emerging contaminants / emerging treatment program
TRANSCRIPT
EMERGING CONTAMINANTS / EMERGING TREATMENT PROGRAMPOLY- & PERFLUOROALKYL SUBSTANCES (PFAS)- A U.S. PERSPECTIVE
MARK NIELSENRAMBOLL ENVIRONMENT AND HEALTHSeptember 2019
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• New awareness or understanding about how they move in the environment or affect public health, or
• Contaminants with known or potentially unacceptable risks to human health or the environment, and either:
• No regulatory standards, or
• Regulatory standards are evolving due to new science, detection capabilities, or pathways.
PFAS – A CLASS OF EMERGING CONTAMINANTS
PFAS have been identified as a significant class of emerging contaminant
o Growing public awareness
o Lack of approved analytical methods
o Exhibit complex fate and transport characteristics
o Uncertainties in human and ecological toxicology
o Limited remediation options
o Lack of federal and state regulatory response
IN THE U.S. PRESS, GROWING PUBLIC AWARENESS
DetectedNot detectedNo data
From Hu et. al. 2015. Detection of Poly- and Perfluoroalkyl Substances (PFASs) in U.S. Drinking Water Linked to Industrial Sites, Military Fire Training Areas, and Wastewater Treatment Plants. ES&T Letters. July.
LATEST PFAS NEWS, 17 SEPTEMBER 2019
MARKET DRIVERS
Public and Community Pressure
Political Pressure
Regulatory Drivers – Primarily State Driven
Property Transactions
Litigation and Cost Recovery
$160 billion in U.S. alone
Widespread Occurrence
OVERVIEW
Introduction to PFAS
Use and Development
PFAS in the Environment
Site Characterization
Exposure and Toxicity
Remediation
Regulatory Response
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POLY- & PERFLUOROALKYL SUBSTANCES (PFAS)
1 PFAS is the generic term for a large class of fluorinated chemicals
2 Used in a wide range of industrial applications, commercial products, and fire fighting foams
3 Unique because of their ability to repel oil, grease and water
4 Exceptionally stable, non-reactive chemicals, resistant to degradation and heat
5 Relatively mobile in the environment, moderately soluble
6 May be subject to long-range transport
F F F F F F
F F F F F F
F
FF
CC
CC
CC
CC
O
OH
PFOA – perfluorooctanoic acid
F F F F F F
F F F F F F
F
FF
CC
CC
CC
CC
SO3H
F F
PFOS – perfluorooctanesulfonic acid
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Estimated 3,000+ different commercially-produced compounds of varying lengths, functional groups, and degrees of saturation
DEVELOPMENT & USE TIMELINE
Source: ITRC 20188
PFAS USES IN INDUSTRIAL AND COMMERCIAL PRODUCTS
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Surfactants - Oil and Gas Recovery
Fire Suppression Systems
Landfills and Waste Disposal Areas
Chemicals and Pharmaceuticals
Chrome Electroplating
Semiconductors
Apparel Consumer Products
EXPOSURES IN THE HOME
Sources: Danish EPA: Survey of Chemical Substances in Consumer Products, No. 169, October 2018.USEPA: Perflourocarboxylic Acid Content in 116 Articles of Commerce;
https://cfpub.epa.gov/si/si_public_record_report.cfm?dirEntryId=206124
Group ID Article category TPFCA in article
Article quantityb
TPFCA in home (mg)
A Pre-treated carpetingc 48.4ng/cm2 150 m2 72.6
B Commercial carpet-care liquids 12000 ng/g 6 kgd 71.8
C Household carpet/fabric-care liquids and foams 953 ng/g 1 kg 0.95
D Treated apparel 198 ng/g 2 kg 0.40
E Treated home textile and upholstery 336 ng/g 5 kg 1.68
F Treated non-women medical garments 795 ng/g 0 kg 0
G Treated floor waxes and stone/tile/wood sealants 2430 ng/g 1 kg 2.42
H Treated food contact paper 3100 ng/g 0.01 kg 0.03
I Membranes for apparel 124 ng/g 1 kg 0.12
J Thread seal tapes and pastes 603 ng/g 0.02 kg 0.01
K Non-stick cookware 0.028 ng/cm2 1 m2 0.0003
L Dental floss and plaque removers 31.3 ng/g 0.005 kg 0.0002
M Miscellaneous 69.5 ng/g 0 0
aThe average, single-family home size in the US in 2004 was 2330 ft2 (http:www.nahb.org/). bThe quantities of articles are rough estimates. cAssuming 70% of floor area is carpet; conversation factors for total PFCA are given in supporting information. dFor one application; dilution factor is considered.
