Oxidative Dissolution Of Sulfide Minerals Research Articles

Identifying sources of acid mine drainage and major hydrogeochemical processes in abandoned mine adits (Southeast Shaanxi, China).

Acid mine drainage (AMD) has resulted in significant risks to both human health and the environment of the Han River watershed. In this study, water and sediment samples from typical mine adits were selected to investigate the hydrogeochemical characteristics and assess the environmental impacts of AMD. The interactions between coexisting chemical factors, geochemical processes in the mine adit, and the causes of AMD formation are discussed based on statistical analysis, mineralogical analysis, and geochemical modeling. The results showed that the hydrochemical types of AMD consisted of SO4-Ca-Mg, SO4-Ca, and SO4-Mg, with low pH and extremely high concentrations of Fe and SO42-. The release behaviors of most heavy metals are controlled by the oxidation of sulfide minerals (mainly pyrite) and the dissolution/precipitation of secondary minerals. Along the AMD pathway in the adit, the species of Fe-hydroxy secondary minerals tend to initially increase and later decrease. The inverse model results indicated that (1) oxidative dissolution of sulfide minerals, (2) interconversion of Fe-hydroxy secondary minerals, (3) precipitation of gypsum, and (4) neutralization by calcite are the main geochemical reactions in the adit, and chlorite might be the major neutralizing mineral of AMD with calcite. Furthermore, there were two sources of AMD in abandoned mine adits: oxidation of pyrite within the adits and infiltration of AMD from the overlying waste rock dumps. The findings can provide deeper insight into hydrogeochemical processes and the formation of AMD contamination produced in abandoned mine adits under similar mining and hydrogeological conditions.

Incomplete sulfide oxidation under sub-oxic conditions: Rates and aqueous sulfur speciation

The oxidative dissolution of sulfide minerals consumes oxygen and can generate redox gradients in mine wastes that affect the mobility of redox-sensitive solutes. However, the controls of oxygen depletion on sulfide reactivity and sulfur mobilization remain poorly constrained, complicating the long-term assessment of drainage quality dynamics. We investigated pyrite and Fe-rich sphalerite weathering using aqueous S speciation and quantitative mineralogical analyses under controlled, ambient versus sub-oxic, conditions at 6 < pH < 9. Titration assays revealed that oxidation rates for pyrite (up to 10−10 mol m−2 s−1) were higher than for sphalerite (up to 10−11 mol m−2 s−1) and, for both minerals, decreased by two orders-of-magnitude under sub-oxic (<50 ppm O2) conditions. Precipitation of secondary S-bearing minerals was restricted to elemental S, with no sulfate- or thiosulfate-salts detectable >0.01 wt%. Sulfate was the dominant aqueous S species produced in all experiments, but significant amounts of thiosulfate, tetrathionate, and sulfite were also found. These dissolved intermediate S species were abundant under both sub-oxic and oxic conditions, and broadly in line with known sulfide oxidation mechanisms, even though the weathering of pyrite produced several factors less incompletely oxidized S than that of sphalerite, under otherwise comparable conditions. This work shows that a range of intermediate S species may be produced even in low-reactivity conditions and may help optimize the management of such mine waste materials.

Antimony transformation and mobilization from stibnite by an antimonite oxidizing bacterium Bosea sp. AS-1

Soils and waters are heavily contaminated by antimony in Xikuangshan (XKS) mine area. It is widely accepted that oxidative dissolution of sulfide minerals and aqueous dissolution are the most prevalent geochemical mechanisms for the release of Sb to the environment. Bosea sp. AS-1 is an antimonite-oxidizer isolated from the mine slag in Xikuangshan Sb mine. Whole genome sequencing revealed the presence of multiple sulfur-oxidizing genes, antimony (Sb) metabolism genes and carbon fixation genes in AS-1′s genome. We therefore hypothesized that under oxic conditions, AS-1 could mediate the oxidation of sulfide and Sb(III) in stibnite (Sb2S3) and lead to the release of Sb. Indeed, strain AS-1 was discovered as an autotrophic Sb(III)-oxidizer. Antimony mobilization studies conducted with strain AS-1 showed significantly enhanced mobilization of Sb, and complete oxidation of released Sb and sulfur to Sb(V) and sulfate. In addition, AS-1 induced a faster release of Sb under heterotrophic condition, and new acicular minerals might form. These findings support the hypothesis that microorganisms play an important role in the mobilization and transformation of Sb in XKS mine area and may contribute to our further understanding of the Sb biogeochemical redox cycle in natural environment.

