In recent years, biochar has become of considerable interest for environmental applications, it can be used as a catalyst for sulfides reduction of perchloroethylene, but the crucial role of biochar properties played in catalyzing dechlorination remained ambiguous investigation. To pinpoint the critical functional groups, the modified biochars were respectively produced by HNO₃, KOH and H₂O₂ with similar dimensional structures but different functional groups. Combined with the adsorption and catalytic results of different biochars, the acid-modified biochar had the best catalytic performance (99.9% removal) due to the outstanding specific surface area and ample functional groups. According to characterization and DFT results, carboxyl and pyridine nitrogen exhibited a positive correlation with the catalytic rate, indicating that their contribution to catalytic performance. Customizing biochar with specific functional groups removed depth demonstrated that the carboxyl was essential component. Further, alkaline condition was conducive to catalytic reduction, while tetrachloroethylene cannot be reduced under acidic conditions, because HS⁻ and S²⁻ mainly existed in alkaline environment and the sulfur-containing nucleophilic structure formed with biochar was more stable under this condition. Overall, this study opens new perspectives for in situ remediation by biochar in chlorinated olefin polluted anoxic environment and promotes our insight of modifying for biochar catalyst design.

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.

With the burst of silver nanoparticles (AgNPs) applications, their potential entry into the environment has attracted increasing concern. To date, researches about the impacts of AgNPs on microbial communities have been scarcely conducted in the brackish waters. Here, the effects of interactions of AgNPs and Ag⁺ (as a positive control) with dissolved oxygen on natural brackish water microbial communities were investigated for 30 d. The introduction of AgNPs and Ag⁺ in natural brackish waters resulted in distinct bacterial community composition and structure as well as reduction of the richness and diversity, effects that were not eliminated completely during the tested periods. Anoxic conditions could attenuate the effects of AgNPs and Ag⁺ on the community, and dissolved oxygen made more contributions to community compositions for short-term exposure. High doses of AgNPs had more pronounced long-term impacts than Ag⁺ amendment. Compared with the controls, two general AgNP and Ag⁺ responses, namely, sensitivity and resistance, were observed. Sensitive species mainly included those of the genera Synechococcus and unclassified_f_Rhodobacteraceae, while resistant species mostly belonged to the phylum Bacteroidetes and participated in carbon metabolic processes. Our results indicated that the microbial communities that were involved in nutrient cycles (such as carbon, nitrogen, and sulfide) and photoautotrophic bacteria that contained bacteriochlorophyll were adversely affected by AgNPs and Ag⁺. In addition, dissolved oxygen could further change the microbial communities. These results implied that under different oxygen conditions AgNPs possibly resulted in varying microbial survival strategies and affected the biogeochemical cycling of nutrients in natural brackish waters.

Microbial mercury (Hg) methylation transforms inorganic mercury to neurotoxic methylmercury (MeHg) mainly in aquatic anoxic environments. Sampling challenges in marine ecosystems, particularly in submarine canyons, leads to a lack of knowledge about the Hg methylating microbia in marine sediments. A previous study showed an enrichment of mercury species in sediments from the Capbreton Canyon where both geochemical parameters and microbial activities constrained the net MeHg production. In order to characterize Hg-methylating microbial communities from coastal to deeper sediments, we analysed the diversity of microorganisms’ (16S rDNA-based sequencing) and Hg methylators (hgcA based cloning and sequencing). Both, 16S rDNA and hgcA gene analysis demonstrated that the putative Hg-methylating prokaryotes were likely within the Deltaproteobacteria, dominated by sulfur-compounds based reducing bacteria (mainly sulfate reducers). Additionally, others clades were also identified as carrying HgcA gene, such as, Chloroflexi, Spirochaetes, Elusimicrobia, PVC superphylum (Plantomycetes, Verrucomicrobia and Chlamydiae) and Euryarchaea. Nevertheless, 61% of the hgcA sequences were not assigned to specific clade, indicating that further studies are needed to understand the implication of new microorganisms carrying hgcA in the Hg methylation in marine environments. These first results suggest that sulfur cycle drives the Hg-methylation in marine ecosystem.

