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.

Riverine ecosystems can have tipping points at which the system shifts abruptly to alternate states, although quantitative characterization is extremely difficult. Here we show, through critical analysis of two different reach scale (25 m and 50 m) studies conducted downstream of two point sources, two tributaries (main stem and confluences) and a 630 km segment of the Ganga River, that human-driven benthic hypoxia/anoxia generates positive feedbacks that propels the system towards a contrasting state. Considering three positive feedbacks-denitrification, sediment-P- and metal-release as level determinants and extracellular enzymes (β-D-glucosidase, protease, alkaline phosphatase and FDAase) as response determinants, we constructed a ‘river ecosystem resilience risk index (RERRI)’ to quantitatively characterize tipping points in large rivers. The dynamic fit intersect models indicated that the RERRI<4 represents a normal state, 4–18 a transition where recovery is possible, and >18 an overstepped condition where recovery is not possible. The resilience risk index, developed for the first time for a lotic ecosystem, can be a useful tool for understanding the tipping points and for adaptive and transformative management of large rivers.

We investigated the effect of hypoxic-anoxic range of dissolved oxygen (DO) on metal release/bioavailability at sediment-water interface (SWI) in the Ganga River. Here, we consider eight sites in the main river stem along 518 km; sixty sites downstream two point sources and two tributary confluences covering 630 km; and an incubation experiment to verify these results. We found higher concentrations of metals and bioavailable fractions at SWI at two locations of main stem and up to 700 m, 1000 m, 400 m and 500 m downstream Assi drain, Wazidpur drain, Ramganga confluence and Varuna confluence respectively where DO at SWI (DOₛw) was <2.0 mgL⁻¹. The incubation experiment did show higher levels of metal- and P-release and bioavailability under anoxic-hypoxic range of DO. The risk assessment code and eutrophication index indicated high to very high risks of contaminated river sediment and water to aquatic environment at sites with hypoxic-anoxic range of DOₛw. Further, the principal component analyses separated metals and bioavailable fractions opposite to FDAase indicating greater risk at these locations. The study, which forms the first report on benthic hypoxia/anoxia-driven metal release, potential bioavailability and risk to the Ganga River ecosystem will help understanding how human-driven perturbations influence geochemical cycling of metals and ecosystem responses in large rivers.

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.

Hexavalent chromium and nitrate co-contaminated groundwater remediation are attracting extensive attention worldwide. However, the transformation pathways of chromium and nitrate and the interplay mechanism between them remain unclear. In this work, zeolite-supported nanoscale zero-valent iron/palladium (Z-Fe/Pd) was synthesized and used for the first time to simultaneously remediate Cr(VI) and nitrate. Transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy analyses confirmed that nanoscale zero-valent iron/palladium was successfully loaded onto zeolite and it exhibited good dispersibility and oxidation resistance. Results of batch experiments showed that the Cr(VI) and nitrate removal efficiencies decreased from 95.5% to 91.5% to 45% and 73%, respectively, with the initial solution pH increasing from 3.0 to 8.0. The removal rates and efficiencies of Cr(VI) and nitrate under anoxic conditions were higher than those under open atmosphere because the dissolved oxygen diminished the electron selectivity toward the target pollutants. Moreover, the presence of Cr(VI) inhibited nitrate reduction by forming Fe(III)-Cr(III) hydroxide to impede electron transfer. Cr(VI) removal was promoted by nitrate, within limits, by balancing the consumption and generation rate of Fe₃O₄, which enhanced electron migration from the Fe(0) core to the external surface. The removal capacities of Cr(VI) and nitrate reached 121 and 95.5 mg g⁻¹, respectively, which were superior to the removal capacities of similar materials. Results of product identification, XRD, and XPS analyses of spent Z-Fe/Pd indicated that the reduction of Cr(VI) was accompanied by adsorption and co-precipitation, whereas the reduction of nitrate was catalyzed by the synergism of Fe(0) and Pd(0). An alternative to the simultaneous remediation of Cr(VI) and nitrate from groundwater under anoxic conditions is provided.