Oxidative Dissolution of Sulfide Minerals in Single and Mixed Sulfide Systems under Simulated Acid and Metalliferous Drainage Conditions.

Chalcopyrite, galena, and sphalerite commonly coexist with pyrite in sulfidic waste rocks. The aim of this work was to investigate their impact, potentially by galvanic interaction, on pyrite oxidation and acid generation rates under simulated acid and metalliferous drainage conditions. Kinetic leach column experiments using single-minerals and pyrite with one or two of the other sulfide minerals were carried out at realistic sulfide contents (total sulfide <5.2 wt % for mixed sulfide experiments), mimicking sulfidic waste rock conditions. Chalcopyrite was found to be most effective in limiting pyrite oxidation and acid generation with 77-95% reduction in pyrite oxidation over 72 weeks, delaying decrease in leachate pH. Sphalerite had the least impact with reduction of pyrite dissolution by 26% over 72 weeks, likely because of the large band gap and poor conductivity of sphalerite. Galena had a smaller impact than chalcopyrite on pyrite oxidation, despite their similar band gaps, possibly because of the greater extent of oxidation and the significantly reduced surface areas of galena (area reductions of >47% for galena vs <1.5% for chalcopyrite) over 72 weeks. The results are directly relevant to mine waste storage and confirm that the galvanic interaction plays a role in controlling acid generation in multisulfide waste even at low sulfide contents (several wt %) with small probabilities (≤0.23%) of direct contact between sulfide minerals in mixed sulfide experiments.

Arsenic release and transport during oxidative dissolution of spatially-distributed sulfide minerals

The oxidative dissolution of sulfide minerals, naturally present in the subsurface, is one of the major pathways of arsenic mobilization. This study investigates the release and fate of arsenic from arsenopyrite and löllingite oxidation under dynamic redox conditions. We performed multidimensional flow-through experiments focusing on the impact of chemical heterogeneity on arsenic mobilization and reactive transport. In the experimental setups the As-bearing sulfide minerals were embedded, with different concentrations and spatial distributions, into a sandy matrix under anoxic conditions. Oxic water flushed in the flow-through setups triggered the oxidative dissolution of the reactive minerals, the release of arsenic, as well as changes in pore water chemistry, surface-solution interactions and mineral precipitation. We developed a reactive transport model to quantitatively interpret the experimental results. The simulation outcomes showed that 40% of the arsenic released was reincorporated into a freshly precipitated iron-arsenate phase that created a coating on the mineral surface limiting the dissolution reactions. The faster dissolution rate of löllingite compared to arsenopyrite was responsible for sustaining the continuous release of As-contaminated plumes. The model also allowed shedding light on the spatial distribution, on the temporal dynamics, and on the interactions between arsenic sources (As-bearing minerals) and sinks (freshly formed secondary phases) in flow-through systems.

Bacterial and Archaeal Diversity in Sulfide-Bearing Waste Rock at Faro Mine Complex, Yukon Territory, Canada

