obg presents: emerging contaminants illinois …agenda paul hare, obg emerging contaminants...
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OBG PRESENTS:
Emerging ContaminantsIllinois Chamber of Commerce, Environmental Affairs CommitteeNovember 8, 2018
AGENDAPaul Hare, OBG
Emerging Contaminants
1,4‐Dioxane
Per‐ and Polyfluoroalkyl Substances
Hoosick Falls, NY and its Aftermath
Rick Cobb, Illinois EPA
Illinois Activities/Perspective
Discussion / Questions
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EMERGING CONTAMINANTS
Common Characteristics of Emerging Contaminants
Also known as Contaminants of Emerging Concern (CECs)
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In the news
Often with another contaminant, in a commercial product, or as a breakdown product
Not on typical analyte lists
Limited science on health/ecological effects
No enforceable standards
Widespread occurrence
Limited info on treatment technologies
Common trajectory
wwaytv3.com
Emerging Contaminants
1,4‐Dioxane and PFOA/PFOS are significant drinking water issues
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1,4‐Dioxane (14Dx)
PFAAs (PFOA/PFOS)
Plastic Microbeads
NanoparticlesMTBE
Endocrine Disrupting Chemicals (EDCs)
Pharmaceuticals and Personal Care Products (PPCPs) PBDEs (PBBs, PBDDs,
PBDFs, HBCDs)
EDB
UCMR3 sampling of PWSs in 2013‐201514Dx detected >0.35 ppb in 6.9% of PWSs
PFOS and PFOA detected >70 ppt in 0.9% and 0.3% of PWSs
1,2,3‐TCP
Regulation of New Constituents
Required by 1996 SDWA amendments –every 5 years
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Unregulated Contaminant Monitoring Rules (UCMRs)
Requires sampling/analysis of finished water at large PWSs and randomly selected smaller PWSs
Data used to determine the need for and prioritize regulation
Contaminant Candidate List (CCL)List of contaminants not currently regulated
Known or anticipated to occur in public water systems (PWSs)
Used to identify compounds for future UCMRs
Unregulated Contaminant Monitoring Rules (UCMRs)
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#1
#3
#2
UCMR1
September 1999• Required monitoring for 26 contaminants 2001‐2003• Included MTBE and perchlorate
UCMR2
January 2007• Required monitoring for 25 contaminants 2008‐2010• Included five brominated flame retardants (BFRs)
UCMR3
May 2012• Required monitoring for 30 contaminants 2013‐2015• Included 14Dx, PFOA, PFOS, and four other PFAAs
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1,4‐DIOXANEThe forgotten emerging contaminant?
14Dx is most commonly Associated with 1,1,1‐TCA
Also consider its degradation products, 1,1‐DCE and 1,1‐DCA
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Historically, 90% of U.S. production used as stabilizer in chlorinated solvents, mainly 1,1,1‐TCA• 2‐8% typical in 1,1,1‐TCA• Can be higher in spent solvents
Source: USEPA Fact Sheet on 1,4‐Dioxane, 2014
Sources of 14Dx
In many other things besides 1,1,1‐TCA
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Source: USEPA Fact Sheet on 1,4‐Dioxane, 2014
Products:
• Paint strippers• Dyes• Greases• Varnishes• Waxes
Impurity:• Antifreeze• Aircraft de‐icing fluids
Food production:• Food supplements• Food containing residues from packaging adhesives• Food crops treated with pesticides
Solvent/Wetting Agent:
• Solvent for impregnating cellulose acetate membrane filters
• Wetting and dispersing agent in textile production
Manufacturing:• Purifying agent in pharmaceutical manufacturing• By‐product of PET plastic manufacturing
Sources of 14Dx
Also direct users of 14Dx
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“in many products, including paint strippers, dyes, greases, varnishes and waxes”
“also found as an impurity in antifreeze and aircraft deicing fluids”
“as a solvent for impregnating cellulose acetate membrane filters; a wetting and dispersing agent in textile processes; and a laboratory cryoscopic solvent for molecular mass determinations”
“as a purifying agent in the manufacture of pharmaceuticals and is a by‐product in the manufacture of polyethylene terephthalate (PET) plastic”
“in some food supplements, food containing residues from packaging adhesives or on food crops treated with pesticides that contain 1,4‐dioxane as a solvent or inert ingredient”
Source: USEPA Fact Sheet on 1,4‐Dioxane, 2014
14Dx can also be in products used during investigations
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Source: USEPA Practice Area Technical Brief, May 7, 2014
USEPA found 14Dx in:
Commercially‐available detergents (including Alconox)
Nitrile gloves
FLUTe well materials
USEPA concluded:
“Use of these products could potentially result in 1,4‐dioxane detections that are not associated with the site media being sampled.”
