Degradation Of Perfluorooctanoic Acid Research Articles

Enhanced mitigation of membrane fouling and degradation of perfluorooctanoic acid in the treatment of natural surface water through the application of dielectric barrier discharge/sulfite

The present study employed a dielectric barrier discharge (DBD)/sulfite system to mitigate membrane fouling and enhance the degradation of perfluorooctanoic acid (PFOA) in surface water. Results showed that the membrane flux was remarkably enhanced by 93.6%, and the degradation of PFOA showed an impressive increase of 87.9%. The synergistic redox effect of free radicals, including hydroxyl radical (•OH), sulfate radical (SO4∙-), electron (e-/eaq-), su-peroxide anion radicals (∙O2-), and other radical, played a crucial role in mitigating membrane fouling, accounting for 36.26%, 30.10%, 18.69%, 6.75%, and 8.20%, respectively. The correlation analysis revealed that effective removal of UV254 and TOC emerged as the most crucial factors positively contributing to mitigating membrane fouling. Additionally, SO4∙-, •OH, and eaq- were identified as the primary active substances responsible for attacking PFOA, accounting for 41.30%, 25.20%, and 23.70%, respectively. The degradation pathway of PFOA was proposed through analysis using density functional theory and mass spectrometry, reducing the biotoxicity of its degradation products. This study presents a suitable strategy for simultaneous mitigation of membrane fouling and enhancement of PFOA degradation, which holds great potential for advancing the field of water treatment towards practical applications.

Microbial adaptation and biodegradation mechanisms of perfluorinated compounds in different functional zones of the Yellow River Delta, China

Perfluorinated compounds (PFCs) are widespread environmental pollutants that pose risks to ecosystems. Our research in the Yellow River Delta watershed focused on two rivers, Shenxian Gou and Tiao He, representing the impacts of oil extraction and urban wastewater, respectively. The purpose of this study was to evaluate the effects of different concentrations of PFCs on the microbial community structure and to investigate the mechanisms of their degradation by microorganisms. The results suggested that the microbial communities were influenced by the combined effects of PFCs concentration and water quality (0.33), with a notable emphasis on the impact of PFCs (0.28). The 16S rDNA gene amplicon data revealed significant variations in both the structural composition and functional aspects of microbial communities across different concentrations of PFCs (p < 0.05). In particular, perfluorooctanoic acid (PFOA) was found to interfere with several microbial metabolic functions, including DNA functions, structural pathways, and the tricarboxylic acid cycle. Certain bacteria, such as Hydrogenophaga, Luteolibacter, and Pseudorhodobacter, were found to synergistically promote perfluorooctanoic acid degradation. The results improve our understanding of the mechanisms through which microbes adapt to and degrade PFCs in different environments and the complex effects PFCs have on ecosystems.

Novel enhanced defluorination of perfluorooctanoic acids by biochar-assisted ultrasound coupling ferrate: Performance and mechanism

An ultrasound (US)/biochar (BC)/ferrate (Fe (VI)) system was firstly proposed to enhance perfluorooctanoic acid (PFOA) defluorination. It achieved 93 % defluorination optimally, higher than the sum of 77 % (28 % and 49 % for US/BC and US/Fe (VI) respectively), implying synergistic effect. Besides, the mechanism study confirmed that, this system can not only increase the specific surface area of BC and the generation of reactive oxidant species (ROS), enriching the active sites and forming new oxygen-containing functional groups, but also promote the formation of intermediate iron species. The PFOA degradation in the US/BC/Fe (VI) was probably an adsorption-degradation process, both ROS and electron transfer promoted the defluorination. Additionally, its sustainability was also demonstrated with 14 % reduced defluorination percentage after five cycles of BC. Overall, the synergistic effect of the US/BC/Fe (VI) and its enhancing mechanism for PFOA defluorination were clarified firstly, which contributes to the development of biochar for assisting polyfluoroalkyl substances degradation.

