Surface chemistry and structural properties of mackinawite prepared by reaction of sulfide ions with metallic iron

Tetragonal FeS_1−x mackinawite, has been synthesized by reacting metallic iron with a sodium sulfide solution and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), transmission Mössbauer spectroscopy (TMS) and X-ray photoelectron spectroscopy (XPS). Based on XRD and TEM analyses, synthetic mackinawite exhibits crystallization and is identical to the natural mineral. Unit cell parameters derived from XRD data are a = b = 0.3670 nm and c = 0.5049 nm. The bulk Fe:S ratio derived from the quantitative dispersive energy analysis is practically 1. XPS analyses, however, showed that mackinawite surface is composed of both Fe(II) and Fe(III) species bound to monosulfide. Accordingly, monosulfide is the dominant S species observed at the surface with lesser amount of polysulfides and elemental sulfur. TMS analysis revealed the presence of both Fe(II) and Fe(III) in the mackinawite structure, thus supporting the XPS analysis. We propose that the iron monosulfide phase synthesized by reacting metallic iron and dissolved sulfide is composed of Fe(II) and S(-II) atoms with the presence of a weathered thin layer covering the bulk material that consists of both Fe(II) and Fe(III) bound to S(-II) atoms and in a less extent of polysulfide and elemental sulfur.     

Biogeochemistry of pyrite and iron sulfide oxidation in marine sediments

Pyrite (FeS₂) and iron monosulfide (FeS) play a central role in the sulfur and iron cycles of marine sediments. They may be buried in the sediment or oxidized by O₂ after transport by bioturbation to the sediment surface. FeS₂ and FeS may also be oxidized within the anoxic sediment in which NO₃⁻, Fe(III) oxides, or MnO₂ are available as potential electron acceptors. In chemical experiments, FeS₂ and FeS were oxidized by MnO₂ but not with NO₃⁻ or amorphous Fe(III) oxide (Schippers and Jørgensen, 2001). Here we also show that in experiments with anoxic sediment slurries, a dissolution of tracer-marked ⁵⁵FeS₂ occurred with MnO₂ but not with NO₃⁻ or amorphous Fe(III) oxide as electron acceptor. To study a thermodynamically possible anaerobic microbial FeS₂ and FeS oxidation with NO₃⁻ or amorphous Fe(III) oxide as electron acceptor, more than 300 assays were inoculated with material from several marine sediments and incubated at different temperatures for > 1 yr. Bacteria could not be enriched with FeS₂ as substrate or with FeS and amorphous Fe(III) oxide. With FeS and NO₃⁻, 14 enrichments were obtained. One of these enrichments was further cultivated anaerobically with Fe²⁺ and S⁰ as substrates and NO₃⁻ as electron acceptor, in the presence of ⁵⁵FeS₂, to test for co-oxidation of FeS₂, but an anaerobic microbial dissolution of ⁵⁵FeS₂ could not been detected. FeS₂ and FeS were not oxidized by amorphous Fe(III) oxide in the presence of Fe-complexing organic compounds in a carbonate-buffered solution at pH 8. Despite many different experiments, an anaerobic microbial dissolution of FeS₂ could not be detected; thus, we conclude that this process does not have a significant role in marine sediments. FeS can be oxidized microbially with NO₃⁻ as electron acceptor. O₂ and MnO₂, but not NO₃⁻ or amorphous Fe(III) oxide, are chemical oxidants for both FeS₂ and FeS.     