Choice of decon solution (e.g., Seventh Generation Free & Clear) and use of field/equipment blanks are very important
14Dx Properties
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Miscible in water Hydrophilic
Leaches readily from soil to groundwater
Can migrate more rapidly and farther in groundwater
Low volatility Low sorption
Difficult to extract from groundwater
Typically not a VI concern
Single‐bonded cyclical ether
Requires high energy to oxidize chemical
bonds (>2eV)
But can be treated in situC4H8O2
1,4‐Dioxane is flammable, including >2% in aqueous solution
14Dx Plumes
Statistically, less likely to be longer than associated chlorinated solvent plume
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Source: Adamson et al., 2014, 2015 n = 105 sites with co‐occurrence
14Dx longer = 21%
14Dx same = 23%
14Dx shorter = 56%
DioxaneChlorinated Solvent
Dioxane and Chlorinated Solvent
Chlorinated SolventDioxane
14Dx Analyses
Difference in method detection limits is key to method selection
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• 0.35 ppb – the lowest of USEPA’s health‐based reference values
Class B probable human carcinogen
• Method 522 (drinking water)• Method 8260• Method 8260 SIM• Method 8270• Method 8270 SIM
USEPA analytical methods
• Microbiological• Compound‐specific stable isotopes
Specialty analytical methods
Federal Drinking Water Benchmarks for 14Dx
Significant decreases over past 10 years
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USEPA risk assessments (1x10‐6 ELCR) (USEPA, IRIS, 2013)
0.67 μg/L USEPA tap water screening level (1x10‐6 ELCR) (USEPA, 2013)
0.35 μg/L
USEPA regional screening level (RSL)0.46 μg/L
6.1 μg/L USEPA risk‐based goal for tap water (USEPA, 2006)
Example of declining State benchmarks for 14Dx
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NJ interim specific groundwater quality criterion (Feb 2008)3.0 μg/L
NJ interim specific groundwater quality criterion (Nov 2015)0.40 μg/L
Some states have even lower media‐specific values fro 14Dx
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Vermont health advisory
Massachusetts drinking water limit
New Hampshire public water supply reporting limit
0.30 μg/L
0.30 μg/L
0.25 μg/L
Vapor intrusion can be a concern for 14Dx
VI risk increases at higher temperatures (e.g., Caribbean)
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USEPA regional screening level (RSL) for residential air0.56 μg/m3
Groundwater screening level (USEPA, VISL @ default 25oC)2,855 μg/L
Sub‐slab soil gas screening level (USEPA, default α=0.03)18.7 μg/m3
In 2016, Michigan set a VI screening level of 29 ppb for 14Dx in groundwater!
