Journal of hazardous materials最新文献

As an emerging alternative to perfluorooctanoic acid (PFOA), hexafluoropropylene oxide trimeric acid (HFPO-TA) has attracted increasing attention due to its widespread environmental occurrence and strong propensity for bioaccumulation. Nevertheless, the reproductive toxicity of PFOA and HFPO-TA in aquatic animals, as well as their effects on subsequent generations, remains poorly understood. To elucidate the reproductive effects of these compounds, adult male and female zebrafish were exposed to PFOA or HFPO-TA at concentrations of 0.5 and 50 µg/L, after which offspring were generated and collected for subsequent analyses. The findings demonstrated that both compounds disrupted mitochondrial integrity in gonadal cells, induced endocrine disturbances, altered sex hormone levels, and caused abnormal gonadal cell development, collectively impairing reproductive function. HFPO-TA elicited more severe endocrine disruption and gonadal damage in parental zebrafish than PFOA, with females exhibiting greater susceptibility to endocrine perturbation. In the offspring larvae, profound transcriptomic reprogramming was observed, concomitant with disturbances in growth and development, redox homeostasis, apoptotic signaling, and swimming performance. Notably, PFOA exerted stronger intergenerational toxicity, affecting offspring more profoundly than HFPO-TA. In summary, while HFPO-TA produced a more pronounced reproductive toxicity phenotype in parental zebrafish, PFOA posed a substantially greater risk to future generations.

The treatment of semiconductor wastewater containing tetramethylammonium hydroxide (TMAH) presents a formidable challenge to anammox resilience yet the mechanisms governing irreversible sludge deterioration remain obscure. This study elucidates a deterioration pathway driven fundamentally by the disintegration of the granular structural architecture rather than immediate metabolic inhibition. Long-term exposure induced a transition toward a rougher and hydrophilic phenotype where surface roughness increased five-fold and water contact angles declined significantly. Mechanistically this physical unraveling was triggered by the dismantling of the hydrophobic extracellular polymeric substances network characterized by a plummeting protein/polysaccharide ratio and the depletion of tryptophan-like substances. Fourier transform infrared analysis confirmed the disruption of hydrogen bonding and the loss of hydrophobic moieties which compromised the cohesive scaffold. This microenvironmental collapse precipitated a distinct abundance-activity decoupling where the genomic abundance of Candidatus Kuenenia remained robust at 37.73% yet its functional vitality was severely impaired as evidenced by plummeting intracellular ATP and heme c levels. Concurrently the selective washout of filamentous skeleton-forming Chloroflexota and adhesion-promoting Pseudomonas further accelerated the structural fragmentation. These findings establish that the integrity of the hydrophobic EPS protein network is the prerequisite for sustaining anammox resilience against alkaline organic toxicity.

Palladium is a vital industrial precious metal, whose improperly discharged palladium-containing wastes give rise to cumulative heavy metal contamination of environmental media. The efficient recovery of palladium requires high performance adsorbents. This study selects the dicarboxylic acid Bis(carboxyl)-functionalized trithiocarbonate (Cctc) as a regulator to synthesize defect rich Cctc@UiO-66-NH₂ by inducing functional defects, thereby achieving the optimized regulation of UiO-66-NH₂'s performance. In practical wastewater applications, 20.0 mg of Cctc@UiO-66-NH₂ was fabricated into a membrane, which continuously separated 2520 mL of 3 mg L^-1 Pd(II), with 2.5 times the recovery capacity of UiO-66-NH₂. After nine adsorption-desorption cycles of continuous membrane separation, the total treated volume of Pd(II) solution reached 20286 mL, and the adsorption efficiency remained above 70% of the initial value, exhibiting excellent Pd(II) recovery efficiency and reusability. Spectral analysis and theoretical calculations confirm that the defect density of Cctc@UiO-66-NH₂ is significantly increased, thereby exposing a more plentiful array of active sites. The adsorption of Pd(II) by this material is mainly driven by the synergistic coordination of oxygen and sulfur atoms, together with electrostatic attraction from -NH₂. The results outlined above illustrate that Cctc@UiO-66-NH₂ possesses both excellent adsorption capacity and long-term cyclic stability, exhibiting practical utility for the retrieval of noble metals in low-concentration wastewater.

