Journal of hazardous materials最新文献

Antibiotic resistance is currently an unfolding global crisis threatening human health worldwide. While antibiotic resistance genes (ARGs) are known to be pervasive in environmental media, the occurrence of antibiotic resistance at interfaces between two or more adjacent media is largely unknown. Here, we designed a microcosm study to simulate plastic pollution in paddy soil and used a novel method, stimulated Raman scattering coupled with deuterium oxide (D₂O) labelling, to compare the antibiotic resistance in a single medium with that at the interface of multiple environmental media (plastic, soil, water). Results revealed that the involvement of more types of environmental media at interfaces led to a higher proportion of active resistant bacteria. Genotypic analysis showed that ARGs (especially high-risk ARGs) and mobile genetic elements (MGEs) were all highly enriched at the interfaces. This enrichment was further enhanced by the co-stress of heavy metal (arsenic) and antibiotic (ciprofloxacin). Our study is the first to apply stimulated Raman scattering to elucidate antibiotic resistance at environmental interfaces and reveals novel pathway of antibiotic resistance dissemination in the environment and overlooked risks to human health.

This work proposes a novel plasma-assisted 2D/2D g-C₃N₄/Ti₃C₂ system for treatment of organics-heavy metals composite wastewater. Unlike traditional materials in plasma system, 2D/2D g-C₃N₄/Ti₃C₂ not only improved the mass transfer efficiency of plasma by gathering both reactive species and pollutants onto the surface, but also induced photocatalytic reactions. Besides, the higher specific surface area and faster carrier separation rate can enhance the oxidation and reduction activity, and then promoted organic matter degradation and heavy metal reduction. Remarkably, the removal efficiency of sulfamethoxazole (SMX) and Cr(VI) increased by 16.5 % and 73.1 % respectively when introducing 2D/2D g-C₃N₄/Ti₃C₂. Roles of·OH,·H,·O₂^-, ¹O₂, e^-, and h⁺ in SMX oxidation and Cr(VI) reduction are clarified. The primary aggregated·OH and ¹O₂ dominate the degradation of SMX. The influencing factors, synergistic mechanism between plasma and catalyst, and redox mechanism were clarified. This work provides a breakthrough idea for treatment of organics-heavy metals composite wastewater.

Plastic products offer remarkable convenience for modern life. However, growing concerns are emerging regarding the potential health hazards posed by nanoplastics, which formed as plastics break down. Currently, the biological effects and mechanisms induced by nanoplastics are largely underexplored. In this study, we report that polystyrene nanoplastics can enter the bloodstream and enhance thrombus formation. Our findings show that polystyrene nanoplastics adsorb plasma proteins, particularly coagulation factor XII and plasminogen activator inhibitor-1, play a key role in this process, as demonstrated by proteomics, bioinformatic analyses, and molecular dynamics simulations. The adsorption of these proteins by nanoplastics is an essential factor in thrombosis enhancement. This newly uncovered pathway of protein adsorption leading to enhanced thrombosis provides new insights into the biological effects of nanoplastics, which may inform future safety and environmental risk assessment of plastics.

The catalytic membrane-based oxidation-filtration process integrates physical separation and chemical oxidation, offering a highly efficient water purification strategy. However, the oxidation-filtration process is limited in practical applications due to the short residence time of milliseconds within the catalytic layer and the interference of coexisting organic pollutants in real water. Herein, a dual-layer membrane containing a top selective layer and a bottom catalytic layer was fabricated using an in situ co-casting method with a double-blade knife. Experimental results demonstrated that the selective layer rejected macromolecular organic pollutants, thereby alleviating their interference with bisphenol A (BPA) degradation. Concurrently, the catalytic layer activated peracetic acid oxidant and achieved a high BPA degradation exceeding 90 % in milliseconds with reactive oxygen species (especially •OH). The finite-element analysis confirmed a high-concentration reaction field occupying the pore cavity of the catalytic layer, enhancing collision probability between reactive oxygen species and BPA, i.e., the nano-confinement effect. Additionally, the dual-layer membrane achieved a long-term stable performance for emerging contaminant degradation in surface water treatment. This work underscores a novel catalytic membrane structure design for high-performance oxidation-filtration processes and elucidates its mechanisms underlying ultrafast degradation.

