Journal of hazardous materials最新文献

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.

The composition of dissolved black carbon (DBC) could be influenced by adsorption on minerals, subsequently affecting DBC's photoactivity and the photoconversion of contaminants. This study investigated the changes in photoactivity of DBC after absorption on ferrihydrite at Fe/C ratios of 0, 1.75, 7.50, and 11.25, compared the influences of DBC₀ and DBC_7.50 on the photodegradation of four typical antibiotics (AB) including sulfadiazine, tetracycline, ofloxacin, and chloramphenicol. The selective adsorption led to the compounds with high aromaticity, high oxidation states, and more oxygen-containing functional groups being more favorably adsorbed on ferrihydrite, further causing the steady-state concentrations of ³DBC*, ¹O₂, and •OH respectively to drop from 1.83 × 10^-13 M, 7.45 × 10^-13 M, and 3.32 × 10^-16 M in DBC₀ to 1.22 × 10^-13 M, 0.93 × 10^-13 M and 2.30 × 10^-16 M in DBC_11.25, while the light screening effect factor increased from 0.740-0.921 in DBC₀ with above four antibiotics to 0.775-0.970 for that of DBC_11.25. Unexpectedly, DBC after adsorption played a dual role in the photodegradation of various antibiotics. This difference might be caused by antibiotics' chemical composition, functional groups interacting with reactive intermediates, and the overlap in UV-vis spectra between antibiotics and DBC. Our data are valuable for understanding the dynamic roles of DBC in the photodegradation of antibiotics.

The Laizhou Bay (LZB) is of ecological and fishery importance. The discharge of effluents containing numerous pollutants into the LZB via rivers poses significant risks to ecosystem and human health. Estuarine biomonitoring is therefore crucial for assessing the contribution of rivers to coastal pollution and their impacts on species. Estuarine oyster Crassostrea gigas is a preferable bioindicator to pollution conditions. This study measured accumulation of contaminants and expression levels of gene biomarkers in the LZB and Northern Shandong Peninsula (NSP) oysters. The LZB oysters accumulated higher levels of brominated flame retardants (BFRs) and poly- and perfluoroalkyl substances (PFAS), while NSP oysters exhibited greater accumulation of heavy metals. Decabromodiphenyl ethane was the dominant BFR, while perfluorooctanoic acid and perfluoro-2-methoxyacetic acid were the dominant PFASs in oysters. The expression of gene biomarkers effectively distinguished the LZB and NSP oysters, with CYP2 subfamilies expression correlating with BFRs and PFASs and metallothionein expression indicating heavy metals. The reproductive endocrine and neuroendocrine-immune systems in oysters might be the targets of BFRs and heavy metal pollution, respectively. The negative correlation between contaminant accumulation and gene expression might be explained by adaptive evolution, emphasizing the need to consider genetic diversity in ecological risk assessments.

In this study, we investigated the potential benefits of L-Fucose administration to pregnant mice exposed to Ochratoxin A (OTA), a widespread mycotoxin, producing ovarian damage in offspring. The results showed that administration of 3.5 μg/d OTA induced alterations in intestinal tissues and gut microbiota of pregnant mice, leading to heightened local and systemic inflammation. This inflammatory affected the ovaries of their 3 dpp offspring, in which elevated levels of LPS and ROS were found associated to significant decreased oocyte count and impaired primordial follicle assembly. Moreover, mRNA-Seq analysis showed significant changes in ovarian transcriptomes linked to various GO terms and KEGG pathways, notably ferroptosis, a recognized form of cell death observed. Interestingly, administration of 0.3 g/kg b. w. L-Fucose following OTA exposure mitigated these effects on intestinal tissues and gut microbiota in mothers and on the offspring's ovaries. Similar benefits were obtained by gut microbiota transplantation from L-Fucose-treated pregnant females into OTA-exposed mothers. These findings suggest that inflammatory impact of OTA on maternal intestine/gut can pass to the fetus causing offspring ovary defects and support the use of L-Fucose as adjuvant to counteract the adverse effects of mycotoxins on the gut microbiota, particularly reference to those affecting reproductive organs.

Antimony(V) mobility in acid mine drainage (AMD) is often controlled by sorption and coprecipitation with schwertmannite - a poorly-ordered Fe(III) oxyhydroxysulfate mineral. However, due to its metastable nature, schwertmannite transforms over time to more thermodynamically stable Fe(III) phases, such as goethite. This study examines how transformation of Sb(V)-bearing schwertmannite to goethite impacts Sb(V) mobility, while also assessing the role that Sb(V) may play in stabilizing schwertmannite against such transformation. To address these aims, Sb(V)-free, Sb(V)-sorbed and Sb(V)-coprecipitated schwertmannite were allowed to undergo partial transformation to goethite under acid sulfate conditions. Iron K-edge EXAFS spectroscopy revealed that sorbed and coprecipitated Sb(V) partly stabilized schwertmannite against transformation. The onset of schwertmannite transformation to goethite was found to drive clear mobilization of Sb(V) into solution, regardless of the Sb(V) loading or whether Sb(V) was initially sorbed or coprecipitated with the precursor schwertmannite. This initial phase of Sb(V) mobilization was followed by subsequent solid-phase recapture of the released Sb(V), with Sb K-edge EXAFS spectroscopy revealing that this process involved Sb(V) incorporation into the newly-formed goethite. Our findings show that, although schwertmannite transformation to goethite is partially inhibited by co-existing Sb(V), the initial stage of this transformation process drives significant Sb(V) mobilization in AMD systems.

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.

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.

Ferrous iron (Fe(II)) produced by microbial Fe(III) reduction and reactive oxygen species (ROS) generated from aerobic Fe(II) oxidation can mediate iodate (IO₃^-) reduction and iodide (I^-) oxidation, respectively. Nevertheless, how Fe redox cycling under redox fluctuating conditions drives transformation of iodine species remain unclear. In this study, Shewanella oneidensis MR-1 wildtype (WT) and its mutant △dmsEFAB, which lost the ability to enzymatically reduce IO₃^-, were chosen to conduct ferrihydrite/goethite/nontronite culture experiments under consecutive cycles of anoxic reduction of Fe(III) and re-oxidation of Fe(II) by O₂ to reveal the role of Fe redox cycling in the transformation of iodine species. The results showed that both surface-adsorbed and mineral structural Fe(II) chemically reduced IO₃^-. Chemical IO₃^- reduction by biogenic Fe(II) was slower than enzymatic IO₃^- reduction by WT. Compared to △dmsEFAB cultures, WT cultures all showed higher Fe(II) concentrations under anoxic conditions but lower cumulative •OH under oxic conditions, which imply the chemical reaction between I^- and ROS. I^- oxidation by ROS, however, did not lead to a significant production of IO₃^- compared with I^- formed under anoxic conditions. Consequently, Fe redox cycling successively reduced IO₃^- to I^-, which highlights vital roles of Fe(III)-reducing bacteria in I^- formation and mobilization in environments.

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.