14Dx has a low ecotoxicity
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No formal U.S. ecological / aquatic life standards in sediment or surface water
Low Kow (octanol‐water partition coefficient), not expected to bioaccumulate
Ontario MOE has an interim Provincial Water Quality Guideline of 58 mg/L based on toxicity tests with fathead minnows
LC50 values for various aquatic organisms are elevated, 1000s mg/L
EcoSAR modeling results for several aquatic receptors shows 14Dx not a significant risk at typical environmental concentrations
Low toxicity of 14Dx in aquatic environment
Ex Situ Treatment Technologiesfor 14Dx
Advanced Oxidation Processes (AOPs)UV+H2O2 UV+O3 H2O2+O3 UV+TiO2
Synthetic MediaIon exchange resins work; on‐site regeneration needed to compete
Granular Activated Carbon (GAC)Performance very site specific; off‐site regeneration or disposal
Aerobic BioreactorsWorthy of mention, but not simple; maybe as part of treatment train
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Discharge limits generally about 10x the State’s criteria for drinking water and/or groundwater
In Situ Treatment Approaches for 14Dx
Alternatives to pump‐and‐treat
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Monitored natural
attenuation
Enhanced in situaerobic
bioremediationMetabolic and co‐
metabolic
In situchemical oxidation
In situthermal
Boiling point <100oC in aqueous solution
PhytoremediationShort half life in
atmosphere (days)
Extreme SVE
UCMR3 Occurrence Data for Illinois:
1,4‐Dioxane
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▪ 253 public water supplies▪ 87.7% large
▪ 66.4% surface water
▪ 407 locations
▪ 1266 samples
▪ 51 samples >0.35 ppb▪ 22 surface water (max 2.08 ppb, mean 0.41 ppb)
▪ 29 groundwater (max 22.9 ppb, mean 0.69 ppb)
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PER‐ AND POLYFLUOROALKYL SUBSTANCES (PFAS)Most often associated with Class B fire fighting foams, stain/water/oil resistant products, PTFE, fume suppressants
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Per‐ and Polyfluoroalkyl Substances (PFAS)
Consumer Product Uses
Non‐stick coatings
Textile treatment for water/stain/oil repellency
Anti‐fogging / anti‐static treatments
Paints / adhesives
Fluoroelastomers
Personal care products
Sporting equipment
What are PFAS?
Large “class” of compounds (1000s)
Used for many years
Wide range of consumer products
Concerns with PFAS?
Persistent in the environment
Bioaccumulative (but in proteins, not lipids)
Mounting evidence of health concerns at environmental concentrations
Perfluoroalkyl Acids (PFAAs) – The Current Focus
PFSAsPerfluorosulfonic acids
Long chain ≥ PFHxS (6 carbons)Includes PFOS
PFCAsPerfluorocarboxylic acids
Long chain ≥ PFOA (8 carbons)
C1 MethaneC2 EthaneC3 PropaneC4 ButaneC5 PentaneC6 HexaneC7 HeptaneC8 OctaneC9 NonaneC10 DecaneC11 UnodecaneC12 DodecaneC13 TridecaneC14 Tetradecane
Long‐chain PFAAs more toxic and bioaccumulative
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Replacements of increasing concern (e.g., GenX)
Sources of PFOA and PFOS are very widespread
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Class B Firefighting
Foams(e.g., AFFF)
Fume Suppressants
(e.g., Cr plating)
Landfills, Landfill Leachate, POTWs,
Biosolids
Water/Oil/Stain Resistant Textiles and Clothing
Food Packaging
Industrial Coatings, Etchings
(e.g., insulated wire)
In some sampling equipment, PPE, clothing, and personal care products – special field
precautions warranted at ppt reporting limits
Time frames are important for PFAS
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1947/1949 – 3M begins making PFOA/PFOS‐based compounds1951 – DuPont begins purchasing PFOA for PTFE production1954 – First reference to PFAS for fume suppression (Cr plating)1956 – Sales of Scotchgard begin (PFOS a key ingredient)1958 – W.L. Gore formed; insulated wire/cable products1963 – Patent application for AFFF (fire fighting foam)1969 – Navy issues MilSpec for AFFF1970 – Air Force adopts AFFF1990 – CAA requires regulation of Cr emissions1995 – USEPA regs for Cr plating, promote fume suppressants2000 – 3M announces phase‐out of PFOS2002 – DuPont begins PFOA production due to 3M phase‐out2006 – USEPA establishes PFOA Stewardship Program
USEPA’s PFOA Stewardship Program
Goals achieved, but drove usage to shorter‐chain PFAAs and replacements (e.g., GenX)
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2006
Eight companies join USEPA’s stewardship programArkemaAsahiBASF/CibaClariantDaikin3M/DyneonDuPontSolvay Solexis
2010 Goal
95% reduction of PFOA (from 2000 baseline)
2015 Goal
Elimination of PFOA from emissions and products
Ambient concentrations of PFOA and PFOS in the U.S. are on the decline
Are the replacement compounds next?