Substance Product types
PFHxA (C6) Household carpet/fabric-care liquids and foams
PFHpA (C7) Treated apparel
PFOA (C8) Treated home textile and upholstery
PFNA (C9) Treated non-women medical garments
PFDA (C10) Treated floor waxes and stone/tile/wood sealants
PFUnDA (C11) Treated food contact paper
PFDoDA (C12) Membranes for apparel
PFTrDA (C13) Thread seal tapes and pastes
PFTeDA (C14) Non-stick cookware
Primary Sources:PFAS producers
Secondary Sources:PFAS appliers/users:
• Textile/leather/carpet manufacturers• Chrome electroplating• Specialty coatings manufacturing and use• Others: electronics, wire coatings, surfactants,
paper, building materialsFirefighting training/use areas:
• DoD sites• Airports• Oil refineries• Emergency response sites – especially if near a
DoD installation!
Other Sources:• Landfills• Sludge application sites from municipal WWTPs• Others: Car washes, hydraulic oil
WHAT TYPES OF FACILITIES MAY BE IMPACTED?
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From Davis et al. 2007. Chemosphere 67: 2011-19.
WHERE TO LOOK - MOVEMENT IN THE ENVIRONMENTPRIMARY WIND DIRECTION AIR EMISSIONS
MANUFACTURING FACILITY
RIVER
WELL WELL
AQUEOUSDISCHARGE
LEAK/SPILL
GLOBAL OCEANIC AND ATMOSPHERIC TRANSPORT
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Map: From Hu et. al. 2015. Detection of Poly- and Perfluoroalkyl Substances (PFASs) in U.S. Drinking Water Linked to Industrial Sites, Military Fire Training Areas, and Wastewater Treatment Plants. ES&T Letters. July.
Pie Charts: from UCMR3 monitoring data. https://www.epa.gov/dwucmr/occurrence-data-unregulated-contaminant-monitoring-rule#4
PFAS IN THE ENVIRONMENT - U.S. DRINKING WATER CONCERNS
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2279, 95%
81, 63%
47, 37%
128, 5%
BREAKDOWN OF GROUNDWATER PFAS BY WATER SYSTEM
2298, 97%
47, 75%
16, 25%63, 3%
BREAKDOWN OF SURFACE WATER PFAS BY WATER SYSTEM
36379, 98%
400, 67%
199, 33%
599, 2%
TOTAL PFAS SAMPLES
Non Detect PFAS
Detect PFOA/PFAS < 70ppt
Detect PFOS/PFOA >= 70ppt
Environmental Working Group at Northeastern University:https://www.ewg.org/interactive-maps/2017_pfa/Power BI Database at Legacy OBG: https://app.powerbi.com/groups/me/dashboards/e0969635-442e-4246-9239-a9bb23c91e2c?redirectedFromSignup=1
PFAS IN THE ENVIRONMENT– IDENTIFICATION OF SITES IN U.S.
From: Environmental Working Group (EWG)
712 Identified sites in 49 States
Identify sources of PFAS?• Influent/effluent requested (one sample)• Drinking water quality in area• Upstream industrial sources• Landfill leachate• Soil (storm water to treatment plant)Where to sample?• On-site (influent, effluent, and biosolids)• Off-site (at sources)How to analyze?• USEPA method specified for drinking water
(Method 537)• No standard USEPA method for analyzing PFAS
in other media
Challenges• Potential for multiple release
mechanisms
• Atmospheric deposition of PFAS can occur tens of miles away from the release location
• Potential for Cross-Contamination• PPE• Field Equipment• Sunscreens, insect repellants• Water sources
• Several thousands of potential PFAS compounds and precursors - analytical methods being developed/validated
INVESTIGATION CONSIDERATIONS
• Releases may involve complex PFAS mixtures – not just a single compound
• Atmospheric deposition of PFAS can occur tens of miles away from the release location
• Plumes can be very large and diluted, some over 1 mile in length
• PFAS and precursors may be transformed in the environment
INVESTIGATION CHALLENGES
EXPOSURE ASSESSMENT CHALLENGESHow to assess?
