This study presents the first application of ZIF-67, a cobalt-based zeolitic imidazolate framework, as a thermally desorbable analytical sorbent for the quantitative monitoring of atmospheric volatile organic compounds (VOCs) via thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). The ZIF-67 synthesized by a simple solution-phase method exhibited a BET surface area of 1516 m2 g-1, a uniform microporous structure with sodalite topology, and thermal stability up to ∼500 °C, all of which are favorable physicochemical properties for use in TD-GC-MS-based analysis. Method validation was performed across four key parameters-response factor, linearity, precision, and limit of detection-for 24 target VOCs with diverse functional groups, including alkanes, aldehydes, ketones, esters, alcohols, aromatic hydrocarbons, carboxylic acids, phenols, amines, and sulfides. Among the activation temperatures evaluated (240-320 °C), 280 °C was identified as the optimal condition. Comparative validation against commercial sorbents (Tenax TA and the Carbopack series) confirmed that ZIF-67 sorbent tubes achieved performance equivalent to or superior to that of commercial sorbents for aromatic (BTX) and ketone/ester compound classes, with xylene isomers yielding the best overall performance among all evaluated sorbent tubes (RSD ≤ 1.8%). Field validation using ambient BTX samples at concentrations ranging from 0.09 to 1.08 ppbv demonstrated quantitative agreement with Tenax TA, with a mean difference of 7.3%, confirming real-world applicability. The markedly lower production cost of ZIF-67 relative to commercial sorbents, combined with the potential recovery of cobalt from spent lithium-ion batteries, positions ZIF-67 as a competitive and sustainable material for atmospheric VOC monitoring across analytical chemistry, environmental engineering, and environmental materials science.
Water-filled rubber gates are increasingly being installed in rivers and canals as variable barriers for the regulation of water levels. The synthetic cylindrical membranes are in direct and continuous contact with the water body and especially after prolonged water retention inside the enclosed membrane, leached rubber additives may accumulate and enter the river in increased quantities. This study provides the first comprehensive and systematic investigation of material emissions from membranes used for inflatable rubber gates. For this purpose, materials of three different authentic rubber gate membranes were characterized and subjected to leaching in deionized water for subsequent ecotoxicological and chemical analyses. Leachates from all three materials caused significant acute toxic effects on algae, daphnia and luminescent bacteria. Furthermore, two membranes released chemicals causing estrogenic and anti-androgenic effects, one of which also induced aryl hydrocarbon receptor-mediated effects. In parallel, phenanthrene, pyrene, naphthalene, bisphenol A and 4-hydroxydiphenylamine (4HDPA) were detected in several samples by chemical analyses. Zinc was also released in elevated quantities from all tested materials. While 4HDPA and zinc significantly contributed to the estrogenic and acute toxic effects, respectively, the overall ecotoxicological effects could not be fully explained by the selected target compounds. The results of the laboratory experiments and the environmental relevance of materials were confirmed by the field sampling conducted. In total, the comparative assessment presented in this study can support the selection of environmentally compatible membrane materials and provides a basis for improving formulations of rubber materials.
Microplastics (MPs) are known to host dense microbial biofilms and form the plastisphere, which serve as significant sites for various biogeochemical processes, including nitrogen transformation. The communication within these complex microbial communities is facilitated by quorum sensing (QS) signals. However, how this inter-bacteria signal crosstalk impacts the colonization and function of key microbes, such as denitrifiers, remains inadequately elucidated. This research delves into the impact of the external signaling molecule N-3-oxododecanoyl-L-homoserine lactone (C12-oxo-HSL) on biofilm development and denitrification processes by the model bacterium Paracoccus denitrificans (P. denitrificans) on microplastic surfaces. Treatment with 10 μM C12-oxo-HSL increased biofilm biomass 2.67-fold and nitrate removal rates 2.61-fold relative to controls, while planktonic biomass remained comparable to or lower than untreated samples, refuting the hypothesis that increased biofilm mass merely reflects accelerated planktonic growth. Transcriptomic analysis unveiled a sophisticated regulatory network. C12-oxo-HSL not only stimulated the expression of genes involved in initial adhesion and motility but also orchestrated a substantial upregulation of key energy metabolism pathways, including glycolysis, the tricarboxylic acid (TCA) cycle, and oxidative phosphorylation. Metabolic upregulation likely increased ATP availability for the augmented production of extracellular polymeric substances, ultimately leading to the formation of a more resilient and efficient biofilm structure. Our findings suggest a potential energy-centric mechanism where exogenous AHLs prime the cellular bioenergetic status to support the structural and functional demands of plastisphere colonization. This highlights the pivotal role of signal-mediated resource allocation in shaping the biogeochemical impact of microplastic pollution.