Fluorinated Class B Fire Fighting Foams
Stored on‐site or brought on‐site by emergency responders
Aqueous film‐forming foam (AFFF)Patent application in 1963; first Military Specification in 1969
Alcohol resistant aqueous film‐forming foam (AR‐AFFF)For use with polar solvents as well as petroleum products
Film‐forming fluoroprotein foam (FFFP)
Fluoroprotein foams (FP, FPAR)
Alcohol resistant film‐forming fluoroprotein foam (AR‐FFFP)
Where have these products been stored and used for training and/or emergency response? Are these products still in inventory/use?
Properties of PFOA and PFOS
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Highly Soluble in Water
Migrates rapidly in
groundwater
Forms long, dilute plumes
Low Volatility
Difficult to extract from groundwater
Not a VI concern
Extremely Stable
Compounds
Resistant to degradation
Persistent
Bioaccumulates
Half lives in human serum – 3 to 5 years
Laboratory Analysis of PFAS
Method 537 is “modified” if used for other matrices, other PFAS and lower reporting limits
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USEPA Method 537
Promulgated for drinking water in advance of UCMR3
LC followed by tandem MS (LC/MS/MS)
14 compounds, including 6 UCMR3 PFAAs
Modified by labs for other PFASs, other media, and lower reporting limits
Reporting limits about 2 ppt for most PFAAs (as modified)
Typically $200 to $300 per sample with standard turnaround time
Diagnostic Use of Analytical Data
PFAA mixtures vary by manufacturer, date, application …
PTFE used for coated fabrics/textiles
Fume suppressant used for chrome plating
PFOA
PFOS
PFCAs │ PFSAs PFCAs │ PFSAs
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The Dark Pool (Precursors)
Precursors can transform to PFAAs
▪ PFAS include 1000s compounds
▪ Some polyfluorinated compounds break down into the perfluorinated compounds of interest – these are “precursors”
▪ Example:
▪ Concentrations of precursors can be significant (e.g., in most AFFF)
▪ Many/most precursors are not typically quantified
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Is something else present that can degrade to PFAAs?
Federal Regulatory Framework
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▪ No enforceable standards
▪ Certain PFAAs on CCL since 1999
▪ USEPA Method 537 promulgated in 2009
▪ Provisional health advisories issued in 2009o 200 ppt for PFOS, 400 ppt for PFOA
▪ Six PFAAs included in UCMR3 – monitoring 2013‐2015
▪ Lifetime health advisories issued May 2016o 70 ppt PFOS and PFOA (individually and combined)
▪ Recent ATSDR report suggests lower
Federal Regulatory Framework (cont’d)
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▪ USEPA Region IV residential soil guidance (2009)o 16 ppm PFOA, 6 ppm PFOS
o Based on provisional health advisories
o Did not consider protection of groundwater
▪ USEPA Region II project‐specific action limit (2016)o 1 ppm PFOS and PFOA (individually and combined) in soil
o Based on new lifetime health advisories
o Does not consider protection of groundwater
State Regulatory Framework
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▪ Considerable variability, from none to much more than USEPA
▪ Some states adopting USEPA’s lifetime health advisories (e.g., NH, NY, MI)
▪ Some have more stringent criteria for PFOA / PFOS:o MN – 35 ppt for PFOA and 27 ppt for PFOS for drinking water
o NJ – 40 ppt (14 ppt pending) for PFOA for drinking water; 13 ppt pending for PFOS in drinking water
▪ Some have criteria for other PFAAs:o NJ – 20 ppt for PFNA for drinking water (13 ppt pending)
o MN – 7,000 ppt for PFBA and 2,000 ppt for PFBS in drinking water
State Regulatory Framework (cont’d)
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▪ Some states have criteria for other media:o TX – 0.6 ppm for PFOA and 0.3 ppm for PFOS in residential soil
o MN – 2 ppm for PFOA and PFOS for residential soil
▪ Fish advisories established in several stateso PFOS bigger issue than PFOA
o AL, MI, WI have advisories for PFOS
o “Eat None” threshold generally in the 100s ppm
Wisconsin
No restriction < 38 ppm
1 meal/week 38‐160 ppm
1 meal/month >160‐700 ppm
Do Not Eat >700 ppm
Remedial Elements and Approaches for PFAAs
