Perfluorooctanoic Acid Removal Research Articles

Efficient removal of perfluorooctanoic acid from aqueous matrices using cationic surfactant functionalized graphene oxide nanocomposite: RSM and ANN modeling, and adsorption behaviour

Perfluorooctanoic acid (PFOA), a persistent and recalcitrant emerging organic contaminant, has garnered worldwide attention due to its pervasiveness and strong bioaccumulation, emphasizing the urgent necessity for effective removal strategies. To address PFOA contamination in the global aquatic environment, this study prepared cetyltrimethylammonium bromide (CTAB)-functionalized graphene oxide (GO-C) nanocomposites. The functionality of GO-C is controlled by varying loading ratios of CTAB to achieve satisfactory performance. After preliminary experiments that confirmed the superior performance of GO-C0.5 in PFOA removal, the response surface methodology (RSM) revealed the effects of different process parameters, which followed the sequence: adsorbent dose > pH > time. The optimum PFOA removal of 98.5 % was achieved at adsorbent dose: 200 mg/L, pH: 3.5, and time: 50 min, at an experimental temperature of 298 K. Furthermore, a predictive model using an artificial neural network was developed for PFOA adsorption, which closely aligns with the experimental data (R2: 0.9999). The PFOA adsorption was most accurately represented by Freundlich isotherm (R2: 0.9747) and pseudo-second-order kinetics (R2: 0.9995), with a maximum experimental adsorption capacity of ~709.94 mg/g under RSM optimized conditions. The adsorption mechanism involves electrostatic and hydrophobic interactions and hydrogen bonding, as confirmed by the spectroscopic and zeta potential analyses. Lastly, the competitive adsorption and regeneration experiments underscore the potential of GO-C nanocomposite in removing PFOA. Overall, this study provides insights into the development and application of sustainable and promising adsorbent for the removal of PFOA in wastewater stream.

Dual-functional adsorptive membranes for PFAS removal: Mechanism, CFD simulation, and selective enrichment

The remediation of emerging water contaminants, particularly per- and polyfluoroalkyl substances (PFAS), presents challenges due to their refractory nature and the presence of competing substances. Dual-functional adsorptive membranes, with hydrophobic backbone and quaternary ammonium moieties, were thereby designed to selectively intercept organic competitors while enrich PFAS. A 96.8 % removal of perfluorooctanoic acid (PFOA) was achieved and this effective removal (>90 %) maintained across five reuse cycles with a total treatment capacity of 650 L m−2. Rather than the rejection mechanism of nanofiltration process, these adsorptive membranes utilize synergistic electrostatic attraction and hydrophobic interactions, leading to a greater enrichment factor of 18.5 (PFOA over humic acid) and a permeability of 34.6 L m-2h−1 bar−1 (1.9- and 4.5-fold higher than reported NF 270 membranes, respectively). Furthermore, computational fluid dynamics (CFD) modeling revealed that the sponge-like matrix effectively prevents channeling flow and enhance access to adsorption sites. Sensitivity analysis and the high Damkohler number indicated that the adsorption process is mass transfer-controlled, with the key parameters ranked in order of significance: residence time > fluid viscosity > intrinsic adsorption rate. With consistent removal performance with co-existing competitors, efficient regeneration, and reusability, the dual-functional adsorptive membranes offer promising practical efficacy for PFAS remediation.

Advanced Polymer Composites for Effective Removal of Perfluorooctanoic Acid (PFOA) Pollutants From Aqueous Solutions.

Perfluorooctanoic acid (PFOA) is extensively utilized in industrial applications, posing significant environmental and health risks because of its persistence and toxicity. Effective elimination methods are vital to mitigate its adverse effects on ecosystems and human health. In this study, we investigate the potential of biomass-derived polymer composite for PFOA adsorption in aqueous solution. Due to its unique surface interaction and porosity, the polymer-based composite derived from sustainable biomass sources exhibits favorable adsorption characteristics. The physicochemical properties of polymer composites were characterized using FTIR, XRD, SEM-EDS, XPS, and BET analysis. The polymer composites reached a maximum PFOA adsorption efficiency about 93.3% under optimized conditions determined by Box Behnken Design. The Langmuir isotherm model revealed and provided an adsorption capacity of PFOA about 13.98 mg g-1. Moreover, the polymer-based composites demonstrated reusability, with removal rates of PFOA ranging from 93.3% to 52% over the course of four cycles after desorption. Our findings underscore the possibility of biomass-derived polymer composites as long-term and effective adsorbents for PFOA removal from aqueous environments.

