Multicomponent and Surface Charge Effects on PFOS Sorption and Transport in Goethite-Coated Porous Media under Variable Hydrochemical Conditions.

Perfluorooctanesulfonate (PFOS), a toxic anionic perfluorinated surfactant, exhibits variable electrostatic adsorption mechanisms on charge-regulated minerals depending on solution hydrochemistry. This work explores the interplay of multicomponent interactions and surface charge effects on PFOS adsorption to goethite surfaces under flow-through conditions. We conducted a series of column experiments in saturated goethite-coated porous media subjected to dynamic hydrochemical conditions triggered by step changes in the electrolyte concentration of the injected solutions. Measurements of pH and PFOS breakthrough curves at the outlet allowed tracking the propagation of multicomponent reactive fronts. We performed process-based reactive transport simulations incorporating a mechanistic network of surface complexation reactions to quantitatively interpret the geochemical processes. The experimental and modeling outcomes reveal that the coupled spatio-temporal evolution of pH and electrolyte fronts, driven by the electrostatic properties of the mineral, exerts a key control on PFOS mobility by determining its adsorption and speciation reactions on goethite surfaces. These results illuminate the important influence of multicomponent transport processes and surface charge effects on PFOS mobility, emphasizing the need for mechanistic adsorption models in reactive transport simulations of ionizable PFAS compounds to determine their environmental fate and to perform accurate risk assessment.

Vesicles exhibit high-performance removal of per-and polyfluoroalkyl substances (PFAS) depending on their hydrophobic groups.

The removal of per- and polyfluoroalkyl substances (PFAS) from drinking water is urgently needed. Here, we demonstrated high performance of vesicles on PFAS adsorption. Vesicles used in this study were enclosed amphiphile bilayers keeping their hydrophobic groups inside and their hydrophilic groups outside in water. The distribution coefficient Kd of perfluorooctane sulfonic acid (PFOS) for vesicles was 5.3 × 105 L/kg, which is higher than that for granulated activated carbon (GAC), and Kd of perfluorooctanoic acid (PFOA) for vesicles was 103-104 L/kg. The removal efficiencies of PFOA and PFOS adsorption on DMPC vesicles were 97.1 ± 0.1% and 99.4 ± 0.2%, respectively. The adsorption behaviors of PFOA and PFOS on vesicles were investigated by changing the number of cis-double bonds in the hydrophobic chains of the vesicle constituents. Moreover, vesicles formed by membranes in the different phases were also tested. The results revealed that, when vesicles are formed of a membrane in the liquid-crystalline (liquid-like) phase, the adsorption amounts of both PFOA and PFOS increased as the cis-double bond in the hydrocarbon chains decreased, which is considered due to molecular shape similarity. When vesicles are formed of a membrane in the gel (solid-like) phase, they do not adsorb PFAS as much as in the liquid-crystalline phase, even though the hydrocarbon chains do not have any cis-double bond. Our findings demonstrate that vesicles can be utilized as PFAS adsorbents by optimizing the structure of vesicle constituents and their thermodynamical phase. Indeed, the vesicles (DMPC) were demonstrated that they can adsorb PFOA and PFOS, and be coagulated by a coagulant even in environmental water. The coagulation will enable the removal of PFOA and PFOS from the water after adsorption.

The adsorption behavior of perfluorooctane sulphonate on diamane regulated by strain.

The adsorption of per- and polyfluoroalkyl substances (PFAS), such as perfluorooctane sulfonate (PFOS), is currently a critical issue in the environmental domain, yet it is not fully understood. Diamane, as a stable monolayer adsorbent, has garnered significant research interest. Defects and strain are reported to play a crucial role in regulating its electronic structure. In this study, we employ density functional theory (DFT) calculations to investigate the adsorption of PFOS on both pristine and nitrogen-vacancy (N-V) defected diamane, respectively. Additionally, we systematically examine the effects of strain in diamane along both the a- and b-directions (two directions of a monolayer) on PFOS adsorption. This analysis involves studying the adsorption energy (Eads), electron transfer, and the partial density of states. Finally, we propose the synergistic effects of N-V defects and compression strain in diamane, which enhance PFOS adsorption. Diamane is considered a promising candidate for PFOS sensing or capture.