Mineralogical study of base metal tailings with various sulfide contents, oxidized in laboratory columns and field lysimeters

 Oxidation of a flotation-derived, low-sulfide tailings containing approximately 0.4 wt.% S was compared with simultaneously oxidized tailings containing 1.0 wt.% S and 2.5 wt.% S to assess their acid generating characteristics. Each tailings type was exposed to oxidation for three years in laboratory columns and in lysimeter pits in the field. In these tailings the sulfide mineral of principal concern with respect to acid generation is pyrrhotite (Fe _1-x S). In past studies the alteration of pyrrhotite has been characterized by initial replacement with marcasite (FeS₂) and ferric iron sulfates, which are followed by development of ferric oxyhydroxides such as goethite and lepidocrocite. Macroscopic characterization of the tailings shows varying and progressive degrees of oxidation correlative with the three different sulfur contents. As expected, the tailings with the lowest sulfur content are the least oxidized, and those with the highest sulfur content have reacted the most. The column tests, which represent accelerated reaction conditions relative to those for the lysimeter pits, show much higher degrees of oxidation, and a markedly more distinct boundary between the oxidized and unoxidized zones; as well, differences among the three tailings types are more pronounced. Received: 31 October 1997 · Accepted: 27 May 1997     

XPS identification of bulk hole defects and itinerant Fe 3d electrons in natural troilite (FeS)

XPS measurements have been made of vacuum-fractured monoclinic pyrrhotite and troilite that highlight sulfur coordination (S 2p) and iron electronic state (Fe 2p) differences between these two minerals as a result of iron lattice site occupancy. Metal-like Fe states are observed in the Fe 2p spectrum of troilite due to increased occupancy of Fe lattice sites and increased Fe-Fe 3d orbital interaction within the constraints of the mineral structure. Additional electron population near the top of the troilite valence band is confirmed by XPS measurement. These results provide comprehensive experimental evidence for itinerent 3d electrons in the natural iron sulfides.     

Mineralogy and texture of Fe-Ni sulfides in CI1 chondrites: Clues to the extent of aqueous alteration on the CI1 parent body

To better understand the role of aqueous alteration on the CI1 parent body, we have analyzed the texture, composition and mineral associations of iron nickel sulfides in four of the five known CI1 chondrites.The most commonly-occurring sulfide present in the CI1 chondrites is the iron-deficient Fe,Ni sulfide pyrrhotite ([Fe,Ni]_1−xS), that has a composition close to that of stoichiometric troilite (FeS). Three of the CI1s (Alais, Ivuna and Tonk) also contain pentlandite ([Fe,Ni]₉S₈), although pentlandite is a rare phase in Ivuna. Cubanite (CuFe₂S₃) was found in both Alais and Ivuna in this study, although it has also been reported in Orgueil (MacDougall and Kerridge, 1977). The pyrrhotite grains in all four chondrites form hexagonal, rectangular or irregular shapes, and show no evidence of Ni or Co zoning. The pyrrhotite grains in Orgueil and Ivuna are, in general, smaller, and show more “corrosions,” or “embayments,” than those in Alais or Tonk.We suggest that the precursor sulfide present in the CI1 chondrites was troilite which, during brecciation and oxidation on the parent body at a temperature of 100°C or less, converted the troilite to magnetite and pyrrhotite with pentlandite inclusions. Subsequently, continued alteration on the parent body removed pentlandite—partially from Alais, Tonk and Ivuna, completely from Orgueil—leaving behind pyrrhotite with spaces (“corrosions”) where the pentlandite had been. Ni derived from the pentlandite was incorporated into ferrihydrite, onto the surface of which the Ni,Na sulfate Ni-bloedite formed.Based on the size and abundant “corrosions” within pyrrhotite grains, combined with observations from other authors, we conclude that Orgueil and Ivuna have undergone a greater degree of alteration than Alais and Tonk. Further work is needed to assess the conditions under which pentlandite would be dissolved preferentially to pyrrhotite, as the study of terrestrial literature indicates that the latter mineral is preferentially removed.     

