Journal of hazardous materials最新文献

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.

The presence of pathogenic bacteria and antibiotic resistance genes (ARGs) in urban air poses a significant threat to public health. While prevailing research predominantly focuses on the airborne transmission of ARGs by bacteria, the potential influence of other vectors, such as bacteriophages, is often overlooked. This study aims to investigate the characteristics of phages and ARGs in aerosols originating from hospitals, public transit centers, wastewater treatment plants, and landfill sites. The average abundance of ARGs carried by phages in the public transit centers was 8.81 ppm, which was 2 to 3 times higher than that at the other three sites. Additionally, the abundance of ARGs across different risk levels at this site was also significantly higher than at the other three sites. The assembled phage communities bearing ARGs in public transit centers are chiefly governed by homogeneous selection processes, likely influenced by human movement. Furthermore, observations at public transit sites revealed that the average abundance ratio of virulent phages to their hosts was 1.01, and the correlation coefficient between their auxiliary metabolic genes and hosts' metabolic genes was 0.59, which were 20 times and 3 times higher, respectively, than those of temperate phages. This suggests that virulent phages may enhance their survival by altering host metabolism, thereby aiding the dispersion of ARGs and bacterial resistance. These revelations furnish fresh insights into phage-mediated ARG transmission, offering scientific substantiation for strategies aimed at preventing and controlling resistance within aerosols.

Herein, copper sulfide (CuS) was introduced to the Fenton-like (Fe(III)/H₂O₂) system for the efficient removal of phenylarsonic acid (PAA). Results of reactive oxygen and Fe/Cu species showed that CuS preferentially reacted with Fe(III) and H₂O₂ to generate Cu(I) and superoxide anion (•O₂^-). These reductive species could efficiently promote the Fe(III)/Fe(II) and Cu(II)/Cu(I) cycles, and are beneficial to the sequential Fenton reaction to generate •OH. The organoic/inorganic arsenic species detected in the CuS/Fe(III)/H₂O₂ system confirmed that PAA was oxidized by •OH to hydroxylated organoarsenic and phenolic intermediates, which were further mineralized to oxalate and formic acid. Meanwhile, the inorganic As(III)/As(V) released during PAA degradation were efficiently immobilized by CuS. The PAA removal efficiency remained as high as 92.9 % after 5 cycles of the CuS-mediated Fenton-like process. These results demonstrate an innovative method for the treatment of organoarsenic-contaminated water, and provide new insights into the enhanced Fenton-like process utilizing sulfide minerals.

Aggregation of antiviral drugs (ATVs) in waste activated sludge (WAS) poses considerable environmental risk, so it is crucial to understand the behavior of these agents during WAS treatment. This study investigated the effects of ritonavir (RIT), an ATV used to treat human immunodeficiency virus infection and coronavirus disease 2019, on anaerobic digestion (AD) of WAS to reveal the mechanisms by which it interferes with anaerobic flora. The dosage influence results showed that methane production in AD of WAS decreased by 46.56 % when RIT concentration was increased to 1000 μg/kg total suspended solids (TSS). The AD staging test revealed that RIT mainly stimulated microbial synthesis of the extracellular polymeric substance (EPS), limiting organic matter solubilization. At 500 μg/kg TSS, RIT decreased CHO and CHON levels in dissolved organic matter by 23.12 % and 56.68 %, respectively, significantly reducing substrate availability to microorganisms. Metagenomic analysis of microbial functional gene sets revealed that RIT had greater inhibitory effects on protein and amino acid metabolism than on carbohydrate metabolism. Under RIT stress, methanogens switched from hydrogenotrophic and acetotrophic methanogenesis to methylotrophic and acetotrophic methanogenesis.

