Search Results (89)

Controlling radical selectivity within nanoreactors remains a formidable challenge due to the inherent high reactivity and short half-lives of reactive species. Herein, we report a novel size-matched nanoconfinement strategy using a cobalt-nickel-layered double hydroxide (CoNi-LDH) nanoreactor for the highly selective generation and stabilization of sulfate radicals (SO₄^∙−) via piezoelectric activation of peroxymonosulfate (PMS). By precisely tailoring the LDH interlayer spacing to 5.27 Å to match the kinetic diameter of SO₄^∙−, the nanoreactor effectively suppresses non-selective side reactions and radical quenching. Consequently, the CoNi-LDH achieves an unprecedented reaction rate (k_obs = 0.40 min⁻¹) and superior defluorination efficiency (78.9%) for fluoroquinolone antibiotics, significantly outperforming non-size-confined counterparts. Mechanistic insights reveal a synergistic pathway where piezo-generated hot electrons, mediated by Ni sites, accelerate the Co²⁺/Co³⁺ redox cycle to ensure long-term catalytic stability. The robustness of this nanoconfined system is further demonstrated by its exceptional tolerance to complex water matrices and its practical operability in a continuous-flow reactor. This study provides a pioneering approach for spatial radical control at the nanoscale to achieve efficient and targeted environmental remediation. Full article

The exceptional stability of C-F bonds renders PFAS highly persistent in aqueous environments, posing significant challenges for conventional treatment technologies. While plasma-based technologies show promise, their efficiency is often limited by poor gas–liquid mass transfer in bulk liquid. Here, an in-house constructed ultrasonic atomization–dielectric barrier discharge (UEN-DBD) system was developed to promote PFAS degradation under non-thermal plasma conditions. Ultrasonic atomization generated microdroplets, which promoted PFAS enrichment at the surface of microdroplets and facilitate interactions with plasma-generated reactive species. Using perfluorooctanoic acid (PFOA) and perfluorooctanesulfonate (PFOS) as model compounds, degradation behavior was evaluated over an initial concentration range of 0.01–1.0 ppm. At 0.01 ppm, degradation efficiencies of 96.06% for PFOA and 94.86% for PFOS were achieved within 5 min. Electron paramagnetic resonance (EPR) spectroscopy confirmed the formation of oxidative radicals (·OH) and suggested a mixed redox environment involving reactive species, potentially including superoxide (O₂·⁻) or hydrated electrons (e_aq⁻), in the discharge-treated system. High-resolution mass spectrometry results are consistent with a stepwise chain-shortening pathway dominated by successive –CF₂– scission, while fluoride-release measurements provided supporting evidence for partial defluorination. These findings advance the understanding of plasma-assisted PFAS degradation at the gas–liquid interface and provide a basis for the further development of plasma-assisted PFAS treatment strategies. Full article

Soil contamination by per- and polyfluoroalkyl substances (PFAS) represents a pressing environmental and public health concern due to the exceptional persistence of carbon–fluorine bonds, which prevent natural attenuation and limit the effectiveness of conventional remediation. Agricultural and industrial soils serve as long-term sinks for PFAS, continuously releasing these pollutants into groundwater and facilitating their transfer through the food chain. Conventional chemical and physical remediation methods are often costly, energy-intensive, and yield incomplete removal, underscoring the need for sustainable and biologically driven alternatives. Microbial consortia have emerged as a promising solution due to their metabolic complementarities, cross-feeding interactions, and ecological resilience, which together enable PFAS transformation and partial defluorination under complex soil and subsurface conditions. Key enzymes such as oxygenases, reductive dehalogenases, and hydrolases are often operating within co-metabolic networks, which play central roles in these processes. Advances in metagenomics, CRISPR-based functional screening, and metabolic modelling are rapidly uncovering novel PFAS-degrading microbes and pathways. Integration of machine learning with multi-omics and environmental datasets further enables the prediction of degradation mechanisms, identification of keystone degraders, and rational design of synthetic consortia. Emerging sustainable strategies, including biochar- and nutrient-amended soil microcosms, plant–microbe partnerships for coupled soil–groundwater phytoremediation, and bioelectrochemical systems that offer new avenues for enhancing PFAS biodegradation in situ. This review synthesises recent research progress and provides critical perspectives on the mechanistic, ecological, and engineering dimensions of PFAS bioremediation, proposing an integrated conceptual framework linking microbial consortia dynamics, enzymatic pathways, and environmental engineering interventions to guide scalable field applications and sustainable management of PFAS-contaminated soil–groundwater ecosystems. Full article