Enhanced adsorption of aqueous perfluorooctanoic acid on iron-functionalized biochar: elucidating the roles of inner-sphere complexation

Perfluorooctanoic acid (PFOA) is ubiquitously detected in various water bodies, which raises the urgent need for developing effective and economic remediation methods in response to its health risks. The adsorptive removal of PFOA by biochar (BC) is regarded as a simple, effective, and economical technique. However, engineered BCs, including FeCl3-activated BC, for PFOA removal and adsorption mechanisms have been ill-studied. In this study, a FeCl3-activated dairy manure-derived biochar (Fe@MBC) was prepared via one-step pyrolysis/activation, and its properties and adsorption characteristics were compared with a pristine manure-derived biochar (P-MBC). The FeCl3 activation largely increased the surface area of Fe@MBC and the deposition of FexOy minerals on surface of Fe@MBC while significantly elevating the surface roughness of Fe@MBC. The maximum adsorption capacity of Fe@MBC for PFOA (233 mg·g−1) was five times higher than that of P-MBC (46 mg·g−1). PFOA adsorption was favorable at low solution pH and was independent on ionic strength, which supported the major contribution by inner-sphere complexation rather than out-sphere complexation. This mechanism was further confirmed by the disappearance of FeO peak on Fourier transform infrared spectrum and the blue-shift of Fe binding energies on X-ray photoelectron Fe 2p spectrum of Fe@MBC after PFOA adsorption. Fe@MBC maintained a near 100% adsorption capacity for PFOA after 4 cycles of chemical regeneration. Fe@MBC also exhibited efficient removal for PFOA and other PFAS compounds at trace levels in the lake water and wastewater treatment plant effluent. Thus, this study highlights a promising insight for selectively eliminating PFASs from water.

Cation-Doped Nanocarbons for Enhanced Perfluoroalkyl Substance Removal: Exotic Bottom-Up Solution Plasma Synthesis and Characterization.

Perfluorinated alkyl substances (PFAS), such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), are pervasive organic contaminants that are widespread in aquatic environments, posing significant health risks to humans and wildlife. Due to their persistent nature, urgent removal is necessary. Conventional adsorbents are inefficient at removing PFOS and PFOA, highlighting the need for alternative materials. Herein, we present a synthetic method for quaternary ammonium cation-doped carbon nanoparticles (QACNs) using a solution plasma process for the efficient removal of PFOS and PFOA. QACN is formed simultaneously through a one-step discharge of nonequilibrium plasma at the interface of benzene and pyridinium chloride. The resulting material exhibited a high surface electrical charge and enhanced hydrophilicity as well as an amorphous structure of a nonporous nature, involving nanoparticles with an undefined shape. The obtained adsorbent demonstrated high adsorption efficiency and stability, adsorbing 998.45 and 889.37 mg g-1 of PFOS and PFOA, respectively, exceeding the efficiencies of conventional carbon-based adsorbents (80.89-313.15 mg g-1). The adsorption performance was dependent on the adsorbent dosage, pH of the solution, and the coexisting ionic species. Adsorption studies, including adsorption kinetics, isotherms, and thermodynamics, revealed that PFOS and PFOA were chemisorbed to the QACN surface, forming multilayers endothermically and spontaneously. Experimental and computational analyses revealed that adsorption primarily occurs via electronic interactions between the PFAS active sites and the quaternary ammonium group in the carbon framework. The slightly lower adsorption potential of the PFOS and PFOA fluorocarbon chains on the adsorbent was elucidated. Furthermore, the dispersibility of the adsorbent in solution significantly affected the adsorption performance. These findings highlight the potential of the novel synthetic method proposed in this study, offering a pathway for the development of highly effective carbon adsorbents for environmental remediation.