PFAS remediation: Evaluating the infrared spectra of complex gaseous mixtures to determine the efficacy of thermal decomposition of PFAS.

Due to their widespread production and known environmental contamination, the need for the detection and remediation of per- and polyfluoroalkyl substances (PFAS) has grown quickly. While destructive thermal treatment of PFAS at low temperatures (e.g., 200-500 °C) is of interest due to lower energy and infrastructure requirements, the range of possible degradation products remains underexplored. To better understand the low temperature decomposition of PFAS species, we have coupled gas-phase infrared spectroscopy with a multivariate curve resolution (MCR) analysis and a database of high-resolution PFAS infrared reference spectra to characterize and quantify a complex mixture resulting from potassium perfluorooctanesulfonate (PFOS-K) decomposition. Beginning at 375 °C, nine prevalent decomposition products (namely smaller perfluorocarbon species) are identified and quantified.

Natural mineral and industrial solid waste-based adsorbent for perfluorooctanoic acid and perfluorooctane sulfonate removal from surface water: Advances and prospects.

PER: and polyfluorinated alkyl substances, especially perfluorooctanoic acid and perfluorooctane sulfonic acid (PFOX), have attracted considerable attention lately because of their widespread occurrence in aquatic environment and potential biological toxicity to animals and human beings. The development of economical, efficient, and engineerable adsorbents for removing PFOX in water has become one of the research focuses. This review summarized the recent progress on natural mineral and industrial solid based adsorbent (NM&ISW-A) and removal mechanisms concerning PFOX onto NM&ISW-A, as well as proposed the current challenges and future perspectives of using NM&ISW-A for PFOX removal in water. Kaolinite and montmorillonite are usually used as model clay minerals for PFOX removal, and have been proved to adsorb PFOX by ligand exchange and electrostatic attraction. Fe-based minerals, such as goethite, magnetite, and hematite, have better PFOX adsorption capacity than clay minerals. The adsorbent prepared from industrial solid waste by high temperature roasting has great potential application prospects. Fabricating nanomaterials, amination modification, surfactant modification, fluorination modification, developing versatile composites, and designing special porous structure are beneficial to improve the adsorption performance of PFOX onto NM&ISW-A by enhancing the specific surface area, positive charge, and hydrophobicity. Electrostatic interaction, hydrophobic interaction, hydrogen bond, ligand and ion exchange, and self-aggregation (formation of micelle or hemimicelle) are the main adsorption mechanisms of PFOX by NM&ISW-A. Among them, electrostatic and hydrophobic interactions play a considerable role in the removal of PFOX by NM&ISW-A. Therefore, NM&ISW-A with electrostatic functionalities and considerable hydrophobic segments enables rapid, efficient, and high-capacity removal of PFOX. The future directions of NM&ISW-A for PFOX removal include the preparation and regeneration of engineerable NM&ISW-A, the development of coupling technology for PFOX removal based on NM&ISW-A, the in-depth research on adsorption mechanism of PFOX by NM&ISW-A, as well as the development of NM&ISW-A for PFOX alternatives removal. This review paper would be helpful the comprehensive understanding of NM&ISW-A potential for PFOX removal and the PFOX removal mechanisms, and identifies the gaps for future research and development.

Mobilization of per- and poly-fluoroalkyl substances (PFAS) in soils with different organic matter contents.

There is considerable interest in addressing soils contaminated with per- and polyfluoroalkyl substances (PFAS) because of the PFAS in the environment and associated health risks. The neutralization of PFAS in situ is challenging. Consequently, mobilizing the PFAS from the contaminated soils into an aqueous solution for subsequent handling has been pursued. Nonetheless, the efficiency of mobilization methods for removing PFAS can vary depending on site-specific factors, including the types and concentrations of PFAS compounds, soil characteristics. In the present study, the removal of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) from artificially contaminated soils was investigated in a 2D laboratory setup using electrokinetic (EK) remediation and hydraulic flushing by applying a hydraulic gradient (HG) for a duration of 15 days. The percent removal of PFOA by EK was consistent (∼80%) after a 15-day treatment for all soils. The removal efficiency of PFOS by EK significantly varied with the OM content, where the PFOS removal increased from 14% at 5% OM to 60% at 50% OM. With HG, the percent removal increased for both PFOA and PFOS from about 20% at 5% OM up to 80% at 75% OM. Based on the results, the mobilization of PFAS from organic soil would be appropriate using both hydraulic flushing and EK considering their applicability and advantages over each other for site-specific factors and requirements.