Options currently limited, but lots of research underway
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Monitored natural
attenuation
Institutional controls (including point‐of‐entry treatment systems)
Groundwater pump‐and‐treatPresumptive remedy
Groundwater immobilization
e.g., PlumeStop
Soil stabilizatione.g., RemBind,
matCARE
Soil excavationfor treatment /
disposal
Ex Situ Treatment Technologiesfor PFAAs in Water
Reverse Osmosis (RO) / NanofiltrationWorks well on different chain lengths, but expensive and requires management of significant amount of high‐concentration residual
Granular Activated Carbon (GAC)Presumptive treatment method for drinking water and groundwater; GAC selection and background/other constituents critical; faster breakthrough of shorter chain lengths
Synthetic MediaIon exchange more expensive than GAC; works equally well on shorter chain lengths; may require on‐site regeneration to compete with GAC
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Ex Situ Technologiesfor Concentration or Treatment of High‐Strength Residuals
PerfluorAdConcentration technique; may be stand‐alone treatment if discharge limits are generous
SonolysisPotential high‐energy, on‐site destruction for concentrated residuals
PlasmaPotential high‐energy, on‐site destruction for concentrated residuals
IncinerationOff‐site thermal destruction (but on‐site also possible)
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UCMR3 Occurrence Data for Illinois
Six PFAAs:PFHpA, PFOA, PFNA, PFBS, PFHxS, PFOS
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▪ 253 public water supplies▪ 87.7% large; 66.4% surface water
▪ 1266 samples at 407 locations
▪ No PFHpA, PFNA or PFBS
▪ One PFHxS (31.7 ppt)
▪ One PFOS (180 ppt)
▪ Three PFOA (23.4, 40 and 59 ppt)
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THE NEW YORK EXPERIENCEIt Started With the Village of Hoosick Falls
villageofhoosickfalls.com
The Story of Hoosick Falls
New York’s Flint?
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news10.com
Little village 30 miles east of Albany
3,500 residents
Not included in UCMR3 (testing 2013‐2015)
Discovery of PFOA in water attributed to Michael Hickey
Father died of cancer in late 2013
Internet search in March 2014
Soon thereafter, collected water samples for analysis
PFOA above 400 ppt, the provisional HA set by USEPA in 2009
Village informed in August 2014; sampled its supply wells in October
Confirmed up to 540 ppt
Subsequent testing showed up to 1,010 ppt
Hoosick Falls:
Addressing the Drinking Water Problem
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More than 2 years from initial discovery to eliminating
bottled watertownofhoosick.orgNYSDOH
Bottled water provided as an interim measure
Large carbon treatment system designed, constructed, and commissioned
Surrounding Town of Hoosick not on PWS• Private wells are sampled• 100s of POET systems are installed (carbon, carbon, UV)
Hoosick Falls:
The Local Aftermath
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People have safe
drinking water now, but the story goes on…
NYSDOH
Erin Brockovich comes to village in January 2016
Class action lawsuit filed in February 2016
NYSDEC adds Saint‐Gobain’s McCaffrey Street facility to state Superfund list in February 2016
Site proposed for federal Superfund list in September 2016; added in July 2017
Assessments also commenced at other potential PFOA sources in the Village
news10.com
State‐wide Action:
Regulatory
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April 25, 2016 Proposed final rule
January 27, 2016 Emergency rulemaking begins
•Amended chemical bulk storage regs(6 NYCRR Part 597)
•Added PFOA/PFOS to list of hazardous substanceswith an RQ of 1 pound
•Impacted storage/use of fire fighting foams
•Enabled use of state Superfund to address problems (e.g., Hoosick Falls)
•Adoption effective April 25, 2016
March 3, 2017 Adoption of final rule
State‐wide Action:
Fire Fighting Foams
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Emergency and final rules included:• Foams with >1% PFOA/PFOS (by volume)• Stored in underground tanks, aboveground tanks (>185 gallons), containers