Bioelectricity drives transformation of nitrogen and perfluorooctanoic acid in constructed wetlands: Performances and mechanisms

In this study, constructed wetland-microbial fuel cell (CW-MFC) filled with modified basalt fiber (MBF) via iron modification was utilized for treating perfluorooctanoic acid (PFOA) containing sewage. Results showed the significant promotion by bioelectricity on ammonium and total nitrogen by 7.80–8.14 %. Although such enhancement was suppressed by PFOA, higher removal was still observed with closed circuit, and PFOA removal also increased by 9.05 %. Bioelectricity contributed to enrichment of bacteria involved in nitrifying (Nitrospira and Ellin6067), denitrifying (like Thauera and Dechloromonas), iron redox (Geobacter), and sulfate-reducing (Desulfobacter), aligned with up-regulated of functional genes, including amoA, narG , napA, narK, narS, nrfA, sulp and sqr. Enrichment of autohydrogenotrophic and sulfide-oxidizing autotrophic denitrifiers, and nitrate dependent iron oxidation bacteria by bioelectricity all promoted denitrification. Moreover, bioelectricity boosted relative abundance of organic compounds degradation enzymes, such as dehydrogenase, decarboxylase, and dehalogenase, supporting the enhancement on PFOA removal. Generally, PFOA was converted to short-chain perfluorocarboxylic acids (PFCAs) via decarboxylation, hydroxylation, HF elimination, hydrolysis, F- elimination, C-C bond scission, and dehydration in CW-MFC. The final PFCAs-products determined was perfluorobutyric acid. This work estimated feasibility of treating PFOA containing sewage by CM-MFC, and offered new insights on enhancing mechanisms of nitrogen and PFOA conversion.

Removal of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) by coagulation: Influence of coagulant and dosing conditions

Per- and polyfluoroalkyl substances (PFAS) pose significant risks to the environment and human health. Perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) are two of the most frequently detected PFAS in the environment. In most surface water drinking water treatment works (WTW), coagulation is the first processes exposed to a range of contaminants, including PFAS. While not designed to be a process for removal of micropollutants, it is important to understand the fate of PFAS in coagulation processes, intended or otherwise, to determine whether water treatment sludge can be a significant sink for this group of micropollutants. This work advances understanding of PFAS removal in coagulation processes by comparing the removal of PFOA and PFOS by four metal coagulants (Zr, Zn, Fe, and Al) from real water matrices. The coagulant performance followed the order Al > Fe > Zr > Zn. Al was taken forward for further evaluation, with significant removal of PFAS (>15 % for PFOA and > 30 % for PFOS) being observed when the pH<5.5 and the dose was > 5 mg Al·L-1. The adsorption of PFOA and PFOS onto flocs through hydrophobic interaction was the primary removal route. The impacts of background matrix on the mechanisms of coagulation for PFAS were explored using five organic compounds. Macromolecular organic compounds contributed to an increase in removal due to the sorption of PFAS and subsequent removal of the organic-PFAS aggregate during coagulation. Low molecular weight organic matter inhibited the removal of PFAS due to the ineffective removal of these compounds during coagulation.

Thermal transformations of perfluorooctanoic acid (PFOA): Mechanisms, volatile organofluorine emissions, and implications to thermal regeneration of granular activated carbon

