Element discharge from pyritic mine tailings at limited oxygen availability in column experiments

Sulfide mineral oxidation in mine tailings deposits poses a long term threat to surrounding ground water and surface waters. Soil or water cover remediation aims at reducing the rate of sulfide mineral oxidation by decreasing the O₂ ingress rate. In this study, the authors addressed the rate of sulfide oxidation and pH buffering in ∼33 months long, well-controlled laboratory studies of water saturated columns of sulfidic mine tailings from the Kristineberg site in Sweden at reduced O₂ availability. The element discharge rates slowly declined towards a quasi-steady state over hundreds of days. Non-reactive tracer tests showed an anomalously large dispersion, indicating strong flow heterogeneity, possibly including preferential flow and/or stagnant water zones. Congruent dissolution of pyrite and sphalerite by injected oxidants (dissolved O₂ and Fe(III)) adequately explained the discharge rate of Fe, S and Zn at quasi-steady state. Arsenic, Pb and Cu were partly retained in the tailings. Base cation discharge rates, and thus pH buffering, were apparently controlled by the rate of acidity production, with actual pH levels, available mineral surface area, and water residence times being of less importance.     

Sulfide mineral oxidation in freshly processed tailings: batch experiments

This work focuses on sulfide mineral oxidation rates under oxic conditions in freshly processed pyrite-rich tailings from the ore concentrator in Boliden, northern Sweden. Freshly processed tailings are chemically treated in the plant to kill bacteria and to obtain increased metal yields, resulting in a high pH level of 10–12 in the process water. Different oxidation experiments (abiotic oxidation in untreated tailings, acid abiotic oxidation and acid microbial oxidation), containing the Boliden tailings, were performed at room temperature with dissolved oxygen (0.21 atm O₂) for 3 months. The different pyrite oxidation rates given from the study were 2.4×10⁻¹⁰ mol m⁻² s⁻¹ for the microbial, 5.9×10⁻¹¹ mol m⁻² s⁻¹ for the acidic abiotic and 3.6×10⁻¹¹ mol m⁻² s⁻¹ for the untreated experiments. Because of the potential precipitation of gypsum in the batch solutions, these oxidation rates are considered minimum values. The release rates for copper and zinc from chalcopyrite and sphalerite in the acid experiments were also investigated. These rates were normalized to the metal concentration in the tailings, and then compared to the release rate for iron from pyrite. These normalized results indicated that metal release decreased in the order Cu>Zn>Fe, demonstrating that pyrite is more resistant to oxidation than sphalerite and chalcopyrite. Pyrite was also more resistant to acidic dissolution than to microbial dissolution, while a significant fraction of sphalerite and chalcopyrite dissolved in the acid abiotic solutions.     

Mineralogical,geochemical, and microbial investigation of a sulfide-rich tailings deposit characterized by neutral drainage

Mineralogical, geochemical and microbial characterization of tailings solids from the Greens Creek Mine, Juneau, Alaska, was performed to evaluate mechanisms controlling aqueous geochemistry of near-neutral pH pore water and drainage. Core samples of the tailings were collected from five boreholes ranging from 7 to 26 m in depth. The majority of the 51 samples (77%) were collected from the vadose zone, which can extend >18 m below the tailings surface. Mineralogical investigation indicates that the occurrence of sulfide minerals follows the general order: pyrite [FeS₂] >> sphalerite [(Zn,Fe)S] > galena [PbS], tetrahedrite [(Fe,Zn,Cu,Ag)₁₂Sb₄S₁₃] > arsenopyrite [FeAsS] and chalcopyrite [CuFeS₂]. Pyrite constitutes <20 to >35 wt.% of the tailings mineral assemblage, whereas dolomite [CaMg(CO₃)₂] and calcite [CaCO₃] are present at ?30 and 3 wt.%, respectively. The solid-phase geochemistry generally reflects the mineral assemblage. The presence of additional trace elements, including Cd, Cr, Co, Mo, Ni, Se and Tl, is attributed to substitution into sulfide phases. Results of acid–base accounting (ABA) underestimated both acid-generating potential (AP) and neutralization potential (NP). Recalculation of AP and NP based on solid-phase geochemistry and quantitative mineralogy yielded more representative results. Neutrophilic S-oxidizing bacteria (nSOB) and SO₄-reducing bacteria (SRB) are present with populations up to 10⁷ and 10⁵ cells g⁻¹, respectively. Acidophilic S-oxidizing bacteria (aSOB) and iron-reducing bacteria (IRB) were generally less abundant. Primary influences on aqueous geochemistry are sulfide oxidation and carbonate dissolution at the tailings surface, gypsum precipitation–dissolution reactions, as well as Fe reduction below the zone of sulfide oxidation. Pore-water pH values generally ranged from 6.5 to 7.5 near the tailings surface, and from approximately 7–8 below the oxidation zone. Elevated concentrations of dissolved SO₄, S₂O₃, Fe, Zn, As, Sb and Tl persisted under these conditions.     

