PFAS Ex Situ Water Treatment

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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 various stages of development. Some of these processes may also be applicable to more complex matrices including wastewater and landfill leachate.

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

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Established PFAS Treatment Technologies

Three technologies are well demonstrated for removal of PFAS from drinking water and non-potable groundwater (as described below):

However, these technologies are less demonstrated for removal of PFAS from more complex matrices such as wastewater and leachate. Site-specific considerations that affect the selection of optimum treatment technologies for a given site include water chemistry, required flow rate, treatment criteria, waste residual generation, residual disposal options, and operational complexity. Treatability studies with site water are highly recommended because every site has different factors that may affect engineering design for these technologies.

Membrane Filtration

Figure 1. A RO municipal drinking water plant in Arizona

Given their ability to remove dissolved contaminants at a molecular size level, RO and some NF membranes can be highly effective for PFAS removal. For RO systems (Figure 1), several studies have demonstrated effective removal of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) (see PFAS for nomenclature) from drinking water with removal rates well above 90%[5][6][7]. RO potable water reuse treatment systems implemented in California have also demonstrated effective PFOS and PFOA removal as reported by the Water Research Foundation (WRF)[1]. Analysis of permeate at both sites referenced by the WRF confirmed that short and long chain PFAS concentrations in the treated water were reduced to levels below test method reporting limits.

Full-scale studies using larger effective pore size NF membranes for PFAS removal are limited in number but are promising since NF systems are somewhat less costly than RO and may be nearly as effective in removing PFAS. Recent laboratory or pilot studies have shown good performance of NF membranes[8][9][10][11][12].

Although membrane RO and NF processes are generally capable of providing uniform removal rates relative to short and long chain PFAS compounds (see PFAS for nomenclature), other aspects of these treatment technologies are more challenging:

  • Membranes must be flushed and cleaned periodically, such that overall water recovery rates (process water volumes consumed, wasted, and lost vs. treated water volumes produced) are much lower than those for GAC and IX processes. Membrane fouling can be slowed or avoided depending on operating conditions, membrane modifications, and feed modifications[13]. Typically, 70-90% of the water supplied into a membrane RO process is recoverable as treated water. The remaining 10-30% is reject containing approximately 4 to 8 times the initial PFAS concentration (depending on recovery rate).
  • These cleaning and flushing processes create a continuous liquid waste stream, which periodically includes harsh membrane cleaning chemicals as well as a continuous flow of concentrated membrane reject chemicals (i.e., PFAS) that must be properly managed and disposed of. Management often includes further treatment to remove PFAS from the liquid waste.
  • RO and NF systems are inherently more expensive and complicated systems to implement, operate, and maintain compared to adsorption processes. Treatment system operator certification and process monitoring requirements are correspondingly markedly higher for RO and NF than they are for GAC and IX.
  • Water feed pressures required to drive flow through membrane RO and NF processes are considerably higher than those involved with GAC and IX processes. This results in reduced process efficiency and higher pumping and electrical operating costs.
  • Membrane systems can also be subject to issues with irreversible membrane fouling, clogging, and scaling or other physical membrane damage and failures. Additional water pretreatment and higher levels of monitoring and maintenance are then required, further adding to the higher costs of such systems.

Activated Carbon Adsorption

Figure 2. Typical private water supply well GAC installation for removal PFAS. Pressure gages and sample ports located before the first (or lead) vessel, at the midpoint, and after the second (or lag) vessel allow monitoring for pressure drop due to fouling and for contaminant breakthrough.

Activated carbon is a form of carbon processed to have small pores that increase the surface area available for adsorption of constituents from water. Activated carbon is derived from many source materials, including coconut shells, wood, lignite, and bituminous coal. Different types of activated carbon base materials have varied adsorption characteristics such that some may be better suited to removing certain contaminant compounds than others. Results from laboratory testing, pilot evaluations, and full-scale system operations suggest that bituminous coal-based GAC is generally the best performing carbon for PFAS removal[14][15].