Thermal treatment is effective for the removal of perfluorooctanoic acid (PFOA). However, how temperatures, heating methods, and granular activated carbon (GAC) influence pyrolysis of PFOA, and emission risks are not fully understood. We studied thermal behaviors of PFOA at various conditions and analyzed gaseous products using real-time detection technologies and gas chromatography-mass spectrometry (GC-MS). The thermal decomposition of PFOA is surface-mediated. On the surface of quartz, PFOA decomposed into perfluoro-1-heptene and perfluoro-2-heptene, while on GAC, it tended to decompose into 1 H-perfluoroheptane (C7HF15). Neutral PFOA started evaporating around 100 ℃ without decomposition in ramp heating. During pyrolysis, when PFOA was pre-adsorbed onto GAC, it was mineralized into SiF4 and produced more than 45 volatile organic fluorine (VOF) byproducts, including perfluorocarbons (PFCs) and hydrofluorocarbons (HFCs). The VOF products were longer-chain (hydro)fluorocarbons (C4-C7) at low temperatures (< 500 ℃) and became shorter-chain (C1-C4) at higher temperatures (> 600 ℃). PFOA transformations include decarboxylation, VOF desorption, further organofluorine decomposition and mineralization in ramp heating of PFOA-laden GAC. Decarboxylation initiates at 120 ℃, but other processes require higher temperatures (>200 ℃). These results offer valuable information regarding the thermal regeneration of PFAS-laden GAC and further VOF control with the afterburner or thermal oxidizer.

Removal of per- and polyfluoroalkyl substances (PFAS) from water using magnetic cetyltrimethylammonium bromide (CTAB)-modified pine bark

Per- and polyfluoroalkyl substances (PFAS) have gained global attention in recent years due to their adverse effect on environment and human health. In this study, a novel and cost-effective sorbent was developed utilizing forestry by-product pine bark and tested for the removal of PFAS compounds from both synthetic solutions and contaminated groundwater. The synthesis of the adsorbent included two steps: 1) loading of cetyltrimethylammonium bromide (CTAB) onto the pine bark and followed by 2) a simple coating of magnetite nanoparticles. The developed sorbent (MC-PB) exhibited 100 % perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) removal from synthetic solution (10 µg/L PFOA and PFOS) and enabled quick magnetic separation. A rapid removal of PFOA (> 80 %) by MC-PB was observed within 10 min from synthetic PFOA solution and the adsorption equilibrium was reached within 4 h, achieving > 90 % removal of PFOA (dosage 2 g/L, PFOA 10 mg/L, initial pH 4.2). The PFOA adsorption kinetics fitted well to an optimized pseudo-order model (R2=0.929). Intra-particle diffusion and Boyd models suggested that the adsorption process was not governed by pore diffusion. The maximum PFOA adsorption capacity was found to be 69 mg/g and the adsorption isotherm was best described by the Dual Mode Model (R2=0.950). The MC-PB demonstrated > 90 % PFOA and PFOS removal from contaminated groundwater. Furthermore, both short- and long-chain perfluorosulfonic acids and 6:2 fluorotelomer sulfonate were efficiently removed resulting in 83.9 % removal towards total PFAS (2 g/L dosage).

Efficient defluorination of PFOA by vacuum ultraviolet coupling with sulfite and iodide

Perfluorooctanoic acid (PFOA), as an anthropogenic persistent contaminant, is widely distributed in the natural aquatic environment and has been a considerable threat to ecological security and human health. In this work, we propose and evaluate the vacuum ultraviolet (VUV)/sulfite-iodide system under N2 saturated condition for the decomposition of PFOA. The in situ generated hydrated electrons (eaq−) were demonstrated to be the main active species responsible for the PFOA degradation. With observation of the intermediate products, two major degradation pathways of PFOA in VUV/sulfite-iodide system were proposed: H/F exchange and chains shortening. A significant enhancement of PFOA defluorination was observed with increasing pH values from 9.0 to 12.0, which can be explained by the decreasing quenching effect of eaq− and accelerated disproportionation of I2 to I− and IO3−. Meanwhile, VUV/sulfite-iodide system also exhibited satisfactory performance in degrading high concentration of PFOA (200 μM). However, the presence of Cl−, NO3−, and humic acid inhibited the removal of PFOA via various reaction mechanism. The VUV/sulfite-iodide system was effective toward the chosen PFCAs (trifluoroacetic acid (TFA) and perfluorobutyric acid (PFBA)), demonstrating a chain length independence on the degradation of PFCAs, supporting its broad applicability.