Skin contact is an important route for human exposure to atmospheric pollutants. Many atmospheric pollutants possess photochemical activity, and skin sweat provides a natural environment for the photogeneration of reactive species (RSs) from pollutants. However, the photochemical transformation of atmospheric pollutants in skin sweat and their toxicological effects on the skin remain poorly understood. Herein, 1-nitronaphthalene (1-NN), a common atmospheric pollutant, was used as a model compound to investigate the influence of key components (i.e., Organic acids, Fe3 +) of skin sweat on the degradation and transformation mechanisms of 1-NN, as well as the skin toxicity of its transformation products. Our results show that lactic acid (LA) facilitated the photodegradation of 1-NN. The excited triplet state 1-NN (31-NN*) can oxidize LA to generate carbon-centered radicals (·CH(CH3)OH) that was confirmed by EPR spin trapping and high-resolution mass spectrometry. Histidine (His) further accelerates this process by consuming dissolved oxygen (3O2), thereby inhibiting the quenching of 31-NN* as well as carbon-centered radicals by 3O2. Additionally, the presence of Fe3+ can trigger the generation of carboxyl radicals (CO2•-) via carboxylic acid ligand-to-metal charge transfer, further enhancing the photodegradation of 1-NN. Toxicity assays indicated that the photochemical transformation process of 1-NN can lead to higher cytotoxicity. These findings provide a new strategy for understanding the transformation processes and toxicity evolution of nitrated polycyclic aromatic hydrocarbons on the skin surface.
Anaerobic digestion (AD) and composting are commonly used methods for the biological stabilization of sewage sludges (SSLs). Both solid digestate and compost produced during these processes can be used as organic fertilizers, provided standards are met. However, the presence of potentially toxic elements (PTEs) that remain in the solid digestate and compost poses a risk of their release following soil application. This paper examines the transformations (persistence and bioavailability) of PTEs (Cu, Zn, Pb, Cd, Ni, Cr) in both stabilization processes of SSLs with particular attention to Cu and Ni, which exhibit distinct behavior under different stabilization conditions. Research has shown that AD generally leads to an increase in PTEs content in SSLs, whereas composting may result in either a decrease or an increase in PTEs content in the final product. In composting, reduction is associated with the leaching of PTEs to the compost leachate, determined by the pH level of the composted matter. In most cases, AD and composting are environmentally beneficial, promoting transformations of bioavailable exchangeable and carbonate-bound or reducible fractions of PTEs to stable oxidizable and residual fractions. The introduction of passivation additives during both processes positively influences PTEs immobilization. Available studies demonstrate that AD and composting effectively stabilize SSLs and significantly reduce PTE mobility and bioavailability, thereby lowering potential environmental risks. Appropriate optimization of process conditions allows for control over PTE transformations, enhancing the safety of solid digestate and compost as organic fertilizers.
In order to achieve the harmless and resource-efficient treatment of hazardous elements in vanadium extraction tailings, a one-step reductive smelting separation process was developed to transfer the toxic elements Cr and V into a high valuable vanadium containing ferrochrome alloy. Under the optimal parameter of basicity 1.2, C/O molar ratio 1.2, holding temperature 1550 °C and holding time 50 min, the reduction rate of Fe, V and Cr from vanadium extraction tailings reached 96.14%, 95.98%, 93.60%, respectively, with the simultaneous production of Fe-Cr-V alloy and Ti-rich slag. The hardness of the alloy was 42.27 ± 0.65 HRC and the average friction coefficient was 0.678 ± 0.001, indicating that it basically meets the standards for wear-resistant materials. Toxicity leaching test results demonstrate that the leaching concentrations of Cr and V were 0.030 and 0.013 mg/L, respectively, which were 1/32 and 1/2825 of those in the original slag. These results confirm that the tailings have been effectively rendered harmless and detoxified. Hence, this one-step reductive smelting separation method synchronously realizes metal recovery, wear-resistant alloy preparation and Ti-rich residue co-production, achieving the complete utilization of hazardous vanadium extraction tailings, and provides an effective technical approach for the resource treatment of other toxic waste residues.