The activation of PMS for PFOA degradation by adjustable metal stripping Fe/Co/N@BC catalysts: Degradation performance with single-line oxygen and high-valent metal oxides as the main active substances

In this study, a modified biochar (P-Fe/Co/N@BC) catalyst was prepared with wood chips as raw material by hydrothermal method for the activation of peroxymonosulfate (PMS) and degradation of perfluorooctanoic acid (PFOA). Scanning electron microscopy (SEM), x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS) characterization methods were used to demonstrate the presence of FeNx, CoNx, Fe-Co and CO active sites, which contribute to the improvement of the PMS activation capacity for single-line oxygen (1O2). Electron paramagnetic resonance spectroscopy (EPR), reactive oxygen species (ROS) scavenging experiments and methyl phenyl sulfoxide (PMSO) conversion experiments were performed to clarify the main mechanisms of PFOA degradation by reactive species. Further, 1O2, sulfate radical (SO4−), hydroxyl radical (OH), high-valent metal oxides (Fe(IV) and Co(IV)) were jointly involved in the degradation of PFOA, and nonradical were the main activation pathway of PMS. In particular, Fe3+ decomposed from Fe(IV) in the presence of Fe0 and Co2+ decomposed from Co(IV) are able to enhance iron cycling and cobalt cycling, respectively. Meanwhile, Co0 accelerates the conversion of Co3+ to Co2+. The findings suggested that the removal rate of the P-Fe/Co/N@BC-PMS system (99 %) was much higher than that of the P-Fe-N-C/PMS (68.9 %) over 180 min. It emphasized that the incorporation of PTFE (polytetrafluoroethylene) can regulate metal leaching significantly and improve the cycling stability of the catalysts. This study aimed to prepare efficient and stable modified biochar catalysts to activate PMS, which provided an effective solution to the problem of metal ion leaching from metal-modified biochar materials.

Trap-n-zap: Electrocatalytic degradation of perfluorooctanoic acid (PFOA) with UiO-66 modified boron nitride electrodes at environmentally relevant concentrations

Poly- and per-fluoroalkyl substances (PFAS) are synthetic chemicals of increasing global concern due to their toxicity and environmental persistence. Hexagonal boron nitride (h-BN) is an electrochemically active semiconductor that generates a hydrophobic electron-hole with a high affinity for the fluorinated tail of perfluorooctanoic acid (PFOA), which enhances surface interactions in aqueous solutions. We demonstrate that h-BN electrocatalytically oxidizes PFOA to shorter chains. The degradation is enhanced by modifying the h-BN surface with an adsorbent, UiO-66 (UiO-66@BN), that facilitates proximal adsorption to catalytic sites (trap-and-zap). At the environmentally relevant concentration of 100 µg/L, electrochemical trap-and-zap removes 99.5% of PFOA with 70% defluorination in 3 h at a pH 4.5. Computational results show that PFOA requires an overpotential of 1.87 V vs. SCE, which is close to the experimental overpotential. The electrical energy per order (EE/O) of UiO-66@BN is 6.1 kWh/m3, indicating that it is a competitive material for PFOA electrochemical remediation.

UV/Sulfite reduction kinetics of perfluorobutane sulfonic acid (PFBS), perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA)

Reduction of persistent perfluorinated compounds (PFCs) by UV-activated sulfite (SF) has been recognized as one of the most effective advanced reduction processes (ARPs). With the UV/SF ARP, PFBS degradation reached 66.6 % at 25 °C after 6 h, while PFOS and PFOA were completely degraded within 80 and 20 mins, respectively. PFOA has the largest defluorination efficiency of 77.5 %, greater than 57.8 % for PFOS and 42.7 % for PFBS after 6 h. With the UV/SF system operated at 15, 25, 35 and 45 °C, activation energy (Ea) of PFBS defluorination was determined to be 360.8 kJ/mol, larger than those of PFOS and PFOA (319.4 and 67.3 kJ/mol, respectively), which implies that PFBS is more persistent and difficult to be degraded in the natural environment. Based on the consumption of SF, secondary-order kinetics models were developed to describe the degradation and defluorination of PFBS, PFOS, and PFOA at various reaction times. Concentrations of various intermediate species were determined by liquid chromatography quadrupole time-of-flight mass spectrometry (LC/QTOF-MS) during the PFBS degradation to investigate the reaction pathways in the UV/SF ARP. The proposed reaction mechanisms for PFBS degradation include desulfonation, H/F exchange, and chain shortening via direct C − C bond cleavage.

