Sedimentologic, petrographic, and sulfur isotope constraints on fine-grained pyrite formation at Mount Isa Mine and environs, Northwest Queensland, Australia

Fine-grained pyrite is the earliest generation of pyrite and the most abundant sulfide within the Urquhart Shale at Mount Isa, northwest Queensland. The pyrite is intimately interbanded with ore-grade Pb-Zn miner alization at the Mount Isa mine but is also abundant north and south of the mine at several stratigraphic horizons within the Urquhart Shale. Detailed sedimentologic, petrographic, and sulfur isotope studies of the Urquhart Shale, mostly north of the mine, reveal that the fine-grained pyrite (delta(34)S = -3.3 to +26.3 parts per thousand) formed by thermochemical sulfate reduction during diagenesis. The sulfate source was local sulfate evaporites, pseudo morphs of which are present throughout the Urquhart Shale (i.e., gypsum, anhydrite, and barite). Deep-burial diagenetic replacement of these evaporites resulted in sulfate-bearing ground waters which migrated parallel to bedding. Fine-grained pyrite formed where these fluids infiltrated and then interacted with carbon-rich laminated siltstones. Comparison of the sulfur isotope systematics of fine-grained pyrite and spatially associated base metal sulfides from the Mount Isa Pb-Zn and Cu orebodies indicates a common sulfur source of ultimately marine origin for all sulfide types. Different sulfur isotope ratio distributions for the various sulfides are the result of contrasting formation mechanisms and/or depositional conditions rather than differing sulfur sources. The sulfur isotope systematics of the base metal and associated iron sulfide generations are consistent with mineralization by reduced hydrothermal fluids, perhaps generated by bulk reduction of evaporite-sourced sulfate-bearing waters generated deeper in the Mount Isa Group, the sedimentary sequence which contains the Urquhart Shale. The available sulfur isotope data from the Mount Isa orebodies are consistent with either a chemically and thermally zoned, evolving Cu-Pb-Zn system, or discrete Cu and Pb-Zn mineralizing events linked by a common sulfur source.

Distribution and mobility of trace elements in soils and vegetation around the mining and smelting areas of Tharsis, Riotinto and Huelva, Iberian Pyrite Belt, SW Spain

Trace elements may present an environmental hazard in the vicinity of mining and smelting activities. However, the factors controlling their distribution and transfer within the soil and vegetation systems are not always well defined. Total concentrations of up to 15,195 mg center dot kg (-1) As, 6,690 mg center dot kg(-1) Cu, 24,820 mg center dot kg(-1) Pb and 9,810 mg center dot kg(-1) Zn in soils, and 62 mg center dot kg(-1) As, 1,765 mg center dot kg(-1) Cu, 280 mg center dot kg(-1) Pb and 3,460 mg center dot kg (-1) Zn in vegetation were measured. However, unusually for smelters and mines of a similar size, the elevated trace element concentrations in soils were found to be restricted to the immediate vicinity of the mines and smelters (maximum 2-3 km). Parent material, prevailing wind direction, and soil physical and chemical characteristics were found to correlate poorly with the restricted trace element distributions in soils. Hypotheses are given for this unusual distribution: (1) the contaminated soils were removed by erosion or (2) mines and smelters released large heavy particles that could not have been transported long distances. Analyses of the accumulation of trace elements in vegetation (median ratios: As 0.06, Cu 0.19, Pb 0.54 and Zn 1.07) and the percentage of total trace elements being DTPA extractable in soils (median percentages: As 0.06%, Cu 15%, Pb 7% and Zn 4%) indicated higher relative trace element mobility in soils with low total concentrations than in soils with elevated concentrations.

The interaction of iron pyrite with oxygen, nitrogen and nitrogen oxides: a first-principles study

Sulphide materials, in particular MoS2, have recently received great attention from the surface science community due to their extraordinary catalytic properties. Interestingly, the chemical activity of iron pyrite (FeS2) (the most common sulphide mineral on Earth), and in particular its potential for catalytic applications, has not been investigated so thoroughly. In this study, we use density functional theory (DFT) to investigate the surface interactions of fundamental atmospheric components such as oxygen and nitrogen, and we have explored the adsorption and dissociation of nitrogen monoxide (NO) and nitrogen dioxide (NO2) on the FeS2(100) surface. Our results show that both those environmentally important NOx species chemisorb on the surface Fe sites, while the S sites are basically unreactive for all the molecular species considered in this study and even prevent NO2 adsorption onto one of the non-equivalent Fe–Fe bridge sites of the (1 1)–FeS2(100) surface. From the calculated high barrier for NO and NO2 direct dissociation on this surface, we can deduce that both nitrogen oxides species are adsorbed molecularly on pyrite surfaces.