The extreme persistence of per- and polyfluoroalkyl substances (PFAS), exemplified by perfluorooctanoic acid (PFOA), demands remediation technologies that surpass conventional approaches. This study introduces a novel closed-loop adsorption–regeneration–distillation–plasma (ARDP) process designed for high-efficiency PFOA removal with low energy and chemical consumption. Comparative evaluation of anion-exchange resins identified D311 (macroporous methyl polyacrylate) as the optimal adsorbent. In batch experiments with an initial PFOA concentration of 100 mg/L, D311 achieved an adsorption capacity of ~20 mg/g, exhibited rapid kinetics, and achieved high regeneration efficiency (up to 100% under optimized conditions) via a methanol–NaCl solution. Distillation of the spent regenerant recovered approximately 80% of methanol while simultaneously concentrating PFOA for subsequent destruction, accomplished by utilizing waste heat from the plasma system, without the need for additional thermal energy input. Subsequent dielectric barrier discharge (DBD) plasma treatment of the residue achieved 100% PFOA degradation and up to 69% defluorination. The ARDP process proves to be a highly sustainable strategy, characterized by a low specific energy input (4.15 kWh/m³) and minimized secondary waste, making it a promising approach for practical PFAS remediation. Full article

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) have been identified as forever chemicals and pose a serious threat to the environment due to their stable C–F bond. The current methods are ineffective or costly for PFAS remediation. In response, this study develops a dielectric barrier discharge (DBD) air plasma system capable of simultaneously treating perfluorooctanoic acid (PFOA)-contaminated wastewater and enhancing waste-activated sludge (WAS) solubilization through the subsequent use of plasma-activated water (PAW). Air plasma achieved 94% PFOA degradation and 32% defluorination within 40 min—substantially outperforming Ar and N₂ plasma—due to the co-generation of hydrated electrons (e_aq⁻), ^•OH, and reactive nitrogen species (RNS). Scavenging experiments confirmed that e_aq⁻ is the primary initiator of C–F bond cleavage, while H₂O₂ and NO₂⁻ synergistically form peroxynitrous acid (ONOOH), further promoting chain-shortening reactions. UPLC-MS identified PFHpA, PFHxA, PFPeA, and PFBA as key intermediates. The air plasma effluent contained high concentrations of NO₂⁻-N and H₂O₂ under acidic conditions, enabling PAW to induce strong oxidative stress on WAS, resulting in significant extracellular polymeric substance (EPS) release (DOC up to 134 mg/L), improved sludge filterability (capillary suction time (CST) reduced by ~85%), and shifts in microbial community. This study presents a dual-functional air plasma approach that enables both PFAS degradation and sludge treatment, improving the overall competitiveness and applicability of plasma technology for advanced wastewater treatment. Full article

