Mn2+ recycling in hypersaline wastewater: unnoticed intracellular biomineralization and pre-cultivation of immobilized bacteria.

Microbially induced manganese carbonate precipitation has been utilized for the treatment of wastewater containing manganese. In this study, Virgibacillus dokdonensis was used to remove manganese ions from an environment containing 5% NaCl. The results showed a significant decrease in carbonic anhydrase activity and concentrations of carbonate and bicarbonate ions with increasing manganese ion concentrations. However, the levels of humic acid analogues, polysaccharides, proteins, and DNA in EPS were significantly elevated compared to those in a manganese-free environment. The rhodochrosite exhibited a preferred growth orientation, abundant morphological features, organic elements including nitrogen, phosphorus, and sulfur, diverse protein secondary structures, as well as stable carbon isotopes displaying a stronger negative bias. The presence of manganese ions was found to enhance the levels of chemical bonds O-C=O and N-C=O in rhodochrosite. Additionally, manganese in rhodochrosite exhibited both + 2 and + 3 valence states. Rhodochrosite forms not only on the cell surface but also intracellularly. After being treated with free bacteria for 20 days, the removal efficiency of manganese ions ranged from 88.4 to 93.2%, and reached a remarkable 100% on the 10th day when using bacteria immobilized on activated carbon fiber that had been pre-cultured for three days. The removal efficiency of manganese ions was significantly enhanced under the action of pre-cultured immobilized bacteria compared to non-pre-cultured immobilized bacteria. This study contributes to a comprehensive understanding of the mineralization mechanism of rhodochrosite, thereby providing an economically and environmentally sustainable biological approach for treating wastewater containing manganese.

Unraveling the Mechanisms of Fe Oxidation and Mn Reduction on Mn Indicators of Reduction in Soil (IRIS) Films.

Indicators of reduction in soil (IRIS) devices are low-cost soil redox sensors coated with Fe or Mn oxides, which can be reductively dissolved from the device under suitable redox conditions. Removal of the metal oxide coating from the surface, leaving behind the white film, can be quantified and used as an indicator of reducing conditions in soils. Manganese IRIS, coated with birnessite, can also oxidize Fe(II), resulting in a color change from brown to orange that complicates the interpretation of coating removal. Here, we studied field-deployed Mn IRIS films where Fe oxidation was present to unravel the mechanisms of Mn oxidation of Fe(II) and the resulting minerals on the IRIS film surface. We observed reductions in the Mn average oxidation state when Fe precipitation was evident. Fe precipitation was primarily ferrihydrite (30-90%), but lepidocrocite and goethite were also detected, notably when the Mn average oxidation state decreased. The decrease in the average oxidation state of Mn was due to the adsorption of Mn(II) to the oxidized Fe and the precipitation of rhodochrosite (MnCO3) on the film. The results were variable on small spatial scales (<1 mm), highlighting the suitability of IRIS in studying heterogeneous redox reactions in soil. Mn IRIS also provides a tool to bridge lab and field studies of the interactions between Mn oxides and reduced constituents.

Dissolution and solubility of calcite-rhodochrosite solid solutions [(Ca1-xMnx)CO3] at 25 °C.

A complete series of calcite-rhodochrosite solid solutions [(Ca1-xMnx)CO3] are prepared, and their dissolution processes in various water samples are experimentally investigated. The crystal morphologies of the solid solutions vary from blocky spherical crystal aggregates to smaller spheres with an increasing incorporation of Mn in the solids. Regarding dissolution in N2-degassed water, air-saturated water and CO2-saturated water at 25 °C, the aqueous Ca and Mn concentrations reach their highest values after 1240-2400 h, 6-12 h and < 1 h, respectively, and then decrease gradually to a steady state; additionally, the ion activity products (log_IAP) at the final steady state (≈ solubility products in log_Ksp) are estimated to be - 8.46 ± 0.06, - 8.44 ± 0.10 and - 8.59 ± 0.10 for calcite [CaCO3], respectively, and - 10.25 ± 0.08, - 10.26 ± 0.10 and - 10.28 ± 0.03, for rhodochrosite [MnCO3], respectively. As XMn increases, the log_IAP values decrease from - 8.44 ~ - 8.59 for calcite to - 10.25 ~ - 10.28 for rhodochrosite. The aqueous Mn concentrations increase with an increasing Mn/(Ca + Mn) molar ratio (XMn) of the (Ca1-xMnx)CO3 solid solutions, while the aqueous Ca concentrations show the highest values at XMn = 0.53-0.63. In the constructed Lippmann diagram of subregular (Ca1-xMnx)CO3 solid solutions, the solids dissolve incongruently, and the data points of the aqueous solutions move progressively up to the Lippmann solutus curve and then along the solutus curve or saturation curve of pure MnCO3 to the Mn-poor side. The microcrystalline cores of the spherical crystal aggregates are preferentially dissolved to form core hollows while simultaneously precipitating Mn-rich hexagonal prisms.

Rhodochrosite Oxidation by Dissolved Oxygen and the Formation of Mn Oxide Product: The Impact of Goethite as a Foreign Solid Substrate.

Rhodochrosite conversion to Mn (oxyhydr)oxides significantly affects the fate and transport of various substances in the environment. We examined rhodochrosite oxidation by dissolved oxygen and the oxidation product formation with an emphasis on the effects of goethite substrate. Without goethite, rhodochrosite oxidation was slow as no detectable change was observed for 28 d with microscopic and spectroscopic analyses, except a minor change in X-ray diffraction. Interestingly, by contrast, it was greatly accelerated and completed in 7 d in the presence of goethite, resulting in the heteroepitaxial growth of groutite (α-MnOOH)-like Mn oxides on the goethite (α-FeOOH) tip surfaces. The formation of this secondary Mn oxide likely induced the acidification of the microenvironment in the vicinity of rhodochrosite particles and thereby promoted their dissolution. Subsequently, their oxidative conversion to the Mn oxide was expedited by the surface catalyzed Mn(II) oxidation on the goethite tip. Our results revealed that goethite as a foreign substrate imparts a decisive control on not only the rate but also the type of the reaction product of rhodochrosite oxidation. This study presents a new insight into the geochemical roles of foreign particles on the dynamics of redox-sensitive solid phases in the environment.