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A novel nitrate-dependent manganese (Mn) redox strain was isolated and identified as Dechloromonas sp.YZ8 in this study. The growth conditions of strain YZ8 were optimized by kinetic experiments. The nitrate (NO3--N) removal efficiency was 100.0 % at 16 h at C/N of 2.0, pH of 7.0, and Mn(II) or Mn(IV) addition of 10.0 or 500.0 mg L-1, along with an excellent Mn redox capacity. Transmission electron microscopy supported the Mn redox process inside and outside the cells of strain YZ8. When strain YZ8 was exposed to different concentrations of copper ion (Cu(II)), it turned out that moderate amounts of Cu(II) increased microbial activity and metabolic activities. Moreover, it was discovered that the appropriate amount of Cu(II) promoted the conversion of Mn(IV) and Mn(II) to Mn(III) and improved electron transfer capacity in the Mn redox system, especially the Mn redox process dominated by Mn(IV) reduction. Then, δ-MnO2 and bio-manganese oxides (BMO) produced during the reaction process have strong adsorption of Cu(II). The surface valence changes of δ-MnO2 before and after the reaction and the production of BMO, Mn(III)-rich intermediate black manganese ore (Mn3O4), and Mn secondary minerals together confirmed the Mn redox pathway. The study provided new insights into the promotion mechanism and immobilization effects of redox-coupled denitrification of Mn in groundwater under Cu(II) stress.

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In the context of increasing global nitrogen pollution, traditional biological nitrogen removal technologies like nitrification and denitrification are hindered by high energy consumption. Additionally, the deployment of anaerobic ammonium oxidation (Anammox) technology is constrained due to the slow growth rate of Anammox bacteria and there is a bottleneck in nitrogen removal efficiency. To overcome these technical bottlenecks, researchers have discovered a revolutionary nitrogen removal technology that cleverly combines the redox cycling of manganese with nitrification and denitrification reactions. In this new process, manganese dependent anaerobic ammonium oxidation (Mnammox) bacteria can convert NH4+ to N2 under anaerobic conditions, while nitrate/nitrite dependent manganese oxidation (NDMO) bacteria use NO3-/NO2- as electron acceptors to oxidize Mn2+ to Mn4+. Mn4+ acts as an electron acceptor in Mnammox reaction, thereby realizing the autotrophic nitrogen removal process. This innovative method not only simplifies the steps of biological denitrification, but also significantly reduces the consumption of oxygen and organic carbon, providing a more efficient and environmentally friendly solution to the problem of nitrogen pollution. The article initially provides a concise overview of prevalent nitrogen removal technologies and the application of manganese in these processes, and discusses the role of manganese in biogeochemical cycles, including its discovery, mechanism of action, microbial communities involved, and its impact on these key factors in the process. Subsequently, metabolic principles, benefits, advantages, and environmental considerations of Mnammox coupled with the NDMO process are analyzed in detail. Finally, this article summarizes the shortcomings of current research and looks forward to future research directions. The goal of this article is to provide a valuable reference for researchers to fully understand the application of manganese in nitrogen removal processes.

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Carbon deficits in inflow frequently lead to inefficient nitrogen removal in constructed wetlands (CWs) treating tailwater. Solid carbon sources, commonly employed to enhance denitrification in CWs, increase carbon emissions. In this study, MnO2 was incorporated into polycaprolactone substrates within CWs, significantly enhancing NH4+-N and NO3--N removal efficiencies by 48.26-59.78 % and 96.84-137.23 %, respectively. These improvements were attributed to enriched nitrogen-removal-related enzymes and increased plant absorption. Under high nitrogen loads (9.55 ± 0.34 g/m3/d), emissions of greenhouse gases (CO2, CH4, and N2O) decreased by 147.23-202.51 %, 14.53-86.76 %, and 63.36-87.36 %, respectively. N2O emissions were reduced through bolstered microbial nitrogen removal pathways by polycaprolactone and MnO2. CH4 accumulation was mitigated by the increased methanotrophs and dampened methanogenesis, modulated by manganese. Additionally, manganese-induced increases in photosynthetic pigment contents (21.28-64.65 %) fostered CO2 sequestration through plant photosynthesis. This research provides innovative perspectives on enhancing nitrogen removal and reducing greenhouse gas emissions in constructed wetlands with polymeric substrates.

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Arsenic (As) is a metalloid that can accumulate in eutrophic lakes and cause adverse health effects to people worldwide. However, the seasonal process and dynamic mechanism for As mobilization in eutrophic lake remains effectively unknown. Here we innovatively used the planar optodes (PO), high-resolution dialysis (HR-Peeper) combined with fluorescence excitation-emission matrix coupled with parallel factor (EEM-PARAFAC) analysis technologies. We synchronously investigate monthly O2, As, iron (Fe), manganese (Mn), and naturally occurring dissolved organic matter (DOM) changes in sediments of Lake Taihu at high resolution in field conditions. We find high As contamination from sediments with 61.88-327.07 µg m-2 d-1 release As fluxes during the algal bloom seasons from May to October 2021. Our results show that an increase in DOM, mainly for humic-like components, resulting in high electron transfer capacity (ETC), promoted the reductive dissolution of Fe and Mn oxides to release As. Partial least square-path modeling (PLS-PM) and random forest modeling analysis identified that Mn oxide reductive dissolution directly accelerated sediments As contamination, which is the crucial factor. Understanding crucial factor controlling As release is especially essential in areas of eutrophic lakes developing effective strategies to manage As-rich eutrophic lake sediments worldwide.

