Micrometric pyrite catalyzes abiotic sulfidogenesis from elemental sulfur and hydrogen.

Hydrogen sulfide (H2S) in environments with temperatures below 100 °C is generally assumed to be of microbial origin, while abiotic H2S production is typically restricted to higher temperatures (T). In this study, we report an abiotic process for sulfidogenesis through the reduction of elemental sulfur (S0) by hydrogen (H2), mediated by pyrite (FeS2). The process was investigated in detail at pH 4 and 80 °C, but experimental conditions ranged between 40 and 80 °C and pH 4-6. The experiments were conducted with H2 as reducing molecule, and µm-sized spherical (but not framboidal) pyrite particles that formed in situ from the H2S, S0 and Fe2+ present in the experiments. Fe monosulfides, likely mackinawite, were identified as potential pyrite precursors. The absence of H2 production in controls, combined with geochemical modelling, suggests that pyrite formation occurred through the polysulfide pathway, which is unexpected under acidic conditions. Most spherical aggregates of authigenic pyrite were composed of nanometric, acicular crystals oriented in diverse directions, displaying varying degrees of organization. Although it was initially hypothesized that the catalytic properties were related to the surface structure, commercially sourced, milled pyrite particles (< 50 µm) mediated H2S production at comparable rates. This suggests that the catalytic properties of pyrite depend on particle size rather than surface structure, requiring pyrite surfaces to act as electron shuttles between S0 and H2.

Biosulfidogenesis Mediates Natural Attenuation in Acidic Mine Pit Lakes.

Acidic pit lakes are abandoned open pit mines filled with acid mine drainage (AMD)-highly acidic, metalliferous waters that pose a severe threat to the environment and are rarely properly remediated. Here, we investigated two meromictic, oligotrophic acidic mine pit lakes in the Iberian Pyrite Belt (IPB), Filón Centro (Tharsis) (FC) and La Zarza (LZ). We observed a natural attenuation of acidity and toxic metal concentrations towards the lake bottom, which was more pronounced in FC. The detection of Cu and Zn sulfides in the monimolimnion of FC suggests precipitation of dissolved metals as metal sulfides, pointing to biogenic sulfide formation. This was supported by microbial diversity analysis via 16S rRNA gene amplicon sequencing of samples from the water column, which showed the presence of sulfidogenic microbial taxa in FC and LZ. In the monimolimnion of FC, sequences affiliated with the putative sulfate-reducing genus Desulfomonile were dominant (58%), whereas in the more acidic and metal-enriched LZ, elemental sulfur-reducing Acidianus and Thermoplasma spp., and disproportionating Desulfocapsa spp. were more abundant. Furthermore, the detection of reads classified as methanogens and Desulfosporosinus spp., although at low relative abundance, represents one of the lowest pH values (2.9 in LZ) at which these taxa have been reported, to our knowledge. Analysis of potential biomarker lipids provided evidence that high levels of phosphocholine lipids with mixed acyl/ether glycerol core structures were associated with Desulfomonile, while ceramide lipids were characteristic of Microbacter in these environments. We propose that FC and LZ function as natural bioremediation reactors where metal sulfide precipitation is mediated by biosulfidogenesis starting from elemental sulfur reduction and disproportionation at an early stage (LZ), followed by sulfate reduction at a later stage (FC).

Quantifying, assessing and removing the extreme gas load from meromictic Guadiana pit lake, Southwest Spain.

High gas charges in deep waters of lakes can represent a hazard to the lives of human beings and animals in the surrounding. As this danger was feared, we quantified the amount of dissolved gas in Guadiana pit lake (Las Herrerías, Huelva; southwest Spain) and documented the temporal evolution over a period of two years. Gas pressure due to dissolved gases, such as carbon dioxide, methane and nitrogen was measured. Based on these data, we assessed the risk and the associated danger of limnic eruptions from the lake and concluded that the present situation cannot be considered safe. By deploying a vertical pipe, the updraft of degassing water was tested and demonstrated: the pilot plant provided enough energy to drive a self-sustained flow. Such a system could be implemented to remove the extreme gas pressure from the deep water. Measurements of discharges could be extrapolated to indicate the size for an efficient plant for the gas removal. The construction of such a system would be technically and economically viable. A reintroduction of degassed water into the monimolimnion would be advisable.

Extreme carbon dioxide concentrations in acidic pit lakes provoked by water/rock interaction.

We quantify the gas pressure and concentration of a gas-charged acidic pit lake in SW Spain. We measured total dissolved gas pressure, carbon dioxide (CO2) concentration, major ion concentration, isotopic composition of dissolved inorganic carbon (δ(13)C(DIC)), and other physicochemical parameters. CO2 is the dominant dissolved gas in this lake and results mainly from carbonate dissolution during the interaction of acidic water with wall rocks, followed by diffusive and advective transport through the water column. The δ(13)C(DIC) values suggest that the biological contribution is comparatively small. Maximum CO2 concentrations higher than 0.1 M (∼5000 mg/L) have been measured, which are only comparable to those found in volcanic crater lakes. The corresponding gas pressures of CO2 alone (pCO2 ∼3.6 bar) imply 60% saturation relative to local pressure at 50 m depth. High CO2 concentrations have been observed in other pit lakes of the region. We recommend gas-specific monitoring in acidic pit lakes and, if necessary, the design of feasible degassing strategies.