Triazole fungicides (TFs) are widely detected in various environmental compartments, yet their atmospheric behavior and associated health risks, particularly for particle-bound TFs, remain poorly understood. This study comprehensively investigated the occurrence, atmospheric persistence, and human exposure risks of four typical particle-associated TFs. Urban ambient monitoring showed that all target TFs were detected in PM₂.₅, with total concentrations ranging from 1.1 × 102-9.5 × 102 pg m-3. An oxidation reactor operated under the "OFR-254" mode was employed to explore the heterogeneous •OH-initiated oxidation kinetics of TFs. The measured rate constants ranged from (7.1 ± 0.4) × 10⁻13 to (1.4 ± 0.1) × 10⁻12 cm3 molecule-1 s-1, corresponding to atmospheric lifetimes of 5.2-25 days, suggesting a long-range transport potential in the atmosphere. A total of 16 transformation products derived from •OH heterogeneous oxidation were tentatively identified, six of which were detected in PM2.5. Four photolysis products were also found in PM2.5, indicating that the combined effects of photolysis and •OH heterogenous oxidation dominate the degradation of particle-associated TFs in the real atmospheric environment. The short-term average daily inhalation dose (SADDinh, pg kg-1 d-1) of TFs for urban residents was further estimated to range from 8.2 to 37 pg kg-1 d-1. Our findings provide valuable insights into the atmospheric fate of particle-associated TFs and underscore the necessity of incorporating emerging pesticides into future environmental monitoring and risk assessment frameworks.
Black soldier fly (BSF) manure produced through biological conversion technology still raises safety concerns related to antibiotic resistance genes (ARGs) and heavy metal residues. Composting has emerged as a viable approach for mitigating the proliferation of ARGs within livestock manure matrices. This study evaluated the effects of biochar, humic acid, and tea residue on the fate of ARGs, mobile genetic elements (MGEs), heavy metal resistance genes (HMRGs), and virulence factors (VFs) during BSF manure composting. Results indicate that humic acid exhibits the strongest inhibitory effect on ARGs and MGEs, achieving a 95.6% removal rate for intI1 and reducing the abundance of MLS(B) genes by 80.5%. Biochar demonstrates the strongest suppression of HMRGs, substantially decreasing the abundance of genes such as arsC and copA. However, the abundance of certain genes, such as intl2, catB8, arsM and cusA, increased across all treatments. Although humic acid increased the overall abundance of VFs, it achieved a final suppression rate of 86.3% by the end of the composting process. Interactions between bacterial phyla during composting were predominantly positively correlated. Network analysis revealed that humic acid most significantly suppressed co-occurrence associations among ARGs. Environmental factors such as pH and organic matter were associatively linked to ARGs reduction through a pathway that sequentially involved bacterial abundance and VFs (indirect effect = -0.87), suggesting a potential mechanistic cascade that warrants further experimental validation. This study provides a theoretical framework for optimizing the BSF manure composting process while acknowledging both the potential and limitations of additive amendments.
Developing highly selective adsorbents for antibiotic removal from aquatic environments is often hindered by the instability of molecular recognition sites in aqueous media. Traditional molecularly imprinted polymers (MIPs) frequently exhibit impaired performance in water due to the disruption of non-covalent interactions. This study presented a general strategy for the fabrication of "greenificated" MIPs utilizing a deep eutectic solvent (DES) as both a functional monomer and a structure-directing porogen in a one-pot synthesis. The resulting polymer, MIP-DES/(20% MeOH), targeted sulfamethoxazole (SMX) through a "solvent-reactant synergy" mechanism. Under optimized conditions, the adsorbent achieved a maximum capacity of 59.58 mg/g and an imprinting factor of 1.80. Mechanistic elucidation using density functional theory (DFT) and spectroscopic analysis confirmed that the recognition was governed by specific hydrogen bonding, π-π interactions, and hydrophobic effects, which remained stable despite interference from competitive analytes, 12 water matrices and natural organic matter. Comprehensive assessments including AGREEMIP, life cycle analysis, biological toxicity, and long-term desorption together confirmed environmental friendliness of both pristine and SMX-saturated adsorbent. This work demonstrates that DES-mediated imprinting provides a robust pathway for the sustainable production of high-performance materials capable of selective recognition in complex engineered and natural water systems.