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Coupled mixotrophic denitrification and degradation of organics driven by redox transition of Mn for nitrogen removal has attracted much attention. Herein, this study explored the removal performance and mechanisms for nitrogen and refractory organics from secondary effluent in up-flow MnOx biofilter. Results showed that the removal of organics and nitrate was significantly enhanced by the synergistic process of heterotrophic denitrification and Mn(II)-driven autotrophic denitrification (MnAD), which were originated from the facilitation of Mn circulation. But nitrate removal was closely related to the types of carbon source and Mn(II) concentration. Single small molecular carbon source (glucose) performed better than mixed carbon source (humic acid and glucose) in nitrate removal process (74.8% in stage 1-2 vs. 54.1% in stage 3-5). And raising external Mn(II) concentration increased the contribution of MnAD (60.2% in stage 5 vs. 46.5% in stage 3) to nitrate removal. Furthermore, the relationship between Mn/N transformation and microbial community structure shifts revealed that the redox transition between Mn(II) and Mn(IV) promoted the enrichment of denitrogenation bacteria and functional genes, thus contributing to pollutants removal. Our studies expand the knowledge of MnOx-mediated pollutants removal processes and support the potential application of MnOx for removal of residual refractory organics and nitrogen.

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Simultaneous removal of NH4+-N, NO3--N, COD, and P by manganese redox cycling in nutrient wastewater was established with two moving bed biofilm reactors (MBBRs) with in-situ generated biogenic manganese oxides (BioMnOx) and non-BioMnOx. In-situ generated BioMnOx preferentially promoted the denitrification, and the average removal of NO3--N, NH4+-N, and TN in the experimental MBBR with BioMnOx increased to 89.00%, 70.64%, and 76.06% compared with the control MBBR with non-BioMnOx. The relevant enzymes activity, extracellular polymeric substance (EPS), electron transport system activity (ETSA), and reactive oxygen species (ROS) were investigated. The element valence and morphology of purified BioMnOx were characterized by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM), as well as the effect of BioMnOx on nitrogen and phosphorus removal. The results suggested that BioMnOx could improve nitrogen conversion. Electrochemical characteristic and microbial community were detected. This study provided a new strategy for nutrients removal in BioMnOx-mediated wastewater treatment.

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Water pollutants, such as nitrate and organics have received much attention for their harms to ecological environment and human health. The redox transformation between Mn(Ⅱ) and Mn(Ⅳ) for nitrogen and organics removal have been recognized for a long time. Mn(Ⅱ) can act as inorganic electron donor to drive autotrophic denitrification so as to realize simultaneous removal of Mn(Ⅱ), nitrate and organic pollutants. Mn oxides (MnOx) also play an important role in the adsorption and degradation of some organic contaminants and they can change or create new oxidation pathways in the nitrogen cycle. Herein, this paper provides a comprehensive review of nitrogen and organic contaminants removal pathways through applying Mn(Ⅱ) or MnOx as forerunners. The main current knowledge, developments and applications, pollutants removal efficiency, as well as microbiology and biochemistry mechanisms are summarized. Also reviewed the effects of factors such as the carbon source, the environmental factors and operation conditions have on the process. Research gaps and application potential are further proposed and discussed. Overall, Mn-based biotechnology towards advanced wastewater treatment has a promising prospect, which can achieve simultaneous removal of nitrogen and organic contaminants, and minimize sludge production.

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Manganese is a vital heavy metal abundant in terrestrial and aquatic environments. Anaerobic manganese redox reactions mediated by microorganisms have been recognized for a long time, which promote elements mobility and bioavailability in the environment. Biological anaerobic redox of manganese serves two reactions, including Mn(II) oxidation and Mn(IV) reduction. This review provides a comprehensive analysis of manganese redox cycles in the environment, closely related to greenhouse gas mitigation, the fate of nutrients, microbial bioremediation, and global biogeochemical cycle, including nitrogen, sulfur, and carbon. The oxidation and reduction of manganese occur cyclically and simultaneously in the environment. Anaerobic reduction of Mn(IV) receives electrons from methane, ammonium and sulfide, while Mn(II) can function as an electron source for manganese-oxidizing microorganisms for autotrophic denitrification and photosynthesis. The anaerobic redox transition between Mn(II) and Mn(IV) promotes a dynamic biogeochemical cycle coupled to microorganisms in water, soil and sediment environments. The discussion of reaction mechanisms, microorganism diversity, environmental influence bioremediation and application identify the research gaps for future investigation, which provides promising opportunities for further development of biotechnological applications to remediate contaminated environments.