Acid mine/rock drainage (AMD/ARD) is generated by the microbially-accelerated oxidative dissolution of sulfide minerals in working and abandoned mine sites, and some natural environments. Iron-oxidizing microorganisms (IOM) regenerate the oxidant Fe3+, while sulfur-oxidizing microorganisms (SOM) contribute to AMD/ARD by generating H2SO4 via the oxidation of elemental S and reduced inorganic sulfur compounds. Bacterial and archaeal diversity in 34 samples of sulfide-bearing waste rock recovered from three boreholes at the Faro Mine Complex (Yukon Territory, Canada; Pb/Zn production from 1969 to 1998) was investigated using high-throughput amplicon sequencing of 16S rRNA genes. A majority of the borehole pore water samples had circum-neutral or mildly alkaline pH (6.3 − 8.7), while some had low pH (3.3 − 5.2). Mean relative abundance of prokaryotic SOM/IOM accounted for 3.4% of the total amplicons. The acidophilic genera Alicyclobacillus and Acidithiobacillus were the most abundant sulfur- and iron-metabolizing prokaryotes detected, followed by neutrophilic and moderately acidophilic (non-iron-oxidizing) SOM. Sulfate-reducing bacteria (SRB) were also detected, accounting for 0.6% of total reads. The presence of both acidophilic and neutrophilic prokaryotes catalyzing transformations of sulfur and iron in the same samples suggests development of microenvironments within the waste rock where dynamic biogeochemical transformations of these elements occur.

Acidithiobacillus ferrooxidans.

Acidithiobacillus ferrooxidans is by far the most widely studied of all extremely acidophilic prokaryotes. While it is found in many types of natural low-pH environments in a variety of geoclimatic contexts, it has been more widely cited in anthropogenic (mostly mine-impacted) environments. It is responsible for accelerating the oxidative dissolution of sulfide minerals, causing the generation of polluting acidic metal-rich drainage waters but also facilitating the recovery of base and precious metals from mineral leachates. It can colonize barren mineral landscapes, is a driver of ecological successions in acidic biotopes, and is an important model organism in astrobiology. It catalyses the dissimilatory oxidation of iron, sulfur, and hydrogen, and the reduction of iron and sulfur, and has a major impact in the geochemical cycling of these elements in low-pH environments. This infographic summarizes the fundamental phylogeny, physiology and genomic features of this extremophile.

Ferric-enhanced chemical remediation of dredged marine sediment contaminated by metals and petroleum hydrocarbons

Sediments nearby harbors are dredged regularly, and the sediments require the stringent treatment to meet the regulations on reuse and mitigate the environmental burdens from toxic pollutants. In this study, FeCl3 was chosen as an extraction agent to treat marine sediment co-contaminated with Cu, Zn, and total petroleum hydrocarbons (TPH). In chemical extraction process, the extraction efficiency of Cu and Zn by FeCl3 was compared with the conventional one using inorganic acids (H2SO4 and HCl). Despite the satisfactory level for extraction of Cu (78.8%) and Zn (73.3%) by HCl (0.5 M) through proton-enhanced dissolution, one critical demerit, particularly acidified sediment, led to the unwanted loss of Al, Fe, and Mg by dissolution. Moreover, the vast amount of HCl required the huge amounts of neutralizing agents for the post-treatment of the sediment sample via the washing process. Despite a low concentration, extraction of Cu (70.1%) and Zn (69.4%) was done by using FeCl3 (0.05 M) through proton-enhanced dissolution, ferric-organic matter complexation, and oxidative dissolution of sulfide minerals. Ferric iron (Fe3+) was reduced to ferrous iron (Fe2+) with sulfide (S2-) oxidation during FeCl3 extraction. In consecutive chemical oxidations using hydrogen peroxide (H2O2) and persulfate (S2O82-), the resultant ferrous iron was used to activate the oxidants to effectively degrade TPH. S2O82- using FeCl3 solution (molar ratio of ferrous to S2O82- is 19.8–198.3) removed 42.6% of TPH, which was higher than that by H2O2 (molar ratio of ferrous to H2O2 is 1.2–6.1). All experimental findings suggest that ferric is effectively accommodated to an acid washing step for co-contaminated marine sediments, which leads to enhanced extraction, cost-effectiveness, and less environmental burden.