Transmission electron microscopy on iron monosulfide varieties from the Suizhou meteorite

Transmission electron microscopy on the iron monosulfide (FeS) varieties from the Suizhou meteorite (Hubei, China) reveals the intergrowth of primary hexagonal 2C troilite and minor monoclinic 4C pyrrhotite (SG: F2/d) phases as nanometer-scale domain microstructure. In addition, anti-phase domain boundaries are found to present in the 2C troilite superstructure with the displacement vector 1/4[001]_2C, which is expected to form during the translational symmetry breaking during cooling from higher symmetry, high-temperature modification of the NiAs-type (SG: P6₃/mmc) structure. Furthermore, 60° rotation twinning about the pseudo-hexagonal c-axis is observed in the 4C pyrrhotite superstructure, which may result from rotation symmetry reduction induced by the ordered arrangements of metal vacancies through solid-state transformation during further cooling. All the above microstructural characteristics are discussed with consideration to the thermal metamorphism history experienced by the Suizhou meteorite.     

Surface typochemistry of hydrothermal pyrite: Electron spectroscopic and scanning probe microscopic data. I. Synthetic pyrite

Techniques of X-ray photoelectron and Auger electron spectroscopy, scanning probe microscopy were used to demonstrate that the natural surface of hydrothermally synthesized pyrite, as well as vacuum fractures, contain a number of sulfide-sulfur species: disulfide, monosulfide, and, more rarely, polysulfide. The natural surface of hydrothermal pyrite is chemically modified compared to the inner volume into a nonautonomous phase film up to ～500 nm thick, which has a variable composition resembling that of pyrrhotite but with broader variations toward FeS₂. Its principal distinctive feature is the presence of a peak at ～710 eV in the XPS Fe 2p_3/2 spectrum, which is often higher than the main peak of bivalent low-spin Fe(II) in the pyrite structure (707 eV). The “basic” structure of the nonautonomous phase is a layer of variable composition Fe²⁺[S, S₂, S _n ]^2?, whose S/S₂ ratio varies from ～0.5 to ～2.0, averaging at ～1.1. This layer may include admixtures of minor elements, as follows from the appearance of a nonautonomous phase in the presence of As, which does not, however, form an individual phase. The polymerization of S at the surface is thereby more significant. The major oxisulfide components of this phase may be the sulfite and thiosulfate ions at a subordinate concentration of sulfate because of the instability of coexisting sulfate and disulfide ions, which results, in the presence of oxygen, in sulfite (thiosulfate) and sulfide ions in the nonautonomous phase. In line with XPS, scanning probe microscopic (SPM) data show that, at a high S activity in the “pure” system, the surface of the crystals contains practically no nanometer-sized phases and is characterized by low roughness (14–17 nm). At a low S fugacity in equilibrium with pyrrhotite and sphalerite, the average roughness of the surface increases to 25–65 nm, with the maximum height of the surface features of ～100–500 nm. This is consistent with Auger spectroscopic data, obtained after the etching (ion milling) of the surface with Ar⁺, on the thickness of the nonstoichiometric surface layer. Comparison with analogous data on other sulfides shows that crystals growing in hydrothermal environments have surface layers up to ～500 nm thick, which are different from the main volume of the crystal in chemistry, stoichiometry, and, possibly, also structure. This is scale of the surface heterogeneity at which the typochemistry of mineral surfaces may be manifested. The typochemistry of pyrite stems from the ability of the nonautonomous phase to “record” the growth conditions of crystals in terms of two major factors: the purity of the system (the occurrence of other phases, including virtual ones, i.e., potentially possible phases of admixture elements) and S fugacity (which influences the S/S₂ ratio at the surface). The geochemical role of the surface nonautonomous phase in pyrite may be very significant, particularly when minor elements are captured that are incompatible with the pyrite structure but can be easily accommodated in the less rigid structure of the nonautonomous phase.     

