International audience | Copper, a priority substance on the EU-Water Framework Directive list, is widely used to protect grapevines against fungus diseases. Many vineyards being located on steep slopes, large amounts of Cu could be discharged in downstream systems by runoff water. The efficiency of stormwater detention basins to retain copper in a vineyard catchment was estimated. Suspended solids, dissolved (Cudiss) and total Cu (Cutot) concentrations were monitored in runoff water, upstream, into and downstream from a detention pond. Mean Cutot concentrations in entering water was 53.6 μg/L whereas it never exceeded 2.4 μg/L in seepage. Cutot concentrations in basin water (>100 μg/L in 24% of the samples) exceeded LC50 values for several aquatic animals. Copper was principally sequestered by reduced compounds in the basin sediments (2/3 of Cutot). Metal sequestration was reversible since sediment resuspension resulted in Cu remobilization. Wind velocity controlled resuspension, explained 70% of Cudiss variability and could help predicting Cu mobilization. Copper in stormwater basin is efficiently retained but can be released during windy events or after dredging.

Bacterial communities in antimony (Sb) polluted soils have been well addressed, whereas the important players fungal communities are far less studied to date. Here, we report different responses of bacterial and fungal communities to Sb contamination and the ecological processes controlling their community assembly. Soil samples in the Xikuangshan mining area were collected and subjected to high through-put sequencing of 16S rRNA and ITS1 to investigate bacterial and fungal communities, respectively, along an Sb gradient. Sb speciation in the soil samples and other physicochemical parameters were analyzed as well. Bacterial communities were dominated by Deltaproteobacteria in the soil with highest Sb concentration, whereas Chloroflexi were dominant in the soil with lowest Sb concentration. Fungal communities in high-Sb soils were predominated by unclassified Fungi, whilst Leotiomycetes were dominant in low-Sb soil samples. Multivariate analysis indicated that Sb, pH and soil texture were the main drivers to strongly impact microbial communities. We further identified Sb-resistant microbial groups via correlation analysis. In total, 18 bacterial amplicon sequence variants (ASVs) were found to potentially involve in biogeochemical cycles such as Sb oxidation, sulfur oxidation or nitrate reduction, whereas 12 fungal ASVs were singled out for potential heavy metal resistance and plant growth promotion. Community assembly analysis revealed that variable selection contributed 100% to bacterial community assembly under acidic or high Sb concentration conditions, whereas homogeneous selection dominated fungal community assembly with a contribution over 78.9%. The community assembly of Sb-resistant microorganisms was mainly controlled by stochastic process. The results offer new insights into microbial ecology in Sb-contaminated soils, especially on the different responses of microbial communities under identical environmental stress and the different ecological processes underlining bacterial and fungal community assembly.

The treatment of contaminants from lignocellulosic biorefinery effluent has recently been identified as a unique challenge. This study focuses on removing phenolic contaminants and polycyclic aromatic hydrocarbons (PAHs) from lignocellulosic biorefinery wastewater (BRW) applying a laccase-assisted approach. Cassava waste was used as a substrate to produce the maximum yield of laccase enzyme (3.9 U/g) from Pleurotus ostreatus. Among the different inducers supplemented, CuSO₄ (0.5 mM) showed an eight-fold increase in enzyme production (30.8 U/g) after 240 h of incubation. The catalytic efficiency of laccase was observed as 128.7 ± 8.47 S⁻¹mM⁻¹ for syringaldazine oxidation at optimum pH 4.0 and 40 °C. Laccase activity was completely inhibited by lead (II) ion, mercury (II) ion, sodium dodecyl sulphate, sodium azide and 1,4 dithiothretiol and induced significantly by manganese (II) ion and rhamnolipid. After treating BRW with laccase, the concentrations of PAHs and phenolic contaminants of 1144 μg/L and 46160 μg/L were reduced to 96 μg/L and 16100 μg/L, respectively. The ability of laccase to effectively degrade PAHs in the presence of different phenolic compounds implies that phenolic contaminants may play a role in PAHs degradation. After 240 h, organic contaminants were removed from BRW in the following order: phenol >2,4-dinitrophenol > 2-methyl-4,6-dinitrophenol > 2,3,4,6-tetrachlorophenol > acenaphthene > fluorine > phenanthrene > fluoranthene > pyrene > anthracene > chrysene > naphthalene > benzo(a)anthracene > benzo(a)pyrene > benzo(b)fluoranthene > pentachlorophenol > indeno(1,2,3-cd)pyrene > benzo(j) fluoranthene > benzo[k]fluoranthène. The multiple contaminant remediation from the BRW by enzymatic method, clearly suggests that the laccase can be used as a bioremediation tool for the treatment of wastewater from various industries.

