2018 Annual Seminar for Environmental ProfessionalsAir & Waste Management AssociationJanuary 24, 2018

“Emerging Contaminants and Challenges to New York’s Water Supplies”

Presentation Outline

Introductions

Current State of Technical Knowledge

Emerged: Perchlorate

Emerging: 1,4-Dioxane

Exploding: Per- and Polyfluoroalkyl Substances (PFASs)

“…what we find in the environment often depends on what we look for and how hard we look…”

- USGS

Emerged: Perchlorate

Perchlorate

Manufactured forms – perchloric acid,

salts

Highly water soluble

“Commonly used as an oxidizer in

solid propellants, munitions,

fireworks, airbag initiators for

vehicles, matches and signal flares”

EPA 505-F-14-003 January 2014

Road cuts and quarries

Chilean caliche fertilizers

EPA Health Advisory 15 µg/L, tap water screening level value 11 µg/L

Emerging: 1,4-Dioxane

Sources of 1,4-Dioxane

Stabilizer for 1,1,1-TCA (>95% in 1970s, 3% to 4.5% by volume)

Other less widely used solvents

Painting, coating and paint stripping inks and printing operations

Medical/biological experiments (research landfills)

De-icing products

Home/personal care products

1,4-Dioxane – Risk and Occurrence

U.S. Department of Health and Human Services (HHS) – reasonably anticipated to be a human carcinogen

U.S. EPA – Group B2 human carcinogen

U.S. EPA Integrated Risk Information System (IRIS) database – toxicity factors: oral reference dose (RfD), inhalation reference concentration (RfC), carcinogenic oral slope factor (SFo), and inhalation unit risk (IUR)

June 2015 - EPA redefined volatile, resulting reclassification of 1,4-dioxane from non-volatile to volatile

In 2013, U.S. EPA estimated the concentration of 1,4-dioxane in water corresponding to an increased lifetime cancer risk of one-in-a-million, assuming consumption of 2 liters of water per day each and every day for a lifetime (70 years) is 0.35 ppb. This health-protective criterion is often used as a non-regulatory benchmark for minimal risk

More recent research indicates that the health protection criterion should be as high as 350 ppb (Dourson et al. 2014, Dourson et al. 2017)

1,4-Dioxane Standards/Guidance Values

State/Fed. AgencyDrinking Water Ground Water Soil (residential) Soil (industrial) Air

USEPA No MCL (0.35 μg/L IRIS) or (0.67 μg/L) Establish Cleanup level 4.9 mg/kg 17 mg/kg 0.49 μg/m3 Res.

2.5 μg/m3 Ind.

New Hampshire 3.0 μg/L (AGQS)0.25 μg/L RL

3.0 μg/L (AGQS)0.25 μg/L RL 5.0 mg/kg (SRS) 5.0 mg/kg (SRS) NA

Massachusetts 0.3 μg/L (DWG) 0.3 μg/L (GW-1) 0.2 mg/Kg (S-1/GW-1) 6-500 mg/kg NA

New Jersey NA 0.4 μg/L NA NA NA

Maine NA 4.0 μg/L (MEG) NA NA NA

New York 50 μg/L NA NA NA NA

Vermont 20 μg/L (VT GWPRS) 20 μg/L (VT GWPRS) 4.9 mg/kg (SSVs) 17 mg/kg (SSVs) 0.32 μg/m3 (IA Screening value)

1,4-Dioxane – Regulatory Status

Proposed for reduction to 0.32 μg/L

1,4-Dioxane – In the New York News

1,4-Dioxane Remediation Technologies

Ex-Situ Technologies

Sorption

Advanced Oxidation Processes

Biological Treatment

In-Situ Technologies

Chemical Oxidation

Biodegradation

Thermal

Natural Attenuation

1,4-Dioxane – Remediation Challenges

1,4-Dioxane Treatment Challenges

Completely miscible with water

Low KOW/KOC

Low Henry’s Law Constant

Rapid migration in groundwater

Resistant to biodegradation

** Low clean-up goals (less than 1 part per billion) require high treatment efficiency (>99.99%) **

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Analytical challenges

Methodology

Health advisories / regulatory standards were higher

“out of sight, out of mind”

1,4-dioxane has been on VOC lists since

the 90’s…Not an issue till last

decade – WHY?