Plant-specific root-microbe-soil interactions play an indisputable role in microbial adaptation to environmental stresses. However, the assembly of plant rhizosphere microbiomes and their feedbacks in modification of pollution alleviation under organochlorine stress condition is far less clear. This study examined the response of root-associated bacterial microbiomes to lindane pollution and compared the dissipation of lindane in maize-cultivated dry soils and rice-cultivated flooded soils. Results showed that lindane pollution dramatically altered the microbial structure in the rhizosphere soil of maize but had less influence on the microbial composition in flooded treatments regardless of rice growth, when the reductive dechlorination of lindane was actively coupled with natural redox processes under anaerobic conditions. After 30 days of plant growth, lindane residues dissipated much faster in anaerobic than in aerobic environments, with only 1.08 mg kg⁻¹ lindane remaining in flooded control compared to 12.79 mg kg⁻¹ in dry control soils. Compared to the corresponding unplanted control, maize growth significantly increased, but rice growth slightly decreased the dissipation of lindane. Our study suggests that opposite impacts would lead to the self-purification of polluted soils during the growth of xerophytic maize and hygrocolous rice. This was attributed to the contrasting belowground micro-ecological processes regarding protection of root tissues and thereby assembly of rhizosphere microbiomes shaped by the xerophytic and hygrocolous crops under different water managements, in response to lindane pollution.

The biodegradation of polychlorinated-p-dioxins and dibenzofurans (PCDD/Fs) has been recently demonstrated in a single reactor under hypoxic conditions. Maintaining hypoxic conditions through periodic aerations results in a marked fluctuation of reduction–oxidation (redox) potential. To further assess the effects of redox fluctuations, we operated two fed-batch continuously stirred tank reactors (CSTRs) with sophisticated redox controls at different anoxic/oxic fluctuations to reduce PCDD/Fs in contaminated soil. The results of long-term reactor operation showed that the CSTR with redox fluctuations at a narrow range (−63 ± 68 mV) (CSTR_A) revealed a higher substrate hydrolysis level and PCDD/F degradation rate than did the CSTR with a redox potential that fluctuated at a broad range (−13 ± 118 mV) (CSTR_B). In accordance with analyses of bacterial 16S rRNA genes, the designated hypoxic conditions with added compost supported survival of bacterial populations at a density of approximately 10⁹ copies/g slurry. The evolved core microbiome was dominated by anoxic/oxic fluctuation-adapted Bacteroidetes, Alphaproteobacteria, and Actinobacteria, with higher species diversity and functionality, including hydrolysis and degradation of dioxin-like compounds in CSTR_A than in CSTR_B. Taken together, the overall results of this study expand the understanding of redox fluctuations in association with the degradation of recalcitrant substrates in soil and the corresponding microbiome.

Release of phosphorus (P) from sediment to overlying water has to be dealt with to address algal blooms in eutrophic lakes. In this study, the sediment from the Lake Taihu was amended with lanthanum modified zeolite (LMZ) to reduce P release under different pH, temperature and anaerobic conditions. LMZ performed well, to decreasing P concentration in Lake Taihu water in the presence of sediment. The EPC₀ value, the critical P concentration at which there was neither P adsorption nor P release, was lowered by adding LMZ, suggesting that amendment with LMZ could diminish the risk of P release from the sediment. From the Langmuir isotherm model, the adsorption capacity of phosphate by LMZ was estimated to be 64.1 mgP/g. The LMZ-amended sediment had a higher content of stable P forms (HCl-P and Res-P) and a lower content of P forms with a high (NH₄Cl-P and BD-P) or medium-high (NaOH-P and Org-P) risk of release, when compared with the original sediment. The fractionation simulates conditions which release potentially mobile P which can then be simply re-bound to LMZ. At high pH (>9.0), anaerobic condition or high temperature promoted the liberation of P from sediment. However, P release could be greatly inhibited by LMZ. In addition, although Mn²⁺ and NH₄⁺ ions were released from sediment under the anaerobic condition, the release could also be hindered by adding LMZ. LMZ is a promising P inactivation agent to manage eutrophication in the sediment of Lake Taihu.