The electrochemical behavior of pyrite-pyrrhotite mixtures

To assess the response of common sulfide minerals to oxidizing conditions, a methodology to immobilize mechanically solid particles on carbon surfaces (voltammetry of microparticles, VMP) was employed, to define the influence of the pyrrhotite content in pyrite-pyrrhotite mixtures. The influence of the galvanic interactions and local pH on the oxidation reaction of pyrite was also investigated. With this purpose, artificial two-mineral electrodes were constructed, ranging in weight from 20 to 80% pyrrhotite. The resulting cyclic voltammograms were analyzed and relative quantities of oxidation products were evaluated. The goal of this work was to define the boundary conditions, in terms of pyrrhotite content in the mixture, that determine the SO42-/S ratio obtained and to describe some parameters which influence this ratio: local pH and galvanic interactions. (C) 2003 Elsevier B.V. All rights reserved.

Oxidation of isochemical FeS2 (marcasite-pyrite) by Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans

A research-grade mineral sample that contained marcasite and pyrite (FeS2) was subjected to the oxidation by Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. Oxidation of FeS2 by A. ferrooxidans produced acid, and the redox potential increased with sulfide dissolution and the oxidation of Fe2+. jarosite was detected in solids from spent cultures. Preferential oxidation of either mineral was not consistently observed across all treatments. Neither iron sulfide was oxidized by A. thiooxidans. (C) 2006 Elsevier Ltd. All rights reserved.

Electrochemical kinetic study of surface layer growth on natural pyrite in acid medium

This paper presents electrochemical experiments on natural pyrite that combine potentiostatic and voltammetric techniques. X-ray microanalysis is used as an auxiliary technique. The layer growth on pyrite surface is conducted in a wide range of pH and potential range: 3.4 <= pH <= 5.9 with E = 0.80 V (versus SHE), and 0.80 V <= E <= 1.00 V with pH 4.5 (versus SHE) in acetic acid-acetate buffer. This work is unique for two reasons: (1) phenomenological model about layer growth is applied and mathematical-physic consistence is verified and (2) Meyer's hypotheses of chemical mechanism are used to explain kinetic parameters of the phenomenological model. (c) 2005 Elsevier B.V. All rights reserved.

A study of the main oxidation products of natural pyrite by voltammetric and photoelectrochemical responses

(Photo)electrochemical experiments on pyrite electrodes in acetic acid-acetate buffer (pH = 4.5) are conducted to clarify the main oxidation reactions and the nature of the products. Electrochemical reactions in the -0.40 to 1.25 V (SHE) potential range are studied, and the production of iron (III) polysulfide from anodically formed iron oxides and polysulfides is discussed. Charges experimentally obtained are considered for the estimation of the most likely stoichiometry of the metallic polysulfide. The photoselectivity of the pyrite corrosion process indicates that the oxidation reactions of Fe2+ and S-2(2-) an not consecutive. The changes in stoichiometry and/or annihilation of crystalline structure defects are responsible for the observed photosensitivity of pyrite. A description of light effects on the interfacial behaviour and stability of pyrite is presented in terms of conduction and valence band energies, and thermodynamic potentials. (C) 2001 Elsevier Science B.V. All rights reserved.

Iodide interaction with natural pyrite

29I is one of the major dose-determining nuclides in the safety analysis of deep storage of radioactive waste. Iodine forms anionic species that hardly sorb on the surfaces of common host-rock minerals. Recently, interest has arisen on the role of pyrite, an accessory mineral capable of binding anionic selenium. Whereas the interaction of selenium with pyrite is well documented, corresponding results on iodine sorption are still scarce and controversial. Pyrite is present in argicilleous rocks which are being considered in many countries as potential host rocks for a radioactive waste repository. The uptake of iodide (I−) on natural pyrite was investigated under nearly anoxic conditions (O2 < 5 ppm) over a wide concentration range (10−11–10−3 M total I−) using 125I as the radioactive tracer. Weak but measurable sorption was observed; distribution coefficients (R d) were less than 0.002 m3 kg−1 and decreased with increasing total iodide concentration. Iodide sorption was connected to the presence of oxidized clusters on the pyrite surface, which were presumably formed by reaction with limited amounts of dissolved oxygen. The results obtained indicated that pyrite cannot be considered as an effective scavenger of 129I under the geochemical conditions prevailing in underground radioactive waste geologic storage.