The effect of sulfide concentrate mineralogy and texture on Reactive Oxygen Species (ROS) generation

The generation of Reactive Oxygen Species (ROS), H₂O₂ and OH, has been observed from sulfide mineral containing particles in acidic solutions. The implications of this phenomenon, as a potential microbial stress-causing effect, have been studied previously with respect to thermophilic bioleaching performance in the presence of finely milled pyrite and chalcopyrite concentrates. In this study, the effect of sulfide mineralogy on ROS generation in the absence of microbes under physicochemical conditions typical for the bioleach environment was investigated. The mineralogical and elemental composition of eleven different samples containing sulfide mineral was obtained. These Au, Cu and other base metal-containing sulfide mineral concentrates as well as a milled whole ore of low Cu grade were tested for ROS generation. The whole ore sample and two refractory Au concentrates containing approximately 50% pyrite, generated significantly less ROS compared to the base metal-containing concentrates when compared on a constant surface area loading basis. Sulfide mineral-related variables were correlated with ROS generation. A significant difference was observed between FeS₂ and CuFeS₂ grades separately, whereas a combined measure of both minerals present in samples showed a consistently strong correlation to ROS generation. The Cu grade, total Cu-containing sulfides and the chalcopyrite content of Cu-containing samples correlated well with ROS generation. However, a common deterministic variable with a strong association to increased ROS generation was not found. A sub-set of samples were subjected to QEMSCAN® for textural analysis. Results suggested that a decrease in sulfide mineral liberation, caused by gangue silicate mineral occlusion to solution, resulted in decreased reactivity as shown in one of the Au-containing samples. Well-liberated chalcopyrite and pyrite phases corresponded to increased reactivity of samples. Pyrite, which was present in all of the reactive samples, was shown to be associated with other sulfide minerals, implicating its importance in galvanic interactions. Micro-analysis of chalcopyrite and pyrite phases from highly reactive samples showed an abundance of particles with extensive cracking and the possible presence of secondary transformation phases (szomolnokite). These results suggest that sulfide mineralogy, liberation and extent of physical processing affect sulfide mineral concentrate reactivity in acidic solutions.     

Kinetic tests comparison and interpretation for prediction of the Joutel tailings acid generation potential

Five sulfide mine tailings coming from the Joutel mine tailing ponds (Quebec, Canada) were tested by the humidity cell test (30 to 52 cycles duration) and the column test (11 to 12 cycles duration). The objectives of this study were twofold. First, there was the determination of the tailings acid generation potential for site reclamation. Second, there was the kinetic test comparison for understanding the tailings geochemical behavior under different test conditions. The samples used had a wide diversity in terms of acid-generation potential, particle size distribution, and parameters influencing reaction rates. Leachates produced remained at a near neutral pH for the duration of the tests. Evolution of the main elements involved in the dissolution processes demonstrated neutralization by carbonates as a response to the acid generated by sulfide oxidation. Depletion rates given by sulfates are higher for the humidity cell tests when compared to those obtained for the column tests. This is consistent with most studies to date, the humidity cell test being considered as more severe. However, by taking the ratio between cumulative elements coming from neutralization and the ones coming from oxidation, similar curves (named herein oxidation –neutralization curves) for all tests were obtained. These results show that overall geochemical behavior of the tailings is similar at near neutral pH for both types of tests. With this interpretation method, the acid-generation potential of the Joutel tailings were tested and compared to the static test results to constrain their uncertainty zone with regard to the studied tailings. The tailings geochemical behavior (carbonate dissolution response to sulfide oxidation) at near neutral pH condition appears slightly dependent of test conditions under certain hypothesis.     