Photochemical oxidation and dissolution of arsenopyrite in acidic solutions

Arsenopyrite (FeAsS) is the most common iron sulfide mineral in the nature, and its oxidation causes arsenic (As) release and thus environmental pollution. Sunlight participates in the oxidative dissolution of sulfide minerals in supergene environments, affecting the release of toxic elements. In this work, we investigated the oxidative dissolution process of arsenopyrite in acidic solution under ultraviolet (UV) irradiation. The effects of pH, oxygen partial pressure and waveband of incident light on the dissolution and release of As were further investigated. The results showed that UV irradiation can promote the oxidative dissolution of arsenopyrite and the release of As. As(V), Fe(II) and SO42− were the major forms of the released As, Fe and S, respectively. Reactive oxygen species (ROS) including O2−/HO2, OH and H2O2 were generated through the oxidation of As(III) by oxygen under far-UV irradiation, photo-Fenton reaction of Fe(II)/FeOH2+ and conversion of OH/O2−, which play important roles in arsenopyrite oxidation. A small amount of OH and H2O2 was generated from the decomposition of H2O induced by Fe(III) at the sulfur-deficient sites on arsenopyrite surface. Oxygen accelerated the formation of ROS, which facilitated the oxidative dissolution of arsenopyrite and the release of As. At initial pH 3.0, the released As mainly existed in the form of ions in the solution. With initial pH increasing to 5.0, the formation of ferric arsenate precipitate and goethite contributed to the adsorption and fixation of released As. This work reveals the release mechanism of As in the photochemical oxidation process of arsenopyrite, and expands the understanding about the geochemical cycling of As.

Distribution and migration of antimony and other trace elements in a Karstic river system, Southwest China.

Antimony (Sb) usually occurs associated with arsenic, lead, and other metal elements in sulfide deposits, and most is currently being extracted from the Karst areas, southwest China. In these areas, the acid generated from the oxidative dissolution of sulfide minerals is neutralized by the abundant carbonates but little is known about the effect of this process on the geochemical behavior of Sb and other contaminants. In this study, physicochemical properties (pH, EC) and the trace elements (Sb, As, Cu, Pb, Zn, Sr, etc.) concentrations in waters from mining-impacted Karstic environments were determined in order to determine their distribution and migration potential. It was found that pH values ranged from 6.51 to 9.82, and EC values varied from 369 to 1705μs·cm-1 in river water samples. Waters of various types such as adit waters, flotation drainage, leaching waters, and river waters all contained high concentrations of dissolved trace elements, reaching up to 5475μg·L-1Sb, 1877μg·L-1As, 10,371μg·L-1Zn, 1309μg·L-1 Pb, 46μg·L-1 Cu, and 1757μg·L-1 Sr. The elevated concentrations of dissolved Sr indicated that Sr could be considered as an indicator of oxidative dissolution of sulfide minerals in the Karst rivers. A proportion of the trace elements were removed in the streams in the vicinity of the mine due to adsorption onto particulate matter, whereas migration of trace elements in the downstream of mine area was attributed to dispersion in dissolved forms. Strontium and Sb have a strong hydrophilicity compared to the other elements analyzed; in contrast, Pb had a high affinity for suspended particulate matter (SPM). It was also found that downstream sediments had elevated concentrations of mining-derived trace elements, but there was a significant decrease in concentration of contaminants in aqueous phase, suggesting that contaminant behavior was conservative in the water-sediment systems under the oxic conditions prevailing in these waters. There was a good correlation between Sb and As in water-SPM-sediment system, indicating that Sb and As are homologous in water environment of the study area.

Salt Stress-Induced Loss of Iron Oxidoreduction Activities and Reacquisition of That Phenotype Depend on rus Operon Transcription in Acidithiobacillus ferridurans.

