5-12-16 MASTER Site Remediation Emerging Contaminants

8/16/2019 5-12-16 MASTER Site Remediation Emerging Contaminants

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Environmental Business Council of New England

Energy Environment Economy

Contaminants of Emerging Concern

EBC Site Remediation & Redevelopment

Program:



Jonathan D. Kitchen

Chair, EBC Site Remediation &

Redevelopment Committee

Senior Project Manager, Civil &

Environmental Consultants, Inc.



Welcome



Hamilton Hackney

Shareholder,

Greenberg Traurig, LLP



Welcome



Russell Schuck

Program Chair & Moderator

Vice President, Haley & Aldrich, Inc.



Introduction & Overview



EBC Site Remediation& RedevelopmentProgram:Contaminants ofEmerging Concern

Russell Schuck, P.G.Haley & Aldrich Inc.



What are we

talking about?

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What are Compounds of Emerging concern

• Compounds where the risk to human health and theenvironment are not fully understood

• “New” compounds that were not previously known and arefound to be present in the environment

• Compounds that were known to exist but whose

environmental occurrence was not fully understood• “old” contaminants, for which there is new information on

environmental and human health risks

• Current CECs in the spotlight:

– 1,4-Dioxane

– Perfluorooctanoic acid (PFOA) – Perfluorooctane sulfonic acid (PFOS)

– 1,2,3-Trichloropropane

– TCE toxicity

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http://www.crccare.com/knowledge-sharing/pfos-and-pfoa-guidelines



EPA’s Regulatory process

– The Safe Drinking Water Act (SDWA) directs EPA to publish a list ofcontaminants (referred to as the Contaminant Candidate List, orCCL)

– Potential contaminants derived from research results for “new”compounds or that indicates new toxicity data

• Academia, National Drinking Water Advisory Council (NDWAC), NationalAcademy of Sciences (NAS)

– Development of Contaminant Candidate List (CCL)

• https://www.epa.gov/ccl

– Monitoring: Unregulated Contaminant Monitoring Rule (UCMR)• 3rd-UCMR

• 4th-UCMR

– Regulatory determination

9

https://www.epa.gov/sites/production/files/2015-02/documents/epa815f15001.pdf

https://www.epa.gov/dwucmr/third-unregulated-contaminant-monitoring-rule

https://www.epa.gov/dwucmr/fourth-unregulated-contaminant-monitoring-rule











CECs Challenges: May be Widespread

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CEC Challenges: Without MCL’s = RegulatoryInconsistency

11

• Iowa = 200ug/L

• NH = 0.25

ug/L



CEC Challenges: Public Perception

12



CEC Challenges: Evolving Science

13

• Toxicology

• Contaminant fate & transport

• Remedial Technologies



Tonight’s Program

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• Regulatory Perspective

• Case study on PFC impacted drinking water supply

• Innovation in Remedial Technologies



Gerard Martin & Angela Gallagher

Bureau of Waste Site CleanupMassachusetts Department of

Environmental Protection



Update from MassDEP on




Environmental Business Council of New

England, Inc.

C. Mark Smith, Ph.D., M.S., Director, Office of Research and

Standards, MassDEP, Boston, MA

Gerard M.R. Martin, Deputy Regional Director, BWSC-SERO,MassDEP, Lakeville, MA

Angela Gallagher, BWSC-SERO, MassDEP, Lakeville, MA

Regulatory Perspectives on Addressing

Emerging Contaminants in Massachusetts

May 12, 2016



Presentation Overview

• Why Address Emerging Contaminants?