Application of electric potential and Fe(Ⅲ) to stimulate perfluorooctanoic acid (PFOA) degradation using mixed culture anammox granules

Pollution by perfluorooctanoic acid (PFOA), a highly persistent and toxic substance, is commonly addressed with several approaches, but the need for post-treatment affects their environmental and economic sustainability. Biodegradation, which can efficiently degrade micropollutants in water under optimal conditions, offers a promising solution, but faces challenges from the persistence of the C-F bond and the high reactivity of F-. Despite recent use of various microorganisms for PFOA degradation, performance issues persist. In this study, we aimed to simulate PFOA degradation while mixed culture anammox granules oxidize NH4+ and to confirm the effects of electric potential and Fe(Ⅲ) applications on PFOA degradation. A control reactor containing only anammox granules exhibited NH4+ and PFOA removal efficiencies of 11.52% and 19.2%, respectively, with traceable biodegradation at 3.7%. In contrast, a reactor that applied both electric potential and Fe(Ⅲ) demonstrated enhanced removal efficiencies of 41.98% and 50.93%, with traceable biodegradation at 35.03%. Bio-electrochemical properties also improved, showing an average current generation of 331.95 μA and Coulombic efficiency of 141.79 ± 7.6%. This study shows that mixed-culture anammox granules with electric potential and Fe(Ⅲ) can be introduced for efficient PFOA biodegradation and provides the basis for further studies on overcoming the limitations of PFOA biodegradation.

Efficient photocatalytic degradation of perfluorooctanoic acid by bismuth nanoparticle modified titanium dioxide

Perfluorooctanoic acid (PFOA) is potentially toxic and exceptionally stable attributed to its robust CF bond, which is hard to be removed by UV/TiO2 systems. In this research, bismuth nanoparticle (Bi NP) modified titanium oxides (Bi/TiO2) were synthesized by a simple photochemical deposition-calcination method and were applied as photocatalysts for the first time to degrade PFOA. The removal rate of 50 mg/L PFOA reached 99.3 % with 58.6 % defluorination rate after 30 min of irradiation via a mercury lamp. Bi/TiO2 exhibited superior performance in PFOA degradation compared to commercial photocatalysts (TiO2, Ga2O3, Bi2O3 and In2O3). In addition, Bi/TiO2 showed high degradation activity under actual sunlight, achieved 100 % removal rate and 59.3 % defluorination rate within 2 h. Bi NPs increase the light trapping ability of Bi/TiO2 and promote the separation of photogenerated electron-hole pairs via local surface plasmon resonance (LSPR) effect, which results in more photogenerated holes (h+) and hydroxyl radicals (OH). Combined with DFT calculations and intermediate detections, the degradation reaction is initiated from the oxidation of the PFOA carboxyl group via h+, followed by the loss of the CF2 unit step by step with the participation of OH. This work presents a novel approach for the practical implementation of TiO2-based photocatalysts to achieve highly efficient photocatalytic degradation of perfluorocarboxylic acids (PFCAs).

Simultaneous removal of perfluorooctanoic acid and thiocyanate by modified activated carbon fiber/persulfate system

In this study, NaOH-modified activated carbon fiber (NaOH-ACF) was used as a catalyst to activate persulfate (PS) for the removal of perfluorooctanoic acid (PFOA) and thiocyanate (SCN−) from wastewater. The effects of the crucial parameters in the NaOH-ACF/PS process, including NaOH-ACF dosage, PS concentration and initial pH, were investigated and optimized using response surface methodology. The experimental results indicated showed that under the optimal reaction conditions of NaOH-ACF dosage (0.40 g/L), PS concentration (2.0 mmol/L), pH (3.0), and temperature (25 °C), the removal efficiencies for PFOA and SCN− reached 93.63 % and 95.17 %, respectively, within 60 min of reaction. When PFOA and SCN− coexisted in the reaction system, it was observed that PFOA had minimal effect on the removal of SCN−, while SCN− actually enhanced the removal of PFOA. Free radical identification experiments demonstrated that the NaOH-ACF/PS system generated free radicals (O2−, SO4−, OH) and non-free radicals (1O2), which cooperatively facilitated the degradation of PFOA and SCN−. Furthermore, Liquid Chromatograph-Mass Spectrometer (LC-MS) analysis results have been used to speculate on the possible degradation pathways and intermediates of PFOA. The material characterization results indicated that NaOH-ACF possesses abundant surface functional groups with excellent adsorption and catalytic properties. Thus, the NaOH-ACF-activated PS advanced oxidation process offered a promising approach for the simultaneous removal of Perfluorinated compounds and thiocyanates.

