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PFAS Ex Situ Water Treatment

Well-developed ex situ treatment technologies applicable to treatment of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in drinking water and non-potable groundwater include membrane filtration (reverse osmosis and nanofiltration), activated carbon adsorption (granular and powdered), and anion exchange. There are also a variety of separation and destructive technologies in developmental stages. Some of these processes may also be applicable to more complex matrices including wastewater and landfill leachate.

Related Article(s):

• Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS)
• PFAS Transport and Fate
• PFAS Sources
• PFAS Soil Remediation Technologies

Contributor(s): Dr. Scott Grieco and James Hatton

Key Resource(s):

• Water Research Foundation (Drinking Water): Treatment Mitigation Strategies for PFAS (4)

• Interstate Technical and Regulatory Council: PFAS Liquids Treatment Technologies

• Novel treatment technologies for PFAS compounds: A critical review.

• Degradation and removal methods for perfluoroalkyl and polyfluoroalkyl substances in water and the more mobile compounds are often problematic in groundwater systems. The US EPA has published lifetime drinking water health advisories for the combined concentration of 70 nanograms per liter (ng/L) for two common and recalcitrant PFAS: PFOS, a perfluoroalkyl sulfonic acid (PFSA), and PFOA, a perfluoroalkyl carboxylic acid (PFCA).(See Perfluoroalkyl and Polyfluoroalkyl Substances (PFAS) for nomenclature.)

While many of the earliest sites where these compounds were detected in groundwater were manufacturing sites, some recent detections have been attributed to fire training activities associated with aqueous film-forming foams (AFFF). AFFF is the US Department of Defense (DoD) designation for Class B firefighting foam containing PFAS, which is required for fighting fires involving petroleum liquids. Fire training areas and other source areas where AFFF was released at the surface have the potential to be ongoing sources of groundwater contamination. (See also PFAS Sources.)

No national soil cleanup standards have been promulgated by the US EPA, although Regional Screening Levels (RSLs) have been calculated and published for perfluorobutane sulfonate (PFBS) and data are available to calculate RSLs for PFOA and PFOS. Several states have promulgated standards or screening levels for soil concentrations protective of groundwater, which are several orders of magnitude lower than direct dermal exposure guidelines. These single-digit part per billion criteria will likely drive remedial actions in PFAS source areas in the future. At present, the lack of federally promulgated standards and uncertainty about future standards causes temporary stockpiling of PFAS-impacted soils on sites with soil generated from construction or investigation activities.

Soil Treatment

Figure 1. A full scale PFAS-impacted soil stabilization project at a military base in Australia. Image courtesy of RemBind™.

Addressing recalcitrant contaminants in soil has traditionally been done through containment/capping or excavation and off-site disposal or treatment. Containment/capping may be an acceptable solution for PFAS in some locations. However, containment/capping is not considered ideal given the history of releases from engineered landfills and restrictions on use of land containing capped soils. Innovative treatment approaches for PFAS include stabilization with amendments and thermal treatment.

Excavation and Disposal

Excavation and off-site disposal or treatment of PFAS-impacted soils is the only well-developed treatment technology option and may be acceptable for small quantities of soil, such as those generated during characterization activities (i.e., investigation derived waste, IDW). Disposal in non-hazardous landfills is allowable in most states. However, some landfill operators are choosing to restrict acceptance of PFAS-containing waste and soils as a protection against future liability. In addition, the US EPA and some states are considering or have designated PFOA and PFOS as hazardous substances, which would reduce the number of facilities where disposal of PFAS-contaminated soil would be allowed. Treatment of excavated soils is commonly performed using incineration or other high temperature thermal methods. Recent negative publicity regarding incomplete combustion of PFAS in incinerators has caused some states to ban PFAS incineration.

Stabilization

Figure 2. A portable infrared thermal treatment unit for PFAS-impacted soils.