Co-contamination of soils is an increasingly severe environmental issue, requiring rapid, effect-based tools to assess ecological risks in complex soils. In this study, we developed a high-performance magnetic nano-biosensor by assembling biomimetically synthesized Fe3O4@Mms6 nanoparticles with the marine, luminescent bacterium, Photobacterium phosphoreum (P. phosphoreum), and its proof of concept by the toxicity of metal(loid)s mixtures. Fe3O4@Mms6 exhibited favorable properties for biosensor construction, including a uniform size (16.05 nm), high magnetic responsiveness (74 emu g-1), and minimal toxicity to P. phosphoreum. These attributes enabled enhanced luminescence (approximately 2800 mV) and stable magnetic recovery of the assembled biosensor. Compared with free P. phosphoreum, the biosensor showed greater sensitivity, reducing the EC50 for Hg2+-induced luminescence inhibition from 1.29 to 0.93 mg kg-1 and lowering the coefficient of variation (CV) from 13.02% to 8.39%. Dose-response relationships further confirmed sensitivity to Hg2+ and Zn2+. Optimal biosensor performance was achieved at a salinity of 2.98%, pH 7.01, and a soil-to-water ratio of 0.039 g mL-1 with a 30 min incubation. Field application at a coal chemical site revealed a significant correlation between biosensor responses and the comprehensive potential ecological hazard index (HI) (Pearson r2 = 0.81, p < 0.01). Overall, this study provides a robust and field-applicable approach for assessing the toxic potential of contaminated soils.
Methicillin-resistant Staphylococcus aureus (MRSA) remains a major public health threat owing to its pronounced antibiotic resistance, multiple virulence factors, and robust biofilm-forming capacity, yet effective integrated antimicrobial strategies are still lacking. The global regulator SarA serves as a regulatory hub that simultaneously governs these key MRSA hazard determinants. Here, we report a comprehensive platform for the all-round control of MRSA biological contamination, centered on a label-free electrochemical impedance spectroscopy (EIS)-based biosensing system designed to screen inhibitors targeting SarA. Using this platform, the fruit-derived flavonoid γ-mangostin (γ-MG) was identified as a potent SarA inhibitor. Further MD simulations revealed that γ-MG spontaneously and stably engaged residues within the DNA-binding domain, particularly VAL68 and VAL92, thereby attenuating structural fluctuations. γ-MG markedly reduced MRSA viability (MIC=8 μg/mL) inhibited biofilm formation, and effectively eliminated MRSA in milk. γ-MG quenched the intrinsic fluorescence of SarA and elicited a substantially greater impedance response at the SarA-modified gold electrode (ΔZ'=6.442 kΩ) relative to the positive control Morin (ΔZ'=1.614 kΩ). Transcriptomic and bioinformatic analyses revealed broad perturbation of SarA-regulated pathways, encompassing transcriptional activity, cell adhesion, stress response, and cell wall homeostasis, a profile closely resembling that of the ΔsarA mutant. Animal infection models confirmed the therapeutic efficacy and decontamination capacity of γ-MG against MRSA. Collectively, this study provides an effective strategy and a sensitive analytical tool for the integrated prevention and control of MRSA contamination.
The oxidation of galena is a critical environmental and geochemical process that controls the lead release and causes environmental contamination. However, galena exhibits a paragenetic association with wolframite in tungsten deposits, and the role of galvanic couples between oxides and sulfides remains little explored. This study investigated the effect of wolframite on the oxidation of galena, with a particular focus on the presence of galvanic interaction and the role of reactive oxygen species (ROS). By leaching experiment, electrochemical techniques, reactive oxygen species (ROS) analysis and density functional theory (DFT) calculations, we demonstrate that the galvanic interaction between wolframite and galena occurs and that ROS are generated in the presence of this galvanic effect. Wolframite acts as a cathode and facilitates the anodic oxidation of galena, where the electrons transfer from galena to wolframite. DFT calculations further reveal that the wolframite-galena heterojunction exhibits a type-II staggered band alignment, with a lower work function of galena higher than that of wolframite, which drives directional electron transfer from galena to wolframite. The electron transfer from galena promotes the reduction of O2 on the surface of wolframite, thereby increasing the formation of ROS, which further facilitates the oxidation of galena. ROS analysis indicates that hydroxyl radicals (•OH) play a key role in the oxidation process of galena, which can be additionally generated through the Fenton reaction between hydrogen peroxide (H2O2) and Fe2+ released from wolframite. This work provides new insights into lead release in tungsten mining areas where galena and wolframite coexist, and has powerful implications for mitigating lead pollution.