Superb green cycling strategies for microbe-Fe0 neural network-type interaction: Harnessing eight key genes encoding enzymes and mineral transformations to efficiently treat PFOA

To address time-consuming and efficiency-limited challenges in conventional zero-valent iron (ZVI, Fe0) reduction or biotransformation for perfluorooctanoic acid (PFOA) treatment, two calcium alginate-embedded amendments (biochar-immobilized PFOA-degrading bacteria (CB) and ZVI (CZ)) were developed to construct microbe-Fe0 high-rate interaction systems. Interaction mechanisms and key metabolic pathways were systematically explored using metagenomics and a multi-process coupling model for PFOA under microbe-Fe0 interaction. Compared to Fe0 (0.0076 day−1) or microbe (0.0172 day−1) systems, the PFOA removal rate (0.0426 day−1) increased by 1.5 to 4.6 folds in the batch microbe-Fe0 interaction system. Moreover, Pseudomonas accelerated the transformation of Fe0 into Fe3+, which profoundly impacted PFOA transport and fate. Model results demonstrated microbe-Fe0 interaction improved retardation effect for PFOA in columns, with decreased dispersivity a (0.48 to 0.20 cm), increased reaction rate λ (0.15 to 0.22 h−1), distribution coefficient Kd (0.22 to 0.46 cm3∙g−1), and fraction f´(52 % to 60 %) of first-order kinetic sorption of PFOA in microbe-Fe0 interaction column system. Moreover, intermediates analysis showed that microbe-Fe0 interaction diversified PFOA reaction pathways. Three key metabolic pathways (ko00362, ko00626, ko00361), eight functional genes, and corresponding enzymes for PFOA degradation were identified. These findings provide insights into microbe-Fe0 “neural network-type” interaction by unveiling biotransformation and mineral transformation mechanisms for efficient PFOA treatment.

Exploring Solar Energy Solutions for Per‐ and Polyfluoroalkyl Substances Degradation: Advancements and Future Directions in Photocatalytic Processes

Concerns about per‐ and polyfluoroalkyl substances (PFAS) pollution are escalating globally due to the discovery of their widespread environmental distribution, accompanied by their migration, bioaccumulation, and toxic potential for plants, animals, and humans. Several technologies have been developed for their remediation since standard water treatment methods often fail. However, these approaches require large energy consumption and, at times, exacerbate environmental issues. In this context, photocatalytic degradation holds promise as a reliable technological solution for PFAS mineralization. However, to date, it primarily relies on the degradation of perfluorooctanoic acid using high‐energy gap semiconductor oxides that necessitate high‐power artificial ultraviolet sources for excitation and, at times, the use of strong chemical oxidants. This review examines chemical‐free catalysts and mechanisms recently documented in the literature to outline a roadmap for the realization of solar‐driven mineralization of all PFAS compounds. To this end, conventional wide‐bandgap semiconductor oxides are delved into and strategies to extend their spectral absorbance while enhancing charge separation with a focus on the proposed degradation pathways are explored, that are fundamental to designing technologically relevant photodegradation systems.

Experimental and numerical investigation on the effect of frequency combinations on PFOA defluorination by dual-frequency ultrasound coupling persulfate

Due to the synergistic contribution, dual-frequency ultrasound can significantly enhance the degradation of organic contaminants, but the effects of different frequency combinations have not been clarified and need to be explored. In this study, several frequency combinations were designed firstly both in experimental exploration and numerical simulation within the dual-frequency ultrasound coupling persulfate (PS) system to investigate the effect of frequency combinations on the degradation of perfluorooctanoic acid (PFOA). The monitoring parameters included the defluorination percentage and the simulated maximum expansion ratio (Rmax/R0). The simulated maximum expansion ratios in different frequency combinations showed a high correlation with their defluorination results, indicating that the discrepancy in defluorination effects of different frequency combinations was mostly attributed to their various maximum expansion ratios. Additionally, various maximum expansion ratios could result in different maximum solution temperatures, and the increase in temperature was found positive for PFOA defluorination in this study. In addition, the synergistic parameters that affected the maximum expansion ratio were analyzed, including the phase difference, frequency ratio, and frequency value. The obtained results showed that the maximum expansion ratio varied with different phase differences, and the frequency ratio could affect the variation trend. For the same fundamental frequency, the larger the frequency ratio, the smaller the maximum expansion ratio. Under the same phase difference and frequency ratio, the larger the frequency value, the lower the cavitation.

