EMERGING CONTAMINANTSThe Arcadis Perspective Caitlin Bell

September 29, 2016

© Arcadis 2016

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Discussion Topics

What are Emerging Contaminants?

Arcadis’ Approach

1,4-Dioxane BCEE

PFAS

TCP

© Arcadis 2016

New compounds

New regulatory standards

Expanding prevalence

Health/Eco risk

What are Emerging Contaminants?

1,4-Dioxane

Personal Care Products

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Who Decides What’s Emerging?

Long List of Emerging Contaminants

Industry

DoDEPA

EPA’s Unregulated Contaminant Monitoring Rule

(UCMR)• 30 contaminants• Revised every 5 years• Sample public water supply

wellshttps://www.epa.gov/dwucmr

DoD’s Emerging Contaminants Program

• Proactive approach to identify and manage emerging contaminants

• Watch List: monitored and updated regularly

• Action List: focus of action

Industry Drivers• Advances in toxicology• State/Local regulations• New innovations

How do we focus our effort?

© Arcadis 2016

What is Arcadis’ Approach?Ambition

Trusted advisor in industrial and public markets

Innovation and thought leadership• Risk & readiness management• Investigation & analysis• Treatment

Business line collaboration• Water• Restoration

Focus on current challenges, but prepare for the future…

Prepare

Know

Treat

Poly- and Perfluoroalkyl Substances (PFAS)

Source: https://thestack.com/security/2016/06/07/the-dangers-of-backup-how-to-lull-your-business-into-a-false-sense-of-security/

© Arcadis 2016

PFAS (formerly known as PFCs)

Not quite “POTĀTO” vs. “POTĂTO”.

PFCs

PFOS

PFOAPFAS include PFOS, PFOA, and thousands of

other fluorinated compounds!

Prepare

Carbon chains that range from 2 to 16 atoms

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PFAS in the Headlines

Prepare for these public pressures.

Prepare

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PFAS Sources 1. Fire training areas2. Fire stations3. Airfields/airports4. Hangars5. Landfills6. Wastewater7. Plating8. Photo development

Prepare

© Arcadis 2016

Source: EPA UCMR3

Magnitude of the Problem

Detected in ~2% of public water supplies.Standard has dropped by an order of magnitude.

• UCMR3 sampling identified 60 water utilities with PFOS/PFOA

• Heath advisories for short-term exposure (2009) 200 ppt PFOS 400 ppt PFOA

• Health advisories for long-term exposure (May 2016) 70 ppt for combined PFOS and

PFOA

Prepare

© Arcadis 2016

Regulatory Values

More states, more compounds, lower standards.

Example Drinking Water Criteria (µg/L)PFOS PFOA PFBS PFBA PFPeA PFHxA PFHxS PFOSA PFHpA PFNA PFDA

Minnesota 0.3 0.3 7 7 - - - - - - -

New Jersey - 0.014 - - - - - - - 0.013 -

Vermont 0.02

EPA 0.07 - - - - - - - - -Canada 0.6 0.2 15 30 0.2 0.2 0.6 - 0.2 0.2 -Example Groundwater Criteria (µg/L)

PFOS PFOA PFBS PFBA PFPeA PFHxA PFHxS PFOSA PFHpA PFNA PFDANew Jersey - - - - - - - - - 0.01 -Texas, Residential 0.56 0.29 34 71 0.093 0.093 0.093 0.29 0.56 0.29 0.37

Example Soil Criteria (mg/kg)PFOS PFOA PFBS PFBA PFPeA PFHxA PFHxS PFOSA PFHpA PFNA PFDA

Texas, Residential 1.5 0.6 73 150 5.1 5.1 4.8 0.058 1.5 0.76 0.96

Prepare

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Aerobic Biotransformation Funnel

Know

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Analytical TechniquesEPA Method 537

• LC-MS/MS • C6 to C14 perfluorinated carboxylates (PFCAs), C8 sulfonates (PFSAs), and 2 precursors• Misses the C4 PFCAs, an important group• Detection limits to approx. 0.09 ng/L

Total Oxidizable Precursors (TOP) Assay

• Pre-treatment of samples using conventional chemical oxidation which converts precursors to PFCAs that can be detected by LC-MS/MS

• Detection limits similar to LC-MS/MS to approx. 2 ng/L Particle Induced Gamma Emission (PIGE) and Adsorbable Organic Fluorine (AOF)• Both measure total organic fluorine• Detection limits >1,000 ng/L