Melamine (MA) enhanced Cu-Fenton process was developed for the degradation of anthracyclines. Taking daunorubicin (DNR) degradation as an example, we found that the initial first-order apparent constant of Cu²⁺/MA/H₂O₂ system with a molar ratio of 1:8 for Cu²⁺:MA was 5.2 times higher than that of conventional Cu²⁺/H₂O₂ system. The in-situ reductive coordination between Cu²⁺ and MA facilitated the generation and stabilization of Cu⁺ species, thereby accelerating the rate-limiting step of Cu²⁺/Cu⁺ conversion and maintaining high levels of Cu⁺ during the degradation process. Moreover, pre-synthesized Cu⁺-MA complexes (e.g., CM-250) further enhanced the efficiency of the Cu-Fenton reaction by increasing both the Cu⁺ proportion and MA chelation. The apparent activation energy for DNR degradation in CM-250 mediated Fenton reaction (15.9 kJ mol^-1) was lower than that in systems involving Cu²⁺/MA (41.2 kJ mol^-1) and Cu²⁺ (65.6 kJ mol^-1). Enhanced generation of various reactive oxygen species (·OH,·O₂^-, and ¹O₂) was confirmed, with ¹O₂ playing a dominant role, significantly improving both degradation rate and mineralization degree for DNR. MA-enhanced Cu-Fenton process also offers a convenient alternative to effectively remove other anthracyclines and organic micropollutants, holding great promise for advancing advanced oxidation processes as well as practical large-scale degradation applications targeting multiple pollutants.

Reducing nitrate (NO₃^-) in an aqueous solution to ammonia under ambient conditions can provide a green and sustainable NH₃-synthesis technology and mitigate global energy and pollution issues. In this work, a CuNi_0.75-1,3,5-benzenetricarboxylic acid/nickel foam (CuNi_0.75-MOF/NF) catalyst grown in situ was prepared via a one-pot method as an efficient cathode material for electrocatalytic nitrate reduction reaction (NO₃RR). The CuNi_0.75-MOF/NF catalyst exhibited excellent electrocatalytic NO₃RR performance at -1.0 V versus a reversible hydrogen electrode, achieving an outstanding faradaic efficiency of 95.88 % and an NH₃ yield of 51.78 mg h^-1 cm^-2. The ¹⁵N isotope labeling experiments confirmed that the sole source of N in the electrocatalytic NO₃RR was the NO₃^- in the electrolyte. The reaction pathway for the electrocatalytic NO₃RR was derived by in situ Fourier transform infrared spectroscopy and in situ differential electrochemical mass spectrometry. Density functional theory calculations revealed that the Ni element in the CuNi_0.75-MOF/NF catalyst had excellent O-H activation ability and strong *H adsorption capacity. These *H species were transferred from the Ni sites to the *NO adsorption intermediates located on the Cu sites, providing a continuous supply of *H to Cu, thereby promoting the formation of *NOH intermediates and enhancing the hydrogenation process of the electrocatalytic NO₃RR.

Calcium peroxide nanoparticles (nCP) as a versatile and safe solid H₂O₂ source, have attracted significant research interst for their application potential in groundwater remediation. Compared to the traditional Fenton system, the nCP-based Fenton-like system has a wider pH-working window for contaminants degradation. This results from the dominant radical transformation under different pH. Unlike the traditional Fenton system which is only effective in acid conditions with hydroxyl radical (•OH) as the main active species, the release of H₂O₂ and O₂ from nCP provides multiple contaminants degradation pathways. In acidic environments, •OH and Fe(IV) predominate as the active species, facilitated by substantial H₂O₂ production which activates the Fenton reaction. In neutral or alkaline conditions, the production of H₂O₂ was dramatically decreased. While the O₂ released from nCP can be catalyzed by Fe(II) to form superoxide radical (•O₂^-), which subsequently generate singlet oxygen (¹O₂). The formation pathway of •O₂^- was tracked by O¹⁸ isotope labeling experiment. The impact of the water matrix on radical generation in the Fe(II)/nCP Fenton-like system was also studied. This research deepens the understanding of the radical formation mechanisms in nCP-based Fenton-like system, offering insights to support their application in remediating contaminated groundwater.