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.     

Comparison of dissolution under oxic acid drainage conditions for eight sedimentary and hydrothermal pyrite samples

The abiotic oxidative dissolution behaviors of eight natural pyrite samples, five sedimentary and three hydrothermal, from various geological environments were compared under oxic conditions at pH 3 and 6 in a highly controlled batch reactor dissolution system. The three sedimentary pyrite samples associated with coal had greater specific surface areas and also exhibited greater apparent dissolution rates and extent than the other two sedimentary and three hydrothermal samples under both pH conditions. However, after normalizing for surface area, the dissolution rate constants for the different pyrite samples were similar; the greatest difference was between the two non-coal sedimentary pyrite samples. Pyrite morphology and the presence of trace metals could contribute to the differences in dissolution behavior as reflected in the normalized dissolution rates. The sulfur:iron ratio observed in the aqueous solution at pH 3 increased with time, but was always less than 2.0 (predicted from the stoichiometry of dissolution) for all the pyrite samples during the 24-h experimental duration. This can be explained by the disproportionation dissociation of thiosulfate, an initial product of pyrite dissolution, to elemental sulfur and sulfate which does not occur in a 1:1 ratio. The results of this work indicate the importance of extracting and using the specific pyrite(s) relevant to particular mining areas in order to understand pyrite dissolution rates and the influence of environmental conditions on those rates.     

Investigating dissolution of mechanically activated olivine for carbonation purposes

Mineral carbonation is one of several alternatives for CO₂ sequestration and storage. The reaction rates of appropriate minerals with CO₂, for instance olivine and serpentine with vast resources, are relatively slow in a CO₂ sequestration context and the rates have to be increased to make mineral carbonation a good storage alternative. Increasing the dissolution rate of olivine has been the focus of this paper. Olivine was milled with very high energy intensity using a laboratory planetary mill to investigate the effect of mechanical activation on the Mg extraction potential of olivine in 0.01 M HCl solution at room temperature and pressure. Approximately 30–40% of each sample was dissolved and water samples were taken at the end of each experiment. The pH change was used to calculate time series of the Mg concentrations, which also were compared to the final Mg concentrations in the water samples. Percentage dissolved and the specific reaction rates were estimated from the Mg concentration time series. The measured particle size distributions could not explain the rate constants found, but the specific surface area gave a good trend versus dissolution for samples milled wet and the samples milled with a small addition of water. The samples milled dry had the lowest measured specific surface areas (<4 m²/g), but had the highest rate constants. The crystallinity calculated from X-ray diffractograms, was the material parameter with the best fit for the observed differences in the rate constants. Geochemical modelling of mechanically activated materials indicated that factors describing the changes in the material properties related to the activation must be included. The mechanically activated samples in general reacted faster than predicted by the theoretical models. Mechanical activation as a pre-treatment method was found to enhance the initial specific reaction rates by approximately three orders of magnitude for a sample milled dry for 60 min in a planetary mono mill compared to an unactivated sample. Wet milling in the planetary mill did not produce samples with the same maximum reaction rate as dry milling, but wet milling in general might be easier to implement into a wet carbonation process. Mechanical activation in a planetary mill is likely to consume too much energy for CO₂ sequestration purposes, but the increase in obtained olivine rate constants illustrates a potential for using milling as a pre-treatment method.     

Arsenic speciation in pyrite and secondary weathering phases,Mother Lode Gold District,Tuolumne County,California