Characterization of the structure and the surface reactivity of a marcasite thin film

A thin film of marcasite, FeS₂, was synthesized under vacuum and its structure and reactivity under oxidizing conditions was investigated by means of diffraction and surface analytical techniques, respectively. Synthesis of the film was carried out by codepositing Fe and S₂ onto a Ta support. The thickness of the film could be varied from approximately 10 Å to 1 μm. High-resolution S 2p synchrotron-based photoemission showed S22−, with undetectable amounts of S²⁻ impurity that is typically present on natural sample surfaces. X-ray diffraction of the micron-thick films showed that the film crystallized in the marcasite phase of FeS₂. Atomic force microscopy indicated that the thin film had a nanometer-scale roughness suggesting the film contained defects such as steps and kinks. X-ray photoelectron spectroscopy studies found the thin marcasite film to be more reactive than natural pyrite (the most ubiquitous FeS₂ dimorph) after exposure to a gaseous O₂/H₂O environment on the basis of the amount of sulfate formation. Likely the oxidation of marcasite was dominated by its short-range order (e.g., presence of steps), because the density of nonstoichiometric defect sites (e.g., S²⁻) was low as assessed by photoelectron spectroscopy.     

Computer simulation in hydrothermal systems with allowance for nonideality of sphalerite and pyrrhotite

To enhance the computer simulation of hydrothermal processes using the HCh program package, an external ZnS_FeS module has been created on the basis of a nonideal asymmetric model of sphalerite solid solution. FeS and ZnS activity coefficients computed in line with this model within a temperature range 200?C350°C lead to the decrease in FeS mole fraction (X _FeS) in sphalerite by 3.0?C1.5 times as compared with the ideal model. The calculated data on composition of sphalerite at the pyrite-pyrrhotite buffer with allowance for pyrrhotite nonideality are consistent with experimental results within the limits of 2% X _FeS of its value (0.215). A nonlinear relationship logX _FeS versus $\left( {\log f_{S_2 } } \right)$ . has been established, involving additional calculated data on equilibria of sphalerite with pyrite and magnetite, as well as pyrite and barite. With transition from pyrrhotite to magnetite and barite, a FeS mole fraction in sphalerite decreases to 0.1 and 0.006, respectively, because of increase in sulfur fugacity. The feasibility of using the calculation results based on the nonideal model of sphalerite for interpretation of natural data is exemplified in the Rainbow ore occurrence at the Mid-Atlantic Ridge (MAR). The computed pyrite-pyrrhotite and pyrite-cubanite-chalcopyrite buffer equilibria (X _FeS = 0.215 and 0.10?C0.12, respectively) are consistent with compositions of sphalerite in the pyrrhotite-cubanite-sphalerite and sphalerite ores (X _FeS = 0.20?C0.33 and 0.05?C0.14, respectively).     

Evidence for aqueous activity on comet 81P/Wild 2 from sulfide mineral assemblages in Stardust samples and CI chondrites

The discovery of nickel-, copper-, and zinc-bearing iron sulfides from comet 81P/Wild 2 (Wild 2) represents the strongest evidence, in the Stardust collection, of grains that formed in an aqueous environment. We investigated three microtomed TEM sections which contain crystalline sulfide assemblages from Wild 2 and twelve thin sections of the hydrothermally altered CI chondrite Orgueil. Detailed structural and compositional characterizations of the sulfide grains from both collections reveal striking similarities. The Stardust samples include a cubanite (CuFe₂S₃) grain, a pyrrhotite [(Fe,Ni)_1−xS]/pentlandite [(Fe,Ni)₉S₈] assemblage, and a pyrrhotite/sphalerite [(Fe,Zn)S] assemblage. Similarly, the CI-chondrite sulfides include individual cubanite and pyrrhotite grains, cubanite/pyrrhotite assemblages, pyrrhotite/pentlandite assemblages, as well as possible sphalerite inclusions within pyrrhotite grains. The cubanite is the low temperature orthorhombic form, which constrains temperature to a maximum of 210 °C. The Stardust and Orgueil pyrrhotites are the 4C monoclinic polytype, which is not stable above ∼250 °C. The combinations of cubanite and pyrrhotite, as well as pyrrhotite and pentlandite signify even lower temperatures. The crystal structures, compositions, and petrographic relationships of these sulfides constrain formation and alteration conditions. Taken together, these constraints attest to low-temperature hydrothermal processing.Our analyses of these minerals provide constraints on large scale issues such as: heat sources in the comet-forming region; aqueous activity on cometary bodies; and the extent and mechanisms of radial mixing of material in the early nebula. The sulfides in the Wild 2 collection are most likely the products of low-temperature aqueous alteration. They provide evidence of radial mixing of material (e.g. cubanite, troilite) from the inner solar system to the comet-forming region and possible secondary aqueous processing on the cometary body.     