Permanganate (PM, Mn(VII)) oxidation is attractive for water treatment because of its stability and operational simplicity, yet its moderate oxidizing power often limits the removal of recalcitrant trace organic contaminants, such as sulfonamide antibiotics. Here, we show that metal hydrolysis in situ generates dispersed metal (hydr)oxide colloids that markedly enhance PM oxidation of sulfonamides. Among the tested metals, Fe(III) showed the strongest promotion of sulfamethoxazole (SMX) degradation in a strongly pH-dependent manner. Transmission electron microscopy, zeta potential measurements, graded membrane filtration and preformed-colloid control experiments identified that Fe(OH)3 nanocolloids (80-120 nm) as the dominant active phase. Multiple probe experiments, electron paramagnetic resonance, sulfoxide probing, and Mn(III)-pyrophosphate assays revealed no measurable contribution from reactive oxygen species or reactive Mn intermediates under our experimental conditions. Instead, electrochemical measurements, selective probe reactions, and DFT calculations support a proximity-enabled interfacial electron-transfer pathway, in which Fe(OH)3 colloids associate with MnO4-, weaken Mn-O bonding, and co-enrich MnO4- and SMX at the interface. At a realistic PM dose (10 µM) and an optimized Fe(III) dosage of 0.1 mM, this colloid-assisted system rapidly removed five sulfonamides, with apparent rate constants enhanced by 6-151 times. ECOSAR predictions suggested reduced ecotoxicity of the degradation products, and the system remained effective in multiple real water matrices. These results establish hydrolysis-derived metal colloids as interfacial nanoreactors and offer a tunable strategy to improve PM-based removal of sulfonamide antibiotics.
Microfiltration is widely applied for surface water purification; however, the coexistence of microplastics (MPs) and organic contaminants in source waters of varied salinity and natural organic matter (NOM) may influence contaminant partitioning and fouling behavior during filtration. This study investigates how polymer type (i.e. polyethylene (PE) and polyethylene terephthalate (PET)) and aging of MPs affect their interactions with mixed contaminants, transport and partitioning of the contaminants in cake layer during microfiltration under varying salinity and NOM. PE-MP and PET-MP exhibited a stronger adsorption affinity toward bisphenol A (BPA) than atrazine (ATZ). Density functional theory calculations confirm noncovalent-dominated adsorption on PE-MP and π-π interactions governing adsorption on PET-MP. Aging alters such interactions by modifying surface physicochemical properties, leading to differential adsorption behavior compared to pristine MPs. Increasing ionic strength enhanced BPA adsorption via a salting-out effect (P < 0.05) but suppressed ATZ adsorption, while Suwannee River fulvic acid showed negligible influence due to competitive sorption. Microfiltration experiments demonstrated that polymer type, aging state, operating pressure, and water chemistry jointly regulate MP cake structure, thereby controlling contaminant transport, partitioning, and specific cake resistance. PE-MP and PET-MP held negative surface charge at zeta potentials of -18.07 and -6.39 mV in feed water, respectively. Polymer properties and aging-induced surface modifications governed the transition between interaction-driven fouling and mechanical compaction, which is increasingly important at elevated trans-membrane pressure. Moreover, hetero-aggregation between organic contaminants and MPs alleviated hydraulic resistance. These findings provide mechanistic insights for optimizing membrane processes to improve the removal of MP-associated contaminants.
