaces

n In 2016, 343 million pounds of post-consumer carpet were discarded in California alone

n Most of it ended up in a landfill

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PFAS IN CARPETS

n A large percentage of the PFAS produced worldwide are used to treat carpets, rugs, and other home textiles to confer stain-, soil-, oil- or water-resistance

n Legacy treatments based on C8 sulfonamides with PFOS/PFOA impurities or long chain fluorotelomer side chain polymers

n Replacement products based on shorter chain C4,C6 sulfonamides or short-chain fluorotelomer based side-chain polymers

n Fluorotelomer alcohols can be high in indoor air from carpet off-gassing

PFOSA or FOSA

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PFAS AND LEACHATE (LANG ET AL 2017)

n 95 samples from 18 landfills (2013)

n 70 PFAS measured, 19 PFAS detected in >50% of samples

n Estimated release 600 kg known PFAS per year

n Does not include unmeasured (dark matter) PFAS

21© SGS SA 2016 ALL RIGHTS RESERVED

LEGACY PRODUCTS TRANSFORMATION

n References:• Rhoads et al. Environ. Sci. Technol.

2008, 42, 2873–2878• Benskin et al. Environ. Sci. Technol.

2013, 47(3), 1381-1389

n C8 precursors transform to PFOS

n These reactions have been observed inWWTP/leachate environments

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FLUOROTELOMER TRANSFORMATION

Harding-Marjanovic, K. C., Houtz, E. F., Yi, S., Field, J. A., Sedlak, D. L., & Alvarez-Cohen, L. (2015). Environmental science & technology, 49(13), 7666-7674

Fluorotelomer Thioether Amido Sulfonate (Lodyne) degradation pathways

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PFAS IN WWTP

n PFAS entering conventional wastewater treatmentplants (WWTP) or produced from precursors duringtreatment can exit the plant in either the aqueous orsludge phase.

n Studies have shown that the discharge of wastewater effluent is a significant source of PFAS in theenvironment.

n PFOS and PFOA were still the main forms of PFASin municipal wastewater treatment plant effluentsfive to ten years after the major phase-outs of C8-based PFAS’ commenced.

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CANADA WIDE WWTP STUDYn 20 WWTP across Canada

§ Facultative Lagoon (FL)§ Aerated lagoon (AL)§ Chemical assisted primary (PT)§ Secondary aerobic biological (ST)§ Advanced biological nutrient treatment (AT)

n Samples for each plant (total n for survey)§ Raw influent (149)§ Primary (90) and final effluent (147)§ Primary (110) and waste biological sludge (76)§ Treated biosolids (108)

n Sampling Plan§ Composite samples for water, grabs for solids (

3X each event)§ 4 events per plant – 2 cons. Yrs., winter +

summer

n Analytes§ C4-C12 PFCA§ C4, C6, C8 PFSA§ FOSA

Chemical Management Plan

Data published at Guerra et al. 2014 Journal of Hazardous Substances 272: 148-154)

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CONCENTRATIONS IN CANADA

Effluent Biosolids

n Levels similar to US/Europen Suite of C4-10 PFCA seen in effluent, C8-C12 PFCA in biosolidsn Range and distribution of concentrations indicates strong effect of

source type (industrial vs. not)

27© SGS SA 2016 ALL RIGHTS RESERVED

n Total Median PFAA Effluent (5400 mg/day) > Biosolids (160 mg/day)

n Final Effluent + Biosolids > Influent

n Clear evidence of formation of PFCAs/PFSAs through the treatment process

PFOS AND PFOA MASS BALANCE

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THE WASTEWATER TREATMENT CONUNDRUM

PFOA

AL - Aerated lagoon, AT - Advanced biological nutrient treatment , FL - Facultative Lagoon, PT - Chemical assisted primary, ST - Secondary aerobic biological

n PFOS and PFOA form during wastewater treatmentn The more extensive the treatment/residence time, higher the formationn The precursors not measured drive final PFCA/PFSA levels

Images from Shirley Anne Smyth Environment Canada

C1SummerWinter

STPTFLATALSTPTFLATAL

0

-200

-400

-600

-800

-1000

-1200

-1400

-1600

% R

emov

al

PFOS

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EFFECT OF DIGESTION

n Slide to be added.

