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Subsurface injection of colloidal activated carbon (CAC) is an in situ remediation strategy for perfluoroalkyl acids (PFAA), but the influence of groundwater solutes on longevity is uncertain, particularly for short-chain PFAA. We quantify the impact of inorganic anions, dissolved organic matter (DOM), and stabilizing polymer on PFAA adsorption to a commercial CAC. Surface characterization supported PFAA chain-length dependent adsorption results and mechanisms are provided. Inorganic anions decreased adsorption for short-chain PFAA (<7 perfluorinated carbons) due to competitive effects, while long-chain PFAA (≥ 7 perfluorinated carbons) were less impacted. DOM decreased adsorption of all PFAA in a chain-length dependent manner. High DOM concentrations (10 mg/L, ∼5 mg OC/L) decreased PFOA adsorption by a factor of 2, PFPeA by one order of magnitude, and completely hindered PFBA adsorption. High MW DOM has less impact on short-chain PFAA than low MW DOM, possibly due to differences in the ability to access CAC micropores. Low DOM concentrations (1 mg/L, ∼0.5 mg OC/L) did not impact adsorption. CMC (90 kDa average MW) had negligible impact on PFAA adsorption likely due to minimal CAC surface coverage. Longevity modeling demonstrated that groundwater solutes limit the capacity for PFAA in a CAC barrier, particularly for short-chain PFAA., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Carbon-based adsorbents used to remove recalcitrant water contaminants, including perfluoroalkyl substances (PFAS), are often regenerated using energy-intensive treatments that can form harmful byproducts. We explore mechanisms for sorbent regeneration using hydrated electrons (e aq - ) from sulfite ultraviolet photolysis (UV/sulfite) in water. We studied the UV/sulfite treatment on three carbon-based sorbents with varying material properties: granular activated carbon (GAC), carbon nanotubes (CNTs), and polyethylenimine-modified lignin (lignin). Reaction rates and defluorination of dissolved and adsorbed model perfluorocarboxylic acids (PFCAs), perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA), were measured. Monochloroacetic acid (MCAA) was employed to empirically quantify e aq - formation rates in heterogeneous suspensions. Results show that dissolved PFCAs react rapidly compared to adsorbed ones. Carbon particles in solution decreased aqueous reaction rates by inducing light attenuation, e aq - scavenging, and sulfite consumption. The magnitude of these effects depended on adsorbent properties and surface chemistry. GAC lowered PFOA destruction due to strong adsorption. CNT and lignin suspensions decreased e aq - formation rates by attenuating light. Lignin showed high e aq - quenching, likely due to its oxygenated functional groups. These results indicate that desorbing PFAS and separating the adsorbent before initiating PFAS degradation reactions will be the best engineering approach for adsorbent regeneration using UV/sulfite., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Transformation of endocrine active compounds (EACs) by either chlorination (Cl-D) or UV disinfection (UV-D) was studied by field sampling and bench-scale validation studies. Field testing assessed concentration of 13 EACs in effluent at two Chicago area 250 MGD wastewater reclamation plants (WRP) over two years. One WRP uses chlorination/dechlorination while the other employs UV disinfection. Target compounds included bupropion, carbamazepine, citalopram, duloxetine, estradiol, estrone, fluoxetine, nonylphenol, norfluoxetine, norsertraline, paroxetine, sertraline, and venlafaxine. Concentrations of 9/13 target compounds were partially reduced after disinfection (5-65% reduction). None of the target compounds were fully transformed by either chlorination or UV treatment at the WRP scale. In bench-scale experiments each compound was spiked into deionized water or effluent and treated in a process mimicking plant-scale disinfection to validate transformations. Correlation was observed between compounds that were transformed in bench-testing and those that decreased in concentration in post-disinfection WRP effluent (10/13 compounds). A survey of potential reaction products was made. Chlorination of some amine containing compounds produced chloramine by-products that reverted to the initial form after dechlorination. Transformation products produced upon simulated UV disinfection were more diverse. Laboratory UV-induced transformation was generally more effective under stirred conditions, suggesting that indirect photo-induced reactions may predominate over direct photolysis., (Copyright © 2019 Elsevier Ltd. All rights reserved.)