Arsenian pyrite, formed during Cretaceous gold mineralization, is the primary source of As along the Melones fault zone in the southern Mother Lode Gold District of California. Mine tailings and associated weathering products from partially submerged inactive gold mines at Don Pedro Reservoir, on the Tuolumne River, contain ∼20–1300 ppm As. The highest concentrations are in weathering crusts from the Clio mine and nearby outcrops which contain goethite or jarosite. As is concentrated up to 2150 ppm in the fine-grained (<63 μm) fraction of these Fe-rich weathering products.Individual pyrite grains in albite-chlorite schists of the Clio mine tailings contain an average of 1.2 wt.% As. Pyrite grains are coarsely zoned, with local As concentrations ranging from ∼0 to 5 wt.%. Electron microprobe, transmission electron microscope, and extended X-ray absorption fine-structure spectroscopy (EXAFS) analyses indicate that As substitutes for S in pyrite and is not present as inclusions of arsenopyrite or other As-bearing phases. Comparison with simulated EXAFS spectra demonstrates that As atoms are locally clustered in the pyrite lattice and that the unit cell of arsenian pyrite is expanded by ∼2.6% relative to pure pyrite. During weathering, clustered substitution of As into pyrite may be responsible for accelerating oxidation, hydrolysis, and dissolution of arsenian pyrite relative to pure pyrite in weathered tailings. Arsenic K-edge EXAFS analysis of the fine-grained Fe-rich weathering products are consistent with corner-sharing between As(V) tetrahedra and Fe(III)-octahedra. Determinations of nearest-neighbor distances and atomic identities, generated from least-squares fitting algorithms to spectral data, indicate that arsenate tetrahedra are sorbed on goethite mineral surfaces but substitute for SO₄ in jarosite. Erosional transport of As-bearing goethite and jarosite to Don Pedro Reservoir increases the potential for As mobility and bioavailability by desorption or dissolution. Both the substrate minerals and dissolved As species are expected to respond to seasonal changes in lake chemistry caused by thermal stratification and turnover within the monomictic Don Pedro Reservoir. Arsenic is predicted to be most bioavailable and toxic in the reservoir’s summer hypolimnion.     

Pyrite Oxidation in Leaching Process of Radionuclides and Heavy Metals from Uranium Mill Tailings

Pyrite is a sensitive mineral in the geological environment,and its oxidation produces an important geochemical and environmental effect on the control of the redox and pH conditions.Column experiment results were used for modeling the geochemical processes in uranium mill tailings under leac-hing conditions.Oxidation of pyrite dominates the control of the tailings leaching process.The experi-mental and modeling results show that the leachate chemistry changes substantially with the decrease in pyrite consumption.In the initial stage of the leaching experiment,the pyrite is consumed several hun-dred times grater than that in the later stages,for much more oxygen is present in the tailings in the ini-tial stage.As the experiment continues,the tailings is gradually saturated with water and the oxygen concentration greatly decreases and so does pyrite consumption.The experimental and modeling results are useful for the design of mill tailing decommissioning:oxidation process and transport of radioactive nuclides and heavy metals can be constrained by controlling the oxygen concentration of tailings and the infiltration of meteoric water.     

The dissolution kinetics of shallow marine carbonates in seawater: A laboratory study

The dissolution kinetics of shallow water marine carbonates (low-Mg calcite, aragonite and Mg-calcites) were investigated in seawater (S = 35) at 25°C and a P_CO2 of 10^?2.5 atm. using the pH-stat method. Carbonate dissoluton rates (μmoles g^?1 hr^?1) fit the empirical kinetic expression, R = k(1 - Ω)ⁿ, where R = dissolution rate, k = rate constant, Ω = saturation state, and n = order of reaction. Reaction orders were near 2.9 for low-Mg calcites, 2.5 for aragonites and 3.4 for Mg-calcites.The rate constant, k, expressed as μmoles g^?1 hr^?1, varied by nearly a factor of ten for the different samples, reflecting differences in amount of reactive surface area. Reactive surface area of the biogenic phases ranged from 0.3% to 66% of the total surface area determined by the BET gas adsorption method. The discrepancy between reactive and total surface area was greatest for samples with high BET surface areas (> 1 m² g^?1) and delicate microstructures.Relative dissolution rates of the various biogenic carbonates as a function of seawater calcium carbonate ion molal product (IMP) were related to both mineral stability and grain microstructure. In seawater undersaturated with respect to aragonite, finely crystalline aragonites dissolved more rapidly than thermodynamically less stable high Mg-calcites (15–18 mole% MgCO₃) with lower reactive surface areas. Therefore, under certain conditions, differences in grain microstructural complexity can override thermodynamic constraints and lead to selective dissolution of a thermodynamically more stable mineral phase.     