Biodegradation of microplastics (MPs) in contaminated biowastes has received big scientific attention during the past few years. The aim here is to study the impacts of livestock manure biochar (LMBC) on the biodegradation of polyhydroxyalkanoate microplastics (PHA-MPs) during composting, which have not yet been verified. LMBC (10% wt/wt) and PHA-MPs (0.5% wt/wt) were added to a mixture of pristine cow manure and sawdust for composting, whereas a mixture without LMBC served as the control (CK). The maximum degradation rate of PHA-MPs (22–31%) was observed in the thermophilic composting stage in both mixtures. LMBC addition significantly (P < 0.05) promoted PHA-MPs degradation and increased the carbon loss and oxygen loading of PHA-MPs compared to CK. Adding LMBC accelerated the cleavage of C–H bonds and oxidation of PHA-MPs, and increased the O–H, CO and C–O functional groups on MPs. Also, LMBC addition increased the relative abundance of dominant microorganisms (Firmicutes, Proteobacteria, Deinococcus-Thermus, Bacteroidetes, Ascomycota and Basidiomycota) and promoted the enrichment of MP-degrading microbial biomarkers (e.g., Bacillus, Thermobacillus, Luteimonas, Chryseolinea, Aspergillus and Mycothermus). LMBC addition further increased the complexity and connectivity between dominant microbial biomarkers and PHA-MPs degradation characteristics, strengthened their positive relationship, thereby accelerated PHA-MPs biodegradation, and mitigated the potential environmental and human health risk. These findings provide a reference point for reducing PHA-MPs in compost and safe recycling of MPs contaminated organic wastes. However, these results should be validated with other composting matrices and conditions.

In recent years, the application of green rusts (GRs) for water purification has received significant attention, but its full understanding has not been well achieved. Then, the comprehension about the synthesis and characteristics of GRs can highly favor their decontamination performances for the site-specific conditions. This review comprehensively summarized the synthesis, characteristics and performances of GRs including the GR (Cl⁻), GR (CO₃²⁻) and GR (SO₄²⁻) for sequestration of various aqueous pollutants (e.g., tetrachloride, Cr(VI), Se(VI), and U(VI), etc.). Generally, the different reactivity of GRs toward contaminants is strongly dependent on the GRs’ characteristics (e.g., interlayer distance, specific surface area, and Fe(II) content) and solution chemistry (e.g., pH, background electrolytes, dissolved oxygen, and contaminant concentration, etc.). In addition, the reaction mechanisms of GRs with the contaminants involve the redox reactions, adsorption, catalytic oxidation, interlayer and octahedral incorporation, which can mutually or singly contribute to the decontamination to varying degrees. Particularly, this review addressed the transformation pathways of GRs under various solution chemistry conditions and clarified that the stability of GRs should be the key challenge for the real application. Finally, how to effectively use the GRs for water decontamination was proposed, which will significantly benefit the rational control of environmental pollution.