The removal efficiency of individual PFAS compounds using GAC is a function of both the PFAS functional group (carboxylic acid versus sulfonic acid) and also the perfluoro-carbon chain length[16][17](see PFAS for nomenclature):

  • perfluoro-sulfonate acids (PFSAs) are more efficiently removed than perfluoro-carboxylic acids (PFCAs) of the same chain length
  • long chain compounds of the same functional group are removed better than the shorter chains

Activated carbon may be applied in drinking water systems as GAC or PAC[18][19]. GAC has larger granules and is reusable, while PAC has much smaller granules and is not typically reused. PAC has most often been used as a temporary treatment because costs associated with disposal and replacement of the used PAC tend to preclude using it for long-term treatment. A typical GAC installation for a private drinking water well is shown in Figure 2. Contrary to PAC, GAC used to treat PFAS can be reactivated by the manufacturer, driving the PFAS from the GAC and into off-gas. The extracted gas is then treated with thermal oxidation (temperatures often 1200°C to 1400°C). The reactivated GAC is then brought back to the site and reused. Thus, GAC can ultimately be a destructive treatment technology.

Figure 3. Operational cycle of a packed bed reactor with anion exchange resin beads

Anion Exchange

Anion exchange has also been demonstrated for the adsorption of PFAS, and published results note higher sorption per pound than GAC[16][20][21]. The higher capacity is believed to be due to combined hydrophobic and ion exchange adsorption mechanisms, whereas GAC mainly relies on hydrophobic attraction. Anion exchange resins can be highly selective, or they can also remove other contaminants based on design requirements and water chemistry. Resins have greater affinity for PFAS subgroup PFSA than for PFCA, and affinity increases with carbon chain length. Anion exchange resins are a viable alternative to GAC for ex situ treatment of PFAS anions, and several venders sell resins capable of removing PFAS. Resins available for treating PFAS include regenerable resins that can be used multiple times (Figure 3) and single-use resins that must be disposed or destroyed after use[20]. Regenerable resins generate a solvent and brine solution, which is distilled to recover the solvent prior to the brine being adsorbed onto a small quantity of GAC or resin for ultimate disposal. This use of one treatment technology (GAC, IX) to support another (RO) is sometimes referred to as a “treatment train” approach. Single-use resins can be more fully exhausted than regenerable resins can and may be a more cost-effective solution for low concentration PFAS contamination, while regenerable resins may be more cost effective for higher concentration contamination.

Developing PFAS Treatment Technologies

Table 1. Developmental Technologies
Stage Separation/Transfer Destructive*
Developing
Maturing and
Demonstrated
* There are several other destructive technologies such as alternative oxidants, and activation
methods of oxidants, but for the purpose of this article, the main categories are presented here.

Numerous separation and destructive technologies are in the developmental stages of bench-scale testing or limited field-scale demonstrations. Some of these are listed in Table 1:

Conclusions

The well established processes for removing PFAS from water all produce residuals that require management, and it is likely that newer processes under development will also produce some residuals. Often, it is the residuals that limit the usefulness of the process. For instance, RO and NF may currently provide the most complete treatment of water, but the production of a relatively high volume of PFAS-containing liquid reject (the portion of the liquid that retains the contaminants and is “rejected” from the process) limits their application. Often, a second treatment technology such as an adsorbent is required to support the main technology by concentrating or treating the residuals.

As more testing and operational data on adsorbents are generated, it is becoming evident that no adsorbent technology outperforms the others in all cases. Whether GAC, ion exchange or another technology is the most technically efficient and cost effective long term option for a given site depends on influent water geochemistry and contaminant concentrations, treatment standards, co-contaminants, duration of treatment, and required flow rates. New generation adsorbents are rapidly being introduced into the market at “evaluation scale” which may provide advantages over commercially available adsorbents.

Several newer technologies are being evaluated in the lab and in the field which include electro-oxidation, heat-activated persulfate, sonolysis, electrocoagulation, low temperature plasma, supercritical water oxidation, and foam fractionation. These and other potential treatments for PFAS are still largely in the developmental stage. Several technologies show promise for improved management of PFAS sites. However, it is unlikely that a single technology will be adequate for full remediation at many sites. A multi-technology treatment train approach may be necessary for effective treatment of this complicated group of compounds.


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