PFAS-CTAB Complexation and Its Role on the Removal of PFAS from a Lab-Prepared Water and a Reverse Osmosis Reject Water Using a Plasma Reactor.

Electrical discharge plasma reactors with argon bubbling can effectively treat long-chain perfluoroalkyl acids (PFAAs) in contaminated water, and the addition of a cationic surfactant cetrimonium bromide (CTAB) is known to enhance the removal of short-chain PFAAs. However, the roles of PFAA chain length, functional group, and water matrix properties on PFAA-CTAB complexation are largely unknown. This work investigated the bulk liquid removal of different PFAAs by CTAB in the absence of plasma. Stepwise addition of CTAB was subsequently used to efficiently treat PFAAs in a lab-prepared water and a reverse osmosis (RO) reject water using an enhanced contact plasma reactor. The results show that CTAB inhibited the bulk liquid removal of long-chain PFAAs in the absence of plasma likely due to the formation of hydrophilic CTAB-PFAA mixed micelles and competition for interfacial access between long-chain PFAAs and CTAB. On the contrary, CTAB enhanced the removal of short- and ultrashort-chain PFAAs by forming hydrophobic complexes. After 6 h of treatment in the plasma reactor with CTAB, PFAAs were 86 to >99% removed from the lab-prepared water and 29 to >99% removed from the RO reject water. This study provides important insights for overcoming mass transfer limitations for PFAA treatment technologies.

Plasma-assisted degradation of a short-chain perfluoroalkyl substance (PFAS): Perfluorobutane sulfonate (PFBS).

This study investigates the degradation of perfluorobutane sulfonate (PFBS), a chemical compound belonging to a group of per- and polyfluoroalkyl substances (PFAS), by gas-phase electrical discharge plasma. Plasma alone was ineffective in degrading PFBS due to its poor hydrophobicity, which inhibited the compound from accumulating at the plasma-liquid interface, the region of chemical reactivity. To overcome bulk liquid mass transport limitations, a surfactant, hexadecyltrimethylammonium bromide (CTAB), was introduced to interact with and transport PFBS to the plasma-liquid interface. In the presence of CTAB, ∼99% of PFBS was removed from the bulk liquid and concentrated at the interface, where 67% of the concentrate was degraded and 43% of that amount was defluorinated within one hour. PFBS degradation was further improved by optimizing the surfactant concentration and dosage. Experiments with a range of cationic, non-ionic, and anionic surfactants revealed that the PFAS-CTAB binding mechanism is predominantly electrostatic. A mechanistic understanding of the PFAS-CTAB complex formation, its transport to and destruction at the interface is proposed, alongside the chemical degradation scheme, which includes the identified degradation byproducts. This study shows that surfactant-assisted plasma treatment is one of the most promising techniques for destroying short-chain PFAS in contaminated water.

Systematic Study on the Removal of Per- and Polyfluoroalkyl Substances from Contaminated Groundwater Using Metal-Organic Frameworks.

Harmful per- and polyfluoroalkyl substances (PFAS) are ubiquitously detected in aquatic environments, but their remediation remains challenging. Metal-organic frameworks (MOFs) have been recently identified as an advanced material class for the efficient removal of PFAS, but little is known about the fundamentals of the PFAS@MOF adsorption process. To address this knowledge gap, we evaluated the performance of 3 different MOFs for the removal of 8 PFAS classes from aqueous film-forming foam-impacted groundwater samples obtained from 11 U.S. Air Force installations. Due to their different pore sizes/shapes and the identity of metal node, MOFs NU-1000, UiO-66, and ZIF-8 were selected to investigate the role of MOF structures, PFAS properties, and water matrix on the PFAS@MOF adsorption process. We observed that PFAS@MOF adsorption is (i) dominated by electrostatic and acid-base interactions for anionic and non-ionic PFAS, respectively, (ii) preferred for long- over short-chain PFAS, (iii) strongly dependent on the nature of PFAS head group functionality, and (iv) compromised in the presence of ionic and neutral co-contaminants by competing for ion-exchange sites and PFAS binding. With this study, we elucidate the PFAS@MOF adsorption mechanism from complex water sources to guide the design of more efficient MOFs for the treatment of PFAS-contaminated water bodies.

Breakdown Products from Perfluorinated Alkyl Substances (PFAS) Degradation in a Plasma-Based Water Treatment Process.

Byproducts produced when treating perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) in water using a plasma treatment process intentionally operated to treat these compounds slowly to allow for byproduct accumulation were quantified. Several linear chain perfluoroalkyl carboxylic acids (PFCAs) (C4 to C7) were identified as byproducts of both PFOA and PFOS treatment. PFOA, perfluorohexanesulfonate (PFHxS), and perfluorobutanesulfonate (PFBS) were also found to be byproducts from PFOS degradation. Significant concentrations of fluoride ions, inorganic carbon, and smaller organic acids (trifluoroacetic acid, acetic acid, and formic acid) were also identified. In addition to PFCAs, PFHxS, and PFBS, trace amounts of 43 PFOA-related and 35 PFOS-related byproducts were also identified using a screening and search-based algorithm. Minor concentrations of gas-phase byproducts were also identified (<2.5% of the F originally associated with the parent molecules) some of which are reported for the first time in perfluoroalkyl substance degradation experiments including cyclic perfluoroalkanes (C4F8, C5F10, C6F12, C7F14, and C8F16). The short chain PFCAs detected suggest the occurrence of a stepwise reduction of the parent perfluoroalkyl substances (PFAS) molecule, followed by oxidation of intermediates, perfluoroalkyl radicals, and perfluoro alcohols/ketones. Using a fluorine mass balance, 77% of the fluorine associated with the parent PFOA and 58% of the fluorine associated with the parent PFOS were identified. The bulk of the remaining fluorine was determined to be sorbed to reactor walls and tubing using sorption experiments in which plasma was not generated.

The effects of externally applied pressure on the ultrasonic degradation of Rhodamine B.

The present manuscript compares the ultrasonic degradation of Rhodamine B dye under atmospheric (1 bar) and elevated pressures (1.6 and 2 bar). The degradation was studied as a function of the bulk liquid temperature and initial dye concentration at two different values of mechanical amplitudes (ultrasonic intensities). Results indicate that at the low amplitude an increase in the applied pressure increases the dye removal rate, whereas at the high amplitude, the same increase in the pressure has a minimal effect on the degradation of the dye. Furthermore, at low amplitudes an increase in the bulk liquid temperature from 5 to 35 °C increases the dye degradation by 10%. At higher intensities, the same increase in temperature has negative or no effect on the dye removal. An increase in the initial dye concentration by one order of magnitude significantly lowers the dye degradation rate regardless of the applied amplitude. Though these results are caused by numerous physical and chemical processes taking place during ultrasonic cavitation, the number of cavitation sites, bubble temperature and consequently, the amount of oxidative species inside the bubble seem to be the most important ones in determining the extent of the degradation of molecules in the bulk liquid.