• MassDEP’s Emerging Contaminants Workgroup

• MassDEP’s EC Exposure Response Plan

• Process for Promulgation of Standards

• Current Emerging Contaminants

• 1,4-Dioxane, PFC’s and TCE

• Key Takeaway Points



Why Address Emerging Contaminants?

perfluorooctane sulfonate (PFOS)

1,4-Dioxane

Perfluorooctanoic acid (PFOA)



“The EC Challenge” by the Numbers

• 7M+ chemicals; ~80,000 in use (GAO, 1994)

• TSCA inventory - > 70,000 chemicals in commercial use (2001)

• 650+ chemicals in EPA’s TRI list (EPA, 2015)

• Changing universe

• 1,232 “CAS #s” listed in MOHML (MCP, Subpart P)

Few Chemicals Deemed as EPA “Contaminants ofEmerging Concern” or MassDEP ECs



Key EC Issues for MassDEP

• Increasingly sensitive instrumentation

• Data gaps; toxicity; occurrence; sources

• Sensitive groups; developmental risks

• Many EC-specific confounding sources

• Evolving science & technology

• Technical, programmatic and business challenges abound



The MassDEP EC Workgroup Pre-2000: EC-related information collected/monitored through

MA TURA (1989) and EPA’s SDWA UCMR program

Late 1990s: Perchlorate in Bourne DW triggered Perchlorate WGand assessment. Developmental toxicity concern.

2001-04: PWS testing/policy development

Initially through UCMR-1 program @ 4 µg/L

2002: ORS/DWP issue interim guidance for perchlorate inDW @ 1 µg/L

2006: MA first in the nation to promulgate perchloratedrinking water (MMCL) / GW-1 cleanup standard (2

µg/L)BMPs developed for non-MCP release scenarios

2007: Perchlorate WG Emerging Contaminants WG



The MassDEP EC Workgroup

• Mission: “to centralize MassDEP’s focus on EC, fosterinformation exchange and bring together a broadrange of cross-program expertise”

• Goals include:

–Increasing readiness by identifying potential public healthand environmental problems early on

– Information sharing within DEP and with stakeholders

– Establish/implement EC screening process

– Develop EC-specific exposure response plans & riskmanagement strategies to protect human health



Task 1 – Develop EC Definition

• ECs defined as hazardous chemicals, biological agents, or

radiological substances that:

– Present threats to human health, public safety or the

environment;

– Lack national health standards/guidelines;

– Have toxicological information that is limited, evolving or being

re-evaluated; or

– Have significant new source, pathway or detection limit

information

• May include naturally occurring or manmade chemicals

( MassDEP Emerging Contaminants Workgroup, 2007)



TURA/UCMR data listsSubject Matter Experts (SME)High risk/exposure/visibility/occurrence

Screened Out if not considered “generallyimportant”; addressed ; and/or

jurisdictional/authority issues impedeinvolvement

Considers certainty in available science

Possible tangible outcomesCross-media issues

PRELIMINARY LIST (80 Contaminants)

Ten (10) Priority Emerging Contaminants

identified with a subset of ECs nominated for

action with recommended strategies

Task 2 – Develop EC Screening Process

STEP 1: SCREENING PROCESS

WATCH LIST (30 Contaminants)

STEP 2: SCREENING PROCESS

RESULT (as of 2015)->



Priority ECs:• Pharmaceutical / Personal Care

Prods/Endocrine Disruptors

• 1,4-Dioxane (UCMR-3)1

• Cyanobacteria (Blue Green Algae)

• Nanoparticles

• Perchlorate1

• PolyBrominated Diphenyl Ethers

(PBDEs)

• Tetrachloroethylene (PCE)1

• Trichloroethylene (TCE)1

• RDX1

• Tungsten1

Sample ECsWatchlist:

• 9 VOC’s

• Detergents

• Disinfectants

•Plasticizers• Pesticides

• DEET (insect repellant)

(part of PPCP/EDC)

New Addition for Priority EC Consideration:

•PFCs (including PFOS/PFOA) (UCMR-3)

1

MCP Promulgated Standard(s) have been derived/revised since initial inclusion in EC list.