The evolution of surface layers formed during chalcopyrite leaching

Chalcopyrite (CuFeS₂) leaching in perchloric acid (HClO₄) at an initial pH of one and a temperature of 85 °C has been examined. The rate of leaching of Cu and Fe increased progressively over the duration of the experiment. The Cu leach rate was initially greater (up to 24 h) but thereafter the leach rates for Cu and Fe were approximately equal. After 313 h 81% Cu release was achieved at which time the leach experiment was terminated. Only 25% of the available S was released into solution during the leaching process. Surface speciation over the duration of the leach was examined using X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectrometry (ToF-SIMS) and scanning electron microscopy (SEM). As a result, a three-step reaction pathway is proposed. The first oxidation step involves the release of Cu and Fe into solution and the polymerisation of monosulfide (S²⁻) to polysulfide . The subsequent reduction step does not result in the release of cations to solution but does result in the reformation of surface S²⁻ and other short chain polysulfides, which then on further oxidation restructure to form crystalline elemental sulfur (S⁰). This final oxidation step is accompanied by further cation release.     

攀西基性岩中共生的陨硫铁和磁黄铁矿的穆斯堡尔效应研究

使用穆斯堡尔效应研究攀西基性岩中共生的陨硫铁和磁黄铁矿。陨硫铁的分子式为Fe_(1.009)S,晶胞参数a_0=5.96,c_0=11.74,根据Wuensch表示法,可以把它归结为1B,1C型。与陨硫铁共生的磁黄铁矿的分子式为Fe_(0.892)S,属于六方磁黄铁矿。本文确定了共生的陨硫铁和磁黄铁矿的穆斯堡尔参数,它们的谱分别是由一组磁六线谱和三组磁六线谱组成。比较攀西陨硫铁和人工合成陨硫铁及陨石中陨硫铁,可以得出结论,它们之间没有明显差别。     

Redox potential (Eh) and anion effects of pyrite (FeS2) leaching at pH 1

Pyrite plays the central role in the environmental issue of acid rock drainage. Natural weathering of pyrite results in the release of sulphuric acid which can lead to further leaching of heavy and toxic metals from other associated minerals. Understanding how pyrite reacts in aqueous solution is critical to understanding the natural weathering processes undergone by this mineral. To this end an investigation of the effect of solution redox potential (Eh) and various anions on the rate of pyrite leaching under carefully controlled conditions has been undertaken.Leaching of pyrite has been shown to proceed significantly faster at solution Eh of 900 mV (SHE) than at 700 mV, at pH 1, for the leach media of HCl, H₂SO₄ and HClO₄. The predominant effect of Eh suggests electrochemical control of pyrite leaching with similar mechanism(s) at Eh of 700 and 900 mV albeit with different kinetics. Leach rates at 700 mV were found to decrease according to HClO₄ > HCl > H₂SO₄ while at 900 mV the leach rate order was HCl > HClO₄ > H₂SO₄. Solution Fe³⁺ activity is found to continually increase during all leaches; however, this is not accompanied by an increase in leach rate.Synchrotron based photoemission electron microscopy (PEEM) measurements showed a localised distribution of adsorbed and oxidised surface species highlighting that pyrite oxidation and leaching is a highly site specific process mediated by adsorption of oxidants onto specific surface sites. It appears that rates may be controlled, in part, by the propensity of acidic anions to bind to the surface, which varies according to , thus reducing the reactive or effective surface area. However, anions may also be involved in specific reactions with surface leach products. Stoichiometric dissolution data (Fe/S ratio), XPS and XRD data indicate that the highest leach rates (in HCl media at 900 mV Eh) correlate with relatively lower surface S abundance. Furthermore, there are indications that solution Cl⁻ assists oxidation especially at higher Eh through the prevention of surface S⁰ buildup at reactive surface sites.     