Microaerobic and hypoxic methane oxidation coupled to denitrification (MAME-D and HYME-D) occur in stabilized landfills with leachate recirculation when biological denitrification is limited by lack of organics. To evaluate nitrate denitrification efficiency and culture MAME-D/HYME-D involved bacteria, a leach bed bioreactor semi-continuous experiment was conducted for 60 days in 5 runs, under nitrate concentrations ranging of 20 mg/L–55 mg/L, wherein 5% sterile leachate was added during runs 4 and 5. Although the HYME-D system demonstrated high denitrification efficiency (74.93%) and nitrate removal rate reached 2.62 mmol N/(L⋅d), the MAME-D system exhibited a denitrification efficiency of almost 100% and nitrate removal rate of 4.37 mmol N/(L⋅d). The addition of sterile leachate increased the nitrate removal rate in both systems, but caused the decrease of methane consumption in HYME-D. A stable isotope batch experiment was carried out to investigate the metabolic products by monitoring the 13CO2 and 15N2O production. The production of organic intermediates such as citrate, lactic acid, acetate, and propionic acid were also observed, which exhibited a higher yield in HYME-D. Variations in the microbial communities were analyzed during the semi-continuous experiment. MAME-D was mainly conducted by the association of type Ⅰ methanotroph Methylomonas and the methylotrophic denitrifier Methylotenera. Methane fermentation processed by Methylomonas under hypoxic conditions produced more complex organic intermediates and increased the diversity of related heterotrophic denitrifiers. The addition of sterile real leachate, resulting in increase of COD/N, influenced the microbial community of HYME-D system significantly.

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.

Glyphosate (GLP) herbicide leaching into soil can undergo abiotic degradation and two enzymatic oxidative or hydrolytic reactions in both aerobic and anaerobic conditions; biotic oxidation produces aminomethylphosphonic acid (AMPA). Both GLP and AMPA are phytotoxic. A comprehensive GLP degradation reaction network was developed from the literature to account for the above pathways, and fifteen experimental data sets were used to determine the corresponding Michaelis-Menten-Monod (MMM) kinetic parameters. Various sensitivity analyses were designed to assess GLP and AMPA degradation potential against O2 (aq) and carbon (C) availability, pH, and birnessite mineral content, and showed that bacteria oxidized or hydrolyzed up to 98% of GLP and only 9% of AMPA. Lack of a C source limited the GLP cometabolic hydrolytic pathways, which produces non-toxic byproducts and promotes AMPA biodegradation. Low bacterial activity in O2 (aq)-limited conditions or non-neutral pH resulted in GLP accumulation. Birnessite mineral catalyzed fast GLP and AMPA chemodegradation reaching alone efficiencies of 79% and 88%, respectively, regardless of the other variables and produced non-toxic byproducts. Overall, O2 (aq) and birnessite availability played the major roles in determining the partitioning of GLP and its byproducts mass fluxes across the reaction network, while birnessite, C availability, and pH affected GLP and AMPA biodegradation effectiveness.

High arsenic groundwater generally coexists with elevated Fe2+ concentrations (mg L−1 levels) under reducing conditions, but an explanation for the extremely high arsenic (up to ∼2690) concentrations at very low Fe2+ (i.e., μg L−1 levels) in groundwater of Datong Basin remains elusive. Field groundwater investigation and laboratory microcosm experiments were implemented in this study. The field groundwater was characterized by weakly alkaline (pH 7.69 to 8.34) and reducing conditions (Eh −221.7 to −31.9 mV) and arsenic concentration averages at 697 μg L−1. Acinetobacter (5.9–51.3%), Desulfosporosinus (4.6–30.2%), Brevundimonas (3.9–19%) and Pseudomonas (3.2–14.6%) were identified as the dominant genera in the bacterial communities. Bacterially mediated arsenate reduction, Fe(III) reduction, and sulfate reduction are processes occurring (or having previously occurred) in the groundwater. Results from incubation experiment (27 d) revealed that nitrate, arsenate, and Fe(III)/sulfate reduced sequentially with time under anoxic conditions, while Fe(III) and sulfate reduction processes had no obvious differences, occurring almost simultaneously. Moreover, low Fe2+ concentrations were attributed to initially high pH conditions, which relatively retarded Fe(III) reduction. In addition, arsenic behavior in relation to groundwater redox conditions, matrices, and solution chemistry were elaborated. Bacterial arsenate reduction process proceeded before Fe(III) and sulfate reduction in the incubation experiment, and the total arsenic concentration (dominated by arsenite) gradually increased from ∼7 to 115 μg L−1 as arsenate was reduced. Accordingly, bacterially mediated reductive desorption of arsenate is identified as the main process controlling arsenic mobility, while Fe(III) reduction coupled with sulfate reduction are secondary processes that have also contributed to arsenic enrichment in the study site. Overall, this study provide important insights into the mechanism controlling arsenic mobility under weakly alkaline and reducing conditions, and furnishes that arsenate reduction by bacteria play a major role leading to high accumulation of desorbed arsenite in groundwater.