Various amendments have been manufactured to sorb PFAS to reduce leaching from soil. Although this is a non-destructive approach, stabilization can reduce mass flux from a source area or allow soils to be placed in landfills with reduced potential for leaching. Amendments sorb PFAS through hydrophobic and electrostatic interactions and are applied to soil through in situ soil mixing or ex situ stabilization (Figure 1). Effectiveness of amendments varies depending on site conditions, PFAS types present, and mixing conditions. Good results have been observed in bench and field scale tests with a variety of cationic clays (natural or chemically modified) and zeolites. Bench-scale tests have shown that activated carbon sorbents reduce leachability of PFAS from soils. A commercial product developed in Australia (RemBind™) combines the cation exchange binding capability of clays, the hydrophobic sorption and van der Waals attraction of organic material, and the electrostatic interactions of aluminum hydroxide to create a highly effective soil stabilizer. This material has been mixed into soil at 1 to 5% ratio by weight in ex situ applications and been demonstrated to reduce leachability by greater than 99 percent.

Thermal Treatment

Figure 3. A full scale PFAS-impacted soil washing plant in Australia.

Incineration: Incineration is a well-developed technology for organics destruction, including PFAS-impacted soils. Incineration is generally defined as high temperature (>1,100°C) thermal destruction of waste, and PFAS are thought to mineralize at high temperatures. Generally, incinerators treat off-gasses by thermal oxidation with temperatures as high as 1,400°C, and vaporized combustion products can be captured using condensation and wet scrubbing. Some regulatory officials have expressed concern about possible PFAS emissions in off-gas from these incinerators, and the authors are not aware of any published evidence demonstrating complete mineralization of multiple PFAS in incinerators at the time of this posting. In general, incineration is designed to provide “5 nines of destruction” – destruction of 99.999% of the contaminants, although incinerators are not designed to specifically treat PFAS to this standard. In the absence of approved industry standard test methods, the US EPA is developing off-gas/stack testing procedures capable of detecting PFAS at the levels considered to be harmful.

Thermal Desorption: Thermal Desorption of PFAS from soil has been demonstrated at the field scale in Australia and the US (Alaska) using a rotary kiln operating at temperatures in the range of 900°C or less with treatment times of 10-15 minutes. At these temperatures, some PFAS are mineralized, releasing fluorine that must be captured in off-gas treatment systems. Some PFAS would not be destroyed at these temperatures and therefore must be captured in off-gas treatment systems. Several bench-scale tests have been performed that have narrowed down the optimal temperature for desorption to between 350°C and 400°C. A US Department of Defense (DoD) Strategic Environmental Research and Development Program (SERDP) field-scale demonstration was performed in Oregon, where thermal desorption was conducted at 400°C over several days, and the PFAS were captured on vapor-phase activated carbon and incinerated. An in situ thermal desorption project has been funded under the US DoD’s Environmental Security Technology Certification Program (ESTCP) to demonstrate that vadose zone soil can be heated to the requisite 350°C and held there for the appropriate length of time to desorb and capture PFAS from soil source areas.

Soil Washing

Soil washing has been applied to PFAS in a handful of pilot projects and one full-scale implementation in Australia. This approach requires a large-scale engineered plant to handle the various liquid and solid waste streams generated. Soil washing is less suitable for clay-rich soils, where aggregation of the particulates occurs and is difficult to prevent or mitigate. Treatment of the liquid rinse water waste stream is required, which would then rely on conventional water treatment technologies such as granular activated carbon (GAC) or ion exchange. Additionally, in some cases flocculated sludge is generated, which would require treatment or disposal offsite. At present, the only full-scale soil washing demonstration is occurring in Australia, where a vendor has constructed and is operating a 10 million AUD$ treatment plant in anticipation of future treatment of soils generated from remedial actions at Australian Defense installations. Some Australian installations are stockpiling soils due to the lack of cost-effective soil treatment options. According to the vendor, this system generates no solid waste, instead feeding any solids back into the front end of the process for further removal of PFAS.

Conclusions

Several well-developed remedial technologies have been applied to address soil contaminated with PFAS. Unfortunately, none of the available techniques are ideal, with some reducing leachability but leaving the PFAS-impacted soil in place, while others result in destruction of the contaminants but require high energy inputs with associated high cost.