Task 3 – Develop EC Lists



Sample EC Priority Research Area

Pharmaceutical and Personal Care Products1

/Endocrine Disruptors • 71% increase in use compared to US pop. growth of 9% (1994 – 2005)

• Widely detected downstream of WWTPs & in septic tank effluent

— Documented detections 30 states, 139 streams (USGS, 2002)

• Endocrine disruptor effects

— Mimic/block normal hormonal functioning

— Potential reproductive, developmental, and/or behavioral effects

• WG Recommedations

— Detection & Occurrence Research (DEP/UMass/Private-Muni Partnership)

— Pollution Prevention (Pharma take-back programs)

— Drop-off kiosks / Centers (DEA, DPH and DEP-regulated)

• Continued Awareness & Assessment (Public Outreach)

1. Including “over the counter”.




TCE• Well established VOC contaminant, but ….

• New toxicity data raised concerns about serious fetal

developmental effects

• Extensive effort to evaluate the data and update

MCP standards/Imminent Hazard requirements

relative to the vapor intrusion pathway




SDWA UCMR-Related Emerging Contaminants• “Contaminants suspected to be present in drinking water but

that do not have EPA promulgated drinking water standards

(EPA SDWA’s 3rd UCMR Rule, UCMR 3 )1

• Unregulated or under-regulated contaminants detected inthe environment, most with no MassDEP standards or

guidelines

• Pose perceived/real threats to human health, analytical and

treatability challenges due to rapid change in science, lack oftoxicological data or limited remedial technology

• Recent examples of ECs with program workload nexus

– 1,4-Dioxane & PFCs (PFOS & PFOA)

1. Not exclusively health-based ascost & feasibility also considered



Sample EC Exposure Response Plan

Step 1: Identify Source, Exposure Pathways &Assess Potential Risks1

Step 2: Abate / Eliminate Exposures (if feasible)P-O-U treatment system2

Bottled Water / Municipal Water Line2

Blending / Purchase Water from other Towns2

Step 3: Integrate IRA Actions into CRA (MCP/SW)Redirect source discovery/exposure abatement effortsto nature & extent delineation and remediation(technical/cost feasibility)

Policy Step: Explore promulgating guidelines or

standards

1. Analytical testing may prove challenging2. Examples of abatement measures



Standards Promulgation Considerations

• Problem Identification Considerations

⁻ Occurrence levels / data gaps

⁻ Toxicity information limitations / uncertainties⁻ Analytical method availability & cost

⁻ Treatment feasibility & costs

• Public process (e.g., Hearings)

• Public comments considered in final rulemaking

• Final Rulemaking Takes Time

• 5+ Yr process for Perchlorate (detection->Standards)

ProblemIdentification PublicComment Process

Final Rulemaking /

StandardsPromulgation



1,4-Dioxane



1,4-Dioxane Background • Toxic, widely used

– Possible human carcinogen (liver and kidney cancer)

– 1,1,1-TCA stabilizer, de-icing fluids, personal care products, landfills

• General Chemical/Physical Characteristics

– Miscible, mobile, very soluble, leading edge of a plume

• GW-1 Standard and ORS-Guidance = 0.3 µg/L• Analytical Methods

– Initially, difficult to analyze for 1,4-dioxane, not reliable

– Improved analytical methods (8270SIM, 522 MOD) over past few years

• Remedial technologies limited and costly

– Difficult to remediate to 0.3 µg/L from slightly higher initial

concentrations

– Carbon filtration not always effective

– Other remedial technologies are costly or not appropriate



BWSC Guidance on Sampling and

Analysis for 1,4-Dioxane1

• Provides guidance regarding appropriate scenarios for 1,4-dioxanesampling and analysis at MCP disposal sites, including:

– Facilities where chlorinated solvents have been manufactured or used

/ contaminated groundwater

– Laboratories where 1,4-dioxane used as a reagent

– Landfills where products containing 1,4-dioxane exist / contaminated

groundwater

• MassDEP Solid Waste Regulations – 310 CMR 19.132(2)(h) [1,4-dioxane

sampling requirement, Feb. 2014]

