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Introduction to PFAS Remediation Approaches
AWMA Georgia Chapter Spring Conference
Herwig Goldemund, Ph.D.Geosyntec ConsultantsKennesaw, GA
April 11, 2019
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Agenda
• PFAS Characteristics, Sources and Environmental Fate
• Overview of PFAS Toxicology• Treatment Challenges and Methods
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PFAS Characteristics, Sources, and Environmental Fate
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PFAS Characteristics
• Per- and Polyfluoroalkyl Substances (PFAS)– Family of synthetic organic compounds that contain
multiple fluorine atoms
– Incorrectly referred to as “PFCs”• Greenhouse gases regulated by Kyoto Protocol• PFCs are one of the families of PFAS (all PFCs are PFAS, not all
PFAS are PFCs– Most “famous” compounds are perfluorooctanoic acid
(PFOA) and perfluorooctane sulfonic acid (PFOS)
F9 19.0
Fluorine
Example molecular structures forperfluorooctane sulfonate (PFOS)
Conder et al. (2008)
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PFAS Uses
• Surface treatment/coatings– Carpet and upholstery– Apparel– Paper and packaging– Non-stick cookware
• Performance chemicals– Chromium plating (mist
suppression)– Insecticides– Lubricants– Aqueous Film-Forming Foam
(AFFF)
Oil and water repellency = Excellent surfactants
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Potential Sources
• Sites with very high probability of screening or risk-based criteria exceedances– Airports– Fire-fighting training areas– Petrochemical/chemical plants– Chrome plating facilities– Textile/carpet manufacturers– Waste Water Treatment Plants
(WWTPs) and sewage sludge land application areas
– Landfills• US Military proactive in
PFAS investigation: more than 600 sites so far
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Environmental Fate
• Extremely persistent or transformation to persistent PFAS
• Moderate-high water solubility/mobility– Groundwater plumes
from contaminated areas many miles long
• Can also partition to soils and sediment
• Persistent PFAS at contaminated sites not volatile
Minnesota PFAS plumes in groundwater 10+ miles long, cover over 100 miles2 (MDH, 2012)
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Overview of PFAS Toxicology
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Bioaccumulation of PFAS
• PFAS are detectable in nearly any biological tissue
• Many PFAS bioaccumulate, especially longer PFASs and sulfonated PFASs (e.g., PFOS)
• Partition to protein, not fat– Blood, liver, kidney, muscle
are primary repositories• Can also partition to soils
and sediment• Not metabolized, or
metabolized to persistent PFASs
Less bioaccumulative
More bioaccumulative
Conder et al., 2008. Environ Sci Technol . 42:995-1003
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Human Exposure Pathways
• Major1,2
– Diet (bioaccumulation)• Fish and seafood• Homegrown produce
– Drinking water – Incidental soil/dust
ingestion• Usually insignificant or
minor– Dermal absorption– Inhalation
1 Oliaei et al., 2013. Environ. Sci. Pollut. Res. Manag. 20:1977-19922 Domingo, 2012. Environment International 40:187-195
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Perfect Storm of Environmental Challenges
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Treatment Challenges and Methods
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Treatment Challenges
• PFAS have unique properties – Hydrophobic and oleophobic– Persistent, bioaccumulative and toxic– Moderate solubility – can be transported long distances
• Chemically and biologically stable– Resistant to typical environmental degradation processes– C-F bond is shortest and strongest in nature
• Treatment approaches challenging and costly
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Treatment Approaches
• Soils and sediments– Typically soils are excavated (and
treated/stabilized if needed) followed by off-site disposal or reuse
– Other technologies are incineration, soil washing
• Groundwater (ex situ)– Full-scale PFAS treatment systems use
granulated activated carbon (GAC) or ion exchange
– Membrane treatment (e.g., nanofiltration [NF] or reverse osmosis [RO]) also effective but expensive
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Granular Activated Carbon (GAC)
• The most widely used treatment technology
• Bituminous coal-based re-agglomerated GAC significantly outperforms coconut based GAC
• Less effective for short chain PFAS.
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PlumeStop®
• Commercialized by Regenesis• Liquid Activated Carbon™• Colloidal carbon (1-2 µm) injected into subsurface• PFAS sorb onto carbon in-situ
Images courtesy of Regenesishttps://regenesis.com/en/remediation-products/plumestop-liquid-activated-carbon/
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Ion Exchange (IX)
• Reversible chemical reaction to remove ions
• Cationic or anionic exchange resins
• Contains solid phase (e.g. zeolites or synthetic resin) with functional group(s) and mobile ions
• Can be single use or regenerated
Source: USEPA – Water Treatability Database
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Ion Exchange (IX)
Boodoo, Francis & Kennedy, Sean & Campos, Jonathan. (2017). REMOVAL OF PFOA, PFOS AND OTHER PFAS SUBSTANCES USING ION EXCHANGE.
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Reverse Osmosis & Ultrafiltration
• Design Considerations– High pressure
membrane– High energy usage– Typically used on lower
flow rates– Reject water disposal
• Cost– High capital and O&M
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Aqueous Persulfate Test
Source: Clarkson University
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Peroxide Activated Persulfate
Some PFAS compounds are generated, not removed.
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Sonolysis
• Use of ultrasound to degrade PFOA and PFOS
• Ultrasonic “cavitation” or “bubbles”
• Mainly thermal decomposition1
• Major byproducts: Fluoride ions, fluorine gas, sulfate ion, carbon monoxide, carbon dioxide and shorter-chain PFASs
• Reported near complete transformation of PFOA/PFOS 2
1Moriwaki, H et al. ES&T, 20052Vecitis, C. D., Journal of Physical Chemistry, 2005
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Electrochemical Oxidation
• Use of direct current (DC) to degrade PFAS• Electrode material (Boron-doped diamond, MMO,
lead-dioxide etc.)• Major byproducts: Fluoride ions, shorter-chain
PFAS
PFOA/PFOS
Byproducts
Source: Schaefer, C. D., Journal of Hazardous Materials, 2015
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Plasma
• Pulsed high voltage (16.5 to 25 kV) to generate plasma, which produces aqueous electrons to chemically degrade PFAS
• Reported 90% PFOA removal within 30 minutes
• 20 µM initial PFOA concentration
• Major byproducts: Fluoride ions, fluorinated gases and shorter-chain PFAS
Stratton, G. R et al. “Plasma-based water treatment: Efficient transformation of perfluoroalkyl substances in prepared solution and contaminated groundwater” ES&T, 2017
Bench Scale: 10-cm diameter plasma Pilot Scale Setup
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Conclusions
• Removal of PFAS from aqueous waste streams is challenging and costly
• Proven technologies at full scale are limited to GAC, ion exchange, and membrane technology
• High-strength wastewater even more challenging– Proven technologies may only be applicable as a
polishing step