Zinc oxide@citric acid-modified graphitic carbon nitride nanocomposites for adsorption and photocatalytic degradation of perfluorooctanoic acid

Perfluorooctanoic acid (PFOA) is a highly persistent organic pollutant of global concern. A novel nanocomposite composed of ZnO nanoparticles and citric acid-modified g-C3N4 was synthesized by ball milling process. The synthesized nanocomposite was more efficient than pure ball-milled ZnO nanoparticles for PFOA elimination under visible light irradiation. The optimal hybrid photocatalyst, produced by the addition of 5 wt% of citric acid-modified g-C3N4, demonstrated significantly better performance for PFOA removal than pure ZnO nanoparticles under UV irradiation, with the apparent rate constants of 0.468 h−1 and 0.097 h−1, respectively. The addition of peroxymonosulfate (0.53 g L−1) significantly increased PFOA removal, clarifying the crucial effect of sulfate radicals on PFOA photodegradation. In comparison, citric acid-modified g-C3N4 was not effective for PFOA elimination under visible light irradiation, even with the addition of peroxymonosulfate. Further experiments under dark conditions identified surface adsorption on hybrid photocatalyst as a key process in total PFOA removal. In summary, PFOA removal by ZnO@citric acid-modified graphitic carbon nitride nanocomposites is due to the combined action from adsorption and photodegradation, with adsorption as the dominating mechanism.

Degradation of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in water by use of a nonthermal plasma-ozonation cascade reactor: Role of different processes and reactive species

The widespread use of perfluoroalkyl and polyfluoroalkyl substances (PFAS) in the last century has caused serious pollution of water bodies around the world, threatening the health of humans and other organisms. In this work, a novel cascade reactor configuration, comprised of a dielectric barrier discharge (DBD) plasma chamber connected with an ozonation chamber was used to treat municipal secondary effluent loaded with several PFAS. The electrical energy per order (EE/O) for degradation of perfluorooctanoic acid (PFOA) and perfluorodecanoic acid (PFDA) amounts 180 and 100 kWh/m3, respectively. While the short-chain PFAS (perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA)) were difficult to be degraded, i.e. degradation percentage < 32 % after 60 min, 80–90 % of the longer PFAS (PFOA and PFDA) were degraded within 60 min. The degradation of PFAS mainly occurred in the plasma chamber rather than in ozonation chamber. This is because that reductive species produced in plasma chamber, such as hydrated electrons (eaq−) and Ar+, played a direct role in defluorination, while oxidative species, including OH, O, O2−, 1O2, O3, and H2O2, has a very limited contribution for defluorination. Enhancing the utilization of reductive species is crucial to degrade PFAS. Perfluoroalkyl carboxylic acids (PFCA) generated during the plasma reactions may have a potential risk for environment. As such, further optimization should focus on full mineralization. This study provides an approach to solve the problem of PFAS-contaminated wastewater, which is of the importance to promote the application of nonthermal plasma technique in water treatment.

Investigation on UV Degradation and Mechanism of 6:2 Fluorotelomer Sulfonamide Alkyl Betaine, Based on Model Compound Perfluorooctanoic Acid