Know

See the Dark

Matter…

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Conceptual Site Model - Fire Training Area

Short-term liability may look like less than long-term liability…

Know

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Soil and Groundwater Remediation for PFAS

Excavation/disposalCapping/containment

High-temperature incineration

Solidification/stabilization

No final solution; concentrate in another phase

(no degradation)

SOIL EX-SITU IN-SITU

Granular activated carbon Ion exchange resinsReverse osmosis /

nanofiltrationOther adsorbents

Range of costs with these options; may only be effective

for a portion of PFAS (e.g., GAC)

Potentially effective evolving technologies

Combine various oxidants and catalysts

Combinations, reductants, oxidants

(ScisoR)

Treat

© Arcadis 2016

H4PFOSC7A

C7SC8A

C4SC5A

C4AC6A

C6SC8S

0

5000

10000

15000

20000

25000

30000

35000

Blanco SC2-1 SC2-2 SC2-3 SC2-4

• Destruction of PFAS by chemical oxidation/reduction

• Effective at ambient temperature• Soluble reagents can be injected or mixed with impacted

soil and groundwater

• Applications• In-situ remediation of soil and groundwater• Aboveground treatment of waste/stockpiled soil• Regenerate support media

(e.g., ion exchange resin, GAC)

ScisoR® bench scale data shows promise; now being field tested.

Arcadis’ Patented Chemical Oxidation Method

Treat

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Replicate data; error bars are standard error

ScisoR® Bench Test• Set up

• 10 mg/L PFOS starting concentration• 3 replicate data sets

• Results • 83 to 90% PFOS destruction after 14 days• 71% to 118% fluoride released from PFOS• 86% to 126% of theoretical fluoride mass

balance (fluoride in PFOS + fluoride in solution)

Field Application: Longer reaction times and repeat applications of ScisoR® will cause

complete destruction

Treat

© Arcadis 2016

In Summary…

PFAS understanding is rapidly evolving; hold on tight!

• Identify the sources• Develop strategies that incorporate understanding of

the Dark MatterPrepare• Understand the analytical purposes, benefits, and

limitations• Utilize analytical techniques that meet objectivesKnow• Acknowledge pitfalls of classical treatment techniques

(e.g., GAC)• Consider ScisoR® for pilot testingTreat

1,4-Dioxane

Source: http://www.quantexlabs.com/services/dioxane

© Arcadis 2016

1,4-Dioxane Sources

Chlorinated solvents (1,1,1-TCA)

Manufacturing byproduct

Consumer products Detergents

Direct use

Paint/dye/

grease

Main ingredient: Cellulose Acetate Membrane Production

85 mg/kg

Byproduct from detergent production

6.5-24 mg/kg

50 µg/L in soap/water mix

Prepare

© Arcadis 2016

Detected in ~20% of public water supplies, ~7% exceed health-based standards.

Source: EPA UCMR3

Prepare

Likely human carcinogen• Short-term exposure: nausea,

drowsiness, headache, and irritation of the eyes

• Chronic exposure: dermatitis, eczema, drying and cracking of skin, as well as liver and kidney damage

• Risk-based drinking water heath advisory level of 200 µg/L

Magnitude of the Problem

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Regulatory Values• No federal MCL

• Approaching 40 states with drinking water or groundwater standards

• Standards are already lowering…

Prepare

NJ is now 0.4 µg/LMI is moving to 7.2 µg/L

As of October 2015

Source: Suthersan et al. 2015

© Arcadis 2016

Common Scenario

1. Historical CVOC Plume

Groundwater ExtractionUpgradient Reinjection

2. Operation of P&T System

Treatment via

Stripping

Former Solvent

Degreaser

3. Sample for 1,4-Dioxane as Part of Closure

Prepare

4. Find a 1,4-Dioxane

Plume

1,4-Dioxane is miscible in water, does not readily

adsorb, and is not easily volatilized.

It is expected to be more mobile in groundwater than its CVOC co-contaminants.