The continuous emission of persistent and bioaccumulative pollutants into aquatic environments has become a critical global issue. Among these, per- and polyfluoroalkyl substances (PFASs) are of particular concern due to their exceptional stability, extensive industrial use, and adverse impacts on ecosystems and human health. Their resistance to conventional physical, chemical, and biological treatments stems from the strength of the carbon–fluorine bond, which prevents efficient degradation under standard conditions. This review provides a concise and updated assessment of emerging advanced oxidation processes (AOPs) for PFAS remediation, with emphasis on heterogeneous photocatalysis and electrochemical oxidation. Photocatalytic systems based on In₂O₃, Bi-based oxyhalides, and Ga₂O₃ exhibit high PFAS degradation under UV light, while heterojunctions and MOF-derived catalysts improve defluorination under solar irradiation. Electrochemical oxidation—particularly using Ti₄O₇ reactive electrochemical membranes and BDD anodes—achieves near-complete mineralization with comparatively low specific energy demand. Energy consumption (E_EO) was calculated from literature data for UV- and simulated-solar-driven photocatalytic systems, enabling a direct comparison of their energy performance. Although solar-driven processes offer clear environmental advantages, they generally exhibit higher E_EO values, mainly due to lower apparent quantum yields and less efficient utilization of the incident solar photons compared to UV-driven systems. Hybrid systems coupling photocatalysis and electro-oxidation emerge as promising strategies to enhance degradation efficiency and reduce energy requirements. Overall, the review highlights key advances and future research directions toward scalable, energy-efficient, and environmentally sustainable AOP-based technologies for PFAS removal. Full article

Topaz is one of the most economically important fluorine-rich nesosilicates, which are predominantly colorless in natural crystals. Hence, the trade relies almost entirely on irradiated blue topaz with an unstable color center, which has been shown to fade over time. The cobalt (Co) diffusion treatment is a stable alternative process for converting colorless topaz to blue by a solid-state diffusion mechanism. To investigate the potential role of Co²⁺ substitution in the formation of the blue layer and the coupled behavior of F/OH dehydroxylation in facilitating this process, systematic diffusion treatments have been successfully conducted and compared. In this study, gem-quality topazes were annealed in air at 1000 °C for 20–40 h (hr) along with CoO, Fe₂O₃, Cr₂O₃, and CuO powders. The diffused products were characterized using Scanning Electron Microscope (SEM), Ultraviolet-Visible absorption spectroscopy (UV-Vis), Near-Mid Infrared spectroscopy (NMIR), and X-ray photoelectron spectroscopy (XPS). Parallel runs with CuO, Fe₂O₃, or Cr₂O₃ alone confirmed that none of these oxides produces a stable blue layer, underscoring the unique role of Co. The Co-diffused sample displays an intense blue layer characterized by a Co²⁺ octahedral isomorphism triplet at 540, 580, and 630 nm, which are absent from both untreated and heat-only controls. XPS analysis reveals the emergence of Co²⁺ (binding energy: 780.63 eV) and a concomitant depletion in F⁻, along with the disappearance of the OH overtone absorption at 7123 cm⁻¹. These observations confirm that defluorination generates octahedral vacancies accommodated by the coupled substitution: CoF₂ (solid reactant) + (AlO₂)⁻ (fragment of topaz structure) → AlOF (solid product) + (CoOF)⁻ (fragment of topaz structure). Prolonged annealing leads to decreased relative atomic percentages of K⁺ and F⁻ ions, consistent with volatilization losses during the high-temperature process, thereby directly correlating color intensity with cobalt valence state, which transfers from Co²⁺ to Co³⁺. These findings establish a Co-incorporation chronometer for F–rich aluminosilicate systems, with an optimal annealing time of approximately 20 hr at 1000 °C. Furthermore, the above results demonstrate that the color mechanism in nesosilicate gems is simultaneously governed by volatile release and cation availability. Full article

Synthetic cannabinoids (SCs) are a rapidly developing kind of novel psychoactive substance, frequently associated with acute intoxication and public health concerns. This study aimed to elucidate and compare the phase I metabolic pathways of two structurally related SCs, 5F-ADB-PINACA and 5F-ADBICA, using in vitro and in vivo models. Temporal metabolic profiling was performed to identify potential signature metabolites. Temporal abundance patterns and correlation cluster analysis of metabolites were analyzed to determine metabolite biomarkers. The two SCs were incubated with pooled human liver microsomes for 24 h and were also evaluated in vivo in zebrafish. Metabolite profiles were characterized using UHPLC-QE Orbitrap-MS. HLM analysis identified 21 5F-ADB-PINACA metabolites and 28 5F-ADBICA metabolites. Metabolites of 5F-ADBICA were detected for the first time in vitro and in a zebrafish model. Zebrafish studies confirmed the presence of all key metabolites observed in HLM. Comparative analysis of their metabolic pathways revealed differences in metabolism driven by structural differences between the indazole and indole cores. This is the first time that correlation analysis has been used in the temporal metabolic profiling of SCs. This study comprehensively characterized the metabolism of 5F-ADB-PINACA and 5F-ADBICA, identifying M13 (hydrolytic defluorination) as a potential metabolite biomarker for 5F-ADB-PINACA and M19 (hydrolytic defluorination) as a potential metabolite biomarker for 5F-ADBICA. The metabolic reactions of the main metabolites of the two synthetic cannabinoids are consistent. However, their metabolic processes (i.e., the overall metabolic pathways and temporal progression of these reactions) are different, which illustrates the metabolic similarity of structurally similar synthetic cannabinoids and the impact of different structures on the metabolic processes. Full article