PFAS transport under lower water-saturation conditions characterized with instrumented-column systems.

The transport of PFOS and PFOA in well-characterized sand was investigated for relatively low water saturations. An instrumented column was used for some experiments to provide real-time in-situ monitoring of water saturation and matric potential. The results showed that water saturations and matric potentials varied minimally during the experiments. Flow rates were monitored continuously and were essentially constant. These results demonstrate that surfactant-induced flow and other nonideal hydraulic processes did not materially impact PFAS transport for the experiment conditions. Air-water interfacial adsorption was demonstrated to provide the great majority of retention for PFOS and PFOA. Retention was significantly greater at the lower water saturations (0.35-0.45) compared to the higher saturations (∼0.66) for both PFAS, due to the larger extant air-water interfacial areas. Retardation factors were 5 and 3-times greater at the lower water saturations for PFOS and PFOA, respectively. Early breakthrough was observed for the PFAS but not for the non-reactive tracers at the lower water saturations, indicating the possibility that air-water interfacial adsorption was rate-limited to some degree. Independently determined retention parameters were used to predict retardation factors for PFOS and PFOA, which were similar to the measured values in all cases. The consistency between the predicted and measured values indicates that PFAS retention was accurately represented. In addition, air-water interfacial adsorption coefficients measured from the transport experiments were consistent with independently measured equilibrium-based values. Based on these results, it appears that the air-water interfacial adsorption processes mediating the magnitude of PFOS and PFOA retention under lower water-saturation conditions are consistent with those for higher water saturations. This provides some confidence that our understanding of PFAS retention obtained from work conducted at higher water saturations is applicable to lower water saturations.

Comparison of perfluoroalkyl substance adsorption performance by inorganic and organic silicon modified activated carbon.

Owing to the persistence and increasingly stringent regulations of perfluoroalkyl substances (PFAS), it is necessary to improve their adsorption capacities using activated carbon (AC). However, their adsorption capacities are suppressed by dissolved organic matter (DOM). In this study, two ACs modified with organic silicon (C-OS) and inorganic silicon (C-IS) were synthesized and used for the adsorption of PFAS in raw water (RW). The results showed that the PFAS adsorption capacity of C-IS was much less influenced by DOM than that of the original AC (C-virgin). In RW, perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) adsorption capacities on C-IS were 15.08 and 3.65 times higher than those on C-virgin, respectively. DOM had less influence on the PFOA and PFOS adsorption kinetics of C-IS than C-OS and C-virgin. Under multi-PFAS condition, C-IS also exhibited slower desorption of short-chain PFAS and breakthrough in batch and column tests, respectively. Characterization of the ACs before and after adsorption and independent gradient modelling indicated that hydrogen bond interactions between the O-Si of C-IS and the -COOH or -CSO3H groups of PFAS contributed to PFAS adsorption. Density functional theory calculations demonstrated that the adsorption energy of C-IS was much lower than that of C-OS and C-virgin. The arrangement of PFAS molecules on C-OS was chaotic owing to the hydrophobic siloxane chain, whereas the arrangement of PFAS on C-IS was orderly in multi-layer or semi-micelle status and more favorable to PFAS adsorption. This study provides a new strategy for avoiding adverse effects of DOM on PFAS adsorption.

Enhancing the Thermal Mineralization of Perfluorooctanesulfonate on Granular Activated Carbon Using Alkali and Alkaline-Earth Metal Additives.