As a redox-sensitive element, manganese (Mn) plays a critical role in Cd mobilization, especially in paddy soil. In an anoxic environment, the precipitation of Mn(II)-hydroxides specifically favors Cd retention, while draining the paddy fields results in substantial remobilization of Cd. However, how the change in Mn redox states during the periodical transit of anoxic to oxic systems affects Cd mobility remains unclear. In this study, we demonstrate that the radical effect generated during the oxidation of Mn(II)-hydroxides exerts a significant effect on the oxidative dissolution of Cd during the aeration of paddy soils. The extractable Cd concentration decreased rapidly during the reduction phases but increased upon oxidation, while Cd availability produced the opposite effect with soil pe + pH and the extractable Mn concentration. Inhibiting the oxidation of Mn(II)-containing phases by microbes suppressed the production of hydroxyl free radicals (•OH) and Cd mobilization in the drainage phase. Analysis of X-ray absorption spectroscopy and sequential extraction demonstrated that the transformation from the Mn phase of Mn(II) to Mn(III/IV) determines Cd solubility. Altogether, the oxidization of Mn(II)-hydroxides was associated with the generation of significant amounts of •OH. The dissolution of Mn(II)- incorporating phases lead to a net release of Cd into soils during soil aeration.

Synthetic azo dyes are extensively used in the textile industries, which are being released as textile effluent into the environment presence of azo dyes in the environment is great environmental concern therefore treatment of textile effluent is crucial for proper release of the effluent into the environment. Electrochemical oxidation (EO) is extensively used in the degradation of pollutants because of its high efficiency. In this study, photo-assisted electrooxidation (PEO) followed by biodegradation of the textile effluent was evaluated. The pretreatment of textile effluent was conducted by EO and PEO in a tubular flow cell with TiO₂–Ti/IrO₂–RuO₂ anode and titanium cathode under different current densities (10, 15, and 20 mA cm⁻²). The chemical oxygen demand level reduced from 3150 mg L⁻¹ to 1300 and 600 mg L⁻¹under EO and PEO, respectively. Furthermore, biodegradation of EO and PEO pretreated textile effluent shows reduction in chemical oxygen demand (COD) from 1300 mg L⁻¹ to 900 mg L⁻¹and 600 mg L⁻¹to 110 mg L⁻¹, respectively. The most abundant genera were identified as Acetobacter, Achromobacter, Acidaminococcus, Actinomyces, and Acetomicrobium from the textile effluent. This study suggests that an integrated approach of PEO and subsequent biodegradation might be an effective and eco-friendly method for the degradation of textile effluent.

We investigated the biological response of soluble organic fraction (SOF) and water-soluble fraction (WSF) extracted from particulate matter (PM) emitted by an automotive diesel engine operating in a representative urban driving condition. The engine was fueled with ultra-low sulfur diesel (ULSD), and its binary blends by volume with 13% of butanol (Bu13), and with hydrotreated vegetable oil (HVO) at 13% (HVO13) and 20% (HVO20). Cytotoxicity, genotoxicity, oxidative DNA damage and ecotoxicity tests were carried out, and 16 polycyclic aromatic hydrocarbons (PAH) expressed as tbenzo(a)pyrene total toxicity equivalent (BaP-TEQ) were also analyzed. The Hepatocarcinoma epithelial cell line (HepG2) was exposed to SOF for 24 h and analyzed using comet assay, with the inclusion of formamidopyrimidine DNA glycosylase (FPG) and endonuclease III (Endo III) to recognize oxidized DNA bases. The WSF was evaluated through acute ecotoxicity tests with the aquatic microcrustacean Daphnia pulex (D. Pulex). Results showed that there was no cytotoxic activity for all tested SOF concentrations. Genotoxic responses by all the SOF samples were at same level, except for the HVO13 which was weaker in the absence of the enzymes. The addition of the FPG and Endo III enzymes resulted in a significant increase in the comet tail, indicating that the DNA damage from SOF for all tested fuel blends involves oxidative damage including a higher level of oxidized purines for ULSD and Bu13 in comparison with HVO blends, but the oxidized pyrimidines for HVO blends were slightly higher compared to Bu13. The WSF did not show acute ecotoxicity for any of the fuels. Unlike other samples, Bu13-derived particles significantly increase the BaP-TEQ. The contribution to the genotoxic activity and oxidative DNA from SOF was not correlated to BaP-TEQ, which means that the biological activity of PM might be affected also by other toxic compounds present in particulate phase.

