Characterization and origin of the Mn-rich patinas formed on Lunéville château sandstones

The formation of iron- and/or manganese-rich dark patinas on sandstones is a common natural phenomenon that occurs also on building stones. Lunéville château, in eastern France, presents such patinas that developed either under natural conditions (rain and time) or after an accidental fire and exposure to significant amounts of water as part of attempts to extinguish the fire. The present study aimed at characterizing both types of patinas in an effort to determine their formation mechanisms and Mn sources. In both cases, Mn required for patina formation likely derives from the reductive dissolution of Mn-rich minerals present in pristine sandstones, as suggested by the contrasting mineralogy and chemistry of Mn-rich phases present in the bulk and in the patina of a given building block. Reduced Mn species then migrate to the exposed surface of building blocks where they are re-oxidized via undetermined processes. Patinas developing “naturally” over time result from the alternation of wetting-reducing and drying-oxidizing cycles and appear to be composed of birnessite. Patinas formed after the 2003 fire result from this single accidental event and form a much thinner, heterogeneous, and discontinuous layer of poorly crystalline lithiophorite at the sandstone surface (∼ 0–150 µm compared to ∼ 300–600 µm for “natural” patinas). The lack of Mn-rich patinas on areas of Lunéville château is likely related to the lower Mn content of pristine sandstone blocks.

Bioleaching of Manganese Oxides at Different Oxidation States by Filamentous Fungus Aspergillus niger

This work aimed to examine the bioleaching of manganese oxides at various oxidation states (MnO, MnO·Mn2O3, Mn2O3 and MnO2) by a strain of the filamentous fungus Aspergillus niger, a frequent soil representative. Our results showed that the fungus effectively disintegrated the crystal structure of selected mineral manganese phases. Thereby, during a 31-day static incubation of oxides in the presence of fungus, manganese was bioextracted into the culture medium and, in some cases, transformed into a new biogenic mineral. The latter resulted from the precipitation of extracted manganese with biogenic oxalate. The Mn(II,III)-oxide was the most susceptible to fungal biodeterioration, and up to 26% of the manganese content in oxide was extracted by the fungus into the medium. The detected variabilities in biogenic oxalate and gluconate accumulation in the medium are also discussed regarding the fungal sensitivity to manganese. These suggest an alternative pathway of manganese oxides’ biodeterioration via a reductive dissolution. There, the oxalate metabolites are consumed as the reductive agents. Our results highlight the significance of fungal activity in manganese mobilization and transformation. The soil fungi should be considered an important geoactive agent that affects the stability of natural geochemical barriers.

Effect of organic carbon addition on paddy soil organic carbon decomposition under different irrigation regimes

Anaerobic decomposition of organic carbon (OC) in submerged rice paddies is coupled to the reduction of alternative soil electron acceptors, primarily Fe3+. During reductive dissolution of Fe3+ from pedogenic oxides, previously adsorbed native soil organic carbon (SOC) could be co-released into solution. Incorporation of crop residues could hence indirectly, i.e. through the stimulation of microbially mediated Fe3+ reduction, promote the loss of native SOC via enhanced dissolution and subsequent mineralisation to CO2 and CH4. Our aim was to estimate the relevance of such a positive feedback during the degradation of added OC, and to investigate the impact of irrigation management on this mechanism and on priming effects on native SOC decomposition in general. In a six-week pot experiment with rice plants, two Bangladeshi soils with contrasting SOC to oxalate-extractable Fe (SOC : Feox) ratios were kept under a regime of alternate wetting and drying (AWD) or continuous flooding (CF), and were either amended with maize shoots or not. The δ13C signatures of dissolved organic C and emitted CH4 and CO2 were used to infer the decomposition of added maize shoots (δ13C = −13.0 ‰) versus native SOC (δ13C = −25.4 ‰ and −22.7 ‰). Addition of maize residues stimulated the reduction of Fe as well as the dissolution of native SOC, and the latter to a larger extent under CF, especially for the soil with the highest SOC : Feox ratio. Estimated Fe-bound SOC contents denote that stimulated SOC co-release during Fe reduction could explain this positive priming effect on SOC dissolution after the addition of maize. However, priming effects on SOC mineralisation to CO2 and CH4 were lower than for SOC dissolution, and were even negative under AWD for one soil. Enhanced reductive dissolution of Fe-bound SOC upon exogenous OC addition therefore does not necessarily lead to stimulated SOC mineralisation. In addition, AWD irrigation was found to decrease the above-mentioned priming effects.