Thermal treatment has emerged as a promising approach for either the end-of-life treatment or regeneration of granular activated carbon (GAC) contaminated with per- and polyfluoroalkyl substances (PFAS). However, its effectiveness has been limited by the requirement for high temperatures, the generation of products of incomplete destruction, and the necessity to scrub HF in the flue gas. This study investigates the use of common alkali and alkaline-earth metal additives to enhance the mineralization of perfluorooctanesulfonate (PFOS) adsorbed onto GAC. When treated at 800 °C without an additive, only 49% of PFOS was mineralized to HF. All additives tested demonstrated improved mineralization, and Ca(OH)2 had the best performance, achieving a mineralization efficiency of 98% in air or N2. Its ability to increase the reaction rate and shift the byproduct selectivity suggests that its role may be catalytic. Moreover, additives reduced HF in the flue gas by instead reacting with the additive to form inorganic fluorine (e.g., CaF2) in the starting waste material. A hypothesized reaction mechanism is proposed that involves the electron transfer from O2- defect sites of CaO to intermediates formed during the thermal decomposition of PFOS. These findings advocate for the use of additives in the thermal treatment of GAC for disposal or reuse, with the potential to reduce operating costs and mitigate the environmental impact associated with incinerating PFAS-laden wastes.

Sensitive Detection of Perfluoroalkyl Substances Using MXene-AgNP-Based Electrochemical Sensors.

Per- and polyfluoroalkyl substances (PFAS) pose a significant threat to the environment due to their persistence, ability to bioaccumulate, and harmful effects. Methods to quantify PFAS rapidly and effectively are essential to analyze and track contamination, but measuring PFAS down to the ultralow regulatory levels is extremely challenging. Here, we describe the development of a low-cost sensor that can measure a representative PFAS, perfluorooctanesulfonic acid (PFOS), at the parts per quadrillion (ppq) level within 5 min. The method combines the ability of PFOS to bind to silver nanoparticles (AgNPs) embedded within a fluorine-rich Ti3C2-based multilayered MXene, which provides a large surface area and accessible binding sites for direct impedimetric detection. Fundamentally, we show that MXene-AgNPs are capable of binding PFOS and other long-chain PFAS compounds, though the synergistic action of AgNPs and MXenes via electrostatic and F-F interactions. This binding induced concentration-dependent changes in the charge-transfer resistance, enabling rapid and direct quantification with extremely high sensitivity and no response to interferences. The sensor displayed a linear range from 50 ppq to 1.6 ppt (parts per trillion) with an impressively low limit of detection of 33 ppq and a limit of quantification of 99 ppq, making this sensor a promising candidate for low-cost screening of the PFAS content in water samples, using a simple and inexpensive procedure.

The complex effect of dissolved organic carbon on desorption of per- and poly-fluoroalkyl substances from soil under alkaline conditions.

Per- and poly-fluoroalkyl substances (PFASs) are contaminants of emerging concern, yet the understanding of factors that control their leaching and release from contaminated soils remains limited. This study aimed to investigate the impact of dissolved organic carbon (DOC) on the release of PFASs-specifically, perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), and perfluorooctanoic acid (PFOA)from soils contaminated by aqueous film forming foam (AFFF). Batch aqueous leaching experiments were conducted on AFFF-contaminated soils under alkaline solution conditions (pH 9.5, 10.5, and 12) as it enhances leaching of both PFAS and DOC. Leaching of PFOS was significantly increased under alkaline conditions. Although the leaching of PFAS generally increased with pH, PFOS appeared to be more retained under the very alkaline pH conditions used in this study. At the same solution pH, leaching of PFOS and DOC was less in Ca(OH)2 than in NaOH. The retention of PFOS under these conditions may be attributable to the shielding of the negative charge of the soil components and colloids (e.g., DOC and clay minerals) in the leachates and/or the screening of negative charges on head groups of PFOS due to the high concentration of divalent cations. Solution chemistry affected desorption of PFOS more than PFHxS and PFOA. The study highlights that the influence of DOC on PFAS leaching and transport can be very complex, and depends on leachate chemistry (e.g., pH and cation type), PFAS chemistry, the magnitude of PFAS contamination and factors that influence the solid:liquid partitioning of organic carbon in soil.

Ultrasonic degradation of per-and polyfluoroalkyl substances (PFAS), aqueous film-forming foam (AFFF) and foam fractionate (FF).

