PFAS Impacts Resulting from Fire Protection: Management ... · © Arcadis 2016 Contents PFAS...

Property of Arcadis, all rights reserved

PFAS Impacts Resulting from Fire Protection:

Management and Mitigation Options

Ian Ross, Ph.D., Arcadis, Leeds, United Kingdom

Erika Houtz, Ph.D., Arcadis, San Francisco, CA

Jeffrey McDonough, Arcadis, Newtown, PA

Jonathan Miles Ph.D., Arcadis, Leeds, United Kingdom

Jake Hurst, Leeds, United Kingdom

Peter Storch, Melbourne, Australia

Jeff Burdick, Arcadis, Newtown, PA

© Arcadis 2016

Contents

PFAS Chemistry

Regulatory Evolution

Analytical Challenges / Advanced Analytical Solutions

Fate and Transport / Site Conceptual Model

Foam Evolution

Remediation Case Study

Summary


© Arcadis 2016

Perfluorinated compounds (PFCs)

PFAAs totally resist biodegradation & biotransformation so are extremely persistent

• Perfluorinated Compounds (PFCs) generally are the Perfluoroalkyl acids (PFAAs)

• PFAAs include:

• Perfluoralkyl carboxylates (PFCAs) e.g. PFOA

• Perfluoroalkyl sulfonates (PFSAs) e.g. PFOS

• Perfluoroalkyl phosphinic acids (PFPiS); perfluoroalkylphosphonic acids (PFPAs)

• There are many PFAAs with differing chain lengths, PFOS and PFOA have 8 carbons (C8) -octanoates

July 2016 3

C1 Methane

C2 Ethane

C3 Propane

C4 Butane

C5 Pentane

C6 Hexane

C7 Heptane

C8 Octane

C9 Nonane

C10 Decane

C11 Unodecane

C12 Dodecane

C13 Tridecane

C14 Tetradecane


© Arcadis 2016

Polyfluorinated Compounds -Precursors

Thousands of polyfluorinated precursors to PFAAs have been commercially synthesized for bulk products

The common feature of the precursors is that they will biotransform to make PFAA’s as persistent “dead end” daughter products

PFAS do not biodegrade i.e. mineralise

Some precursors are fluorotelomers

Some are cationic (positively charged) or zwitterionic(mixed charges) –this influences their fate and transport in the environment

Cationic / zwitterionic PFAS tend to be less mobile than anionic PFAAs and so can potentially be retained longer in “source zones”

Environmental fate and transport will be complex as PFAS comprise multiple chain lengths and charges

PFOA


© Arcadis 2016 20 August 2017

Useful Graphics5

Diversity of PFAS Characterised in AFFF


© Arcadis 2016

AFFFComposition

Precursors

% Precursors 1.2 19.5 18.8 21.9 19.1

% PFOS 80.5 66.1 69.6 63.5 65.0

% Shorter Chain PFAAs 18.3 14.4 11.5 14.7 15.9Property of Arcadis, all rights reserved

© Arcadis 2016

100% Precursors

NO PFOS or

PFOA

AFFFComposition


© Arcadis 2016

9

Aerobic Precursor Biotransformation toDead End PFAAs

Fire Training Facilities

Landfill

Biosolids Land Application

Manufacturers of Derivative Products


REGULATORY CLIMATE / PFAS DISTRIBUTION

Evolution of regulatory understanding globally and global distribution


© Arcadis 2016 2016PROPERTY OF ARCADIS, ALL RIGHTS RESERVED 11

Evolving Regulatory PFAS Values – OverviewDrinking, Surface and Ground Water (mg/l)

PFOS O=8

PFOA O=8

PFBS B=4

PFBA B=4

PFPeA/S Pe=5

PFHxA Hx=6

DENMARK(Drinking & Groundwater)

FEDERALGERMANY

(Drinking Water)

(0.1)

UK(Drinking Water)

AUSTRALIA(Drinking Water)

(0.09)

THE NETHERLANDSUS EPA(Drinking Water)

VERMONT(Drinking Water)

MINNESOTA(Drinking Water)

NEW JERSEY

CANADA(Drinking Water)