© Arcadis 2016

Management Strategies

A proactive approach can provide more exit strategies in the long run

Modest• Wait for regulator request

before sampling• No state standard• No human health concerns

present

Proactive• Collect data in advance of

regulatory pressure• Build long-term data set for

decision making (e.g., MNA)

• Optimize remedial approach to address

Prepare

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• Commonly used methods− EPA Method 8260 (sometimes with SIM)− EPA Method 8270 (sometimes with SIM)− EPA Method 522 (drinking water method)− TO-15 (soil gas)− Isotopic dilution application

• Challenges− Reporting limits− Consistent mid-range results− Extraction recovery

Laboratory Analysis

1,4-Dioxane analysis is evolving, be patient and ask questions

(Florida DEP, 2010 )

Example Clean up Target (3.2 µg/L)

SIM: Selective ion monitoring

Current RecommendationsObjective Approach

Low reporting limits EPA Method 8270SIMMid-range results EPA Method 8260SIMUnbiased results Incorporate recovery values

Know

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Related Advanced Laboratory Analyses

Dissolved Gases

Molecular Biology Tools (MBT)

Compound Specific Isotope Analysis (CSIA)

• Full dissolved gas (e.g., AM20GAX) list provides data on primary substrates associated with biodegradation, like propane or methane

• Functional gene targets for metabolic biodegradation (DXMO, ALDH) and cometabolic biodegradation (sMMO, PPO, etc.)

• Carbon-13 and hydrogen-2 isotopes now available• Environmentally relevant detection limits (e.g., 5 µg/L)

Know

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Treatment Options

• Chemical oxidation (ISCO)• Natural attenuation/Bioremediation• Thermal• Extreme soil vapor extraction (XSVE)

In-situ

• Advanced oxidation processes (AOPs)• Specialized synthetic media• Bioreactor

Ex-situ/Drinking Water

Air stripping GAC

Treat

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Advanced Oxidation Processes• Common update to existing P&T systems (capital and O&M cost considerations)• O&M challenges

− Frequent cleaning to maintain system flow rate− Lamp failures leading to exceedances − Additional unit processes for pre-treatment (e.g., iron)

• Formation of byproducts− Acetone and bromate formation is common− Upfront water quality characterization is key

HiPOx uses O3 and H2O2 UVPhoxTM uses UV and H2O2Ray-Ox® uses UV and H2O2 PhotoCat uses UV, TiO2, and oxidant

AOP

Gold Standard!

© Arcadis 2016

In-Situ Chemical Oxidation

ISCO

Persulfate

Peroxide

Percarbonate

Permanganate

Ozone

Persulfate

Peroxide

Percarbonate

Ozone

1,4-Dioxane Oxidants

CVOCOxidants

Permanganate

Less

effe

ctiv

e

Activation method is also important

• Similar oxidants destroy both 1,4-dioxane and CVOCs

• ISCO is a contact sport

• Delivery includes oxidant distribution and residence time

• Rebound/Reinjection is expected

• Safe implementation is required

• Inefficient and cost prohibitive with significant mass storage

• Secondary groundwater quality considerations: pH, metals, unwanted organics

© Arcadis 2016

ISCO Case Study• 30-acre former chemical manufacturing facility• Smart InvestigationTM identified

CVOC source mass and co-occurrence of 1,4-dioxane

• Scope of work− Bench-scale treatability

testing established loading and activation chemistry

− Pilot-scale testing identified injection capability and reinjection frequency

− Full-scale system includes ~45 injection wells

ISCO

Great for Mixed Plume/Source 0

1,000

2,000

3,000

4,000

5,000

6,000

7,000

Baseline 2-Months PostInjection

1,4-

diox

ane

(µg/

L)

MW-1A MW-1BMW-2A MW-2BMW-3A MW-3BMW-4A MW-4BMW-5A MW-5BMW-6A MW-6B

Rebound after

2 months

© Arcadis 2016

Biodegradation: Metabolism vs. Co-Metabolism

Microbe DNA Gene Enzyme

Metabolism: the goal is to produce energy

Co-Metabolism: a fortuitous side reaction

MNA Bio Bioreactor

+ O2e.g., sMMO,

PPO

1,4-Dioxane

Carbon Dioxide

Oxygen

Water

(http://bacmap.wishartlab.com/organisms/1305 )

Primary substratee.g., methane,

propane, toluene, THF

Energy

Carbon Dioxide

Water

© Arcadis 2016

MNA Case StudyLines of evidence approach for natural attenuation demonstration1. Stable/decreasing 1,4-dioxane trends

2. Geochemistry conducive to cometabolic biodegradation (with methane)

3. Genetic testing to confirm presence and activity of microbes

4. Correlation with carbon-13 isotopic shift via CSIA

MW-12-09

MW-14-62

MW-14-60MW-03-07

MW-02-02(6)