0

5

10

15

20

25

30

35

40

45

PFOS PFOA PFNA PFDA PFUnA PFDoA

ng/g

digested non-digested

n=56 n=36 n=44 n=9 n=57 n=25 n=62 n=34 n=51 n=16 n=50 n=170

10

20

30

40

PFOS* PFOA PFNA* PFDA* PFUnA* PFDoA

ng/g

digested non-digested

n=56 n=36 n=44 n=9 n=57 n=25 n=62 n=34 n=51 n=16 n=50 n=17

* p<0.05Image from Shirley Anne Smyth Environment Canada

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BIOSOLIDS AND PFAS

§ Biosolids have been widely used on farms and other landsacross North America for decades.

§ Every US State and Canadian province allows biosolidsuse on soils. US EPA, USDA, and US FDA all supportbiosolids recycling. Biosolids reflect what is in our dailylives.

§ Currently, the United States Environmental ProtectionAgency (US EPA) regulates land application of biosolidsbased on pathogen, metal, and nutrient content under 40CFR Part 503)11. However, PFAS in biosolids are notregulated.

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BIOSOLIDS AND PFAS

§ The core concern being expressed by regulatory officialsregarding biosolids applications to soils is about leaching ofPFAS to groundwater.

§ One famous horror story is given in the application of WWTPbiosolids and resulting perfluorinated compound contamination ofsurface and well water which “describes a situation in Decatur,Alabama, where PFAS contaminated biosolids from a localmunicipal wastewater treatment facility that had received wastefrom local fluorochemical facilities were used as a soilamendment in local agricultural fields for as many as twelveyears.” Biosolids-borne PFAS were implicated in groundwatercontamination.

BIOSOLIDS PILOT TO UNDERSTAND CONTRIBUTION OF UNKNOWN PFAS

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WASTEWATER TREATMENT AND PFAS

PFOA

AL - Aerated lagoon, AT - Advanced biological nutrient treatment , FL - Facultative Lagoon, PT - Chemical assisted primary, ST - Secondary aerobic biological – Images Courtesy Environment Canada Shirley Anne Smyth

n PFOS and PFOA form during wastewater treatment

n The more extensive the treatment/residence time, higher the formation

n The precursors not measured drive final PFCA/PFSA levels

n Is the conversion complete? Unknown!

C1SummerWinter

STPTFLATALSTPTFLATAL

0

-200

-400

-600

-800

-1000

-1200

-1400

-1600

% R

emov

al

PFOS

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TOP: PERFLUORINATED POTENTIALn Can we estimate the potential of

a sample containing a complex mixture of PFAS to eventually transform to stable perfluorinated end-products?

n Measure PFCAs/PFSAs in sample before and after to report conversion rates

n TOP is a strategy to speed up the transformation of the thousands of potential “precursors” into terminal perfluorinated acids

Houtz & Sedlak, D. L. (2012). Environmental Science & Technology, 46(17), 9342–9349.

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PILOT STUDY OBJECTIVES AND DESIGN 1. Validate TOP In Aqueous and Solid Matrices

2. Does TOP identify presence of precursors remaining after WWTP process?

3. How does TOP perform in this high TOC matrix?1. Reproducibility2. Reaction Completeness

n Design§ Five biosolids from US/Canada (n = 3

replicates)§ Sample size 0.25g wet

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SAMPLE WITH LARGEST INCREASE

n Formation seen C4-C14 PFAA

n 175 fold increase in PFOA

n PFOS remains constant

n Monitored precursors FTS and FOSAAs ND post TOP

0

300

600

900

PFBA

PFPeA

PFHxA

PFHpA

PFOA

PFNA

PFDA

PFDoA

PFUnA

PFTrDA

PFTeDA

PFBS

PFPeS

PFHxS

PFHpS

PFOS

PFNS

PFDS

PFDoS

Concentration (ng/g wet)