Microcystin (MC) elimination is a global challenge that is necessary for the health of humans and ecosystems. Biodegradation of MC, one of the most environmental-friendly methods, had previously been focused on the aerobic condition. In this study, two enrichment cultures from Taihu sediments possessed high capacity for MC-leucine arginine (MC-LR) anaerobic biodegradation. Meanwhile, it was firstly found that MC-LR underwent similar degradation process under anaerobic conditions to that in aerobic condition. Furthermore, a novel degradation pathway, hydrolyzing of Ala-Mdha to form a new linear MC-LR intermediate, was proposed under anaerobic conditions. Combining MC-LR degradation with microbial community analysis, this study deduced that Candidatus Cloacamonas acidaminovorans str. Evry may play an important role in the degradation of MC-LR. These findings suggest an additional pathway involved in the environmental cycle of MC-LR, which implies that the biotransformation of MC-LR might play an important role in eliminating MC-LR in eutrophic lake sediments under anaerobic conditions.

The negative effect of carbonate on the rate and extent of bioreduction of aqueous U(VI) has been commonly reported. The solution pH is a key chemical factor controlling U(VI)ₐq species and the Gibbs free energy of reaction. Therefore, it is interesting to study whether the negative effect can be diminished under specific pH conditions. Experiments were conducted using Shewanella putrefaciens under anaerobic conditions with varying pH values (4–9) and bicarbonate concentrations ([CO32−]T, 0–50 mmol/L). The results showed a clear correlation between the pH-bioreduction edges of U(VI)ₐq and the [CO32−]T. The specific pH at which the maximum bioreduction occurred (pHₘbᵣ) shifted from slightly basic to acidic pH (∼7.5–∼6.0) as the [CO32−]T increased (2–50 mmol/L). At [CO32−]T = 0, however, no pHₘbᵣ was observed in terms of increasing bioreduction with pH (∼100%, pH > 7). In the presence of [CO32−]T, significant bioreduction was observed at pHₘbᵣ (∼100% at 2–30 mmol/L [CO32−]T, 93.7% at 50 mmol/L [CO32−]T), which is in contrast to the previously reported infeasibility of bioreduction at high [CO32−]T. The pH-bioreduction edges were almost comparable to the pH-biosorption edges of U(VI)ₐq on heat-killed cells, revealing that biosorption is favorable for bioreduction. The end product of U(VI)ₐq bioreduction was characterized as insoluble nanobiogenic uraninite by HRTEM. The redox potentials of the master complex species of U(VI)ₐq, such as (UO2)4(OH)7+, (UO2)2CO3(OH)3−, and UO2(CO3)34−, were calculated to obtain insights into the thermodynamic reduction mechanism. The observed dynamic role of pH in bioreduction suggests the potential for bioremediation of uranium-contaminated groundwater containing high carbonate concentrations.

Shooting ranges polluted by antimony (Sb), lead (Pb), copper (Cu) and zinc (Zn) are used for animal grazing, thus pose a risk of contaminants entering the food chain. Many of these sites are subject to waterlogging of poorly drained soils. Using field lysimeter experiments, we compared Sb, Pb, Cu and Zn uptake by four common pasture plant species (Lolium perenne, Trifolium repens, Plantago lanceolata and Rumex obtusifolius) growing on a calcareous shooting range soil under waterlogged and drained conditions. To monitor seasonal trends, the same plants were collected at three times over the growing season. Additionally, variations in soil solution concentrations were monitored at three depths over the experiment. Under reducing conditions, soluble Sb concentrations dropped from ∼50 μg L−1 to ∼10 μg L−1, which was attributed to the reduction of Sb(V) to Sb(III) and the higher retention of the trivalent species by the soil matrix. Shoot Sb concentrations differed by a factor of 60 between plant species, but remained at levels <0.3 μg g−1. Despite the difference in soil solution concentrations between treatments, total Sb accumulation in shoots for plants collected on the waterlogged soil did not change, suggesting that Sb(III) was much more available for plant uptake than Sb(V), as only 10% of the total Sb was present as Sb(III). In contrast to Sb, Pb, Cu and Zn soil solution concentrations remained unaffected by waterlogging, and shoot concentrations were significantly higher in the drained treatment for many plant species. Although showing an increasing trend over the season, shoot metal concentrations generally remained below regulatory values for fodder plants (40 μg g−1 Pb, 150 μg g−1 Zn, 15–35 μg g−1 Cu), indicating a low risk of contaminant transfer into the food chain under both oxic and anoxic conditions for the type of shooting range soil investigated in this study.