The worldwide detection of emerging transformation products of organic micropollutants has raised accumulating concerns owing to their unknown environmental fate and undesired toxicity. This work first explored the reaction kinetics and mechanisms of the prevalent N-acetylated sulfonamides (N⁴-AcSAs, the typical sulfonamide metabolites) from wastewater disinfection to solar-irradiated receiving waters. The transformation scenarios included chlorination/bromination, photodegradation, and solar/chlorine treatment. The halogenations of two N⁴-AcSAs (N⁴-acetylated sulfadiazine, N⁴-AcSDZ; N⁴-acetylated sulfamethoxazole, N⁴-AcSMX) were pH-dependent at pH 5.0-8.0, and the reactions between the neutral forms of oxidants and anionic N⁴-AcSAs dominated the process. Furthermore, solar-based photolysis significantly eliminated N⁴-AcSAs in small water bodies with low dissolved organic carbon levels, while the indirect photolysis mediated by hydroxyl radicals and carbonate radicals contributed the most. The presence of chlorine residues in solar-irradiated wastewater effluents promoted the decay of N⁴-AcSAs, in which the generated hydroxyl radicals and ozone played a major role. Product analysis suggested the main transformation patterns of N⁴-AcSAs during the above scenarios included electrophilic attack, bond cleavage, SO₂ extrusion, hydroxylation, and rearrangement. Multiple secondary products maintained higher persistence, mobility, and toxicity to aquatic organisms than N⁴-AcSAs. Overall, the natural and engineered transformations of such micropollutants underlined the necessity of including their degradation products in future chemical management and risk assessment.

The dissolved organic matter (DOM) derived from microplastics (MPs-DOM) can be one of the photoactive components in DOM. However, information on the properties and photoreactivity of MPs-DOM during phototransformation is limited. Here, we investigated the properties and photoreactivity of MPs-DOM from polyolefins (MPs-DOM-POs), MPs-DOM derived from benzene-containing polymers (MPs-DOM-BCPs), and Suwannee River natural organic matter (SR-NOM), during a 168-hour phototransformation. After phototransformation, all examined types of DOM exhibit a decrease in concentration and molecular weight. Notably, MPs-DOM-POs display increased aromaticity and saturation, while MPs-DOM-BCPs and SR-NOM show reduced aromaticity and saturation. MPs-DOM-POs present higher steady-state concentrations of •OH but much lower steady-state concentrations of ¹O₂ than those of MPs-DOM-BCPs. In comparison, MPs-DOM produce more •OH but less ¹O₂ than SR-NOM. This study proposes that the diversification of aliphatic C─H bonds (arylation and carbonylation) by reactive intermediates (especially •OH) is the main pathway for MPs-DOM-POs phototransformation for the first time. On the other hand, the cleavage on the aromatic carboxylic acids by reactive intermediates (especially ¹O₂) is the main mechanism for MPs-DOM-BCPs and SR-NOM phototransformation. Our findings provide new insights into the phototransformation and photoreactivity of MPs-DOM and help to understand the potential risks of MPs in aqueous environment.

Penthiopyrad, a chiral pesticide, has been widely used in agricultural production. However, systematic evaluation of stereoselective bioactivity and biotoxicity of penthiopyrad in soil environment is insufficient. In this study, the stereoselective bioactivity of penthiopyrad against three soil-borne disease pathogens and its stereoselective biotoxicity to soil non-target organisms were investigated. The present results showed that the bioactivities of S-penthiopyrad were 546, 76 and 1.1-fold higher than those of R-penthiopyrad due to their different interaction modes with SDH in different target pathogens. S-penthiopyrad was more persistent in the soil environment and had stronger bioaccumulation than R-penthiopyrad. The accumulation of penthiopyrad in earthworms induced the response of detoxification system, resulting in the significant increases in the activity of detoxifying enzymes, such as GST, CarE, and CYP450. Additionally, both S-penthiopyrad and R-penthiopyrad induced cell apoptosis, intestinal damage and differentially expressed genes in earthworms, especially S-penthiopyrad. Furthermore, S-penthiopyrad has stronger binding capacity with COL6A and ACE proteins, while R-penthiopyrad has stronger binding capacity with CYP450 family proteins, which may be the main reason for the differences in biotoxicity between PEN enantiomers. Considering the differences in bioactivity and biotoxicity of penthiopyrad enantiomers, as well as the modes of action of pesticides on target and non-target organisms, S-penthiopyrad has greater potential for future development.