On death and dying

: Geochemical reaction path modeling is useful for rapidly assessing the extent of water-aqueous-gas interactions both in natural systems and in industrial processes. Modeling of some systems, such as those at low temperature with relatively high hydrologic flow rates, or those perturbed by the subsurface injection of industrial waste such as CO2 or H2S, must account for the relatively slow kinetics of mineral-gas-water interactions. We have therefore compiled parameters conforming to a general Arrhenius-type rate equation, for over 70 minerals, including phases from all the major classes of silicates, most carbonates, and many other non-silicates. These data have been added to a computer code that simulates an infinitely well-stirred batch reactor, allowing computation of mass transfer as a function of time. Actual equilibration rates are expected to be much slower than those predicted by the selected computer code, primarily because actual geochemical processes commonly involve flow through porous or fractured media, wherein the development of concentration gradients in the aqueous phase near mineral surfaces, which results in decreased absolute chemical affinity and slower reaction rates. Further differences between observed and computed reaction rates may occur because of variables beyond the scope of most geochemical simulators, such as variation in grain size, aquifer heterogeneity, preferred fluid flow paths, primary and secondary mineral coatings, and secondary minerals that may lead to decreased porosity and clogged pore throats.

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A Compilation of Rate Parameters of Water-Mineral Interaction Kinetics for Application to Geochemical Modeling

We report on the synthesis of iron-nickel sulfide (INS) ultrathin nanosheets by topotactic conversion from a hydroxide precursor The INS nanosheets exhibit excellent activity and stability in strong acidic solutions as a hydrogen evolution reaction (HER) catalyst, lending an attractive alternative to the Pt catalyst The metallic α-INS nanosheets show an even lower overpotential of 105 mV at 10 mA/cm2 and a smaller Tafel slope of 40 mV/dec With the help of DFT calculations, the high specific surface area, facile ion transport and charge transfer, abundant electrochemical active sites, suitable H+ adsorption, and H2 formation kinetics and energetics are proposed to contribute to the high activity of the INS ultrathin nanosheets toward HER

Metallic Iron–Nickel Sulfide Ultrathin Nanosheets As a Highly Active Electrocatalyst for Hydrogen Evolution Reaction in Acidic Media

Mining and mineral processing generates large volumes of waste, including waste rock, mill tailings, and mineral refinery wastes. The oxidation of sulfide minerals in the materials can result in the release of acidic water containing high concentrations of dissolved metals. Recent studies have determined the mechanisms of abiotic sulfide-mineral oxidation. Within mine wastes, the oxidation of sulfide minerals is catalyzed by microorganisms. Molecular tools have been developed and applied to determine the activity and role of these organisms in sulfide-mineral-bearing systems. Novel tools have been developed for assessing the toxicity of mine-waste effluent. Dissolved constituents released by sulfide oxidation may be attenuated through the precipitation of secondary minerals, including metal sulfate, oxyhydroxide, and basic sulfate minerals. Geochemical models have been developed to provide improved predictions of the magnitude and duration of environmental concerns. Novel techniques have been developed to prevent and remediate environmental problems associated with these materials.

The geochemistry of acid mine drainage

Bioleaching of metal sulfides is performed by a diverse group of microorganisms. The dissolution chemistry of metal sulfides follows two pathways, which are determined by the mineralogy and the acid solubility of the metal sulfides: the thiosulfate and the polysulfide pathways. Bacterial cells can effect this metal sulfide dissolution via iron(II) ion and sulfur compound oxidation. Thereby, iron(III) ions and protons, the metal sulfide-attacking agents, are available. Cells can be active either in planktonic state or in forming biofilms on the mineral surface; however, the latter is much more efficient in terms of bioleaching kinetics. In the case of Acidithiobacillus ferrooxidans, bacterial exopolymers contain iron(III) ions, each complexed by two uronic acid residues. The resulting positive charge allows an electrostatic attachment to the negatively charged pyrite. Thus, the first function of complexed iron(III) ions is the mediation of cell attachment, while their second function is oxidative dissolution of the metal sulfide, similar to the role of free iron(III) ions in non-contact leaching. In both cases, the electrons extracted from the metal sulfide reduce molecular oxygen via a redox chain forming a supercomplex spanning the periplasmic space and connecting both outer and inner membranes. In this review, we summarize some recent discoveries relevant to leaching bacteria which contribute to a better understanding of these fascinating microorganisms. These include surface science, biochemistry of iron and sulfur metabolism, anaerobic metabolism, and biofilm formation. The study of microbial interactions among multispecies leaching consortia, including cell-to-cell communication mechanisms, must be considered in order to reveal more insights into the biology of bioleaching microorganisms and their potential biotechnological use.

Joan E. Thomas

Papers

The evolution of surface layers formed during chalcopyrite leaching

The role of surface sulfur species in the inhibition of pyrrhotite dissolution in acid conditions

Transacting self-preservation: a grounded theory of the spiritual dimensions of people with terminal cancer.

A comparison of the dissolution behavior of troilite with other iron(II) sulfides; implications of structure

Geochemical effects of oxidation products and framboidal pyrite oxidation in acid mine drainage prediction techniques