PFHxS Hx=6

PFHpA Hp=7

PFOSA O=8

PFNA N=9

PFDA D=10

COMPOUND REGULATED AND CHAIN LENGTH KEY

(0.07)

ITALY(Drinking Water)

(0.07)

TEXAS-Residential(Groundwater)

0.56

(1)

0.3/0.3/

0.3/

0.3/

0.3/

3/

7/

3/1/

.030.5

0.5

(0.1)

1

0.60.2

15

30

0.20.2

0.2

0.2

.014.013

(0.02)

.027.035

7

7

0.56

0.29

34

71

.093.093

0.56

0.290.37

.093

0.6

.53

.023ground

drinking

0.5

drinkingdrinking.01ground

0.29

SWEDEN(Drinking Water)

(0.5)(0.5)

(0.5)(0.5)

(0.5)(0.5)

5

STATE OF BADEN-WÜRTTEMBERG

(Groundwater)

0.23/(0.3)

European Surface Waters (PFOS) 0.00065

Australian Surface Waters (PFOS) 0.00023

(0.07)

.005.005

PENNSYLVANIA(Drinking Water

-proposed)

© Arcadis 2016 12Property of Arcadis, all rights reserved

PFPeA = 0.07

PFHxA = 0.07

PFHxS = 0.07

PFHpA = 0.07

PFOA = 0.07

PFOS = 0.07

PFNA = 0.07

PFOA = 0.07 (0.7)

PFOS = 0.07 (1)

PFOA = 0.4

PFOS = 0.2

PFOA = 0.07 (0.13)

PFOS = 0.07 (0.56)

PFOA = 0.42 (0.089)

PFOS = 0.011 (0.08)

PFBA = 7 (7) [7]

PFBS = (9) [7]

PFOA = [0.3]

PFOS = [0.3]

PFOA = 0.07

PFOS = 0.07

CL = groundwater cleanup level

AL = private well action level

RL = reporting level

PHG = public health goal

Applies to the individual and summed PFOA, PFOS, PFHpA, PFNA, and PFHxS

State YearStandard/

GuidanceType

AK 2016 CL GW

CT 2016 AL GW

DE 2016 RL GW

IA 2016Statewide

Standards

Protected GW

(Non-protected GW)

KY 2016 PHG DW

ME2016

2016

Health-base MEG

RAG

DW

(GW)

MI2015

2016

HNV

GCC

SW

GW

MN

2011

2011

2011

Short-term HRL

Short-term HRL

Chronic HRL

GW

(GW)

[GW]

US GUIDANCE VALUES

PFOA = 0.40

PFOS = 0.40

MEG = maximum exposure guideline

RAG = remedial action guideline

HNV = human noncancer value for surface drinking water

GCC = generic cleanup criteria

HRL = health risk limit

Applies to individual and summed PFOA and PFOS

Draft/proposed values

All concentrations provided as µg/L

© Arcadis 2016

PFOA = 0.07

PFOS = 0.07

PFBS = 667

PFOA = [0.014]

PFNA = 0.010 (0.013)

PFOA = 2

PFHpA = 300

PFOA = 24

PFOS = 300

PFOSA = 0.2

PFNA =1

PFBA = 71

PFBS = 34

PFPeA = 0.093

PFHxA = 0.093

PFHxS = 0.093

PFHpA = 0.56

PFOA = 0.02

PFOS = 0.02

BCL = basic comparison level

AGQS = ambient groundwater quality standard

ISGWQC = interim specific groundwater quality criterion

MCL = maximum contaminant level

IMAC = interim maximum allowable standard

ILR = initiation level

PCL = protective concentration level

PGWES = primary groundwater enforcement standard

Final recommendation from advisory body

State YearStandard/

GuidanceType

NV 2015 BCL DW

NH 2016 AGQS GW

NJ

2015

2016

2017

ISGWQC

MCL

MCL

GW

(DW)

[DW]