CSIA Results“Stock” = -33‰Groundwater = -30.80‰The difference suggests biodegradation occurred

MNA

Gaining Acceptance

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In-Situ Bioremediation Case Study• Gas injection

• Air • Propane

• Liquid injection• Bioaugmentation culture

(e.g., Rhodococcus ruber ENV425)• Nitrogen/phosphate

• Considerations• Explosion safety/controls• Cycled injection to stress the microbes• Vapor intrusion of CVOCs or propane

Bio

PropaneTank

Line to SpargeWell

MixingPoint

LEL Meter

SpargeWell Control

Panel

Air Compressor

© Arcadis 2016

In-Situ Bioremediation Case Study

Stable isotope probing confirmed biodegradation mechanism

Bio

Graphic Sources: Kerry Sublette and Microbial Insights

1,4-Dioxane Mineralization to CO2

Background 24-MW-5A 24-SW-2B

1,4-Dioxane Microbial Uptake

24-SW-2B24-MW-5ABackground

Things in white text

Things in white

whiteBio-Trap®

Sampler

1. “Bait” Bio-Trap® sampler with 13C 1,4-dioxane

2. Deploy down-well for ~30 days(let the microbes do their work)

13C Biomolecules

13C 1,4-Dioxane

13C CO2

3. Analyze for 13C 1,4-dioxane(acts as a tracer through the

microbial system)First Field-Application

of SIP

© Arcadis 2016

Ex-Situ Bioreactor• Economic alternative option to AOP for

updating existing systems– ~15% less capital cost – ~40% cheaper to operate

• Couple with directed groundwater recirculation to expedite remedial timeframes

• Few groundwater remediation field applications – Transferring knowledge from water/wastewater

treatment– Currently pilot testing ex-situ remediation

applications

Bioreactor

Growing Industry Interest

© Arcadis 2016

In Summary…

It’s an exciting, evolving time for 1,4-dioxane!

• Know the regulatory climate• Consider analyzing for 1,4-dioxane proactivelyPrepare• Acknowledge the analytical challenges• Ask questions of the laboratoryKnow• Identify the best option when retrofitting a system• Embrace the biological treatment mechanismTreat

1,2,3-Trichloropropane (TCP)

Source: http://www.urbancultivator.net/pesticides-food/

© Arcadis 2016

TCP Sources and Prevalence

No federal MCL; 5 ppt draft MCL put forth in California

CVOC production byproduct

Degreasing agent

Pesticide intermediateSoil fumigant/pesticide

Cross-linking

agent in production

of polysulfides

Source: EPA UCMR3

Prepare

© Arcadis 2016

Treatment Options

• ISCO: reacts with hydroxyl and sulfate radicals• Hydrolysis: alkaline and heat activation enhance rates• ISCR: reduction by zero valent zinc most promising• Biological: potential pathways, but very slow

In-situ

• GAC: best available technology identified in CA MCL development, although relatively low efficiency

• Air stripping: best used at elevated temperatures• AOPs

Ex-situ/Drinking Water

Treat

Bis(2-chloroethyl) ether (BCEE)

Source: http://www.commondreams.org/news/2013/07/09/pesticide-use-spikes-gmo-failure-cripples-corn-belt

© Arcadis 2016

BCEE Sources and Treatment

Pesticide production Paint/varnish

SolventChemical intermediate

Cleaner

Prepare Treat

Viable Options

• Chemical oxidation

• Biodegradation• Natural

attenuation

Less Likely Options

• Sorption-based technologies

• Air stripping• Thermal

treatment

© Arcadis 2016

In Conclusion…

There are emerging options for emerging contaminants

Risk & readiness management – know what you’re getting into and what the requirements are

Prepare

Know

Treat

Investigation & analysis – understand the approaches and associated concerns

Treatment – choose the best option, there are many

© Arcadis 2016

About the Presenter, and Other Resources

c 857 488 0490e caitlin.bell@arcadis.com

CAITLIN BELLSenior Engineer and Arcadis North America 1,4-Dioxane Lead

OTHER ARCADIS RESOURCESJoe Quinnan: Arcadis North America Emerging Contaminants Leade joseph.quinnan@arcadis.com

Jeff Burdick and Jeff McDonough: Arcadis North America PFAS Leadse jeff.burdick@arcadis.com or jeffrey.mcdonough@arcadis.com

Margy Gentile: BCEE and TCP Knowledge Leade margaret.gentile@arcadis.com

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Arcadis.Improving quality of life.