storing >2,200 pounds for >90 days• Reportable quantity of 1 pound for PFOA/PFOS
No use for training on/after April 25, 2016
No use for fire fighting on/after April 25, 2017
Compliance with handling/storage requirements by April 25, 2017
Replacement foams must not contain RQ of 1 pound when used
Prohibited foams should be safely/properly disposed after April 25, 2017
State‐wide Action:
Statutory
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April 26, 2017Governor signs Clean Water Infrastructure Act
Outgrowth of PFOA in
Hoosick Falls and 14Dx on Long Island
$2.5B funding for various activities related to
drinking water quality
Specific provisions for:
Gabreski Air National Guard Base (PFOS)
U.S. Navy / Northrop Grumman
Bethpage site (14Dx)
Requires all PWSs to test for ECs such as 14Dx, PFOA, and
PFOS
Establishes a Drinking Water Quality Council
State‐wide Action:
Other Activities 2016‐2017
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February 2016
Governor creates Water Quality Rapid Response Team (NYSDEC and NYSDOH)
State surveys >1750 fire departments, airports, and petroleum storage facilities
June 2016
NYSDEC sends information requests to >150 industrial facilities; 30 days to respond
NYSDEC begins asking some NPDES permittees to sample PFOA/PFOS as part of renewal process
April 2017
NYSDEC starts requiring PFAS/14Dx analyses for all remedial sampling programs
Summer / Fall 2017
NYSDEC begins to look at closed landfills
NYSDEC amends solid waste regs to require sampling of 14Dx and PFAS at operating landfills during permit renewals
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THOUGHTS, ISSUES, AND IMPACTS
General Thoughts
PFAS are not done emerging
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Advances in analytical capabilities are intersecting with scientific interest and public concern• With 1 ppt detection limits, have to worry about many things
As for many contaminants, the only good number is zero
If you look for PFAS at ppt levels, you are likely to find some
Even if PFOA/PFOS <70 ppt, you might not be done
Regulatory standards, advisories, and criteria are generally lacking for most PFAS and for most environmental media
Emerging contaminants seem to be emerging much faster now
NPDES
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Established ambient water quality standards?
Many questions when trying to apply well‐defined NPDES processes, and similar issues for other programs (e.g., solid waste)
Treatment capability using Best Available Technology (BAT)?
Statutory/regulatory authority to request information and/or require sampling/analyses?
Promulgated analytical method(s):• Under Clean Water Act?• For wastewater effluent?• Published method detection limit(s)?• Published practical quantitation limit(s)?
Emergency Response (Class B Fire Fighting Foams)
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Can existing foams be used for training?
What foams are in currently in inventory?
Can existing foams be used to fight actual fires?
Does the performance of replacement foams compare favorably to the older foams?
What is in the replacement foams?
Where have fluorinated foams been stored and used for training and/or emergency response?
Waste Disposal
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Will landfills stop taking some waste?
For ECs, more questions than answers in many arenas
Will more waste require treatment?
Will additional information be requested for waste profiles?
Will more waste have to be shipped out‐of‐state?
Will testing be required for waste profiles?• Using what approved analytical method(s)?• For what constituents?• With comparison to what thresholds?
Will POTWs stop accepting some wastewaters?
Other Considerations
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Insurance recovery
Allocation (or reallocation) of responsibility
Stakeholder relations (community, elected officials, media)
Constituents in products/processes (historic and current)• Regulators are requesting information and asking for sampling/analysis• How to require information from supply chain / vendors?
Litigation (cost recovery, tort)
Due diligence, property transactions and brownfields