Bioleaching of Transition Metals From Limonitic Laterite Deposits and Reassessment of the Multiple Roles of Sulfur-Oxidizing Acidophiles in the Process

Using acidophilic bacteria to catalyze the reductive dissolution of oxidized minerals is an innovative process that facilitates the extraction of valuable base metals (principally cobalt and nickel) from limonites, which are otherwise often regarded as waste products of laterite mining. The most appropriate conditions required to optimize reductive mineral dissolution are unresolved, and the current work has reassessed the roles of Acidithiobacillus spp. in this process and identified novel facets. Aerobic bio-oxidation of zero-valent sulfur (ZVS) can generate sufficient acidity to counterbalance that consumed by the dissolution of oxidized iron and manganese minerals but precludes the development of low redox potentials that accelerate the reductive process, and although anaerobic oxidation of sulfur by iron-reducing species can achieve this, less acid is generated. Limited reduction of soluble iron (III) occurs in pure cultures of Acidithiobacillus spp. (Acidithiobacillus thiooxidans and Acidithiobacillus caldus) that do not grow by iron respiration. This phenomenon (“latent iron reduction”) was observed in aerated cultures and bioreactors and was independent of electron donor used (ZVS or hydrogen). Sufficient ferrous iron was generated in the presence of sterilized hydrophilic sulfur (bio-ZVS) to promote the effective reductive dissolution of Mn (IV) minerals in limonite and the solubilization of cobalt in the absence of viable acidophiles.

The Influence of Cascade Reservoir Construction on Labile Phosphorus in the Sediment of Lancang River

The influence of cascade reservoirs construction on labile phosphorus (P) is an important scientific problem in the Lancang River. The concentration of labile P in cascade deep-water reservoirs were determined, and the influence of cascade reservoirs construction on the DGT-labile P was analyzed. The construction of cascade reservoirs led to significant differences in concentrations of DGT-labile P, which in the upstream of Xiaowan (XW) Reservoir were differences from that in the downstream Nuozhadu (NZD) Reservoir. The P diffusion fluxes in XW Reservoir were − 8.59–250.50 ng·cm− 2·d− 1, and that in NZD Reservoir were 3.82–24.80 ng·cm− 2·d− 1. The P pollution of XW Reservoir was higher, highlighting the importance of controlling P pollution of XW Reservoir. The construction of cascade reservoirs had made the release of DGT-labile P more dependent on the reductive dissolution of Mn oxides. The early diagenesis transformed bio-availability P (BAP) remobilization into DGT-labile P that made the increase of DGT-labile P/BAP with depth. However, the DGT-labile P/BAP of upstream XW Reservoir was 7.8 times larger than that of downstream NZD Reservoir, which indicated that the construction of cascade reservoirs weakened the remobilization of P in sediment.

Reductive dissolution of pyrite by methanogenic archaea

The formation and fate of pyrite (FeS2) modulates global iron, sulfur, carbon, and oxygen biogeochemical cycles and has done so since early in Earth’s geological history. A longstanding paradigm is that FeS2 is stable at low temperature and is unavailable to microorganisms in the absence of oxygen and oxidative weathering. Here, we show that methanogens can catalyze the reductive dissolution of FeS2 at low temperature (≤38 °C) and utilize dissolution products to meet cellular iron and sulfur demands associated with the biosynthesis of simple and complex co-factors. Direct access to FeS2 is required to catalyze its reduction and/or to assimilate iron monosulfide that likely forms through coupled reductive dissolution and precipitation, consistent with close associations observed between cells and FeS2. These findings demonstrate that FeS2 is bioavailable to anaerobic methanogens and can be mobilized in low temperature anoxic environments. Given that methanogens evolved at least 3.46 Gya, these data indicate that the microbial contribution to the iron and sulfur cycles in ancient and contemporary anoxic environments may be more complex and robust than previously recognized, with impacts on the sources and sinks of iron and sulfur and other bio-essential and thiophilic elements such as nickel and cobalt.