Lithium-ion batteries (LIBs) have become the core driving force for the global clean energy transition, and silicon carbide nanoparticles (SiC NPs) could be used anode material for lithium-ion batteries. With the rapid development of new energy industries, exposure to SiC NPs has increased significantly. However, the detrimental effects of SiC NPs on the heart and the underlying mechanisms remained largely unexplored. In the present study, we established a 5d exposure SiC NPs mice model through intratracheal instillation and mouse cardiomyocyte (HL-1 and primary cardiomyocytes) model. By single-nucleus RNA sequencing (snRNA-seq) analysis, we investigated the adverse reactions of heart and potential molecular mechanisms associated with SiC NPs exposure. Our results showed that short-term exposure of SiC NPs exposure could cause myocardial injury in mice. SiC NPs regulated METTL1 to reduce the m7G modification level and abundance of mt-tRNA-Trp, causing mitochondrial translational dysfunction, thereby inducing cardiomyocyte senescence. Supplementation of METTL1 alleviated SiC NPs-induced cellular senescence in vitro and in vivo. This study elucidated novel insights into the prevention and treatment of myocardial injury, while providing a solid experimental foundation for the development of mitochondrial-targeted therapeutic strategies.
Characterizing and quantifying the biotransformation of per- and polyfluoroalkyl substances (PFAS) in aqueous film forming foam (AFFF)-impacted groundwater is crucial for the long-term success of remediation efforts. The objective of this study is to understand the role of hydrocarbon-mediated aerobic transformation of PFAS precursors from AFFF-impacted site samples. Microcosms were prepared using sediments and groundwater from a legacy fire-fighter training area where both fluorotelomer (FT)-based foams (predominantly C8) and electrochemical fluorination (ECF)-based foams (predominantly C6) were present. Methane, propane, or octane were added as primary substrates in aerobic microcosms, which were then sacrificed after 60 or 120 days. Both ECF and FT precursors were observed to transform in the hydrocarbon-amended microcosms by 120 days, producing intermediates and terminal perfluoroalkyl acids (PFAAs). The dominant FT-based precursors included 8:2 FTS (21 µg/L, 40 nM), 8:2 fluorotelomer sulfonyl propanoamido dimethylethyl sulfonate (8:2 FTSO2-PrAd-DiMeEts; 6 µg/L, 9 nM), and 6:2 fluorotelomer sulfonate (6:2 FTS; 2 µg/L, 5 nM) all of which transformed > 95% in alkane-amended microcosms. Notably, these biotransformation reactions occurred in the presence of sulfate (∼10 mg/L), contrary to prior literature. The ECF-based precursors, dominated by compounds with 6 fluorinated carbons (C6), produced the intermediate N-dimethyl ammoniopropyl perfluorohexane sulfonamide (AmPr-FHxSA; 1.4 µg/L, 3 nM), along with two homologs in the AmPr-FASA class (C4 and C8) as well as the terminal PFAS perfluorohexane sulfonic acid (PFHxS; 15 µg/L, 37 nM). Using the total oxidizable precursor assay (TOP), the mass balance closed to 119% ± 10%. This work presents the first comprehensive look at the simultaneous transformation of all legacy PFAS present at an AFFF site using native bacteria stimulated with alkane hydrocarbons.
Indigenous microbiota adapted to uranium-contaminated environments often exhibit strong uranium resistance and environmental adaptability, making them promising candidates for bioremediation. In this study, a functional consortium (WE) was established through long-term acclimation and was dominated by Enterobacter (97.52%). Genomic analysis of the dominant strain, Enterobacter sp. SA187, revealed diverse and active metabolic potentials, providing a genetic basis for its environmental adaptability and competitive advantage. The WE consortium showed a maximum tolerance concentration (MTC) of 50 mg·L-1and a minimum inhibitory concentration (MIC) of 5 mg·L-1 for U(Ⅵ). Under optimized conditions (6% inoculum, pH 6.00 ± 0.01, 30℃), it achieved 98.51% removal of U(Ⅵ) at an initial concentration of 10 mg·L-1. Mechanistic analyses showed that U(Ⅵ) removal occurred mainly through synergistic biosorption and biomineralization. Uranium was associated with cell surface functional groups, including carboxyl, phosphoryl, and amino groups, and was also immobilized in extracellular products. Stable uranium phosphate minerals, predominantly Na((UO2)(PO4))·3 H2O and (UO2)(HPO4)·4 H2O, were identified as the main end-products, confirming phosphate-mediated biomineralization as a key removal pathway. These findings highlight the important role of medium-driven microbial acclimation in enhancing consortium function and provide a practical strategy for the bioremediation of uranium-contaminated water.