Effective removal of perfluorooctanoic acid from water using PVA@UiO-66-NH2/GO composite materials via adsorption

This study introduces an innovative approach using highly efficient nanocomposite materials to effectively remove PFAS from water, demonstrating remarkable adsorption capabilities. The nanocomposite was synthesized by integrating a zirconium-based metal-organic framework (MOF) called UiO-66 with graphene oxide (GO) within a polyvinyl alcohol (PVA) matrix. The resulting PVA@UiO-66/GO material features flower-like UiO-66 MOF crystals embedded in the PVA and GO matrix. Various kinetic models were applied to determine the rate constants and adsorption capacities, with the Langmuir isotherm indicating an adsorption capacity of 9.904 mg/g. Thermodynamic analysis confirmed the process's spontaneity and exothermic nature. The UiO-66-NH2/GO/PVA composite also demonstrated high reusability, maintaining substantial PFOA removal efficiency across multiple cycles, with optimal reduction occurring at approximately pH 5. Overall, the PVA@UiO-66/GO composites offer an effective, sustainable, and environmentally friendly solution for PFAS removal in water purification.

Removal of PFOA from water by activated carbon adsorption: Influence of pore structure

Activated carbon (AC) adsorption is a practical process for the removal of perfluorooctanoic acid (PFOA) in aquatic environments, but the relationship between its pore structure and adsorption performance is not well understood. In this study, the KOH-activated carbons (KACs) with different tailored pore structures were prepared, and presented a 2.61-fold higher adsorption capacity and a 2.21-fold higher adsorption rate than the raw AC. An in situ characterization method and a modified adsorption model were introduced to investigate the impact of pore size, which demonstrated that the ultra-micropores (<1.2 nm) and small mesopores (2.0–3.0 nm) contributed significantly to the adsorption of PFOA, with the highest mean contribution factor (k) of 0.45 and the second highest of 0.39, respectively. Molecular dynamics simulations revealed that PFOA molecules tend to attach to the pore walls at various pore sizes. The adsorption of PFOA in the ultra-micropores was dominated by enhanced interactions due to the overlapping potentials of the bilateral pore walls (maximum of −567.32 Kcal·mol−1) and hydrophobic interactions. PFOA micelles or hemi-micelles could be formed in the small mesopores, allowing them to function as both the molecule transportation channels and strong adsorption sites. This study would guide the development of activated carbon tailored for the selective adsorption of PFOA from water.

Perfluorooctanoic acid efficient chain reaction degradation in multifunctional iron-sulfur mineral augmentation geobiochemical remediation system

Serious contamination of perfluorooctanoic acid (PFOA) has aroused global concern. General biotransformation or iron-based materials did not meet efficient PFOA elimination. Here, specific green and low-carbon microorganism-biochar pellets, multi-component and multifunctional iron-sulfur (FexSy) mineral pellets, and a microbe-FexSy interaction device were developed to solve this problem. The multi-scale (molecular, interface, and column scales) research method combined with the multi-process reaction model was constructed to explore PFOA removal mechanism. Results revealed that microbe-FexSy interaction achieved excellent PFOA degradation performance and retention effect, with degradation rate λ (0.213 h−1) increased by 113 % than FexSy (0.100 h−1) device. The distribution coefficient Kd and kinetic adsorption α increased by 18.54 % and 22.61 %; the fraction of kinetic sorption increased by 63.83 % in microbe-FexSy device (77 %) than alone FexSy (47 %) device. Delftia and Pseudomonas combined with Fe2+ drove an efficient cycle chain reaction for PFOA. Quantitative structure–activity relationship (QSAR) model prediction results indicated that intermediates exhibited lower biotoxicity than PFOA. Furthermore, NO3– further increased the retention effect of microbe-FexSy device for PFOA with little reaction rate fluctuation, making it promising for eliminating PFOA contamination, especially in NO3– type of groundwater. It provided an efficient technology and device based on microbe-mineral interaction in remediating PFOA-contaminated groundwater.