Internally consistent data for sulphur‐bearing phases and application to the construction of pseudosections for mafic greenschist facies rocks in Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–CO2–O–S–H2O

The Holland and Powell internally consistent data set version 5.5 has been augmented to include pyrite, troilite, trov (Fe_0.875S), anhydrite, H₂S, elemental S and S₂ gas. Phase changes in troilite and pyrrhotite are modelled with a combination of multiple end‐members and a Landau tricritical model. Pyrrhotite is modelled as a solid solution between hypothetical end‐member troilite (trot) and Fe_0.875S (trov); observed activity–composition relationships fit well to a symmetric formalism model with a value for w_trot?trov of ?3.19 kJ mol^?1. The hypothetical end‐member approach is required to compensate for iron distribution irregularities in compositions close to troilite. Mixing in fluids is described with the van Laar asymmetric formalism model with a_ij values for H₂O–H₂S, H₂S–CH₄ and H₂S–CO₂ of 6.5, 4.15 and 0.045 kJ mol^?1 respectively. The derived data set is statistically acceptable and replicates the input data and data from experiments that were not included in the initial regression. The new data set is applied to the construction of pseudosections for the bulk composition of mafic greenschist facies rocks from the Golden Mile, Kalgoorlie, Western Australia. The sequence of mineral assemblages is replicated successfully, with observed assemblages predicted to be stable at X(CO₂) increasing with increasing degree of hydrothermal alteration. Results are compatible with those of previous work. Assemblages are insensitive to the S bulk content at S contents of less than 1 wt%, which means that volatilization of S‐bearing fluids and sulphidation are unlikely to have had major effects on the stable mineral assemblage in less metasomatized rocks. The sequence of sulphide and oxide phases is predicted successfully and there is potential to use these phases qualitatively for geobarometry. Increases in X(CO₂) stabilized, in turn, pyrite–magnetite, pyrite–hematite and anhydrite–pyrite. Magnetite–pyrrhotite is predicted at temperatures greater than 410 °C. The prediction of a variety of sulphide and oxide phases in a rock of fixed bulk composition as a function of changes in fluid composition and temperature is of particular interest because it has been proposed that such a variation in phase assemblage is produced by the infiltration of multiple fluids with contrasting redox state. The work presented here shows that this need not be the case.     

Pyritization processes and greigite formation in the advancing sulfidization front in the upper Pleistocene sediments of the Black Sea

Pyritization in late Pleistocene sediments of the Black Sea is driven by sulfide formed during anaerobic methane oxidation. A sulfidization front is formed by the opposing gradients of sulfide and dissolved iron. The sulfidization processes are controlled by the diffusion flux of sulfide from above and by the solid reactive iron content. Two processes of diffusion-limited pyrite formation were identified. The first process includes pyrite precipitation with the accumulation of iron sulfide precursors with the average chemical composition of FeS_n (n = 1.10-1.29), including greigite. Elemental sulfur and polysulfides, formed from H₂S by a reductive dissolution of Fe(III)-containing minerals, serve as intermediates to convert iron sulfides into pyrite. In the second process, a “direct” pyrite precipitation occurs through prolonged exposure of iron-containing minerals to dissolved sulfide. Methane-driven sulfate reduction at depth causes a progressive formation of pyrite with a δ³⁴S of up to +15.0‰. The S-isotopic composition of FeS₂ evolves due to contributions of different sulfur pools formed at different times. Steady-state model calculations for the advancement of the sulfidization front showed that the process started at the Pleistocene/Holocene transition between 6360 and 11 600 yr BP. Our study highlights the importance of anaerobic methane oxidation in generating and maintaining S-enriched layers in marine sediments and has paleoenvironmental implications.     