Sizing by Elutriation of Finely Ground Quartz and Pyrite

Elutriation, as a means of sorting mineral particles, has received marked attention during the last fifteen years. Its use in the ceramics industry for the sorting of clays was recognized even before this.

(Table 1) U and Th isotope analyses of pyrite and anhydrite of ODP Site 158-957

Hydrothermal circulation at oceanic spreading ridges causes sea water to penetrate to depths of 2 to 3 km in the oceanic crust where it is heated to ~400 °C before venting at spectacular 'black smokers'. These hydrothermal systems exert a strong influence on ocean chemistry (Edmond et al., 1979, doi:10.1016/0012-821X(79)90061-X), yet their structure, longevity and magnitude remain largely unresolved (Elderfield and Schultz., 1996, doi:10.1146/annurev.earth.24.1.191). The active Transatlantic Geotraverse (TAG) deposit, at 26° N on the Mid-Atlantic Ridge, is one of the largest, oldest and most intensively studied of the massive sulphide mounds that accumulate beneath black-smoker fields. Here we report ages of sulphides and anhydrites from the recently drilled (Humphris et al., 1995, doi:10.1038/377713a0) TAG substrate structures -determined from 234U-230Th systematics analysed by thermal ionization mass spectrometry. The new precise ages combined with existing data (Lalou et al., 1993, doi:10.1029/92JB01898; 1998, doi:10.2973/odp.proc.sr.158.214.1998) show that the oldest material (11,000 to 37,000 years old) forms a layer across the centre of the deposit with younger material (2,300-7,800 years old) both above and below. This stratigraphy confirms that much of the sulphide and anhydrite are precipitated within the mound by mixing of entrained sea water with hydrothermal fluid (James and Elderfield, 1996, doi:10.1130/0091-7613(1996)024<1147:COOFFA>2.3.CO;2). The age distribution is consistent with episodic activity of the hydrothermal system recurring at intervals of up to 2,000 years.

(Table 1) Elemental composition, pyrite-Fe and degree of pyritisation in Upper Pliensbachian and Lower Toarcian sediments from the costal section of Yorkshire

Profiles of Mo/total organic carbon (TOC) through the Lower Toarcian black shales of the Cleveland Basin, Yorkshire, United Kingdom, and the Posidonia shale of Germany and Switzerland reveal water mass restriction during the interval from late tenuicostatum Zone times to early bifrons Zone times, times which include that of the putative Early Toarcian oceanic anoxic event. The degree of restriction is revealed by crossplots of Mo and TOC concentrations for the Cleveland Basin, which define two linear arrays with regression slopes (ppm/%) of 0.5 and 17. The slope of 0.5 applies to sediment from the upper semicelatum and exaratum Subzones. This value, which is one tenth of that for modern sediments from the Black Sea (Mo/TOC regression slope 4.5), reveals that water mass restriction during this interval was around 10 times more severe than in the modern Black Sea; the renewal frequency of the water mass was between 4 and 40 ka. The Mo/TOC regression slope of 17 applies to the overlying falciferum and commune subzones: the value shows that restriction in this interval was less severe and that the renewal frequency of the water mass was between 10 and 130 years. The more restricted of the two intervals has been termed the Early Toarcian oceanic anoxic event but is shown to be an event caused by basin restriction local to NW Europe. Crossplots of Re, Os, and Mo against TOC show similar trends of increasing element concentration with increase in TOC but with differing slopes. Together with modeling of 187Os/188Os and d98Mo, the element/TOC trends show that drawdown of Re, Os, and Mo was essentially complete during upper semicelatum and exaratum Subzone times (Mo/TOC regression slope of 0.5). Drawdown sensitized the restricted water mass to isotopic change forced by freshwater mixing so that continental inputs of Re, Os, and Mo, via a low-salinity surface layer, created isotopic excursions of up to 1.3 per mil in d98Mo and up to 0.6 per mil for 187Os/188Os. Restriction thereby compromises attempts to date Toarcian black shales, and possibly all black shales, using Re-Os chronology and introduces a confounding influence in the attempts to use d98Mo and initial 187Os/188Os for palaeo-oceanographic interpretation.