The type strain of the mineral-oxidizing acidophilic bacterium Acidithiobacillus ferridurans was grown in liquid medium containing elevated concentrations of sodium chloride with hydrogen as electron donor. While it became more tolerant to chloride, after about 1 year, the salt-stressed acidophile was found to have lost its ability to oxidize iron, though not sulfur or hydrogen. Detailed molecular examination revealed that this was due to an insertion sequence, ISAfd1, which belongs to the ISPepr1 subgroup of the IS4 family, having been inserted downstream of the two promoters PI and PII of the rus operon (which codes for the iron oxidation pathway in this acidophile), thereby preventing its transcription. The ability to oxidize iron was regained on protracted incubation of the culture inoculated onto salt-free solid medium containing ferrous iron and incubated under hydrogen. Two revertant strains were obtained. In one, the insertion sequence ISAfd1 had been excised, leaving an 11-bp signature, while in the other an ∼2,500-bp insertion sequence (belonging to the IS66 family) was detected in the downstream inverted repeat of ISAfd1 The transcriptional start site of the rus operon in the second revertant strain was downstream of the two ISs, due to the creation of a new "hybrid" promoter. The loss and subsequent regaining of the ability of A. ferriduransT to reduce ferric iron were concurrent with those observed for ferrous iron oxidation, suggesting that these two traits are closely linked in this acidophile.IMPORTANCE Iron-oxidizing acidophilic bacteria have primary roles in the oxidative dissolution of sulfide minerals, a process that underpins commercial mineral-processing biotechnologies ("biomining"). Most of these prokaryotes have relatively low tolerance to chloride, which limits their activities when only saline or brackish waters are available. The study showed that it was possible to adapt a typical iron-oxidizing acidophile to grow in the presence of salt concentrations similar to those in seawater, but in so doing they lost their ability to oxidize iron, though not sulfur or hydrogen. The bacterium regained its capacity for oxidizing iron when the salt stress was removed but simultaneously reverted to tolerating lower concentrations of salt. These results suggest that the bacteria that have the main roles in biomining operations could survive but become ineffective in cases where saline or brackish waters are used for irrigation.

A method for preparation and cleaning of uniformly sized arsenopyrite particles.

BackgroundThe oxidative dissolution of sulfide minerals, such as arsenopyrite (FeAsS), is of critical importance in many geochemical systems. A comprehensive understanding of their dissolution rates entails careful preparation of the mineral surface. Measurements of dissolution rates of arsenic from arsenopyrite are dependent on the size and degree of oxidation of its particles, among other factors. In this work, a method was developed for preparation and cleaning of arsenopyrite particles with size range of 15-250 μm. Four different cleaning methods were evaluated for effectiveness based on the removal of oxidized species of iron (Fe), arsenic (As) and sulfur (S) from the surface. The percentage oxidation of the surface was determined using X-ray photoelectron spectroscopy (XPS), and surface stoichiometry was measured using scanning electron microscopy - energy dispersive X-ray spectroscopy (SEM-EDS).ResultsResults indicate that sonicating the arsenopyrite particles and then cleaning them with 12N HCl followed by 50% ethanol, and drying in nitrogen was the most effective method. This method was successful in greatly reducing the oxide species of Fe while completely removing oxides of As and S from the arsenopyrite surface.ConclusionsAlthough sonication and acid cleaning have been widely used for mineral preparation, the method described in this study can significantly reduce grain size heterogeneity as well as surface oxidation, which enables greater control in surface and dissolution experiments.Electronic supplementary materialThe online version of this article (doi:10.1186/s12932-014-0014-9) contains supplementary material, which is available to authorized users.

Biogeochemical processes governing natural pyrite oxidation and release of acid metalliferous drainage.

The oxidative dissolution of sulfide minerals (principally pyrite) is responsible for the majority of acid metalliferous drainage from mine sites, which represents a significant environmental problem worldwide. Understanding the complex biogeochemical processes governing natural pyrite oxidation is critical not only for solving this problem but also for understanding the industrial bioleaching of sulfide minerals. To this end, we conducted a simulated experiment of natural pyrite oxidative dissolution. Pyrosequencing analysis of the microbial community revealed a distinct succession across three stages. At the early stage, a newly proposed genus, Tumebacillus (which can use sodium thiosulfate and sulfite as the sole electron donors), dominated the microbial community. At the midstage, Alicyclobacillus (the fifth most abundant genus at the early stage) became the most dominant genus, whereas Tumebacillus was still ranked as the second most abundant. At the final stage, the microbial community was dominated by Ferroplasma (the tenth most abundant genus at the early stage). Our geochemical and mineralogical analyses indicated that exchangeable heavy metals increased as the oxidation progressed and that some secondary sulfate minerals (including jarosite and magnesiocopiapite) were formed at the final stage of the oxidation sequence. Additionally, we propose a comprehensive model of biogeochemical processes governing the oxidation of sulfide minerals.