The ubiquitousness of per- and polyfluoroalkyl substances (PFAS) is a big concern and PFAS remediation is urgently needed such as via degradation. While previous studies have explored ultrasonic degradation of PFAS, work evaluating the operational parameters is rare, especially concerning real wastes such as aqueous film-forming foam (AFFF) and foam fractionate (FF). This study investigates the key operational parameters affecting the degradation efficiency of PFAS, encompassing ultrasonication frequency (580-1144 kHz), power intensity (125-187.5 W), initial concentration (0.08-40 ppm), treatment duration (0.5-3 h), sample volume (100-500 mL), and PFAS structure (perfluorooctanoic acid or PFOA; perfluorooctane sulfonate or PFOS; 6:2 fluorotelomer sulfonate or 6:2 FTS). The defluorination kinetics is different from the removal/degradation kinetics due to the generation of degradation intermediates, suggesting the complex degradation mechanism, which should be evaluated to close the mass balance effectively. Notably, the optimised ultrasonic system achieves ∼125%/∼115% defluorination in AFFF/FF example wastes (compared to ∼65%/∼97% removal) despite their complex composition and the involvement of total oxidizable precursor (TOP) assay. In the meantime, a few new PFAS are detected in the post-treatments, including perfluorohexane sulfonic acid (PFHxS) and 10:2 fluorotelomer sulfonate (10:2 FTS) in the AFFF, and perfluorooctane sulfonamide (FOSA) and 8:2 fluorotelomer sulfonate (8:2 FTS) in the FF, again suggesting the complex degradation mechanism. Overall, ultrasonication is effective to degrade PFAS real example wastes, advancing its potential for scale-up applications.

Molecularly imprinted resin modified with ionic liquid for dispersive filter extraction and determination of perfluoroalkyl acids in eggs.

Perfluoroalkyl acids (PFAAs) are emerging pollutants that endangers food safety. Developing methods for the selective determination of trace PFAAs in complex samples remains challenging. Herein, an ionic liquid modified porous imprinted phenolic resin-dispersive filter extraction-liquid chromatography-tandem mass spectrometry (IL-PIPR-DFE-LC-MS/MS) method was developed for the determination of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in eggs. The new IL-PIPR adsorbent was prepared at room temperature, which avoids the disorder and instability of the template at high temperatures. The imprinting factor of IL-PIPR for PFOA and PFOS exceeded 7.3. DFE, combined with IL-PIPR (15 mg), was used to extract PFOA and PFOS from eggs within 15 min. The established method exhibits low limits of detection (0.01-0.02 ng/g) and high recoveries (84.7%-104.7%), which surpass those of previously reported methods. This work offers a new approach to explore advanced imprinted adsorbents for PFAAs, efficient sample pretreatment technique, and analytical method for pollutants in foods.

Application of cobalt-cerium-iron ternary layered double hydroxide for extraction of perfluorooctane sulfonate followed by HPLC-MS/MS analysis.

Herein, Ce-doped CoFe layered double hydroxide (LDH), noted as CoCeFe ternary LDH, was prepared using the co-precipitation route. Prosperous synthesis of CoFe LDH and successful partial replacement of iron cations with cerium cations in CoCeFe ternary LDH were confirmed by X-ray diffraction patterns, energy-dispersive X-ray spectroscopy, and elemental dot-mapping images. Nanosheet morphology was recognized for both CoFe LDH and CoCeFe ternary LDH from scanning electron microscopy and transmission electron microscopy micrographs. In the following, a dispersive solid phase extraction (DSPE) method was developed using the synthesized CoCeFe ternary LDH as a sorbent for extracting perfluorooctanesulfonic acid (PFOS) from wastewater samples. For the selective analysis of PFOS, high-performance liquid chromatography-tandem mass spectroscopy (HPLC-MS/MS) in multiple reaction monitoring mode was used. Analytical parameters such as the limit of detection equal to 0.02 µg/L, with a linear range of 0.05-300 µg/L, the limit of quantification equal to 0.05 µg/L, and an enrichment factor equal to 23.3 were achieved for PFOS at the optimized condition (sorbent: 5 mg of CoCeFe ternary LDH, eluent type and volume: 150 µL mobile phase, pH: 3, adsorption time: 3 min, and desorption time: 5 min). The developed strategy for the analysis of PFOS was tested in real wastewater samples, including copper mine and petrochemical wastewater. The amount of analytes in real samples was calculated using the standard addition method, and good relative recovery in the range of 86%-105% was obtained. The main novelty of this research is the application of CoCeFe ternary LDH to extract the PFOS from wastewater using the DSPE method for determination by HPLC-MS/MS.