Biosolid 1Biosolid-Post Biosolid-Pre

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OTHER RESULTS CONFIRM

n Data shows high, reproducible increases post-TOP

n Highlights presence of unmeasured PFAS in biosolids

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THERMAL TREATMENT AND INCINERATION

n Temperatures >1000 °C maybe required for destruction (Research is still ongoing)

n This is expensive!n Low temperatures may result in volatilization and

long range atmospheric transport, not desirablen Stack/scrubber capture untested, waste

capture/diversion, not treatment

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LONG RANGE TRANSPORT

n Long range transportand transformationongoing

n Long chain PFAS usein other jurisdictionscould still impactNorth America

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PFAS: RCRA LEGAL CONSIDERATIONS

n In February 2017, a U.S. District Court denied motions to dismissRCRA “imminent and substantial endangerment” claims relating toPFAS. See Tennessee Riverkeeper, Inc. v. 3M Co., No. 5:16-cv-01029-AKK, 2017 WL 784991 (N.D. Ala. Feb. 10, 2017). This case involvedthe alleged continuing contamination of the Tennessee River andassociated public drinking water supplies with PFAS that the plaintiffclaims originated from a local manufacturing facility and two locallandfills

n RCRA 7002 orders have been filed to address PFAS contamination as“solid waste” that “may present an imminent and substantialendangerment”§ Solid waste can be “any discarded material”§ “May present endangerment”§ RCRA 7002 lawsuits have been filed in AL, NC, and MI

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REGULATION: WHAT’S NEXT?

n EPA currently only has advisory Health Action Levels(HALs) for PFOS and PFOA

n Determination as a hazardous contaminant with MaximumContaminant Load (MCL) determination awaited.

n Future NPDES permits for WWTP wastewater discharge,stormwater and other industries for PFAS-relatedcompounds.

n Reduction and restriction on waste impacted with PFAS tolandfills and other waste storage facilities.

n Groundwater standard consideration for PFAS by differentstates.

n PFAS air emission regulation and monitoringn Litigation continued many years after production and use

of MTBE, PCBs and Asbestos.

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PFAS CAPABILITIES BY FACILITYSGS Orlando, FL

n Full Service Regulatory Analysis

n PFAS in Drinking Water, Water and Solids by internalstandard

n PFAS in Water and Solids by isotope dilution (ID)

n DoD / NELAP / ISO 17025 accredited (with stateaccreditations for DW, NPW, Solids where available)

SGS Wilmington, NC

n HRMS Specialty (Dioxin/Furans, PCB Congeners, HRMS PAHs) + PFAS

n Serve Source Evaluation, Con. Sites, NPDES

n PFAS in Drinking Water, Water and Solids by internal standard (non-ID)

n DoD / NELAP / ISO 17025 accredited

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PFAS CAPABILITIES BY FACILITY

SGS AXYS, Victoria, BC (Since 1973)n Ultra-trace Persistent Organic Pollutants (POPs) and

Contaminants of Emerging Concern (CECs) by GC-HRMS, GC-MS and LC-MS/MS

n PFAS in water, solids, tissue, serum, industrial productssince 2004

n TOP (Total Oxidizable Precursor Assay) for estimatingunknown precursors

n Method development and validation: Multiple EPAmethods including 1668, 1614, 1694, 1699, upcomingPFAS isotope dilution method and more

SGS West Creek, NJ

n PFAS-free North American Environmental Drilling Division

n Sampling for PFAS in Drinking Water, Water and Solids

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CONTACT INFORMATION

Bharat Chandramouli, Ph. DProduct Manager and Senior ScientistEmail: bharat.chandramouli@sgs.com Off: 250-655-5813

Richard GraceDirector - Sales, Marketing, and ServiceSGS AXYS ( Center of Excellence)Email: Richard.Grace@sgs.com Cell: 905-484-2314

Norm FarmerPFAS Program Director- US Technical DirectorEmail: Norman.Farmer@sgs.com Cell: 407 595 9987

Andrea ColbyUS National PFAS Project ManagerEmail: Andrea.Colby@sgs.com Cell: 609 495 5321

Geoffrey PellechiaUS National Sales Manager - Ultratrace and PFASEmail: Geoffrey.Pellechia@sgs.com Cell: 508 630 4940

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