Perfluorooctane sulfonate (PFOS), a persistent and bioaccumulative perfluoroalkyl substance, poses significant environmental and human health risks due to the extraordinary stability of its C–F bonds. Conventional remediation strategies largely fail to achieve mineralization, instead transferring contamination or producing secondary waste streams. In this study, we investigate neutron irradiation as a potential destructive approach for PFOS remediation in both solid and aqueous matrices. Samples were exposed to thermal neutrons (flux: 3.2 × 10⁹ n·cm⁻²·s⁻¹, 0.0025 eV) at the Argonauta reactor for 6 h. Raman and FTIR spectroscopy revealed that PFOS in powder form remained largely resistant to degradation, with only minor structural perturbations observed. In contrast, aqueous PFOS solutions exhibited pronounced spectral changes, including attenuation of C–F and S–O vibrational signatures, the emergence of carboxylate and carbonyl functionalities, and enhanced O–H stretching, consistent with radiolytic oxidation and partial defluorination. Notably, clear peak shifts were predominantly observed for PFOS in aqueous solution after irradiation (overall displacement toward higher wavenumbers), whereas in powdered PFOS the main spectral signature of irradiation was the attenuation of CF₂ and S–O related bands with comparatively limited band relocation. To evaluate the biological relevance of these structural alterations, cell viability assays (MTT) were performed using human umbilical vein endothelial cells. Non-irradiated PFOS induced marked cytotoxicity at 100 and 50 μg/mL (p < 0.0001), whereas neutron-irradiated PFOS no longer exhibited significant toxicity, with cell viability comparable to the control. These findings indicate a matrix-dependent response: neutron scattering in solids yields negligible molecular breakdown, whereas radiolysis-driven pathways in water facilitate measurable PFOS transformation. The cytotoxicity assay demonstrates that neutron irradiation promotes sufficient molecular degradation of PFOS in aqueous media to suppress its cytotoxic effects. Although complete mineralization was not achieved under the tested conditions, the combined spectroscopic and biological evidence supports neutron-induced radiolysis as a promising pathway for perfluoroalkyl detoxification. Future optimization of neutron flux, irradiation duration, and synergistic catalytic systems may enhance mineralization efficiency. Because PFOS concentration, fluoride release (F⁻), and TOC were not quantified in this study, remediation was assessed through spectroscopic fingerprints of transformation and the suppression of cytotoxicity, rather than by mass-balance mineralization metrics. This study highlights neutron irradiation as a promising strategy for perfluoroalkyl destruction in contaminated water sources. Full article