The solubility of FeS

The solubility of FeS_m, synthetic nanoparticulate mackinawite, in aqueous solution was measured at 23 °C from pH 3-10 using an in situ precipitation and dissolution procedure and the solution species was investigated voltammetrically. The solubility is described by a pH-dependent reaction and a pH-independent reaction. The pH-dependent dissolution reaction can be described by

FeS_m+2H⁺→Fe²⁺+H₂S     

Ferrihydrite dissolution by pyridine-2,6-bis(monothiocarboxylic acid) and hydrolysis products

Pyridine-2,6-bis(monothiocarboxylate) (pdtc), a metabolic product of microorganisms, including Pseudomonas putida and Pseudomonas stutzeri was investigated for its ability of dissolve Fe(III)(hydr)oxides at pH 7.5. Concentration dependent dissolution of ferrihydrite under anaerobic environment showed saturation of the dissolution rate at the higher concentration of pdtc. The surface controlled ferrihydrite dissolution rate was determined to be 1.2 × 10⁻⁶ mol m⁻² h⁻¹. Anaerobic dissolution of ferrihydrite by pyridine-2,6-dicarboxylic acid or dipicolinic acid (dpa), a hydrolysis product of pdtc, was investigated to study the mechanism(s) involved in the pdtc facilitated ferrihydrite dissolution. These studies suggest that pdtc dissolved ferrihydrite using a reduction step, where dpa chelates the Fe reduced by a second hydrolysis product, H₂S. Dpa facilitated dissolution of ferrihydrite showed very small increase in the Fe dissolution when the concentration of external reductant, ascorbate, was doubled, suggesting the surface dynamics being dominated by the interactions between dpa and ferrihydrite. Greater than stoichiometric amounts of Fe were mobilized during dpa dissolution of ferrihydrite assisted by ascorbate and cysteine. This is attributed to the catalytic dissolution of Fe(III)(hydr)oxides by the in situ generated Fe(II) in the presence of a complex former, dpa.     

Low temperature anaerobic bacterial diagenesis of ferrous monosulfide to pyrite

In vitro enrichment cultures of dissimilatory sulfate-reducing bacteria precipitated FeS and catalyzed its transformation into FeS₂ at ambient temperature and pressure under anaerobic conditions. When compared to purely abiotic processes, the bacterially mediated transformation was shown to be more efficient in transforming FeS into FeS₂. This occurred due to the large, reactive surface area available for bacterially catalyzed diagenesis, where the biogenic FeS precursor was immobilized as a thin film (∼25 nm thick) on the μm-scale bacteria. The bacteria also contained the source(s) of sulfur for diagenesis to occur. Using a radiolabeled organic-sulfur tracer study, sulfur was released during cell autolysis and was immobilized at the bacterial cell surface forming FeS₂. The formation of FeS₂ occurred on both the inner and outer surfaces of the cell envelope and represented the first step of bacterial mineral diagenesis. Pyrite crystals, having linear dimensions of ∼1 μm, grew outward from the bacterial cell surfaces. These minerals were several orders of magnitude larger in volume than those originating abiotically.     

