Regeneration of conventional and emerging PFAS-selective anion exchange resins used to treat PFAS-contaminated waters

Abstract

Anion exchange resins (AERs) have emerged as a promising separation technology to remediate PFAS-contaminated waters due to their improved selectivities and capacities in comparison to legacy activated carbon adsorbents. Presently, site managers choose between AER systems employing resins defined as being ‘regenerable’ with relatively low PFAS selectivity, and PFAS-selective resins that are marketed as ‘single-use’ media intended for disposal upon PFAS breakthrough. However, the potential for these highly-selective adsorbents to be regenerated and/or reused remains poorly characterized. This study presents a comprehensive evaluation of the efficacy of various regenerant solution constituents, mixtures, and operational considerations on the regenerability of both ‘regenerable’ and ‘PFAS-selective’ AERs that were loaded during a pilot treatment study of PFAS-contaminated groundwater. Batch screening of regenerant solution constituents found that both classes of resins may be effectively regenerated using combinations of salt brine and organic cosolvent, with high cosolvent fractions being necessary for PFAS-selective AERs. While neither brine-only nor solvent-only regenerant solutions led to effective PFAS desorption, the efficacy of regeneration with brine/cosolvent mixtures varied with salt type and cosolvent composition. Chloride salts outperformed sulfate and bicarbonate salts, cosolvent efficacy depended on the volume fraction and type used, and highly non-polar solutions led to optimal PFAS desorption. Continuous-flow regeneration experiments showed near-complete PFAS desorption from regenerable AERs using 10 bed volumes (BVs) of 70 % methanolic brine solutions, whereas PFAS-selective resins required more bed volumes (30) of brines with higher methanol content (90 %) or a more hydrophobic cosolvent (n-propanol); increasing regenerant empty-bed contact time had minimal effect on PFAS desorption. > 90 % methanol recovery from the resulting waste regenerant mixtures was accomplished with negligible PFAS contamination using distillation, leaving a minimal volume of a PFAS-concentrated still bottoms waste that may be further treated for PFAS destruction. Life cycle analyses revealed that groundwater treatment using PFAS-selective AERs operated in a regenerable mode have lower environmental impacts and costs than systems using conventional regenerable AERs, and lower treatment costs than systems operated using PFAS-selective resins in a single-use mode. Although counterintuitive, these findings stem from the fact that higher cosolvent requirements for regeneration of PFAS-selective resins lead to greater internal recycling of regenerant solutions and much lower volumes of residual waste still bottoms that require off-site incineration or disposal.