Release of trace elements during bioreductive dissolution of magnetite from metal mine tailings: Potential impact on marine environments.

Adverse impacts of mine tailings on water and sediments quality are major worldwide environmental problems. Due to the environmental issues associated with the deposition of mine tailings on land, a controversial discussed alternative is submarine tailings disposal (STD). However, Fe(III) bioreduction of iron oxides (e.g., magnetite) in the tailings disposed might cause toxic effects on coastal environments due to the release of different trace elements (TEs) contained in the oxides. To study the extent and kinetics of magnetite bioreduction under marine conditions and the potential release of TEs, a number of batch experiments with artificial seawater (pH 8.2) and a marine microbial strain (Shewanella loihica) were performed using several magnetite ore samples from different mines and a mine tailings sample. The elemental composition of the magnetite determined in the tailings showed relatively high amounts of TEs (e.g., Mn, Zn, Co) compared with those of the magnetite ore samples (LA-ICP-MS and EMPA analyses). The experiments were conducted at 10 °C in the dark for up to 113 days. Based on the consumption of lactate and production of acetate and aqueous Fe(II) over time, the magnitude of Fe(III) bioreduction was calculated using a geochemical model including Monod kinetics. Model simulations reproduced the release of iron and TEs observed throughout the experiments, e.g., Mn (up to 203 µg L-1), V (up to 79 µg L-1), As (up to 17 µg L-1) and Cu (up to 328 µg L-1), suggesting a potential contamination of pore water by STD. Therefore, the results of this study can help to better evaluate the potential impacts of STD.

Dissimilatory bioreduction of iron(III) oxides by Shewanella loihica under marine sediment conditions.

Shewanella is a genus of marine bacteria capable of dissimilatory iron reduction (DIR). In the context of deep-sea mining activities or submarine mine tailings disposal, dissimilatory iron reducing bacteria may play an important role in biogeochemical reactions concerning iron oxides placed on the sea bed. In this study, batch experiments were performed to evaluate the capacity of Shewanella loihica PV-4 to bioreduce different iron oxides (ferrihydrite, magnetite, goethite and hematite) under conditions similar to those in anaerobic sea sediments. Results showed that bioreduction of structural Fe(III) via oxidation of labile organic matter occurred in all these iron oxides. Based on the aqueous Fe (II) released, derived Fe(II)/acetate ratios and bioreduction coefficients seem to be only up to about 4% of the theoretical ones, considering the ideal stoichiometry of the reaction. A loss of aqueous Fe (II) was caused by adsorption and mineral transformation processes. Scanning electron microscope images showed that Shewanella lohica was attached to the Fe(III)-oxide surfaces during bioreduction. Our findings suggest that DIR of Fe(III) oxides from mine waste placed in marine environments could result in adverse ecological impacts such as liberation of trace metals in the environment.

Direct nanoscale observations of the coupled dissolution of calcite and dolomite and the precipitation of gypsum.

In-situ atomic force microscopy (AFM) experiments were performed to study the overall process of dissolution of common carbonate minerals (calcite and dolomite) and precipitation of gypsum in Na2SO4 and CaSO4 solutions with pH values ranging from 2 to 6 at room temperature (23 ± 1 °C). The dissolution of the carbonate minerals took place at the (104) cleavage surfaces in sulfate-rich solutions undersaturated with respect to gypsum, by the formation of characteristic rhombohedral-shaped etch pits. Rounding of the etch pit corners was observed as solutions approached close-to-equilibrium conditions with respect to calcite. The calculated dissolution rates of calcite at pH 4.8 and 5.6 agreed with the values reported in the literature. When using solutions previously equilibrated with respect to gypsum, gypsum precipitation coupled with calcite dissolution showed short gypsum nucleation induction times. The gypsum precipitate quickly coated the calcite surface, forming arrow-like forms parallel to the crystallographic orientations of the calcite etch pits. Gypsum precipitation coupled with dolomite dissolution was slower than that of calcite, indicating the dissolution rate to be the rate-controlling step. The resulting gypsum coating partially covered the surface during the experimental duration of a few hours.