Bioleaching of metal sulfides is caused by astonishingly diverse groups of bacteria. Today, at least 11 putative prokaryotic divisions can be related to this phenomenon. In contrast, the dissolution (bio)chemistry of metal sulfides follows only two pathways, which are determined by the acid-solubility of the sulfides: the thiosulfate and the polysulfide pathway. The bacterial cell can effect this sulfide dissolution by “contact” and “non-contact” mechanisms. The non-contact mechanism assumes that the bacteria oxidize only dissolved iron(II) ions to iron(III) ions. The latter can then attack metal sulfides and be reduced to iron(II) ions. The contact mechanism requires attachment of bacteria to the sulfide surface. The primary mechanism for attachment to pyrite is electrostatic in nature. In the case of Acidithiobacillus ferrooxidans, bacterial exopolymers contain iron(III) ions, each complexed by two uronic acid residues. The resulting positive charge allows attachment to the negatively charged pyrite. Thus, the first function of complexed iron(III) ions in the contact mechanism is 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 the non-contact mechanism. In both cases, the electrons extracted from the metal sulfide reduce molecular oxygen via a complex redox chain located below the outer membrane, the periplasmic space, and the cytoplasmic membrane of leaching bacteria. The dominance of either At. ferrooxidans or Leptospirillum ferrooxidans in mesophilic leaching habitats is highly likely to result from differences in their biochemical iron(II) oxidation pathways, especially the involvement of rusticyanin.

Bioleaching review part A: progress in bioleaching: fundamentals and mechanisms of bacterial metal sulfide oxidation.

: 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

Concentrations of naturally occurring arsenic in ground water vary regionally due to a combination of climate and geology Although slightly less than half of 30,000 arsenic analyses of ground water in the United States were 1 μg/L, about 10% exceeded 10 μg/L At a broad regional scale, arsenic concentrations exceeding 10 μg/L appear to be more frequently observed in the western United States than in the eastern half Arsenic concentrations in ground water of the Appalachian Highlands and the Atlantic Plain generally are very low ( 1 μg/L) Concentrations are somewhat greater in the Interior Plains and the Rocky Mountain System Investigations of ground water in New England, Michigan, Minnesota, South Dakota, Oklahoma, and Wisconsin within the last decade suggest that arsenic concentrations exceeding 10 μg/L are more widespread and common than previously recognized

Arsenic release from iron oxide appears to be the most common cause of widespread arsenic concentrations exceeding 10 μg/L in ground water This can occur in response to different geochemical conditions, including release of arsenic to ground water through reaction of iron oxide with either natural or anthropogenic (ie, petroleum products) organic carbon Iron oxide also can release arsenic to alkaline ground water, such as that found in some felsic volcanic rocks and alkaline aquifers of the western United States Sulfide minerals are both a source and sink for arsenic Geothermal water and high evaporation rates also are associated with arsenic concentrations 10g/L in ground and surface water, particularly in the west

Arsenic in Ground Water of the United States: Occurrence and Geochemistry

Aqueous pyrite oxidation by dissolved oxygen and by ferric iron

(Bio)chemistry of bacterial leaching - direct vs. indirect bioleaching

The authors studies of aqueous, abiotic pyrite oxidation in oxygen-saturated and anaerobic Fe(III)-saturated systems span pH values from 2 to 9 and include analyses of sulfite, thiosulfate, polythionates, and sulfate. In addition, they evaluated procedures for cleaning oxidation products from pyrite surfaces. As in silicate experiments, the preparation of the pyrite surface is critical to a valid interpretation of the onset of pyrite oxidation. The rates in oxygen-saturated systems (1) were relatively independent of pH, (2) gave linear sulfoxy anion production, (3) produced thiosulfate and polythionates at pH >3.9, and (4) produced intermediate sulfoxy anions only at high stirring rates. In anaerobic Fe(III)-saturated systems no intermediates were observed. From these results, along with the generally faster rate of oxidation in Fe(III)-saturated systems, we conclude that Fe(III) is the more important, direct oxidant of pyrite. This conclusion is supported by theoretical consideration regarding the low probability of a direct reaction between paramagnetic molecular oxygen and diamagnetic disulfide. The authors findings extend earlier models for the pyrite oxidation mechanism because of the larger range of experimental conditions that they have studied. Preliminary results from studies of sphalerite oxidation, in which they have found thiosulfate, support the hypothesis that thiosulfate is a keymore » intermediate related to the reaction mechanisms, independent of the bounding structure of the sulfide mineral.« less

D.K. Nordstrom

Papers

Initiation of aqueous pyrite oxidation by dissolved oxygen and by ferric iron

Sampling and analysing mixtures of sulphate, sulphite, thiosulphate and polythionate.