Effects of human activities on atmospheric nitrate (NO₃⁻) formation remain unclear, though the knowledge is critical for improving atmospheric chemistry models and nitrogen deposition reduction strategies. A potentially useful way to explore this is to compare NO₃⁻ oxidation processes in urban and rural atmospheres based upon the oxygen stable isotope composition of NO₃⁻ (Δ¹⁷O–NO₃⁻). Here we compared the Δ¹⁷O–NO₃⁻ from three-years of daily-based bulk deposition in urban (Shenyang) and forested rural sites (Qingyuan) in northeast China and quantified the relative contributions of different formation pathways based on the SIAR model. Our results showed that the Δ¹⁷O in Qiangyuan (26.2 ± 3.3‰) is significantly higher (p < 0.001) than in Shenyang (24.0 ± 4.0‰), and significantly higher in winter (Shenyang: 26.1 ± 6.7‰, Qingyuan: 29.6 ± 2.5‰) than in summer (Shenyang: 22.7 ± 2.9‰, Qingyuan: 23.8 ± 2.4‰) in both sites. The lower values in the urban site are linked with conditions that favored a higher relative contribution of nitrogen dioxide reaction with OH pathway (0.76-0.91) than in rural site (0.47-0.62), which should be induced by different levels of human activities in the two sites. The seasonal variations of Δ¹⁷O–NO₃⁻ in both sites are explained by a higher relative contribution of ozone-mediated oxidation chemistry and unfavorable conditions for the OH pathway during winter relative to summer, which is affected by human activities and seasonal meteorological condition change. Based on Δ¹⁷O, wintertime conditions led to a contribution of O₃ related pathways (NO₃ + DMS/HC and N₂O₅ hydrolysis) of 0.63 in Qingyuan and 0.42 in Shenyang, while summertime conditions led to 0.15 in Qingyuan and 0.05 in Shenyang. Our comparative study on Δ¹⁷O–NO₃⁻ between urban and rural sites reveals different anthropogenic effects on nitrate formation processes on spatial and temporal scales, illustrating different responses of reactive nitrogen chemistry to changes in human activities.

The effectiveness and feasibility of the three biochar materials for remediation of arsenic (As) and lead (Pb) contaminated soil were explored in this study. Significant reduction of bioaccessibility and migration risks of both heavy metals have been explained mechanistically by incubation, column experiments and numerical simulation. Langmuir equation fitted As and Pb sorption isotherms better in the control and biochar (BC) amended soils, while Freundlich model was more suitable for iron modified biochar (Fe-BC) and sulfur/iron modified biochar (S/Fe-BC) amended soils, indicating that modified biochar promoted chemical adsorption process for As and Pb. For the three biochar materials, S/Fe-BC showed the best effects on reducing the bioavailability of As and Pb, with a decrease of 40.42%–64.21%. The reduction in bioaccessibility by metal portioning into available and non-available fractions was better for illustrating the mechanisms including adsorption, precipitation/coprecipitation and As(III) oxidation behind S/Fe-BC efficacy. Moreover, S/Fe-BC can effectively inhibit the leaching behavior of As and Pb under acid rain, which increased by 99.89% and 90.18%, respectively, compared with the control. The HYDRUS-1D modeling indicated that S/Fe-BC could continuously treat As (100 mg/L) and Pb (1000 mg/L) contaminated water for 16.22 years and 40.86 years, respectively, and ensure the groundwater quality criteria being met. Based on these insights, we believe that our study will provide meaningful information about the potentials of biochar derived materials for soil heavy metals’ remediation.