1,4 Dioxane

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• Sample preparation

– Treat it like a VOC?• Purge & trap, solubility / purging efficiency

• Dilutions due to CVOCs?

– Treat it like a SVOC?• Liquid / liquid extraction?

– Analyte loss / ext. concentration step

• Solid phase extraction?

– DW –specific method, applicability?

• Instrumental analysis

– All GC/MS

Challenging Physical Properties Lead to Difficult Choices for Aqueous Samples

SAMPLE

purge & trap,heated (?)

liquid / liquid extraction

SPE

Preparative Stage

GC/MSSIM

GC/MSSIM ID

Determinative Stage

GC/MSSIM

8260 SIM 8270 SIM ID 522 SIM

AQ Low Level Analysis

Compound ID Gas Chromatography – retention time Mass Spectrometer – mass spectra

Gas Chromatography / Mass Spectrometry (GC/MS)

full scan mode

Mass Spectrometric Techniques

Selected Ion Monitoring (SIM)

Scanning mode in which only a limited mass-to-charge ratio range is transmitted/detected by the instrument

Focus on specific COCs Vs. full TCL INCREASED SENSITIVITY

No library searches / TICs

Isotopic Dilution (ID)

Addition of known amount of isotopically-enriched, compound-specific internal standard PRIOR TO SAMPLE PREPARATION

Analysis-specific, analyte-specific concentration normalization

As a VOC…

Method 8260 full scan

NA for low level work

Method 8260 SIM

Lower RLs Heated purge & trap?

w/ HCl preservative?

Sub 1 PPB “pushes the envelope”

NON – dioxane VOCs present requiring dilution?

Raises dioxane RL

As a SVOC… Method 8270 SIM

L / L extraction, extract concentration

Generally poor % recovery

observed without ID

With Isotope Dilution:

1,4-dioxane-d8, internal standard role

spiked into the sample

before / at the time of extraction

Acceptable performance for low level analysis

ID accounts for extraction efficiency,

normalizes result

High VOC concentrations do not interfere

As a SVOC… Method 522

Solid phase extraction (SPE)

GC/MS SIM

Acceptable performance for low level analysis

Most sensitive method

High VOC concentrations do not interfere

Drinking water method

Other matrices, applicability to GW,

turbidity, silty samples, etc.

Sample preservation requirements

2016 Alpha Method Comparison StudyHDC SETAC

Methods 8260 SIM, heated* purge &

trap

8270 SIM ID, L / L extraction

522 SIM, SPE

Two spike concentrations 0.25 & 3.0 ug/L

Seven replicates each

Sampling for 1,4-Dioxane – March 2017

“From this point forward, groundwater monitoring performed during remedial investigations at State Superfund (SSF) sites must include analysis for 1,4-dioxane. “

“The detection limit for 1,4-dioxane should be no higher than 0.28 µg/l (ppb). The only analytical method that ELAP offers certification for is USEPA method 8260C. In order to get the detection limits we need, the lab would need to use the mass spectrometer in “selective ion monitoring” (SIM) mode. “

UPDATE - October 2017

“ELAP is now offering certification for 1,4-dioxane for 8270, specifically including the ability to run in SIM mode. 8270 provides a more robust extraction procedure, uses a larger sample volume, and is less vulnerable to interference from chlorinated solvents, while 8260 has been shown to have a higher recovery in some studies. 8270 should generally provide lower detection limits, and we expect this to be the preferred analytical method from this point forward, but we can accept analysis by 8260 when justified”

Also offers DW certification by Method 522

Exploding: Per- and Polyfluoroalkyl Substances (PFASs)