Zn isotope can help to clarify the migration, transformation and source contribution of Zn in farmland soil. However, the research on Zn isotope value of different end members in farmland soil is incomprehensive, and the variation of Zn isotope in farmland soil caused by different factors in different polluted areas is unclear, which hinders the usage of Zn isotope tracing method in farmland soil. Thus, a Pb-Zn mine polluted farmland in southwest China was selected as the research object and the end elements and farmland soil samples with different Zn contamination were systematically collected to analyse Zn content, fraction and isotopic composition. The effects of different end members and processes of eluviation, organic adsorption and inorganic adsorption on Zn isotopic composition in soil were analysed, and the relationship between these three processes and environmental variables was analysed to clarify the change mechanism. The results can enrich the fractionation mechanism of Zn isotopes, expand the application of Zn isotope in tracing the sources, and provide geochemical evidence for remediation of Zn pollution in farmland soil.

Antibiotic resistance (AR) is a major public health concern. Antibiotic intermediates (AIs) used in the production of semisynthetic antibiotics have the same bioactive structure as parent antibiotics and synthetic antibiotic production wastewater usually contains high concentrations of residual AIs; however, the effects of AIs and their interactive effects with antibiotics on the emergence of AR are unknown. In this study, antibiotic-sensitive E. coli K12 was exposed to five types of β-lactam AIs and their parent antibiotic ampicillin to analyze their impact on the evolution of multiple AR. The results indicated that AI 6-APA inhibits bacterial growth and stimulates the production of reactive oxygen species, as well as induces AR and antibiotic persistence like the parent antibiotic AMP. Combined exposure to 6-APA and AMP synergistically stimulated the induction of multiple AR and antibiotic persistence. The resistance mutation frequency increased up to 6.1 × 10⁶-fold under combined exposure and the combination index reached 1326.5, indicating a strong synergy of 6-APA and AMP. Phenotypic and genotypic analyses revealed that these effects were associated with the overproduction of reactive oxygen species, enhanced stress response signatures, and activation of efflux pumps. These findings provide evidence and mechanistic insights into AR induction by AIs in antibiotic production wastewater.

Microplastics (MPs) pose significant concerns for marine ecological security due to their minuteness and ubiquity. However, comprehensive knowledge on their distribution and fate in seawater columns remains limited. This study investigated the abundances and characteristics of MPs across 3-6 water layers in the South Yellow Sea and East China Sea. Results indicate that high-abundance small MPs (< 100 µm) (average 6567 items/m³) were hidden beneath the sea-surface, predominantly fine-grained particles (< 20 µm) and high-density polymers (> 1.03 g/cm³). The total suspended MPs (5.0-834.2 µm) are estimated at 2.9-3.1 × 10¹⁷ particles, with most of them occurring in upper layers. In profiles, their distribution varied by physical properties with depth; fragment-shaped and high-density MPs increased in proportion at greater depths, contrasting with fibrous MPs. These MPs originated primarily from the Yangtze River and their winter transport was driven by the Yangtze River Dilution Water, East China Sea Coastal Current, and Yellow Sea Warm Current, resulting in their accumulation in coastal and estuarine regions. Consequently, the Yangtze River Estuary ecosystem faces substantial risks from MP pollution throughout the water column. This work unveils the prevalence of small MPs in coastal water columns and intricate interaction between their fate and hydrodynamic conditions.

Silicosis represents a form of interstitial lung disease induced by the inhalation of silica particles in production environments. A key pathological characteristic of silica-induced pulmonary fibrosis is its localized tissue heterogeneity, which presents significant challenges in analyzing transcriptomic data due to the loss of important spatial context. To address this, we integrate spatial gene expression data with single-cell analyses and achieve a detailed mapping of cell types within and surrounding fibrotic regions, revealing significant shifts in cell populations in normal and diseased states. Additionally, we explore cell interactions within fibrotic zones using ligand-receptor mapping, deepening our understanding of cellular dynamics in these areas. We identify a subset of fibroblasts, termed Inmt fibroblasts, that play a suppressive role in the fibrotic microenvironment. Validating our findings through a comprehensive suite of bioinformatics, histological, and cell culture studies highlights the role of monocyte-derived macrophages in shifting Inmt fibroblast populations into profibrotic Grem1 fibroblast, potentially disrupting lung homeostasis in response to external challenges. Hence, the spatially detailed deconvolution offered by our research markedly advances the comprehension of cell dynamics and environmental interactions pivotal in the development of pulmonary fibrosis.