Hydrogeochemistry and microbiology of mine drainage: An update

The extraction of mineral resources requires access through underground workings, or open pit operations, or through drillholes for solution mining. Additionally, mineral processing can generate large quantities of waste, including mill tailings, waste rock and refinery wastes, heap leach pads, and slag. Thus, through mining and mineral processing activities, large surface areas of sulfide minerals can be exposed to oxygen, water, and microbes, resulting in accelerated oxidation of sulfide and other minerals and the potential for the generation of low-quality drainage. The oxidation of sulfide minerals in mine wastes is accelerated by microbial catalysis of the oxidation of aqueous ferrous iron and sulfide. These reactions, particularly when combined with evaporation, can lead to extremely acidic drainage and very high concentrations of dissolved constituents. Although acid mine drainage is the most prevalent and damaging environmental concern associated with mining activities, generation of saline, basic and neutral drainage containing elevated concentrations of dissolved metals, non-metals, and metalloids has recently been recognized as a potential environmental concern. Acid neutralization reactions through the dissolution of carbonate, hydroxide, and silicate minerals and formation of secondary aluminum and ferric hydroxide phases can moderate the effects of acid generation and enhance the formation of secondary hydrated iron and aluminum minerals which may lessen the concentration of dissolved metals. Numerical models provide powerful tools for assessing impacts of these reactions on water quality.     

安徽铜陵矿集区铜官山矿田胶状黄铁矿矿物学特征及其对成矿作用的制约

铜官山矿田是铜陵矿集区内五大矿田之一,矿田内顺层产出的层状硫化物矿体是铜金矿床的主矿体,矿体内含有较多的胶状黄铁矿,其成因的争议制约了对铜金矿床成矿作用的解析。本文主要利用场发射扫描电镜(FE-SEM)等纳米矿物学手段,并结合光学显微镜、粉晶X射线衍射(XRD)、微区激光拉曼光谱分析等方法,对矿田内铜官山矿床及天马山矿床内层状硫化物矿体中胶状黄铁矿矿石的矿物组成、微形貌、微结构等特征进行系统研究,结果表明胶状黄铁矿矿石多呈胶状、鲕状结构,具有同心环状构造,同心环被赤铁矿、菱铁矿与黄铜矿脉穿切。同心环主要由白铁矿+有机质与胶状黄铁矿交替组成。胶状黄铁矿的黄铁矿颗粒粒径从纳米至亚微米均有分布,以自形-半自形立方体为主,少数呈他形,脉体边部胶状黄铁矿颗粒较大,自形程度较高,重结晶显著。矿石中含有少量白云石、伊利石微晶体,与胶状黄铁矿紧密共存,显示典型沉积特征。共存石英磨圆度较高,存在次生加大现象,表面存在胶状黄铁矿印模,显示为碎屑成因。这些综合信息表明胶状黄铁矿非岩浆热液成因,而是与石炭系地层同沉积成岩成因,并可能有微生物作用参与。高孔隙率、高化学活性及较高有机质含量的胶状黄铁矿可能为燕山期岩浆热液演化的含铜成矿流体提供了沉淀剂,对矿田内铜金硫化物矿体的层控性发挥了重要的控制作用。     

Characterisation of the Sarcheshmeh copper mine tailings,Kerman province,southeast of Iran

Mineral processing operation at the Sarcheshmeh porphyry copper mine has produced huge quantities of tailings materials containing sulphide minerals in particular pyrite. These tailings materials were geochemically and mineralogically characterised to assess pyrite and chalcopyrite oxidation, acid mine drainage generation, and trace element mobility to lead development of a proper remediation plan. Five vertical trenches up to 4.2 m deep were excavated from the tailings surface, and 70 solid samples were taken in 0.3 m intervals. The samples were first mineralogically analysed. Pyrite was the main sulphide mineral found in the tailings. The gangue minerals include quartz ± muscovite–illite ± chlorite ± albite ± orthoclase ± halite. The samples were geochemically analysed for total concentrations of 62 elements, paste pH, SO₄ ^2?, CO₃ ^2?, and HCO₃ ^?. The maximum concentrations of SO₄ ^2? (1,300, 1,170, 1,852, 1,960 and 837 mg/L) were observed at a depth of 0.9 m in profiles A, B, C, D and E, respectively. The tailings have a high acid-producing potential and low acid-neutralising potential (pyrite 4–6 wt %, calcite 1 wt %). Fe₂(SO₄)₃, CuSO₄, MgSO₄ and MnSO₄ were the dominant secondary sulphate minerals in the tailings. The lowest pH values (2.9, 3 and 3) were measured at a depth of 0.3 m in the profiles A, B and C, 3.9 at a depth of 0.6 m in the profile D and 3 at a depth of 0.9 m in the profile E. The upper portions of the profiles C (1.8 m) and D (2.1 m) were moderately oxidised, while oxidation in the profiles A, B and E did not extend more than 1.2, 1.2 and 1.5 m beneath the tailings surface. Zn, Pb, Rb, U, Hf, Nd, Zr and Ga show almost a constant trend with depth. Cd, Sr, Th, La and Ce increased with increasing depth of the tailings materials while, Co, V, Ti, Cr, Cu, As, Mn, Ag, Mo and Ni exhibit initially a decreasing trend from tailings surface to the depths that vary between 0.9 and 1.2. They then remained constant with the depth. The results show pyrite and chalcopyrite oxidation at surface layers of the tailings and subsequent leaching of the oxidation products and trace elements by infiltrated atmospheric precipitation.     