New insights into removal efficacy of perfluoroalkyl substances by layered double hydroxide and its composite materials

Though the use of per-and polyfluoroalkyl substances (PFAS) is strictly restricted worldwide, PFAS have been increasingly detected in aqueous environment with high human exposure risk. Effective PFAS remediation requires the simultaneous concentration and decomposition of these compounds from dilute solutions, presenting a significant challenge. The present work evaluated the suitability of layered double hydroxide (LDH) materials, promising adsorbents for anionic pollutants, for the removal of long-chain and short-chain PFAS in micro-polluted water. Additionally, it explored their potential for PFAS degradation after modification. The results suggested that LDH adsorbents have limited ability to extract short-chain PFAS such as perfluorobutane sulfonate (PFBS) from water matrices, especially in dilute solutions. Although organic modification of LDHs could enhance their uptake efficacy on PFAS, it cannot improve the decomposition of PFAS. Innovatively, a composite featuring zero-valent iron (ZVI) particles coupled with LDH was developed, in which the nanoscale ZVI core is coated with LDH to adsorb and decompose perfluorooctanoic acid (PFOA) synergistically. Characterization of the composite showed that LDH coating not only hinders the aggregation of ZVI particles, but also reduces the passivation of ZVI. The PFOA removal efficacy of the composite can be further facilitated in acid environment. By-product analysis revealed that the composite decomposed PFOA mainly through decarboxylation and formation of unstable alcohol.

3D-printed indium oxide monoliths for PFAS removal

More efficient removal methods for per- and polyfluoroalkyl substances (PFAS), anthropogenic compounds with high persistence in the environment, are urgently needed due to their significant adverse health effects. Current technologies for PFAS removal in water are limited by incomplete degradation or practical concerns about the use of slurry-based adsorbents. In this study, self-supported indium oxide (In2O3) monoliths were produced via extrusion-based 3D printing and used for the removal of perfluorooctanoic acid (PFOA) via adsorption in a recirculating flow system. A detailed study of the sintering temperature, monolith geometry, and flow rate allowed maximising PFOA adsorption due to the improvement of PFOA diffusion and the increased number of active sites on the monolith, resulting in 53 % of PFOA removal with fast adsorption kinetics in 3 h. Additionally, a low-temperature pyrolysis process at 500 °C effectively regenerated the In2O3 monoliths, allowing reusing the monoliths for three adsorption cycles, while also improving the PFOA removal to 75 % in 3 h. The regenerated In2O3 monoliths not only have a high adsorption capacity (0.16 mg g−1), but also required a much shorter time to reach the adsorption equilibrium compared with other adsorbents reported in the literature. The effectiveness, robustness and reusability of the 3D printed In2O3 monoliths highlight their potential as an efficient and sustainable adsorbent for PFAS removal. The approach presented here represents an effective strategy for the fabrication of complex adsorbents, which are reusable and can be easily handled, eliminating the expensive downstream removal required for slurries while offering a clear route for scale-up towards industrial use.

Efficient removal of perfluorooctanoic acid using fluorinated ionic liquids and granular activated carbon

Perfluoroalkylated and polyfluoroalkylated substances (PFAS) are persistent and bioaccumulative compounds in the environment and the human body. Their presence in high concentrations brings devastating consequences to health. Nowadays, there is an urgent need to develop efficient and sustainable processes that mitigate the damage caused by PFAS to improve the life quality of individuals. In the present work, perfluorooctanoic acid (PFOA) extraction properties with fluorinated ionic liquids (FILs) in aqueous media were evaluated for the first time. The most promising FIL is [P44414] [C4F9SO3] obtaining uptake capacities up to 280 mg·g−1 in 72 h. To verify if this performance is competitive for the best materials used so far in the literature for PFAS removal, adsorption processes were carried out with granular activated carbon (GAC) obtaining adsorption capacities up to 666 mg·g−1 (best fitted with the pseudo-second-order kinetic model) with an equilibrium time of 48 h. Equilibrium assays showed maximum uptake capacities around 500 mg.g−1, and multilayer adsorption due to the best fit to the Freundlich model. Both materials (FILs and GAC1240W) can open new paths in PFAS removal processes from aqueous solutions. Taking advantage of the properties of each one of these compounds, new, more efficient, and sustainable processes can be optimised in the future.

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.