Hydrometallurgy is currently the mainstream industrial process for recovering valuable components (nickel, cobalt, manganese, lithium, etc.) from spent ternary lithium-ion battery cathode materials. During the crushing of lithium batteries, cathode materials, anode materials (graphite), and electrolytes become mixed. Consequently, fluoride ions inevitably enter the leaching solution during the hydrometallurgical recycling process, with concentrations as high as 100–300 mg/L. These fluoride ions not only adversely affect the quality of the recovered precursor products but also pose environmental risks. To address this issue, this study employs a synthesized lanthanum–zirconium (La@Zr) composite material, with a specific surface area of 67.41 m²/g and a pore size of 2–50 nm, which can reduce the fluoride ion concentration in the leaching solution to below 5 mg/L, significantly lower than the 20 mg/L or higher that is typically achieved with traditional calcium salt defluorination processes, without introducing new impurities. Under optimal adsorption conditions, the lanthanum–zirconium adsorbent exhibits a fluoride ion adsorption capacity of 193.4 mg/g in the leaching solution, surpassing that of many existing metal-based adsorbents. At the same time as the valuable metals, Li, Ni, and Co, are basically not adsorbed, the selective adsorption of fluoride ions can be achieved. Adsorption isotherm studies indicate that the adsorption process follows the Langmuir model, suggesting monolayer adsorption. The secondary adsorption process is primarily governed by chemical adsorption, and elevated temperatures facilitate the removal of fluoride ions. Kinetic studies demonstrate that the adsorption process is well described by the pseudo-second-order model. After desorption and regeneration with NaOH solution, the adsorbent still has a favorable fluoride removal performance, and the adsorption rate of fluoride ions can still reach 95% after four cycles of use. With its high capacity, rapid kinetics, and excellent selectivity, the adsorbent is highly promising for large-scale implementation. Full article

Brick tea is a type of post-fermented food that involves microorganisms. Long-term consumption of brick tea exposes consumers to high fluoride levels, which can adversely affect their health. This study explored the feasibility of selective defluorination of Qingzhuan brick tea through membrane separation technology, and pilot production was conducted to produce defluorinated instant brick tea. The concentration of tea polyphenols increased by more than 10 times after nanofiltration, demonstrating the high selectivity of nanofiltration membranes toward fluoride. Defluorination trends were studied at different initial material concentrations (0.5–4%) and operating pressures (0.1–0.5 MPa) under cyclic defluorination. Defluorinated instant brick tea products were also industrially prepared using 300- (DF-300) and 1000-Da (DF-1000) membranes, followed by vacuum freeze-drying. The DF-1000 and DF-300 products exhibited a defluorination rate of 51.46% and 67.96%, respectively. The products have excellent characteristics in terms of color, aroma, and flavor quality, as well as solubility. Gas chromatography–mass spectrometry indicated that the volatile components in the defluorinated instant brick tea were slightly different from those in the original tea, but the key aroma and flavor characteristics of the defluorinated brick tea remained unchanged. Membrane separation provides technical support for the large-scale production of low-fluoride post-fermented tea. Full article

The utilization of carbon dioxide (CO₂) offers an effective approach for alleviating the carbon-reduction pressures associated with fossil energy consumption. However, studies on the use of CO₂ as an auxiliary agent in water treatment to enhance the removal of emerging contaminants are limited. In this study, the photodegradation of ciprofloxacin (CIP) was investigated using ultraviolet (UV) irradiation combined with CO₂ dosing (UV/CO₂). The results demonstrated that the UV/CO₂ system effectively degraded CIP, with CO₂ concentration and solution pH exerting a critical influence. Inorganic anions and metal cations had negligible effects on CIP degradation efficiency, whereas natural organic matter (NOM) had a pronounced inhibitory effect. Mechanistic analysis revealed that superoxide radicals ($·{\mathrm{O}}_2^{-}$) and carbonate radicals (${\mathrm{CO}}_3^{•-}$) were the primary oxidizing species, whereas the excited triplet state of CIP (³CIP*) and singlet oxygen played crucial roles in initiating radical generation. LC–MS analysis and density functional theory calculations indicated that the main degradation routes involved defluorination, decarboxylation, and epoxidation of the piperazine ring. Toxicity assessment indicated that the transformation products generated by UV/CO₂ were less toxic than the parent compound. Furthermore, the UV/CO₂ process demonstrated high energy efficiency, with a low electrical energy per order (EEO) value of 0.4193 kWh·m⁻³·order⁻¹. These findings suggest that the UV/CO₂ system is a promising alternative for the treatment of photosensitive organic pollutants and provides a beneficial pathway for CO₂ utilization. Full article

