Mechanochemical destruction of per- and polyfluoroalkyl substances in aqueous film-forming foams and contaminated soil.

Per- and polyfluoroalkyl substances (PFASs) are a class of synthetic chemicals of concern that exhibit extreme persistence within the environment and possess physicochemical properties that are resistant to targeted degradation. Comprising substantial concentrations of PFASs, aqueous film-forming foams (AFFFs) present a major exposure pathway to the environment having been applied to land at firefighting-training sites globally for decades. This has led to significant contamination of environmental media. Herein, we demonstrate that mechanochemical destruction (MCD) is an effective method for the destruction of PFASs in an AFFF concentrate and an authentic sample of PFAS-contaminated soil derived from a decommissioned firefighting training facility. Both targeted analysis and non-targeted analysis were used in this study to evaluate the degradation of PFASs in complex substrates during MCD treatment. Destruction efficiencies of target PFAS subgroups ranged from 99.88% to 100%. The only additive employed for MCD treatment was quartz sand, which was used only for the liquid AFFF sample, with no additives required for the destruction of PFASs in the contaminated soil. This confirms the viability of MCD for both the remediation of PFAS-contaminated land and the destruction of stockpiled AFFFs.

Solvent-Free, Ambient Temperature and Pressure Destruction of Perfluorosulfonic Acids under Mechanochemical Conditions: Degradation Intermediates and Fluorine Fate.

Perfluorosulfonic acids (PFSAs) are a recalcitrant subclass of per- and polyfluoroalkyl substances (PFASs) linked to numerous negative health effects in humans. Scalable technologies that effectively destroy PFSAs will greatly reduce the future health and ecological impact of these "forever chemicals". Herein, we show that several PFSAs undergo facile mechanochemical destruction (MCD) in the presence of quartz sand (SiO2). This process operates in the absence of solvent, at ambient temperature and pressure, generating a benign solid byproduct. Quantitative analysis of milled samples revealed high destruction efficiencies of 99.95% to 100% for five different PFSAs subjected to MCD conditions in the presence of SiO2 only. Extensive nontargeted analysis showed that, during degradation, other PFASs form and are ultimately destroyed upon extended mechanochemical treatment. Direct polarization (DP) and cross-polarization (CP) solid-state nuclear magnetic resonance (SSNMR) spectroscopy showed abundant silicon-fluorine (Si-F) bond formation post-MCD, indicating that fluorine was secured in a stable reservoir. Collectively, these results identified the degradation profile for an environmentally sound and effective PFSA degradation process that is amenable to scale-up.

Adsorptive removal of propranolol under fixed-bed column using magnetic tyre char: Effects of wastewater effluent organic matter and ball milling.

We investigated the competitive effects of different fractions of wastewater treatment plant effluent organic matter (EfOM) on adsorption of an organic micro pollutant (OMP), propranolol (PRO), in a fixed bed column packed with magnetic tyre char (MTC). The results showed that the presence of EfOM inhibited PRO adsorption in wastewater leading to decreased PRO adsorption capacity from 5.86 to 2.03 mg/g due to competitive effects and pore blockage by smaller EfOM fractions. Characterization of EfOM using size exclusion chromatography (LC-OCD) showed that the principal factor controlling EfOM adsorption was pore size distribution. Low molecular weight neutrals had the highest adsorption onto MTC while humic substances were the least interfering fraction. Effect of important parameters such as contact time, linear velocity and bed height/diameter ratio on MTC performance was studied in large-lab scale columns. Linear velocity and contact time were found to be effective in increasing adsorption capacity of PRO on MTC and delaying breakthrough time. Increase in linear velocity from 0.64 cm/min to 1.29 cm/min increased mass transfer and dispersion, resulting in considerable rise of adsorbed amount (5.86 mg/g to 22.58 mg/g) and increase in breakthrough time (15.8-62.7 h). Efficiency of non-equilibrium Hydrus model considering dispersion and mass transfer mechanism was demonstrated for real wastewater and scale up purposes. Ball milling for degradation of adsorbed PRO and regeneration of MTC resulted in 79% degradation of PRO was achieved after 5 h milling (550 rpm), while the addition of quartz sand increased the efficiency to 92%.

Remediation of poly- and perfluoroalkyl substances (PFAS) contaminated soils - To mobilize or to immobilize or to degrade?

Poly- and perfluoroalkyl substances (PFASs) are synthetic chemicals, which are introduced to the environment through anthropogenic activities. Aqueous film forming foam used in firefighting, wastewater effluent, landfill leachate, and biosolids are major sources of PFAS input to soil and groundwater. Remediation of PFAS contaminated solid and aqueous media is challenging, which is attributed to the chemical and thermal stability of PFAS and the complexity of PFAS mixtures. In this review, remediation of PFAS contaminated soils through manipulation of their bioavailability and destruction is presented. While the mobilizing amendments (e.g., surfactants) enhance the mobility and bioavailability of PFAS, the immobilizing amendments (e.g., activated carbon) decrease their bioavailability and mobility. Mobilizing amendments can be applied to facilitate the removal of PFAS though soil washing, phytoremediation, and complete destruction through thermal and chemical redox reactions. Immobilizing amendments are likely to reduce the transfer of PFAS to food chain through plant and biota (e.g., earthworm) uptake, and leaching to potable water sources. Future studies should focus on quantifying the potential leaching of the mobilized PFAS in the absence of removal by plant and biota uptake or soil washing, and regular monitoring of the long-term stability of the immobilized PFAS.