NC 2006 IMAC GW

OR 2011 IL SW

TX 2016 Tier 1 PCL GW

VT 2016 PGWES GW/DW

PFOA = 0.29

PFOS = 0.56

PFOSA = 0.29

PFNA = 0.29

PFDA = 0.37

PFDS/PFUnA/PFDoA/PFTrDA, PFTeDA = 0.29

Applies to individual and summed PFOA and PFOS

13Property of Arcadis, all rights reserved

US GUIDANCE VALUES

All concentrations provided as µg/L

AL, AZ, CO, CT, MA, WV have adopted the EPA HA as their DW guidance

ANALYTICAL TOOLS

© Arcadis 2016

Useful Graphics 15

• Total oxidizable precursor (TOP) Assay

– Initial LC-MS/MS analysis with re-analysis following oxidative digest

– Detection limits to ~ 2 ng/L (ppt)

– Commercially available in UK, Australia, under development in US

• Particle-induced gamma emission (PIGE) Spectroscopy

– Isolates organofluorine compounds on solid phase extraction,

measures total fluorine

– Detection limits to ~ 15 ug/L ( ppb) F

– Commercially available in US

• Adsorbable organofluorine (AOF)

– Isolates organofluorine compounds with activated carbon and

measures F by combustion ion chromatography

– Detection limits to ~ 1 ug/L (ppb) F

– Commercially available in Germany, Australia

• Time of Flight MS (LCQTOF) MS– Identifies multiple precursors via mass ions capture and accurate mass

estimation (to 0.0001 of a Dalton) to give empirical formulae (e.g.

C10F21O3N2H4)

Advanced Analytical TechniquesExpanding analytical tool box to assess total PFAS


© Arcadis 2016

Total Oxidizeable Precursor Assay (TOP)Oxidation of Precursors to PFAAs with OH

S2O82- 2 SO4

-

Heat

OH-SO4

2- + OHpH>11

NaOH + K2S2O8

Dilute

Sample

pH >12

85 oC

OH•

Approach described in Houtz and Sedlak, ES&T, 2012

R + shorter PFAA

products

PFSA

Precursors

PFCA

Precursors

OH•PFPA

Precursors +8

8

8

OH•

OH•


© Arcadis 2016

TOP Assay Applied to AFFF Formulations: Many formulations appear PFAS-free until precursors are revealed by TOP Assay

0

5

10

15

20

ECF,2001

FT 1,2005

FT 2,2002

FT 3,2009

FT 4,2003

Co

nce

ntr

atio

n, g

/LAFFF Formulations, Pre-TOPA

PFOS

PFHpS

PFHxS

PFBS

PFNA

PFOA

PFHpA

PFHxA

PFPA

PFBA

0

5

10

15

20

ECF,2001

FT 1,2005

FT 2,2002

FT 3,2009

FT 4,2003

Co

nce

ntr

atio

n, g

/L

AFFF Formulations, Post-TOPA

PFOS

PFHpS

PFHxS

PFBS

PFNA

PFOA

PFHpA

PFHxA

PFPA

PFBA

FT = Fluorotelomer-based AFFF

ECF = Electrochemical Fluorination- based AFFF

© Arcadis 2016

Total Oxidizable Precursor (TOP) AssayFire Training Area

Soil CompositeGroundwater Composite

240%

increase

75%

increase

EPA Method 537 Underestimates the PFAS Mass

© Arcadis 2016

Comparison of AOF & TOP Assay with AFFF Impacted Groundwater


R² = 0.8034

0

10

20

30

40

50

0 10 20 30 40 50

AO

F µ

g/L

(o

rganofluorine e

quiv

ale

nt)

LC-MS/MS Sum PFAS Post-TOP Assay, µg/L(organofluorine equivalent)

© Arcadis 2016

Digest AFFF precursors and measure the hidden mass: TOP Assay

Analytical tools fail to measure the hidden PFAS precursor mass, the TOP assay solves this

Microbes slowly make simpler PFAA’s (e.g. PFOS / PFOA) from PFAS (PFAA precursors) over 20+ years

Need to determine precursor concentrations as they will form PFAAs

Too many PFAS compounds and precursors –so very expensive analysis

Oxidative digest convert PFAA precursors to PFAA’s

Indirectly measure precursors as a result of the increased PFAAs formed


Conceptual Site Model

Increasing mobility of shorter perfluoroalkyl chain PFAS

C6 C4 C5 C3? C2?