Kinetics, surface chemistry, and structural evolution of microbially mediated sulfide mineral dissolution

The effects of different microbial populations on the oxidative dissolution of sulfide minerals at 37°C and pH 1.5 were examined over a period of 22 days. Samples of pyrite, marcasite, and arsenopyrite were exposed to a sulfur-oxidizing isolate ( Thiobacillus caldus), an iron-oxidizing isolate ( Ferroplasma acidarmanus), and a mixed enrichment culture containing T. caldus, F. acidarmanus, and Leptospirillum ferrooxidans. Changes in chemical speciation of the mineral surface products were monitored by Raman spectroscopy over the course of the experiment, structural evolution was examined with scanning electron microscopy, and the total soluble iron was used as a measure of the dissolution rate. In the case of all three minerals, an increase in dissolution rate was observed only in the presence of iron-oxidizing microorganisms (i.e., F. acidarmanus or the enrichment culture). The chemical speciation at the mineral surface in the presence of these iron-oxidizing species is indistinguishable from that of abiotic control reactions under the same conditions; both are dominated by elemental sulfur. In contrast, experiments with T. caldus indicate that the quantity of elemental sulfur on the mineral surface is <1% of the amount observed on samples exposed to the F. acidarmanus culture. It is surprising that removal of the elemental sulfur from the mineral surface by the sulfur-oxidizing species is not accompanied by an increase in the dissolution rate of the mineral. This finding suggests that although elemental sulfur forms on the surface during oxidative dissolution, it does not passivate the mineral surface.

Chemistry, isotope values (δD, δ 18O, δ 34S SO 4) and temperatures of the water inflows in two Gotthard tunnels, Swiss Alps

Water inflows in the Gotthard Highway Tunnel and in the Gotthard Exploration Tunnel are meteoric waters infiltrating at different elevations, on both sides of an important orographic divide. Limited interaction of meteoric waters with gneissic rocks produces Ca–HCO 3 and Na–Ca–HCO 3 waters, whereas prolonged interaction of meteoric waters with the same rocks generates Na–HCO 3 to Na–SO 4 waters. Waters circulating in Triassic carbonate-evaporite rocks have a Ca–SO 4 composition. Calcium-Na–SO 4 waters are also present. They can be produced through interaction of either Na–HCO 3 waters with anhydrite or Ca–SO 4 waters with a local gneissic rock, as suggested by reaction path modeling. An analogous simulation indicates that Na–HCO 3 waters are generated through interaction of Ca–HCO 3 waters with a local gneissic rock. The two main SO 4-sources present in the Alps are leaching of upper Triassic sulfate minerals and oxidative dissolution of sulfide minerals of crystalline rocks. Values of δ 34S SO 4 < ∼+9‰ are due to oxidative dissolution of sulfide minerals, whereas δ 34S SO 4 >∼+9‰ are controlled either by bacterial SO 4 reduction or leaching of upper Triassic sulfate minerals. Most waters have temperatures similar to the expected values for a geothermal gradient of 22°C/km and are close to thermal equilibrium with rocks. However relatively large, descending flows of cold waters and ascending flows of warm waters are present in both tunnels and determine substantial cooling and heating, respectively, of the interacting rocks. The most import upflow zone of warm, Na-rich waters is below Guspisbach, in the Gotthard Highway Tunnel, at 6.2–9.0 km from the southern portal. These warm waters have equilibrium temperatures of 65–75°C and therefore constitute an important low-enthalpy geothermal resource.

Geochemical and biological aspects of sulfide mineral dissolution: lessons from Iron Mountain, California

The oxidative dissolution of sulfide minerals leading to acid mine drainage (AMD) involves a complex interplay between microorganisms, solutions, and mineral surfaces. Consequently, models that link molecular level reactions and the microbial communities that mediate them to field scale processes are few. Here we provide a mini-review of laboratory and field-based studies concerning the chemical, microbial, and kinetic aspects of sulfide mineral dissolution and generation of AMD at the Richmond ore body at Iron Mountain, California.