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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.

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Flooding in paddy soils alters the soil redox of manganese (Mn) and produces elevated concentrations of soluble Mn that can reduce cadmium (Cd) uptake by rice. To better understand the fates of Mn and Cd, along with changes in soil redox conditions, we conducted microcosm incubations in paddy soil covering the reduction to oxidation to re-reduction phases. The extractable Cd concentration decreased rapidly during the reduction phases but increased upon oxidation, and Cd availability largely depended on soil pH, Eh, pe + pH, and the extractable Mn concentration. Exogenous Mn can promote Cd binding with Fe-Mn(oxyhydro)oxides. A trade-off effect between the soil-extractable Cd and Mn concentrations across changes in pH, Eh, pe + pH was identified, and attaining an optimal pe + pH value of 6.8 was targeted. Furthermore, to provide insights into how the redox status of Mn changes to alter Cd mobilization in a paddy soil-rice system, Cd isotope ratios across the paddy soil-rice tissue continuum were investigated using planted rhizobox experiments under different irrigation regimes. The heavy Cd isotopes from the soil to liquid-phase (Δ114/110Cdextract-soil = 0.40-0.82‰) and from the soil to rice grain (Δ114/110Cdgrain-soil = 0.84-0.89‰) were preferentially enriched. Light isotopes were likely to be enriched in Cd bound to Fe/Mn-oxides, a process that was promoted by increased Mn availability. These results suggest that Cd isotopes are systematically fractionated within the paddy soil-rice system, which is caused by the unsteady soil redox, and the stabilization of Cd in the bound soil pool such as Fe-Mn(oxyhydro)oxides-Cd under reducing conditions could be developed as a Cd retention mechanism in paddy soils.

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Sulfamethoxazole (SMX), a typical sulfonamide antibiotic, is ubiquitous in secondary effluent and may pose undesirable effects on the aquatic ecosystem and human health. Constructed wetland (CW) is more and more applied in advanced sewage treatment, and the substrate plays an important role in removing pollutants. Manganese (Mn) ore has been widely concerned as a new type of substrate to remove pollutants in CW due to its high adsorption and redox properties. However, the removal mechanism of antibiotics by Mn ore CW is still unclear. In this study, Mn ore was selected as the substrate of a vertical flow constructed wetland (VFCW) while gravel substrate was selected as a control group, and the removal efficiencies of SMX in two VFCWs were investigated and compared. Experimental devices were layered as different regions, including anaerobic (0-32 cm), anoxic (32-64 cm) and aerobic (64-80 cm) zones, to examine the removal characteristics of SMX in different regions. And the removal mechanism of SMX was also explored by examining the adsorption and oxidation of Mn ore and the microbial degradation performance. The results showed that the final removal efficiency of SMX in CW filled with Mn ore substrate (M-CW) (48.4%) increased by 39.6%, compared with CW filled with gravel substrate (G-CW) (8.8%). According to the calculation of mass balance, the total loss of SMX caused by the oxidation of Mn ore and biodegradation accounted for 33.0% of the total SMX input in M-CW, the SMX loss caused by the biodegradation in G-CW accounted for 13.0%, and the substrate adsorption in M-CW and G-CW occupied 15.0% and 7.0% of the total SMX input, respectively. Mn(II) was formed during the oxidation of SMX by Mn(III, IV) and dissimilated Mn(III, IV) reduction by microorganisms in anaerobic environment (0-32 cm). Whereafter, the produced Mn(II) entered into the aerobic zone (64-80 cm) with the water flow and was re-oxidized into biogenic Mn oxides (BioMnOx) which had high adsorption and oxidation performance for SMX. Therefore, Mn ore could enhance SMX removal efficiency in anaerobic and aerobic zones by Mn redox process.

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Ciprofloxacin (CIP), as an extensively used antibiotic, has been widely detected at a high level in the environment and has raised environmental pollution concerns. Thus, efficient and cost-effective methods for CIP degradation are highly desired. Biologically produced manganese oxides (BioMnOx) offer a promising perspective for CIP degradation because of their catalytic reactivity and cost-effectiveness. However, the release of Mn(II) from BioMnOx prevents the further oxidation of pollutants. As a consequence, continuous CIP degradation by BioMnOx is not feasible. In this work, a manganese redox cycling system driven by Pseudomonas putida MnB-1 was constructed for continuous degradation of CIP. In such a system CIP was oxidized continuously and rapidly by re-oxidizing the formed Mn(II) to regenerate reactive BioMnOx, which also protected the strain from CIP toxicity. CIP was degraded through N-dealkylation passway. No significant loss of BioMnOx reactivity was observed in three-cycle CIP degradation process, suggesting the stability of this system. An overlooked intracellular BioMnOx, which was involved in CIP degradation, was discovered in P. putida MnB-1. Moreover, the important role of Mn(III) in facilitating CIP removal in this system was also identified. This work provides useful information to better understand the degradation of antibiotic compounds mediated by microbes in environments.

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