C8 C7 C6 C4 C5 C3? C2?Hidden anionic mobile PFAA

precursors

Anionic precursor biotransformation

increases as aerobic conditions develop

Direction of groundwater flow

0 C8

Anionic PFAA dead

end daughters

0

0

C F S

08 17

0

00H3C 0

C 4H9

0

C8F17 S 0

0

0

00H3C 0

C 4H9

0

0

S 0C8F17

C F

0

0

S 08 17

0

0

C6F13

S 0

0

0

C8F17

0

0

S 0S 0 C8F17

0

0

S 0C8F17

0

S 0C8F17

0

0

S 0

C6F13

0

C6F13

0 0

0

S 0S 0

0 C6F13

Source Zone - Hidden Cationic and Zwitterionic PrecursorsLess mobile as bound via ion exchange to negatively charged fine grain soils

(e.g. silts & clays). Precursor biotransformation is limited by the anaerobic redox

conditions created by the co-occuring hydrocarbons.F

N+

0

0H

0

00

C1H9

C F

H3C 0

0

0

S 08 17

0

0

S

N H

C 8F17

NH+

F

F Cn

0

0 0H

NS

F

F C

F n0

0

H3C 00 C 4H9

0

0H

0

N+F

F

F C

F

C6F13

0

0

S 0 N

NN

S

0 H

0

F

F C

F n

0

0-C5F11

0

H3C 0

0

00H3C 0

C 4H9

0 C4H9

0 0

C6F17 S 0

0

CH

CH

CH

CHCH

CH

CH

AFFF/FFFP/FP

CH3

CH3

CH3

CH3

CH3

Hydrocarbon NAPL Short hydrocarbon plume

-300mV -200mVREDOX

ZONATION-100mV 0mV 100mV 200mV

C7C8

PFAS Source Zones, a CSM


© Arcadis 2016

AFFFComposition

% Cationic 1.2 8.2 9.7 10.6 8.0

% Anionic 98.8 80.5 81.2 78.1 80.9

% Zwitterionic 0.0 11.2 9.1 11.2 11.1


© Arcadis 2016

100% Precursors

NO PFOS or

PFOA

AFFFComposition

% Cationic 0.0 0.0 30.2 30.3 0.0 34.1

% Anionic 100.0 100.0 69.8 0.7 0.0 0.9

% Zwitterionic 0.0 0.0 0.0 69.0 100.0 65.0

© Arcadis 2016

Excessive Costs

August 20, 2017

28

http://greensciencepolicy.org/wp-

content/uploads/2016/09/Rolland-Weber-PFOS-

PFAS-German-activities-Final.pdf

Risk based approaches not adopted in Germany

© Arcadis 2016

Groundwater Risks to Receptors

AFFF / FFFP / FP

Fire training

Incident Response Source – Pathway – Receptor

High concentration, spill site, route

via groundwater to receptor e.g.

drinking water well

Diffuse

Ground level impacts and

ground/surface water

Landfill Leachate

Municipal / Domestic WWTP

Industry & Manufacturing

Agricultural Land

Commercial / Domestic Products

Metal Plating

ASTs –Fuel storage (FFFP / FP)

Grasshopper effect

via widening of source zones

e.g. concentrated plume intercepts crop spray irrigation to make secondary wider source area for more dilute plume

?

?

?

Foams

32

© Arcadis 2016

• Fires involving liquid hydrocarbons are class B and extinguished with fluorosurfactantfoams such as:

o Aqueous Film Forming Foams (AFFF)

o Fluoroprotein (FP)

o Film Forming Fluoroprotein Foam (FFFP)

• AFFF’s were develop in 1960’s and have been used widely to extinguish class B (liquid hydrocarbon) fires

• PFAS foam composition is chemically complex with multiple organofluorinecompounds many of which are not detected by commercially available analytical methods (i.e. precursors or polyfluorinated compounds)

• PFAS foams contains both polyfluorinated and perfluorinated compounds

Class B Fire Fighting Foams


© Arcadis 2016

PFAS Foams being Replaced

• C8 (PFOS and PFOA) phased-out

• C8 replaced with compounds with shorter (e.g., C4, C6) perfluorinated chains

• C4, C6 PFAS are less bioaccumulative, still extremely persistent and more mobile in aquifer systems vs C8 - more difficult and expensive to treat in water and concentrating in fruits and vegetables