Electrochemical advanced oxidation of PFOA by Ti4O7 reactive electrochemical membrane anode

In recent years, per and polyfluoroalkyl substances (PFAS) have garnered significant attention due to their persistent and harmful effects on the environment and human health. Traditional treatment methods often fall short of effectively removing PFAS from water, prompting the need for innovative techniques. One promising approach is electrochemical advanced oxidation, based on highly reactive chemical species generated through electrochemical reactions to degrade organic pollutants. In this study, a specific reactive electrochemical membrane (REM) anode was used to degrade perfluorooctanoic acid (PFOA). The anode is a tubular Ti4O7-based REM (mixture of Ti4O7 and Ti5O9 Magneli phases) with a water permeability of 3300 L m−2 h−1 bar−1. The impact of various operating parameters, including current density, flux through REM, and feed concentration, on PFOA degradation efficiency was investigated. It was found that higher current densities, feed concentrations and lower flux through REM led to increased PFOA removal rates. With this type of REM, a total degradation of PFOA was observed at PFOA flux (passing throw the REM) under 0.2 g h−1 m−2 even at the lowest current density (71 A/m2). The degradation mechanism was investigated by evaluating the generated by-products after several degradation cycles, and the results confirmed that the degradation occurs via the decomposition cycle of CF2. Energy consumption has been taken into account, as it is the major limitation of advanced oxidation processes, exhibiting value under 5 kWh/g for the lowest current density and the highest PFOA flux. The originality of this study relies on the use of a specific anode; a tubular shape Ti4O7-based REM (by Saint Gobain Company). Such concentric REM reactor is optimal for the treatment of recalcitrant effluent containing PFOA as it significantly improved mass transfer leading to a very interesting energy efficient system that can easily be scale up.

Zirconium-Based Metal-Organic Frameworks with Free Hydroxy Groups for Enhanced Perfluorooctanoic Acid Uptake in Water.

Perfluorooctanoic acid (PFOA) is a highly recalcitrant organic pollutant, and its bioaccumulation severely endangers human health. While various methods are developed for PFOA removal, the targeted design of adsorbents with high efficiency and reusability remains largely unexplored. Here the rational design and synthesis of two novel zirconium-based metal‒organic frameworks (MOFs) bearing free ortho-hydroxy sites, namely noninterpenetrated PCN-1001 and twofold interpenetrated PCN-1002,are presented. Single crystal analysis of the pure ligand reveals that intramolecular hydrogen bonding plays a pivotal role in directing the formation of MOFs with free hydroxy groups. Furthermore, the transformation from PCN-1001 to PCN-1002 is realized. Compared to PCN-1001, PCN-1002 displays higher chemical stability due to interpenetration, thereby demonstrating an exceptional PFOA adsorption capacity of up to 632mgg-1 (1.53mmolg-1), which is comparable to the reported record values. Moreover, PCN-1002 shows rapid kinetics, high selectivity, and long-life cycles in PFOA removal tests. Solid-state nuclear magnetic resonance results and density functional theory calculations reveal that multiple hydrogen bonds between the free ortho-hydroxy sites and PFOA, along with Lewis acid-base interaction, work collaboratively to enhance PFOA adsorption.

Innovative application of basalt fibers as biological carrier in constructed wetland-microbial fuel cell for improvement of performance under perfluorooctanoic acid exposure

Basalt fiber (BF) was filled in constructed wetland-microbial fuel cell (CW-MFC) as bio-carrier for enhancement of operation performance under perfluorooctanoic acid (PFOA) exposure. In this study, although PFOA caused significant decline of ammonium removal by 7.5–7.7 %, slight promotion on nitrogen and phosphorus removal was observed with BF filling, compared to control. PFOA removal also increased by 1.7–3.4 % in BF filling group. Besides, improved electrochemical performance was discovered with BF filling, in which the highest power density increased by 86.6 % than control, even under PFOA stress. Enhanced stability and performance of CW-MFC resulted from stimulation of functional bacteria on electrodes like Dechloromonas, Thauera, Zoogloea, Gemmobacter, and Pseudomonas, which were further enriched on BF carrier. Higher abundance of nitrogen metabolism and related genes on electrodes and BF carrier was also discovered with BF filling. This study offered new findings on application of BF in CW-MFC systems with PFOA exposure.