Adsorption of per- and poly-fluoroalkyl substances (PFAS) on Ni: A DFT investigation.

Electrocatalytic destruction of per- and polyfluoroalkyl substances (PFAS) is an emerging approach for treatment of PFAS-contaminated water. In this study, a systematic ab initio investigation of PFAS adsorption on Ni, a widely used electrocatalyst, was conducted by means of dispersion-corrected Density Functional Theory (DFT) calculations. The objective of this investigation was to elucidate the adsorption characteristics and charge transfer mechanisms of different PFAS molecules on Ni surfaces. PFAS adsorption on three of the most thermodynamically favorable Ni surface facets, namely (001), (110), and (111), was investigated. Additionally, the role of PFAS chain length and functional group was studied by comparing the adsorption characteristics of different PFAS compounds, namely perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorobutanesulfonic acid (PFBS), and perfluorobutanoic acid (PFBA). For each PFAS molecule-Ni surface facet pair, different adsorption configurations were considered. Further calculations were carried out to reveal the effect of solvation, pre-adsorbed atomic hydrogen (H), and surface defects on the adsorption energy. Overall, the results revealed that the adsorption of PFAS on Ni surfaces is energetically favorable, and that the adsorption is primarily driven by the functional groups. The presence of preadsorbed H and the inclusion of solvation produced less exothermic adsorption energies, while surface vacancy defects showed mixed effects on PFAS adsorption. Taken together, the results of this study suggest that Ni is a promising electrocatalyst for PFAS adsorption and destruction, and that proper control for the exposed facets and surface defects could enhance the adsorption stability.

Effect of ligand interactions within modified granular activated carbon (GAC) on mixed perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) adsorption.

A new adsorbent based on commercial granular activated carbon (GAC) and loaded with Cu(II) (GAC-Cu) was prepared to enhance the adsorption capacity of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). The surface area (SA) and pore volume of GAC-Cu decreased by ∼15% compared to those of pristine GAC. The scanning electron microscopy-energy dispersive spectrometry (SEM-EDS) and leaching test results indicated that, compared with GAC, the Cu atomic ratio and Cu amount in GAC-Cu increased by 2.91 and 2.43 times, respectively. The point of zero charge (PZC) measured using a salt addition method obtained a pH of 6.0 (GAC) and 5.0 (GAC-Cu). According to the isotherm models obtaining highest coefficient of determination (R2), GAC-Cu exhibited a 20.4% and 35.2% increase for PFOA and PFOS in maximum uptake (qm), respectively, compared to those of GAC. In addition, the adsorption affinity (b) for GAC-Cu increased by 1045% and 175% for PFOA and PFOS, respectively. The pH effect on the adsorption capacity of GAC-Cu was investigated. The uptake of PFOA and PFOS decreased with an increase in pH for both GAC and GAC-Cu. GAC-Cu exhibited higher uptake than GAC at pH 6 and 7, but no enhanced uptake was observed at pH 4.0, 5.0, and 8.5. Therefore, ligand interaction was effective at weak acid or neutral pH.

Kinetics and mechanism analysis of advanced oxidation degradation of PFOA/PFOS by UV/Fe3+ and persulfate: A DFT study.