The removal of hazardous Cr(III) complexes via advanced oxidation processes can generate highly toxic Cr(VI), posing significant environmental risks. Therefore, there is an urgent need to develop alternative methods that completely suppress the generation of Cr(VI). In this study, with no detectable Cr(VI) in the solution (below the detection limit of 0.004 mg/L), the carbon nanotubes-modified micron-sized zero-valent aluminum (CNTs@mAl⁰) can effectively remove 99.50% of Cr(III)-EDTA and 83.34% of TOC under the typical acidic conditions of industrial chromium wastewater (pH = 3.00) by activating molecular oxygen. Then the following alkaline precipitation can easily remove the decomplexed free chromium, lowering total chromium concentration to 0.11 mg/L, which meets most national and regional standards, whereas direct alkali precipitation fails to meet them. Serving as a strong electron reservoir (E⁰ = - 1.662 V), micron-sized zero-valent aluminum (mAl⁰) synergizes with highly conductive carbon nanotubes (CNTs) to effectively activate O₂, facilitating the production of reactive oxygen species (primarily ¹O₂ and •OH) that drive the oxidative decomplexation of Cr(III)-EDTA. Furthermore, the organic ligands are efficiently mineralized, thus preventing Cr(III)'s re-complexation. More interestingly, once the Cr(VI) is possibly generated, it would be rapidly absorbed by CNTs and be immediately reduced by mAl⁰ with strong reducing power, thereby completely suppressing the generation of any Cr(VI) in bulk solution. In conclusion, this study presents an environmentally friendly and straightforward treatment system for Cr(III)-complexes, offering an effective solution to mitigate the environmental risks posed by chromium, particularly Cr(VI), in wastewater.

Fluorinated liquid crystal monomers (FLCMs) have recently emerged as persistent organic pollutants, while microplastics serve as important environmental carriers of persistent organic pollutants. However, their interactions with aged microplastics and the consequent ecological risks remain a critical blind spot. This study examined the adsorption-desorption dynamics of a representative FLCM (4-ethoxy-2,3-difluoro-4'-(trans-4-propylcyclohexyl) biphenyl, EDPB) on aged polyethylene, polypropylene, polystyrene, and polyvinyl chloride under both abiotic (i.e., environmental) and biotic (i.e., simulated gastrointestinal) conditions. Surface oxidation and increased roughness of aged polymers markedly enhanced EDPB adsorption, through combined hydrophobic attraction and fluorine‑mediated dipole interactions. Desorption was strongly medium dependent. In simulated gastric fluid, pepsin facilitated partial release (12.6-24.8%) by disrupting π-π interactions and promoting surface hydration. In contrast, intestinal components induced substantial remobilization (up to 52.8%) via the formation of hydrophobic cavities and micelle-like structures, increasing dissolved EDPB concentrations by approximately 20 μg L^-1. This biphasic desorption profile highlights the critical role of intestinal processes in remobilizing adsorbed FLCMs and elevating their bioaccessible fractions. Subsequent cytotoxicity assays in Caco‑2 cells showed dose‑ and time‑dependent inhibition of cell viability, with transcriptomic analysis delineating a mitochondrial dysfunction-driven cascade. EDPB acts as a metabolic disruptor that impairs mitochondrial energetics and redox homeostasis, triggering downstream genomic instability and cell cycle arrest, which ultimately implicating oxidative stress-mediated apoptosis. This work synthesizes critical insight into the coupled environmental and biological behaviors of FLCMs, revealing their potential as transboundary persistent toxic substances and advancing the understanding of their risks in microplastic‑dominated systems.

Electrochemical sulfite activation represents a novel member of advanced oxidation processes effective for pollutant degradation, yet systems based on soluble sulfite sources (e.g., Na₂SO₃) remain plagued by radical self-quenching, excessive sulfate accumulation, and limited long-term sustainability. To overcome these limitations, we developed a controlled-release sulfite-electrochemical oxidation system (EC/CaSO₃) employing CaSO₃ as a solid-phase sulfite reservoir. Arsenite (As(III)) was chosen as the model contaminant due to its pronounced toxicity and environmental prevalence. Under mild operating conditions (2.0 V, pH 8.5, 25°C), the EC/CaSO₃ system achieved complete As(III) oxidation within 12 min, exhibiting a kinetic rate constant 18-fold higher than that of the EC-only process. The controlled dissolution of CaSO₃ facilitated the sustained and stable release of SO₃^2 -, concurrently promoting the generation of reactive oxygen species (ROS) and reactive oxysulfur species (RSS). Mechanistic interrogation identified SO₄^•- as the predominant oxidant, with HO^• and SO₅^•- acting as secondary contributors. The process ultimately converted sulfite into stable CaSO₄ precipitates, effectively mitigating secondary salt contamination. Based on this mechanism, the oxidation performance of this system significantly outperforms that of conventional EC/Na₂SO₃ systems. By supplanting soluble Na₂SO₃ with solid-phase CaSO₃, this study pioneered a self-regulating and environmentally benign electrochemical oxidation strategy that integrated controlled sulfite supply with synergistic RSS/ROS generation, presenting an energy-efficient and scalable platform for water remediation.