• Solutions for characterizing all PFAS species important to cover current and future risks / liabilities

• Regulations addressing multiple chain length PFAS (long and short) are evolving globally

• Fluorine free (F3) foams contain no persistent pollutants

• F3 foams pass ICAO tests with highest ratings for extinguishment times and burn-back resistance, so are widely available as replacements to AFFF

Non-fluorinated replacement foams are being increasingly adopted

Manufacturer F3 Foam

National Foam Jetfoam (Aviaton)

National Foam Respondol (Class B)

Auxquimia UNIPOL

Vsfocum Silvara

Bioex Ecopol

Fomtec Enviro 3x3 Plus

Solberg Re-healing Foam RF6 / RF3

Dr. Sthamer Moussol F-F3/6

© Arcadis 2016

PFAS and F3 Foam Certification

• Currently certification of Fluorine Free (F3) foams differs

• F3 Foams pass ICAO (International Civil Aviation Organisation) tests with the highest possible rankings

• F3 foams not currently US Military Specification (MILspec) certified because.

• Different F3 foams cannot be blended.

• Training required to aerate correctly, challenge for untrained personnel.

• F3 foams cannot work between ½ and 5x correct dose.

• Currently not considered to offer equal protection to the safety of the user as PFAS based foams (shorter projection distance).

• MILSpec created for AFFF -stipulates flourosurfactants

• Costs to change nozzles, pumps for F3 foams, especially large sites.

© Arcadis 2016

Main implications of New Policy

• PFOS legacy foams must be removed from service

• Must be destroyed by high temperature (>1100 C) destruction

• Long chain foams (>C7) must be phased-out by July 2019

• Must be destroyed by high temperature (>1100 C) destruction

• Facility and equipment cleaning with solvent may be required to remove PFOS, PFHxS, PFOA, and PFOA precursors below acceptable levels

• Disposal of impacted infrastructure?

• MSDSs do not provide the information needed for

management decisions

© Arcadis 2016

Main implications of New Policy

• Non-Persistent foam usage going forward

• Needs to be certified fluorine free

– Adsorbable organic fluorine technique can work - ~ <50 mg/kg F acceptable as F free

• Should be contained and disposed of without direct release to the environment where possible

• Emergency use of non-persistent foams is acceptable

• These foams do not form films

Treatment and Restoration


© Arcadis 2016

Dickenson and Higgins, 2016

• Green lines show lead vessel GAC replacement; Orange line shows lead and lag GAC replacement

• Shortest chain (PFBA) breaks through first; PFBA is not regulated currently, but may be subject to future regulation

• Routine O&M/GAC change outs controls contaminant breakthrough; large GAC vessel sizes and lower flow rate will extended GAC lifetime

Property of Arcadis, all rights reserved 40

ACTIVATED CARBON

© Arcadis 2016

• PFAS do not biodegrade (mineralise) but biotransform to PFAAs as dead-end

daughter products

• Regulations surrounding PFAS are evolving with lowering drinking water standards

and a focus on increased interest in additional PFAAs and precursors

• Concern over short chain concentration in fruits

• Precursors mass and multiple PFAAs likely accompany PFOS & PFOA in sources and

plumes –depending on exact nature of source material

• Analysis of just PFAA’s can significantly underrepresent the actual PFAS mass

• A CSM is proposed based on TOP and AOF data from a FTA sources and plumes

• Fluorine Free (F3) foams are evolving and being widely accepted

• Remediation options are evolving and being proven using TOP assay

Summary

© Arcadis 2017

Recent Publications

43August 20, 2017


Download at:https://www.concawe.eu/publications/558/40/Environmental-fate-and-effects-of-poly-and-perfluoroalkyl-substances-PFAS-report-no-8-16

https://www.concawe.eu/publications/558/40/Environmental-fate-and-effects-of-poly-and-perfluoroalkyl-substances-PFAS-report-no-8-16

PFAS Impacts Resulting from Fire Protection: Management ... · © Arcadis 2016 Contents PFAS...

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