– Military sites with historic use of 1,4-dioxane as an additive to

chlorinated solvent formulations and releases to groundwater

– Airports that may have employed de-icing fluids

1. June 2015



BWSC Guidance on Sampling and

Analysis for 1,4-Dioxane1

• PRPs/LSPs encouraged to sample for 1,4-dioxane during chlorinatedsolvent site assessment

– Extensive migration potential in groundwater (due to miscibility and resistance to

degradation), coupled with associated impacts to human health (EPA IRIS, 2010)

• Detections above MCP standards require notification and may require

remedial actions• BWSC recognizes potential elevated concentrations of 1,4-dioxane levels

in certain “confounder” scenarios

– Assessment activities should ascertain whether source stems from “21E/MCP release” or

other sources (e.g., septic systems that may retain detergents, for example)

•BWSC recognizes wide spectrum of available analytical methods – Modifications of methods & sample preparations needed to achieve adequate RLs

– 1,4-Dioxane is included on the WSC-CAM-II A and B analyte lists for SW-846 methods

8260B and 8270D, respectively

– EPA Method 522 must be used when analyzing drinking water samples

1. June 2015



1,4-Dioxane MCP Reporting Requirements

• Only exceedances of RCGW-1 Standard (0.3 µg/L)

have been reported to MassDEP BWSC SERO thus far

– RCGW-2 Reportable Concentration is 6,000 µg/L

• Typically, MCP 2-Hour or 72-Hour reporting

condition – 2-Hour Reporting condition: 1,4-Dioxane detected in a

private well

– 72-Hour Reporting Condition: 1,4-Dioxane detected near a

private well (e.g. Landfill Monitoring Well within 500’ of

private well)



1,4-Dioxane Case Studies

• Eastham Landfill – Landfill is source to several downgradient and “crossgradient”

residential private wells downgradient in the deep aquifer

– Potential septic source in shallow aquifer

– No viable remedial technology. Some success with coconut based

carbon filtration – Bottled water provided and municipal water system being installed

• Barnstable Water Department – 1,4-Dioxane in public wells downgradient of the airport

–Shut down wells, blended water and installed overland connectionwith Yarmouth

– 1,4-Dioxane detected in waste water effluent

– Other sources being evaluated



Perfluorinated Compounds Background • Toxic, widespread presence

– Developmental toxicity (low birth weight, birth defects); insufficient data to

assess cancer risk; EPA evaluating “likely carcinogenic to humans” descriptor.

– Used/found in Teflon, AFFF, aqueous gore-tex paper, food packaging materials

(voluntary phase out of PFOS by 3M)

• General Chemical/Physical Characteristics

– Very stable, resistant to degradation

• No MCP GW-1 standard or Massachusetts ORS/ORS-G. EPA Provisional

Health Advisories (PFOS – 0.2 µg/L; PFOA – 0.4 µg/L)

• Analytical methods

– EPA Method 537 (PFOS MRL – 0.04 µg/L and PFOA MRL – 0.02 µg/L)

• Remedial Technologies

– Dependent on concentrations entering treatment system

– Resistant to most in-situ technologies

– Carbon filters, reverse osmosis, and incineration have been effective



Perfluorinated Compounds Case Study

•Barnstable Water Department – PFCs at very high concentrations in public wells

downgradient of Fire Training Academy

–Evaluation at Fire Training Academy indicates PFCsin groundwater significantly higher than PHAs

– Wells shut down

–Well went back on line with carbon filtration



TCE Background

•Vapor intrusion of TCE and newly discoveredrisks put TCE on the EC list:

– Fetal heart abnormalities within the first few

weeks of fetal development with low TCE exposure

• MassDEP looking closely at TCE sites

• Focusing on vapor intrusion pathway

Imminent Hazards



TCE Case Study

• Attleboro Day Care

– Several current and former manufacturing facilities in the

area

– TCE detected in groundwater above GW-2

– MassDEP sampled indoor air at day care in area• TCE and 1,2-DCA above TVr and other contaminants

below TVr CEP present

• Method 3 NSR

• Building owner to install SSDS – Follow up inspection – NO SSDS – NOR with request for IRA

issued



Key Takeaway Points • Occurrence of Several “New” Contaminants Led to EC

Workgroup Formation – Identifying and assessing public health and environmental challenges

associated with currently unregulated or under-regulated contaminants

– Recommending coordinated Agency EC Efforts

• Improved Technologies Allowed Health-Protective Standards

For 1,4-Dioxane— Other ongoing efforts underway (EC Confounder assessment, analytical

methods certification, remedial treatability research)

— BWSC recommends analysis at chlorinated solvent plume Sites (June 2015)

• PFCs (PFOS & PFOA) EC Position Paper and Proposed Action

Plan Underway including: – BWSC’s request for MCP standards derivation by ORS

– Monitoring / reviewing EPA’s UCMR-3 findings in Public WS wells

– ORS comments on EPA’s Preliminary HA revisions



There’s No Shortage of ECs…ManyOthers in the Queue!

Thank You!

Questions:

C. Mark Smith, Director, ORS, 617-292-5509

Gerard Martin, DRD, BWSC SERO, 508-946-2799

Angela Gallagher, BWSC-SERO, 508-946-2790



Blake Martin

Senior Associate,Weston & Sampson



Water System Responds to

Perfluorochemicals: A Case Study



Andrew Bishop

Chief Operating Officer,

ect2



Advances in Treatment Technologies

for CECs Including Perfluorinated

Compounds and 1,4-Dioxane



Advances in Treatment Technologies for

Emerging Contaminants

Andy Bishop

Steve Woodard, Ph.D., P.E.



Presentation outline

• Intro to ECT

• AMBERSORBTM for 1,4-dioxane removal

• PFAS (PFCs): The next big emerging contaminant

• Air/vapor treatment





What is synthetic media?

Derived from plastics, synthetic media can be used to collect

various contaminants from liquids, vapor or atmospheric streams

and be reused indefinitely.

CarbonaceousPolymericIon exchange



What contaminants does ECT treat

using synthetic media?

• 1,4-dioxane

• Chlorinated VOCs

• PFCs

• 1,2,3-TCP

• Other niche organics

• Metals

• Perchlorate

• Contaminated vapors

• BTEX

• Chlorinated VOCs

• Fragrance compounds

• Other VOCs



Quick refresher:

Why is 1,4-dioxane such a challenge to treat?

• Miscible in water

• Low volatility, low sorption

• Difficult to measure

• Difficult to remediate (recalcitrant)

• Travels rapidly in subsurface; plume often

extends beyond extraction wells

• Once discovered, often the driver for cleanup



Challenges with existing 1,4-D pump &

treat technologies (AOP)

• Struggle with variable influent loadings

• Delivery, storage and consumption of regulated

chemicals (e.g. H2O2)

• Frequent change-out of UV lamps

• Bromate and hex chrome formation potential

• TSS/turbidity/TDS reduces effectiveness

• Subject to free radical scavengers

• O&M intensive



Alternative solution:

Dow’s AMBERSORBTM 560

• Hydrophobic

• Unique pore size distribution

• High affinity for organic compounds:

(simple adsorption mechanism)

• Can achieve non-detect effluent

concentration at substantial loading rates

• Can typically reuse (regenerate in-place)

indefinitely

• Durable structure



Animated process flow diagram

http://www.ect2.com/products/water/1-4-dioxane










Pre-engineered, modular solutions

W l h MA i ll i



Waltham, MA installation

Influent and effluent 1,4-dioxane



Case study: St. Petersburg, FL

• A unique approach to iron management

• Phase 2: Long-term plume control

• Design basis:

•Flow = 100-175 gpm

• 1,4-dioxane = 2,535 ppb

• Total organics = 17,450 ppb

• Iron = 6-30 mg/l



Iron pretreatment = half the battle

Iron pretreatment AMBERSORB vessels



Iron sludge dewatering

Iron sludge

Plate and frame filter press



Influent and effluent iron

Stopped adding oxidant



Influent and effluent 1,4-dioxane



Lifecycle cost analysis



Full-scale mobile demonstration unit



1,4-dioxane treatment summary

• AOP systems dominate the existing pump & treat installations, but have

their limitations

• AMBERSORB provides a reliable treatment alternative

o Adsorption = simple

o Media can be regenerated in place, enhancing sustainability

o Results have been consistent/dependable

o AMBERSORB systems can be skidded, containerized and mobile

• AMBERSORB typically has a lower lifecycle cost than AOP

• In groundwater, high iron concentrations result from reduced(negative ORP) conditions

• AMBERSORB works

o Treated over 45 million gallons at St. Petersburg so far

o > 99% up-time

o Effluent 1,4-dioxane is consistently < 0.04 ug/l (ppb)



PFAS: The next big emerging contaminant



PFAS sources, regulation & treatment

• Sources of PFAS include firefighting foam,

TeflonTM, ScotchgardTM, Gore-Tex®, etc.

• USEPA has issued a drinking water

Provisional Health Advisory (PHA) for:

o Perfluorooctane sulfonate(PFOS) = 0.2 µg/L

o Perfluorooctanoic acid

(PFOA) = 0.4 µg/L

• The carbon-fluorine bond is the strongest

in nature

• Granular activated carbon (GAC) is the

“go to” treatment

Bench test apparatus using groundwater



Bench test apparatus using groundwater

from Pease AFB (I/X resins)

Resin A

Control GW

Drum

Feed Pump

Resin B

Resin C

• Polypropylene columns

• Polypropylene fittings

• HDPE tubing

• 100 mL resin A, B, C

• 6.7 mL/min (15 min EBCT)



Pilot test flow diagram



Pilot test flow diagram

I/X resin vs. carbon



Volume treated before breakthrough: all PFAS

0

50,000

100,000

150,000

200,000

250,000

300,000

350,000

6:2 FS 8:2 FS PFBS PFBA PFHpS PFHpA PFHxS PFHxA PFOA PFOS PFPeA

G A L L O N S

GAC-EFF-2 (10 min EBCT) IX-EFF-2 (5 min EBCT)



PFOS breakthrough results



PFC treatment summary

• Resin demonstrated superior longevity to GAC (higher removal capacity),especially at removing PFOS

• Resin demonstrated comparable or better performance than GAC at

removing branched and shorter-chain PFCs

• Regeneration has been proven at the pilot scale

• Lower lifecycle costs over GAC systems for PFAS treatment

• 5-10 year simple payback for a resin solution at the Site 8 project site

• Some applications may allow for disposable media



Synthetic media for air/ vapor treatment



Vapor: low flow, high concentration

• Typically applied to vented tanks and other process vents

• Compact, skidded, fixed-bed systems

• Often replaces existing carbon vessels

•More sustainable, cost-effective solution

• Resin can be regenerated in place



Vapor: high flow, low concentration

• Moving-bed resin treatment systems

• Concentrate contaminants 100 times, vs rotary concentrators, which

concentrate contaminants 12 times

• Typically replace existing thermal oxidizers, or make them much

more efficient

• Reduced natural gas use: burn contaminants

instead of fuel and relatively clean air

• Reduced NOx and SOx production

• Rapid payback – months, not years



Andy Bishop

(207) 274-3700

[email protected]

Steve Woodard

(207) 210-1551

[email protected]

Questions?

mailto:[email protected]








Jonathan D. Kitchen

Chair, EBC Site Remediation &

Redevelopment Committee

Senior Project Manager, Civil &

Environmental Consultants, Inc.



Closing

EBC Site Remediation & Redevelopment





p

Program:

5-12-16 MASTER Site Remediation Emerging Contaminants

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