Per- and polyfluoroalkyl substances represent a group of chemical (believed to be in the thousands) of anthropogenic or synthetic fluorinated organic compoundss referred to as PFASs

Perfluoroalkyl carboxylic acids (PFCAs), including perfluorooctanoic acid (PFOA)

Perfluoroalkane sulfonates (PFSAs), including perfluorooctane sulfonic acid (PFOS)

Per-fluorinated “long-chain” PFAS chemicals are

Very stable - carbon bonds shielded by fluorine

Persistent and resistant to degradation

Bioaccumulative in wildlife and humans

There has been a general shift from use of long-chain PFASs to short-chain PFASs

Polyfluorinated compounds - partially fluorinated alkyl chain

Per- and Polyfluorinated CompoundsWhat are they?

PFAS are used in many manufacturing and industrial applications because they imparted useful properties, including fire resistance and oil, stain, grease and water repellency:

cleaners, textiles, leather, paper and paints, wire insulation, and treated carpets

Fire-fighting foams for fuel fires

Sites commonly associated with PFAS: use/storage of fire-fighting foams, aviation, plating/semi-conductor industry, landfills, fluoropolymer production, WWTP

Sources of PFAS

PFAS – The New Frontier

Parts per million (ppm, equivalent to mg/L)

0.000001, 10-6 or

1.25 2-Liter bottles in 1 Olympic-size swimming pool

Parts per billion (ppb, equivalent to µg/L)

0.000000001, 10-9, or

½ tsp in Olympic-size swimming pool

Parts per trillion (ppt, equivalent to ng/L)

0.00000000001, 10-12 or

1 drop of water (0.05 milliliters) in 2 Olympic-size swimming pools

Exposure pathways:

Food (expected to be primary, except where water exposure occurs)

Water

Secondary pathways (air, indoor dust, consumer products)

Under USEPA’s Guidelines for Carcinogen Risk Assessment (USEPA 2005a), there is “suggestive evidence of carcinogenic potential”

May 25, 2016 – USEPA Published a Lifetime Health Advisory of 0.07 parts per billion (70 parts per trillion) for individual or combined concentrations of PFOA and/or PFOS (Federal Register / Vol. 81, No. 101)

States beginning to regulate more than just PFOA and PFOS (e.g., NJ –PFNA; CT and MA – five; TX - protective concentration levels for 16)

UCMR3 data released in July 2016 indicated approximately 2% (95 of 4909) of the large municipal water supplies across the US have detectable conentrations of PFOS (between 2013 and 2015). 1% (123 of 4909) have PFOS above 70 ppt)

PFAS – Risk and Occurrence

PFAS Standards/Guidance Values

State/Fed. Agency Drinking Water Ground Water

USEPA No MCL (70 ng/L IRIS -PFOA, PFOS, combo)

No MCL (70 ng/L IRIS -PFOA, PFOS, combo)

New Hampshire 70 ng/L (AGQS - PFOA,PFOS, combo)

70 ng/L (AGQS- PFOA,PFOS, combo)

Connecticut 70 ng/L (DWAL sum of five PFAS)

70 ng/L (GWPC sum of five PFAS)

New Jersey NA 14 ng/L (Screening Level PFOA)

Maine 70 ng/L (MEG) 70 ng/L (MEG)

New York NA NA

Vermont 20 ng/L (VT HAL) 20 ng/L (VT HAL)

PFAS – Regulatory Status

Proposed MCLs of 14 ng/L for PFOA and 13 ng/L for PFNA.

PFAS – In the New York News

March 3, 2017 – addition of PFOA and PFOS to the hazardous substance list

April 25, 2017 – prohibits use of fire fighting foams that contain PFOA or PFOS

April 25, 2018 – existing facilities will be required to comply with handling and storage requirement by this date

Understand site history, and surrounding property use

Determine target analyte list

Establish sampling SOP: communicate prohibited materials/practices to field staff

Teflon containing materials (Teflon tubing, waterproof notebooks, blue ice packs)

Clothing or PPE treated with PFAS (Gore-Tex, Tyvek, fabric softener)

No cosmetics, moisturizers, hand cream or other related products as part of a morning cleaning/shower routine.