• Body burden from multiple sources vs. (e.g.) a drinking water exposure
• Additive effects of multi-component exposures
• Differences in adult/child and male/female dose-responses
Source: From: F. Oliaei et al., 2013, Environ Sci Pollut Res 20:1977–1992
Human exposure
Soil/farm land
Fruits, vegetables and crops
Animal
Fire fighting practice and fires
PFC firefighting foam
PFOS treated food packaging
PFC treated material
Landfill
Effluent
WWTPDrinkingwater
Surface water
Ground water
PFC producing/using factory
Fish
Wastes
Dust/fibre
Leachate Sludge
Waste
Air
Air
ASSOCIATED HEALTH EFFECTS
Humans
• Mainly present in the liver, blood, and kidneys• Binds to proteins with fatty acid or hormone substrates such as serum albumin, liver
fatty acid-binding protein• Does not readily accumulate in fat tissue• Apparent linkages to
• Kidney disease
• Kidney and testicular cancers
• Diabetes
• Thyroid hormone suppression
Animal studies
• Reduced birth size, physical developmental delays, endocrine disruption, and neonatal mortality
• Altered lipid metabolism
• Elevated cholesterol and uric acid
• Decreased fertility (women)
• Decreased birth weight
Current state of practice relies on separation technologies
Research funding being spent on finding a destruction technology
Off-site disposal or off-site destruction (energy and economically intensive)
Goal: Find a technology that actually breaks the carbon-fluorine bond and destroys the PFAS molecule
ADDRESSING ENVIRONMENTAL IMPACTS- TREATMENT TECHNOLOGIES CURRENTLY LIMITED
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U.S. DoD ACTIVE RESEARCH TOPICS- 26 DIFFERENT TECHNOLOGIES
• Activated persulfate• Advanced oxidation/reduction + membrane
concentration• Cationic hydrophobic adsorbents• Chem ox + bioremediation• Combined photo/electrochemical reduction• Composite material: AC & photocatalyst• Electrically assisted sorption/desorption• Electrochemical membrane system• Electrochemical oxidation• Electrocoagulation + electrooxidation• Electron beam• Hydrated electrons• Hydrothermal technology
• Infrared thermal• Ion exchange with regeneration• Modified SiC-based photocatalysts• Molecularly engineered coatings• Novel adsorbent & ultrasound• Plasma based process• Polymer adsorbents• Protein-based adsorbents• Reactive barrier wall + bio• Regenerable resin sorbents• Smoldering• Thermal decomposition• Thermal desorption + thermal oxidation
REGULATORY RESPONSE- FEDERAL RESPONSE
• 2000: PFOS production was voluntarily phased out by product manufacturer
• 2006: PFOA production/import phased out in US as part of the PFOA Stewardship Program
• Goal: Reduce by 95% by 2010 and eliminate production and import by 2015, achieved 100% compliance
• May 2016: USEPA promulgated PFOA and PFOS lifetime drinking water health advisory values
• HA limits: 70 ng/L (individual and combined)
• May 2018: National Leadership Summit
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• February 2019: PFAS Action Plan released
• Propose a reg determination for PFOA and PFOS (i.e., a MCL) by end of 2019
• Begin process for listing PFOA and PFOS as CERCLA hazardous substances
• Develop interim groundwater cleanup levels for PFOA and PFOS
• Finalize draft tox assessments for several PFAS
• Issue additional significant use rules for PFAS under TSCA
• Add PFAS to TRI
• April 2019: CDC announces PFAS health study
• Excludes cancer from evaluation
REGULATORY RESPONSE- 2006 EPA PFOA STEWARDSHIP PROGRAM
• The last time PFOS manufacture was reported to EPA was 2002
• The manufacture and import of PFOA has also been phased out in US as part of the PFOA Stewardship program.