骨炭钝化含黄铁矿多重金属尾矿的研究

钝化处理被广泛应用于含重金属尾矿的处理,可以从源头上防止酸矿废水(AMD)的产生,寻找一种价廉易得且对环境危害小的钝化剂十分必要。本文主要研究在骨炭作用下,用pH值为4的双氧水对黄铁矿进行氧化,探讨骨炭对黄铁矿氧化释放重金属的钝化作用。实验结果表明,添加不同含量的骨炭(分别为0.5、2.5和5 g)能将溶液的pH值分别提高到8.93、10.01和10.42,表明骨炭具有较强的中和能力,同时黄铁矿氧化释放的Pb、Zn和Cd等重金属离子浓度明显地降低。但当骨炭含量超过2.5 g时,对As有促进释放的趋势。红外光谱分析显示钝化后黄铁矿样品位于420、563、603、1 044、1 091 cm~(-1)处的特征峰主要来自PO_4~(3-)的振动,XRD进一步揭示了黄铁矿表面主要含磷次生矿物是磷铁矿和羟磷铁铅石,这些次生矿物对重金属钝化起着重要作用。因此,骨炭有望作为钝化含多重金属尾矿的钝化剂。     

An experimental study of the mechanism of the replacement of magnetite by pyrite up to 300 °C

We present the results of an experimental study into the sulfidation of magnetite to form pyrite/marcasite under hydrothermal conditions (90-300 °C, vapor saturated pressures), a process associated with gold deposition in a number of ore deposits. The formation of pyrite/marcasite was studied as a function of reaction time, temperature, pH, sulfide concentration, solid-weight-to-fluid-volume ratio, and geometric surface area of magnetite in polytetrafluoroethylene-lined autoclaves (PTFE) and a titanium and stainless steel flow-through cell. Marcasite was formed only at pH_21°C <4 and was the dominant Fe disulfide at pH_21°C 1.11, while pyrite predominated at pH_21°C >2 and formed even under basic conditions (up to pH_21°C 12-13). Marcasite formation was favored at higher temperatures. Fine-grained pyrrhotite formed in the initial stage of the reaction together with pyrite in some experiments with large surface area of magnetite (grain size <125 μm). This pyrrhotite eventually gave way to pyrite. The transformation rate of magnetite to Fe disulfide increased with decreasing pH (at 120 °C; pH_120°C 0.96-4.42), and that rate of the transformation increased from 120 to 190 °C.Scanning electron microscope (SEM) imaging revealed that micro-pores (0.1-5 μm scale) existed at the reaction front between the parent magnetite and the product pyrite, and that the pyrite and/or marcasite were euhedral at pH_21°C <4 and anhedral at higher pH. The newly formed pyrite was micro-porous (0.1-5 μm); this micro-porosity facilitates fluid transport to the reaction interface between magnetite and pyrite, thus promoting the replacement reaction. The pyrite precipitated onto the parent magnetite was polycrystalline and did not preserve the crystallographic orientation of the magnetite. The pyrite precipitation was also observed on the PTFE liner, which is consistent with pyrite crystallizing from solution. The mechanism of the reaction is that of a dissolution-reprecipitation reaction with the precipitation of pyrite being the rate-limiting step relative to magnetite dissolution under mildly acidic conditions (e.g., pH_155°C 4.42).The experimental results are in good agreement with sulfide phase assemblage and textures reported from sulfidized Banded Iron Formations: pyrite, marcasite and pyrrhotite have been found to exist or co-exist in different sulfidized Banded Iron Formations, and the microtextures show no evidence of sub-μm-scale pseudomorphism of magnetite by pyrite.     