Pharmaceutical residues are persistent contaminants that resist conventional wastewater treatment and can disrupt ecosystems; however, microorganisms provide a promising biobased solution to transform or mineralize these complex xenobiotics. Whether pollutant-adapted communities maintain their degradative capacity under realistic environmental conditions remains a long-standing debate in environmental biotechnology. Here, microbial consortia enriched in six membrane bioreactors under high pharmaceutical concentration (100 mg/L) retained full biodegradation capacity across a 5000-fold concentration range. After prolonged exposure to six model compounds (atenolol, caffeine, diclofenac, enalapril, ibuprofen, and paracetamol) complete removal occurred for all except diclofenac. Degradation remained efficient even at lower and environmentally relevant concentrations (1 mg/L-20 µg/L) and recovered rapidly upon re-exposure to higher loads (100 mg/L). Metagenomic profiling revealed enrichment of oxygenase-mediated catabolic pathways supporting this resilience. When transferred to a 7 liters bioreactor treating real wastewater, the adapted community removed targeted and untargeted pharmaceuticals, demonstrating robustness, scalability, and strong potential for sustainable micropollutant remediation.

The mining of polymetallic sulfide deposits is causing increasingly severe environmental issues. Galvanic interactions in systems where multiple sulfide minerals coexist play a key regulatory role in their oxidative dissolution under abiotic conditions. In carbonate-rich environment, the impact of galvanic interactions on the mobilization behavior of heavy metals remains unclear. This study focuses on the galvanic effect in sulfide mineral coexisting carbonate-rich systems. The research results indicate that galvanic interactions drive sulfide mineral oxidation in carbonate-rich systems, but alkaline conditions weaken the process compared to acidic environments. Pyrite, serving as a cathode, promotes the release of Pb and Cd via galvanic interactions. The alkaline environment suppresses pyrite-mediated ·OH generation through galvanic processes, consequently reducing the mobilization of Pb and Cd from galena and sphalerite. CO₃²⁻ and HCO₃⁻ exhibit multiple roles: they react with ·OH to form CO₃·⁻ and function as electrolytes to enhance electron transfer. However, the precipitation of carbonates and their electrochemical inertness effectively suppress Pb and Cd mobilization. Additionally, naturally weathered products lack electrochemical activity and form surface barriers that impede electron transfer, thereby further reducing the mobilization of Pb and Cd.

Anaerobic degradation of recalcitrant pollutants remains a significant challenge due to insufficient electron supply. Interspecies electron transfer (IET) based on extracellular electron transfer (EET) processes plays a crucial role in supporting the cooperative metabolism of complex microbial consortia. Here, an Fe₂O₃-coupled anaerobic system driven by a potential gradient was constructed to enhance the degradation of 4-chlorophenol (4-CP), achieving a removal efficiency 1.38 times that of conventional anaerobic treatment. Fe(II)/Fe(III) redox cycling coupled with cytochrome c-mediated EET overcame the limitation of short-range electron transfer between outer-membrane electroactive proteins and conductive materials, thereby activating direct IET among methanogens, fermentative bacteria, degraders, and iron-reducing bacteria. Fe₂O₃ not only reshaped the microbial community but also enhanced pyruvate metabolism and gluconeogenesis, promoted heme biosynthesis and cytochrome c assembly, and strengthened cytochrome c-mediated electron transport for extracellular electron uptake, while reducing dependence on NADH dehydrogenase. The stimulated interspecies cooperation facilitated multiple 4-CP degradation routes, including dechlorination, hydrolysis, and substitution. Molecular dynamics simulations (MDS) further verified efficient electron exchange between Fe₂O₃ and the heme, which contributes to the establishment of a long-range microbial electron transfer network. Fe₂O₃-mediated directional electron transfer restructured microbial energy metabolism and interspecies interactions, providing a robust strategy for the anaerobic remediation of chlorophenol-contaminated wastewater.

This study investigated the effects of combined pollution by MPs (PE/PS/PVC) and PFASs (PFHxA/PFOA) on soil microbial communities via soil culture experiments. Results showed that PFASs significantly reduced bacterial Shannon diversity and evenness, with PS and PVC exerting marked inhibitory effects on bacteria while PE had a weaker impact. Fungal communities maintained high overall stability, but the PFHxA-PS combined treatment significantly decreased fungal diversity, showing a synergistic inhibitory effect. Acting as carriers, MPs in combined pollution enhanced contaminant retention and bioavailability, significantly increasing the number of differential species and simplifying community structure. Functional prediction suggested that bacterial defense mechanisms, secondary metabolite synthesis, and lipid metabolism might have been inhibited, whereas energy metabolism and post-translational protein modification may have been enhanced. Structural equation modeling (SEM) revealed that contaminants influenced microbial community assembly both directly and indirectly by altering environmental factors (pH, EC, C, N), with interactions among these factors increasing the complexity of ecological effects under combined pollution. This study provides a basis for understanding MPs-PFASs combined ecological effects and offers guidance for soil remediation and risk management.