The UV treatment of 6:2 FTAB involves the mitigation of this persistent chemical by the impact of ultraviolet radiation, which is known for its resistance to environmental breakdown. UV treatment of PFOA and/or 6:2 FTAB, and the role of responsible species and their mechanism have been presented. Our investigation focused on the degradation of perfluorooctanoic acid (PFOA) and 6:2 fluorotelomer sulfonamide alkyl betaine (6:2 FTAB, Capstone B), using UV photolysis under various pH conditions. Initially, we used PFOA as a reference, finding a 90% decomposition after 360 min at the original (unadjusted) pH 5.6, with a decomposition rate constant of (1.08 ± 0.30) × 10−4 sec−1 and a half-life of 107 ± 2 min. At pH 4 and 7, degradation averaged 85% and 80%, respectively, while at pH 10, it reduced to 57%. For 6:2 FTAB at its natural pH 6.5, almost complete decomposition occurred. The primary UV transformation product was identified as 6:2 fluorotelomer sulfonic acid (6:2 FTSA), occasionally accompanied by shorter-chain perfluoroalkyl acids (PFAAs) including PFHpA, PFHxA, and PFPeA. Interestingly, the overall decomposition percentages were unaffected by pH for 6:2 FTAB, though pH influenced rate constants and half-lives. In PFOA degradation, direct photolysis and reaction with hydrated electrons were presumed mechanisms, excluding the involvement of hydroxyl radicals. The role of superoxide radicals remains uncertain. For 6:2 FTAB, both direct and indirect photolysis were observed, with potential involvement of hydroxyl, superoxide radicals, and/or other reactive oxygen species (ROS). Clarification is needed regarding the role of eaq− in the degradation of 6:2 FTAB.

Reactive species and mechanisms of perfluorooctanoic acid (PFOA) degradation in water by cold plasma: The role of HV waveform, reactor design, water matrix and plasma gas

The scope of this study was to optimize dielectric barrier discharge (DBD) plasma for the degradation of perfluorooctanoic acid (PFOA) in water by comparing several critical aspects such as pulsed-plasma waveform (nanosecond and microsecond high voltage (HV) pulses), reactor configuration (gas–liquid treatment and underwater plasma bubbles), water matrix and plasma gas. The physicochemical properties and species concentration of plasma-treated water, under the aforementioned conditions, were also determined and correlated with PFOA degradation. PFOA was more efficiently degraded by air–liquid DBD compared to DBD-based underwater air-plasma bubbles consistent with the surfactant nature of PFOA and the more intense plasma-liquid interaction and species formation prevailing during gas–liquid treatment compared to plasma bubbles treatment. After 30 min of gas–liquid DBD treatment, the degradation of PFOA in ultrapure water was >99.9, 98.8, 95.1 and 63% under air-, N2-, Ar- and O2-plasma respectively, whereas its degradation was almost equally effective in the whole range of its initial concentration (10 to 0.1 mg/L). Air was almost equally effective at degrading PFOA in ultrapure and tap water, while argon was much more effective at degrading PFOA in tap water (>99.9% after 20 min) possibly due to the prevailing alkaline conditions (pH ∼8.7) favoring its degradation. Faster PFOA degradation was achieved under HV micropulses compared to HV nanopulses. Nevertheless, in terms of energy requirements, HV nanopulses were superior to HV micropulses, with the lowest electrical energy per order achieved under nanopulsed-argon (∼23.6 kWh/m3). The results of this study could contribute important knowledge to the development of plasma-based treatment of PFOA-contaminated water.

Degradation of perfluorooctanoic acid by inductively heated Fenton-like process over the Fe3O4/MIL-101 composite

To efficiently remove perfluorooctanoic acid (PFOA), we developed a composite of magnetic Fe3O4 nanocrystals and MIL-101 (an iron-based metal organic framework). Because of its high surface area, porous structure, and complexation between PFOA as confirmed by experimental results and density functional theory simulation, the magnetic composite showed a Langmuir adsorption capacity of 415 mg/g in the presence of various groundwater components, and thus adsorbed PFOA at environment-relevant concentration within 20 min. The catalyst loaded with PFOA can then be magnetically separated from the synthetic groundwater. This adsorption step concentrated PFOA near MIL-101 and resulted in a fast decomposition rate in the decomposition step, where MIL-101 served as an efficient Fenton agent due to its abundant Fe3+/Fe2+ sites. Meanwhile, the alternative magnetic field was introduced to change the production pathway of reactive oxygen species and superoxide radical anions were produced, which was critical for PFOA degradation. In addition, the inductive heating effect heat the magnetic particles to 445 K through an in-situ approach, which thus further accelerated Fenton reactions rate. In addition, and achieved a complete degradation of PFOA within 30 min. This newly developed Fenton catalyst demonstrates advantages over conventionally heterogeneous and homogeneous catalysts, and thus is promising for practical applications.