No containers with LDPE or glass (sorption), no Teflon-lined caps

No food or drink packaging

Because of anthropogenic background, QA samples are essential

trip blanks

field blanks

rinsate blanks

Background samples are important

PFAS – Investigation Challenges

Ex Situ Technologies

Carbon Sorption**inefficient

Emerging technologies:

Reverse Osmosis

Membrane filtration

AOP

In Situ Technologies

Emerging technology:

Carbon injection

PRB

Chemical Oxidation

Low Volatility (rules out stripping)

Moderate solubility

Strength of C-F Bond

Treatment efficiency must be very high because of low (ppt) remediation objectives

Fate and Transport/ Remediation Challenges

PFAS – Remediation Challenges

Remediation Technology Takeaways

While there are certainly remediation challenges, similar comments were made for chlorinated solvents 20 years

ago and the science of 1,4-dioxane and PFAS is constantly evolving

Requires Innovative Remedial Strategies

PFAS Analytical Methodologies

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MOVING TARGET

– Analytical methodologies– What methods, are they

applicable?

– Reference standard availability?

– Regulatory requirements– Requested target compound lists

– Compliance guidelines, required reporting limits

– What’s next?

PFAS Analysis

Primary methodology

Method 537 rev1.1 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), aqueous samples

Analytical Instrumentation

Liquid chromatography / tandem mass spectrometry (LC/MS/MS)

815-B-16-021, September 2016

PFAS can exist as linear & branched isomers

Method 537 addresses both for PFOS (2009)

Standards not available at the time for PFOA

Discrepancies in PFOA reporting Addressed in Tech Advisory

Modified Method 537

Method 537

“as specifically written”

Is not amenable to expanded list of compounds or other sample matrices without modification

Other methodologies

“Laboratory proprietary method” LC/MS/MS

May use different or multiple SPE cartridges

May use isotope dilution approach

Different sample preservation / handling potentially

3 New EPA SW-846 Methods Proposed

(1) LC/MS/MS direct injection AQ method

10 ng/L reporting limit, screening or determinative

(2) LC/MS/MS isotope dilution AQ method

(3) LC/MS/MS soil method

Will employ an extraction & potentially direct injection

Other Methodologies

ASTM

ISO

TOP Assay

PIGE

Time-of-flight high resolution mass spectrometry (qTOF-MS)

Acids or Anions – Laboratory Implications

Terms interchangeable in literature, regulatory guidance & media

(PFOA) perfluorooctanoic acid (ACID form)

(PFOS) perfluorooctane sulfonate (ANION form)

Dissolved in water, PFAS exists in anionic form

MS only detects/measures the anion

Lab reporting acid or anion?

Different compounds, different CAS#’s

EPA Method 537.1 specifies reporting the acid form

Form of lab calibration standard?

If prepared with salts, concentration must be adjusted to account for difference in mass acid vs. salt

New York - March 2017

SSF sites must include analysis for PFAS

Drinking water

6 UCMR compounds

Other matrices

Refers to “modified Method 537”

“the lab should be directed to report all per- and polyfluoroalkyl substances that they have standards for”

“more specific list will likely be developed within the coming year”

New York - October 2017

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October 2017

For GW, SW, soils, & sediments lab should be directed to report all calibrated PFAS cmpds.

Reported cmpds will include at a minimum (current Oct 2017)

ELAP offers DW cert for PFOA / PFOS. No certification for other matrices but lab should hold PFAS DW cert. "modified" method 537 or ISO 25101

Expected PFOA / PFOS RL 2 ng/L AQ, 3 ug/Kg soil

Questions and Comments

Nikki Roy, P.G., Senior Geologist603-668-0880nikki_roy@golder.com

Jim Occhialini(508) 380-8618jocchialini@alphalab.com