Ciprofloxacin (CIP), a persistent fluoroquinolone antibiotic, poses serious environmental concerns due to its low biodegradability and widespread presence in aquatic ecosystems. This study investigates the synergistic application of low-frequency ultrasonic cavitation and biological treatment to enhance CIP removal efficiency. Experiments have shown that under the optimal biological treatment conditions (6 g/L sludge concentration, pH 8), single biological treatment for 48 h can only remove 41.9% CIP and 24.9% total organic carbon (TOC). Ultrasonic pretreatment was conducted under varying frequencies and pH conditions to determine optimal cavitation parameters, while biodegradation performance was evaluated at different sludge concentrations and pH levels. Results indicated that in 10 mg/L CIP wastewater under alkaline conditions (pH 9.0), CIP and TOC removal efficiencies reached 58.9% and 35.2%, respectively, within 30 min using 15 kHz ultrasound irradiation. When ultrasonic pretreatment was followed by biological treatment, overall removal rates increased to 96.3% for CIP and 90.4% for TOC, significantly outperforming either method alone. LC-MS analysis identified several degradation intermediates during ultrasonic pretreatment, revealing key transformation pathways such as piperazine ring cleavage, hydroxylation, and defluorination. Furthermore, toxicity evaluation using the T.E.S.T. model confirmed a substantial reduction in ecological risk after ultrasonic treatment. Overall, the combined ultrasonic–biological process offers a cost-effective and environmentally sustainable strategy for the efficient removal of fluoroquinolone antibiotics from wastewater. Full article

The deep defluorination of water remains a significant environmental challenge. In this work, aluminum was loaded onto the bifunctional resin S957 containing a phosphoric-sulfonic acid difunctional group for efficient fluoride removal. Al-S957 demonstrated excellent fluoride removal performance across a broad pH range. When anions and organics coexisted, Al-S957 exhibited significantly better fluoride adsorption performance compared to aluminum-loaded monofunctional resins. The adsorption followed an endothermic chemisorption process on a monolayer surface. FTIR and XPS analyses further revealed that fluoride removal relied on a ligand exchange mechanism. Column adsorption conducted over five cycles highlighted the strong practical potential of Al-S957. The results suggested that Al-S957 exhibits significant potential for practical applications. Full article

Fluorinated xenobiotics, such as per- and polyfluoroalkyl substances (PFAS), fluorinated pesticides, and pharmaceuticals, are extensively used across industries, but their extreme persistence, driven by the high carbon–fluorine (C–F) bond dissociation energy (~485 kJ/mol), poses serious environmental and health risks. These compounds have been detected in water, soil, and biota at concentrations from ng/L to µg/L, leading to widespread contamination and bioaccumulation. Traditional remediation approaches are often costly (e.g., EUR >100/m³ for advanced oxidation), energy-intensive, and rarely achieve complete degradation. In contrast, microbial defluorination offers a low-energy, sustainable alternative that functions under mild conditions. Microorganisms cleave C–F bonds through reductive, hydrolytic, and oxidative pathways, mediated by enzymatic and non-enzymatic mechanisms. Factors including electron donor availability and oxygen levels critically influence microbial defluorination efficiency. Microbial taxa, including bacteria, fungi, algae, and syntrophic consortia, exhibit varying defluorination capabilities. Metagenomic and microbial ecology studies continue to reveal novel defluorinating organisms and metabolic pathways. Key enzymes, such as fluoroacetate dehalogenases, cytochrome P450 monooxygenases, reductive dehalogenases, peroxidases, and laccases, have been characterised, with structural and mechanistic insights enhancing the understanding of their catalytic functions. Enzyme engineering and synthetic biology tools now enable the optimisation of these enzymes, and the design of microbial systems tailored for fluorinated compound degradation. Despite these advances, challenges remain in improving enzyme efficiency, broadening substrate specificity, and overcoming physiological constraints. This review emphasises the emerging promise of microbial defluorination as a transformative and green solution, uniquely integrating recent multidisciplinary findings to accelerate the development of sustainable microbial defluorination strategies for effective remediation of fluorinated xenobiotics. Full article