Biochar and surfactant synergistically enhanced PFAS destruction in UV/sulfite system at neutral pH

The UV/sulfite-based advanced reduction process (ARP) emerges as an effective strategy to combat per- and polyfluoroalkyl substances (PFAS) pollution in water. Yet, the UV/sulfite-ARP typically operates at highly alkaline conditions (e.g., pH > 9 or even higher) since the generated reductive radicals for PFAS degradation can be quickly sequestered by protons (H+). To overcome the associated challenges, we prototyped a biochar-surfactant-system (BSS) to synergistically enhance PFAS sorption and degradation by UV/sulfite-ARP. The degradation and defluorination efficiencies of perfluorooctanoic acid (PFOA) depended on solution pH, and concentrations of surfactant (cetyltrimethylammonium bromide; CTAB), sulfite, and biochar. At high pH (8–10), adding biochar and BSS showed no or even small inhibitory effect on PFOA degradation, since the degradation efficiencies were already high enough that cannot be differentiated. However, at acidic and neutral pH (6–7), an evident enhancement of PFOA degradation and defluorination efficiencies occurred. This is due to the synergies between biochar and CTAB that create favorable microenvironments for enhanced PFOA sorption and deeper destruction by prolonging the longevity of reductive radicals (e.g., SO3•−), which is less affected by ambient pH conditions. The performance of UV/sulfite/BSS was further optimized and used for the degradation of four PFAS. At the optimal experimental condition, the UV/sulfite/BSS system can completely degrade PFOA with >30% defluorination efficiency for up to five continuous cycles (n = 5). Overall, our BSS provides a cost-effective and sustainable technique to effectively degrade PFAS in water under environmentally relevant pH conditions. The BSS-enabled ARP technique can be easily tied into PFAS treatment train technology (e.g., advanced oxidation process) for more efficient and deeper defluorination of various PFAS in water.

Size-selective trapping and photocatalytic degradation of PFOA in Fe-modified zeolite frameworks

Removal and destruction of perfluorooctanoic acid (PFOA) are challenging due to its extreme persistence and dilute concentrations. This study investigated dual-function adsorptive-photocatalytic zeolite materials to selectively adsorb and degrade PFOA via tuning pore structures and doping transition metals. It is found that the pore opening is critical in the size-selective trapping of PFOA, while the iron doped zeolites present excellent adsorption of PFOA (>80 mg g−1) combining hydrophobic and electrostatic interactions. The formation of PFOA-iron complexes has reduced bond dissociation energy of C−F, calculated from density functional theory, for favorable stepwise defluorination (over 60% defluorination in 4 hours) by superoxide radicals and ligand-to-metal charge transfer. This mechanistic investigation extends the potential of the concentrate-and-degrade concept to remove PFOA selectively and effectively from contaminated water.

Degradation and mechanism of PFOA by peroxymonosulfate activated by nitrogen-doped carbon foam-anchored nZVI in aqueous solutions

Perfluorooctanoic acid (PFOA) is an emerging pollutant that is non-biodegradable and presents severe environmental and human health risks. In this study, we present an effective and mild approach for PFOA degradation that involves the use of nitrogen-doped carbon foam anchored with nanoscale zero-valent iron (nZVI@NCF) to activate low concentration peroxymonosulfate (PMS) for the treatment. The nZVI@NCF/PMS system efficiently removed 84.4% of PFOA (2.4 μM). The active sites of nZVI@NCF including Fe0 (110) and graphitic nitrogen played crucial roles in the degradation. Electrochemical analyses and density functional theory calculations revealed that nZVI@NCF acted as an electronic donor, transferring electrons to both PMS and PFOA during the reaction. By further analyzing the electron paramagnetic resonance and byproducts, it was determined that electron transfer and singlet oxygen were responsible for PFOA degradation. Three degradation pathways involving decarboxylation and surface reduction of PFOA in the nZVI@NCF/PMS system were determined. Finding from this study indicate that nZVI@NCF/PMS systems are effective in degrading PFOA and thus present a promising persulfate-advanced oxidation process technology for PFAS treatment.