Geochemical and mineralogical aspects of sulfide mine tailings

Tailings generated during processing of sulfide ores represent a substantial risk to water resources. The oxidation of sulfide minerals within tailings deposits can generate low-quality water containing elevated concentrations of SO₄, Fe, and associated metal(loid)s. Acid generated during the oxidation of pyrite [FeS₂], pyrrhotite [Fe_(1−x)S] and other sulfide minerals is neutralized to varying degrees by the dissolution of carbonate, (oxy)hydroxide, and silicate minerals. The extent of acid neutralization and, therefore, pore-water pH is a principal control on the mobility of sulfide-oxidation products within tailings deposits. Metals including Fe(III), Cu, Zn, and Ni often occur at high concentrations and exhibit greater mobility at low pH characteristic of acid mine drainage (AMD). In contrast, (hydr)oxyanion-forming elements including As, Sb, Se, and Mo commonly exhibit greater mobility at circumneutral pH associated with neutral mine drainage (NMD). These differences in mobility largely result from the pH-dependence of mineral precipitation–dissolution and sorption–desorption reactions. Cemented layers of secondary (oxy)hydroxide and (hydroxy)sulfate minerals, referred to as hardpans, may promote attenuation of sulfide-mineral oxidation products within and below the oxidation zone. Hardpans may also limit oxygen ingress and pore-water migration within sulfide tailings deposits. Reduction–oxidation (redox) processes are another important control on metal(loid) mobility within sulfide tailings deposits. Reductive dissolution or transformation of secondary (oxy)hydroxide phases can enhance Fe, Mn, and As mobility within sulfide tailings. Production of H₂S via microbial sulfate reduction may promote attenuation of sulfide-oxidation products, including Fe, Zn, Ni, and Tl, via metal-sulfide precipitation. Understanding the dynamics of these interrelated geochemical and mineralogical processes is critical for anticipating and managing water quality associated with sulfide mine tailings.     

Kinetics of brucite dissolution at 25°C in the presence of organic and inorganic ligands and divalent metals

Brucite (Mg(OH)₂) dissolution rate was measured at 25°C in a mixed-flow reactor at various pH (5 to 11) and ionic strengths (0.01 to 0.03 M) as a function of the concentration of 15 organic and 5 inorganic ligands and 8 divalent metals. At neutral and weakly alkaline pH, the dissolution is promoted by the addition of the following ligands ranked by decreasing effectiveness: EDTA ≥ H₂PO₄⁻ > catechol ≥ HCO₃⁻ > ascorbate > citrate > oxalate > acetate ∼ lactate and it is inhibited by boric acid. At pH >10.5, it decreases in the presence of PO₄³⁻, CO₃²⁻, F⁻, oxine, salicylate, lactate, acetate, 4-hydroxybenzoate, SO₄²⁻ and B(OH)₄⁻ with orthophosphate and borate being the strongest and the weakest inhibitor, respectively. Xylose (up to 0.1 M), glycine (up to 0.05 M), formate (up to 0.3 M) and fulvic and humic acids (up to 40 mg/L DOC) have no effect on brucite dissolution kinetics. Fluorine inhibits dissolution both in neutral and alkaline solutions. From F sorption experiments in batch and flow-through reactors and the analysis of reacted surfaces using X-ray Photoelectron Spectroscopy (XPS), it is shown that fluorine adsorption is followed by its incorporation in brucite lattice likely via isomorphic substitution with OH. The effect of eight divalent metals (Sr, Ba, Ca, Pb, Mn, Fe, Co and Ni) studied at pH 4.9 and 0.01 M concentration revealed brucite dissolution rates to be correlated with the water molecule exchange rates in the first hydration sphere of the corresponding cation.The effect of investigated ligands on brucite dissolution rate can be modelled within the framework of the surface coordination approach taking into account the adsorption of ligands on dissolution-active sites and the molecular structure of the surface complexes they form. The higher the value of the ligand sorption constant, the stronger will be its catalyzing or inhibiting effect. As for Fe and Al oxides, bi- or multidentate mononuclear surface complexes, that labilize Mg-O bonds and water coordination to Mg atoms at the surface, enhance brucite dissolution whereas bi- or polynuclear surface complexes tend to inhibit dissolution by bridging two or more metal centers and extending the cross-linking at the solid surface. Overall, results of this study demonstrate that very high concentrations of organic ligands (0.01-0.1 M) are necessary to enhance or inhibit brucite dissolution. As a result, the effect of extracellular organic products on the weathering rate of Mg-bearing minerals is expected to be weak.