UV/Fe3+ and persulfate are two promising advanced oxidative degradation systems for in situ remediation of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), yet a lack of comprehensive understanding of the degradation mechanisms. For the first time, we used density functional theory (DFT) to calculate the entire reaction pathways of the degradation of PFOA/PFOS in water by UV/Fe3+ and persulfate. In addition, we have deeply explored the different attack pathways driven by •OH and SO4-•, and found that SO4-• determines PFOA/PFOS to obtain PFOA/PFOS free radicals through single electron transfer to initiate the degradation reaction, while •OH determines the speed of PFOA/PFOS degradation reaction. Both degradation reactions were thermodynamically advantageous and kinetically feasible under calculated conditions. Based on the thermodynamic data, persulfate was found to be more favorable for the advanced oxidative degradation of Perfluorinated compounds (PFCs). Moreover, for SO4-• and •OH co-existing in the persulfate system, pH will affect the presence and concentration of these two types of free radicals, and low pH is not necessary for the degradation of PFOA/PFOS in the persulfate system. These results can considerably advance our understanding of the PFOA/PFOS degradation process in advanced oxidation processes (AOPs), which is driven by •OH and SO4-•. This study provides a DFT calculation process for the mechanism calculation of advanced oxidation degradation of other types of PFCs pollutants, hoping to elucidate the future development of PFCs removal. Further research should focus on determining the advanced oxidation degradation pathways of other types of PFCs, to support the development of computational studies on the advanced oxidation degradation of PFCs.

Activation of sawdust biochar with water and wastewater treatment residuals for sorption of perfluorooctanesulfonic acid in water.

Recent research has found biochar to be a cost-effective adsorbent for removal of perfluoroalkyl substances in water. To promote cleaner production and sustainable waste management, this study explored the potential to produce activated biochars by co-pyrolyzing sawdust with iron-rich biosolids and polyaluminum sludge. The maximum capacity to adsorb perfluorooctanesulfonic acid (PFOS) reached 27.2 mg g-1 with biosolids-activated biochar and 19.2 mg g-1 with aluminum sludge-activated biochar, compared to 6.2 mg g-1 with sawdust biochar. The increased adsorption capacities were attributed to electrostatic interactions between the anionic PFOS and metal functionalities on the biochar surface. In contrast, hydrophobic interaction was the dominant adsorption mechanism of sawdust biochar. The presence of dissolved organic matter at 5-50 mg L-1 was found to inhibit adsorption of PFOS in water, while pH as low as 3.0 and sodium chloride concentrations up to 100 mM enhanced removal of PFOS by all the three adsorbents. In batch adsorption tests at environmentally relevant PFOS dosages and adsorbent dosage of 0.25 g L-1, the biosolids-sawdust biochar and Al sludge-sawdust biochar removed 71.4% and 66.9% of PFOS from drinking water and 77.9% and 87.9% of PFOS from filtrate of sludge digestate, respectively. The biosolids-sawdust biochar additionally removed Fe, although the Al sludge-sawdust biochar released Al into the alkaline drinking water and filtrate. Overall, this study proved co-pyrolyzing sawdust and Fe-rich biosolids to be an effective approach to activate sawdust biochar for enhanced removal of PFOS while recycling wastewater treatment residuals and sawdust.

Defluorination of PFAS by Acidimicrobium sp. strain A6 and potential applications for remediation.

Acidimicrobium sp. strain A6 is a recently discovered autotrophic bacterium that is capable of oxidizing ammonium while reducing ferric iron and is relatively common in acidic iron-rich soils. The genome of Acidimicrobium sp. strain A6 contains sequences for several reductive dehalogenases, including a gene for a previously unreported reductive dehalogenase, rdhA. Incubations of Acidimicrobium sp. strain A6 in the presence of perfluorinated substances, such as PFOA (perfluorooctanoic acid, C8HF15O2) or PFOS (perfluorooctane sulfonic acid, C8HF17O3S), have shown that fluoride, as well as shorter carbon chain PFAAs (perfluoroalkyl acids), are being produced, and the rdhA gene is expressed during these incubations. Results from initial gene knockout experiments indicate that the enzyme associated with the rdhA gene plays a key role in the PFAS defluorination by Acidimicrobium sp. strain A6. Experiments focusing on the defluorination kinetics by Acidimicrobium sp. strain A6 show that the defluorination kinetics are proportional to the amount of ammonium oxidized. To explore potential applications for PFAS bioremediation, PFAS-contaminated biosolids were augmented with Fe(III) and Acidimicrobium sp. strain A6, resulting in PFAS degradation. Since the high demand of Fe(III) makes growing Acidimicrobium sp. strain A6 in conventional rectors challenging, and since Acidimicrobium sp. strain A6 was shown to be electrogenic, it was grown in the absence of Fe(III) in microbial electrolysis cells, where it did oxidize ammonium and degraded PFAS.