• Commit to achieve a 95 percent reduction in emissions and product content no later than 2010
• PFOA
• Precursor chemicals
• Related higher homologues
• Eliminate by 2015
2014 EPA Progress Report – US Operations(all 8 manufacturers reporting)
• %Reduction, PFOA Emissions: >91%
• %Reduction, PFOA Product Content: >94%
0
5
10
15
20
25
30
35GEOMETIC MEAN SERUM CONC
(UG/L)
NHANES SURVEY YEARS
PFAS LEVELS IN THE US POPULATION OVER TIME
PFOS
PFOA
REGULATORY RESPONSE - US PFOA DRINKING WATER ADVISORY TREND
* Values are proposed standards
70 ppt - Equivalent to 70 drops of water in an Olympic swimming pool
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25
REGULATORY RESPONSE - EPA AND STATE DRINKING WATER VALUES
70
667
70
35
20
14 14
9
70
667
70
15
20
13 138
0
10
20
30
40
50
60
70
80
90
DW
Val
ue
(ng
/L)
PFOA PFOS
COMPARISON OF PFOA GUIDELINES
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USEPA Drinking Water Health Advisory NJ MCL (Proposed) Vermont
Screening Value 70 ng/L 14 ng/L 20 ng/L
Oral RfD (mg/kg-day) 2E-05 2E-06 2E-05
Test species Mouse Mouse Mouse
Test endpoints Developmental Organ weight changes Developmental
Critical Effect Reduced ossification, accelerated puberty
Increased liver weight Reduced ossification, accelerated puberty
RfD derivation LOAEL/Avg Serum Level/Humanequivalent dose/UF
Benchmark dose modeling, Target Human Serum Level,
Clearance Factor
LOAEL/Avg Serum Level/Human equivalent
dose/UF
Uncertainty Factors 300 (10 Intra-species, 3 inter-species, 10 LOAEL to NOAEL)
300 (10 Intra-species, 3 inter-species, 10 more sensitive
effects)
300 (10 Intra-species, 3 inter-species, 10 LOAEL to NOAEL)
Population to protect Developing fetus, breastfed infants
Infants Developing fetus, breastfed infants
Water Ingestion Rate 0.054 L/kg/day(lactating women)
0.029 L/kg/day (standard adult)
0.175 L/kg/day (infants <1 year old)
Relative Source Contribution 0.2 0.2 0.2
Studies Lau et al. 2006 Lau et al 2006, Loveless et 2006, Macon et al 2011, Perkins
et al 2004
Lau et al. 2006
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REGULATORY RESPONSE - STATE INQUIRIES TO POTENTIAL PFAS SITES
95 Wastewater Treatment Plans with Industrial Pretreatment Programs
1. Screen industrial users for PFAS.
2. Sample users and effluent for PFAS.
3. Control/reduce discharges to treatment plant.
4. On-going performance monitoring.
PROJECTED NEED FOR PFAS REMEDIATION
• EBJ survey: 70% “Strong” to “Very Strong” demand for PFAS remediation work in the next two to three years
Contaminant Very
Strong Strong Good Flat Decline PFAS 32% 39% 25% 4% 0%Other Emerging Contaminants 11% 29% 46% 14% 0%1,4-Dioxane 7% 30% 41% 22% 0%Hydrocarbons 10% 20% 37% 30% 3%Heavy Metals 7% 17% 41% 34% 0%PCBs 4% 4% 41% 48% 4%Nuclear Waste 4% 0% 30% 67% 0%Asbestos 0% 15% 11% 59% 15%Medical Waste 0% 4% 15% 81% 0%
U.S. REMEDIATION ESTIMATE FOR PFAS
Site Category Estimated number of impacted sites
Total remediation or upgrade costs
($$M)Wastewater POTWs 2,525 $59,630Manufacturing Sites Using PFAS 875 $26,250Water Utilities 8,100 $21,000DoD/DoE 2,840 $17,560Airports* 1,675 $15,450Landfills 4,895 $4,540State Sites 8,400 $4,200Other Manufacturing Sites 6,750 $3,375NPL: Superfund 460 $2,310RCRA 1,700 $2,350Civilian Agencies 810 $1,620Other 3,500 $1,750
Total 42,530 $160,035
From: Environmental Business Journal (EBJ) Vol. XXXII, Numbers 5/6, 2019
RAMBOLL PFAS SUBJECT MATTER EXPERT TEAM
• Jim Fenstermacher• Mark Nielsen• Paul Hare • Jason Wilkinson • Dorte Harrekilde (EU)• Fabiana Gomes (Brasil)• Annette Nolan (AUS)• Imants Reks• Linda Dell• Bob DeMott• Ellen Donovan
Ramboll has experience with PFAS issues since the late 1990s.
SMEs from Site Solutions, Health Sciences, Ecoservices, Air, and
Water Service Lines are engaged in PFAS projects to provide
technical guidance, and assistance with proposals, workplans, and reports.
Please contact Ramboll SMEs when working on PFAS-
related projects.
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• Cliff Yantz• Roz Schoof• Rebecca Siebenaler• Yvonne Sutter• Scott Warner• Steve Washburn• Steven Fecht• Tamara House-Knight• Debra Kaden• Steve Luis• Janet Egli