Hydrogel exhibits distinct advantages for constructing advanced antifouling membranes due to its high water permeability and water retention capacity. To overcome the weak interfacial adhesion and limited functionality of conventional hydrogel coatings, the stable dual-light responsive fibrous composite membrane (FCM) was engineered by anchoring 3D artichoke-like CuO@GO microsphere within poly(vinyl alcohol)-tannic acid hydrogel network onto poly(arylene ether nitrile) (PEN) nanofibrous scaffold via multi-interface bonding. Compared with traditional 2D laminar structure, the distinctive 3D microspherical architecture effectively suppressed the compact restacking of GO nanosheets, which preserved abundant water-transport channels for enhancing permeability while constructing hierarchical hydrophilic/underwater oleophobic surface. Consequently, the modified membrane delivered efficient separation across various oil-in-water emulsions, achieving high permeation flux up to 3028 L·m⁻²·h⁻¹ and separation efficiency above 99.5%. Benefiting from multiple interfacial covalent bonds and nano-reinforcement, the PEN FCM membrane exhibited high tensile strength of 22.763 MPa and maintained structural stability even under aggressive chemical environments and physical scouring. Furthermore, the 3D hierarchical artichoke-like CuO@GO heterojunction enabled broad-spectrum light harvesting and rapid photothermal conversion (rising from 36.38 °C to 92.71 °C within 80 s), which effectively reduced oil viscosity to mitigate membrane fouling. Moreover, the activation of peroxymonosulfate imparted efficient degradation of various organic dyes within 1 h (92.81% removal of methyl orange), enabling the potent photocatalytic self-cleaning capability to the membrane. Collectively, this dual-light-responsive strategy offers a promising route for treating complex oily wastewater while alleviating membrane fouling.
Passive samplers, for instance Chemcatcher, Microporous Polyethylene Tube passive samplers (MPTs) and Diffusive Gradients in Thin Films (DGT), are widely used for monitoring time-weighted average concentrations (CTWA) of contaminants in waters. This study presents ChemTRAP, a novel passive sampler using two macroporous filters (MFs) as both sorbent support and diffusion matrix for analyte uptake. This design enables analyte recovery by solid-phase extraction (SPE), thereby reducing per-unit costs and simplifying workflows. Six organic analytes and six heavy metals were used to evaluate ChemTRAPs embedded with Hydrophilic-Lipophilic Balanced resin or Chelex100 resin. The ChemTRAP, as an SPE device, achieved a mean recovery of 94.3% for all 12 analytes in both simulated and Lake Nanhu water. The performance of Chelex100 resin remained stable over 10 reuse cycles. In a preliminary field test, ChemTRAPs showed an average sampling rate of 2.4 mL/d, comparable to MPTs and DGTs. The average recovery of 12 analytes was 73.4% (95% Confidence Interval: 54-92%), indicating that ChemTRAP-derived CTWA are representative of ambient concentrations, despite a slight negative bias likely attributable to biofouling. While further field validation is necessary, investigation of analyte diffusion in MFs is also desirable to develop a predictive RS model comparable to that established for DGTs.
Amine-functionalized graphene quantum dots (A-GQDs) are emerging environmental contaminants, yet their developmental neurotoxicity is not well understood. This study shows that A-GQDs (<10 nm) accumulate in zebrafish brain tissue, inducing anxiety-like and aggressive behaviors lasting at least 14 days. To elucidate the underlying mechanisms, we utilized two-way analysis of variance (ANOVA) to analyze the interactions between developmental stages and A-GQDs exposure. We subsequently performed weighted gene co-expression network analysis (WGCNA) on interaction-related genes and identified a developmentally sensitive co-expression module enriched in both mitophagy and ferroptosis pathways. Gene Ontology (GO) enrichment analysis of the shared differentially expressed genes identified at both time points further revealed significant enrichment of processes related to mitochondrial respiratory chain complex assembly, mitophagy, and iron ion homeostasis. Mechanistically, A-GQDs induced mitochondrial dysfunction, activating pink1/parkin-mediated mitophagy, which disrupted iron homeostasis and triggered ferroptosis. Importantly, pharmacological inhibition of either pathway alleviated behavioral deficits, thereby validating the mitochondria-mitophagy-ferroptosis axis as a central mechanism of A-GQDs neurotoxicity. These findings unveil a novel neurotoxic pathway involving A-GQDs and underscore the urgent need for integrating mechanism-based endpoints into the risk assessment frameworks for nanomaterials, enhancing our understanding of their potential implications for environmental and public health.