Arsenic and iron speciation in uranium mine tailings using X-ray absorption spectroscopy

In northern Saskatchewan, Canada, high-grade U ores and the resulting tailings can contain high levels of As. An environmental concern in the U mining industry is the long-term stability of As within tailings management facilities (TMFs) and its potential transfer to the surrounding groundwater. To mitigate this problem, U mill effluents are neutralized with lime to reduce the aqueous concentration of As. This results in the formation of predominantly Fe³⁺–As⁵⁺ secondary mineral phases, which act as solubility controls on the As in the tailings discharged to the TMF. Because the speciation of As in natural systems is critical for determining its long-term environmental fate, characterization of As-bearing mineral phases and complexes within the deposited tailings is required to evaluate its potential transformation, solubility, and long-term stability within the tailings mass. In this study, synchrotron-based bulk X-ray absorption spectroscopy (XAS) was used to study the speciation of As and Fe in mine tailings samples obtained from the Deilmann TMF at Key Lake, Saskatchewan. Comparisons of K-edge X-ray absorption spectra of tailings samples and reference compounds indicate the dominant oxidation states of As and Fe in the mine tailings samples are +5 and +3, respectively, largely reflecting their generation in a highly oxic mill process, deposition in an oxidized environment, and complexation within stable oxic phases. Linear combination fit analyses of the K-edges for the Fe X-ray absorption near edge spectra (XANES) to reference compounds suggest Fe is predominantly present as ferrihydrite with some amount of the primary minerals pyrite (8–15% in some samples) and chalcopyrite (5–15% in some samples). Extended X-ray absorption fine structure (EXAFS) analysis of As K-edge spectra indicates that As⁵⁺ (arsenate) present in tailings samples is adsorbed to the ferrihydrite though an inner-sphere bidentate linkage.     

Spatial variations and controls of acid mine drainage generation

Spatial variations of historical and ongoing pyrite oxidation rates were quantified near the Nanisivik Mine on Baffin Island in northern Canada. The variations observed depend mainly on the degree of water saturation, pH and temporal trends in mineral reactivity. Maximum oxidation rates were observed in an untreated tailings spill, while minimum oxidation rates were noted for tailings deposited under water. Spatial trends in oxidation rates were in the order of three orders of magnitude. Spatial trends were only possible to quantify by a combination of closed chambers (well-drained conditions) and micro sensors (water-covered conditions). Oxygen uptake rates in tailings at various ages (up to 7 years) indicate a decrease by more than a factor of 3 over time. Total oxygen uptake over 7 years was calculated and found to be in a fair agreement with the overall pyrite depletion evaluated as high-resolution mineral mass balance (by quantitative powder X-ray diffraction).     

Characterisation of sphalerite and pyrite flotation samples by XPS and ToF-SIMS

The surface analytical techniques of X-ray Photoelectron Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectroscopy (ToF-SIMS) have provided information on the type and concentration of species on the surface of sphalerite and pyrite particles in flotation concentrate and tail samples, but also on their distribution on each particle and across particles of different sizes. From this surface analytical study, a more accurate interpretation of the flotation results of sphalerite and pyrite minerals in a mixed mineral system could be made as a function of the concentrations of copper sulphate activator and xanthate collector, and particle size. In particular, it was found that sphalerite particles reporting to the concentrate are larger in size and contain less iron hydroxide on their surface than particles reporting to the tail. As for the pyrite particles, their lower recovery than the sphalerite particles is the result of a larger proportion of iron hydroxide on their surface inhibiting copper and collector adsorption.     

Comparison of laboratory testing protocols to field observations of the weathering of sulfide-bearing mine tailings

A laboratory weathering study using a humidity cell procedure was conducted on two sulfide-bearing tailing samples from a metallurgical site in Ontario (Canada). The test was accompanied by microbiological studies to enumerate the major groups of sulfur-oxidizing bacteria and determine their potential role at different stages during the oxidation process. To evaluate the utility of this method, results were compared with those of previous laboratory and field studies on the same materials. The mineralogy of the laboratory samples differs only by the addition of a small amount of hydronium-bearing natrojarosite [(Na,H₃O)Fe₃(SO₄)₂(OH)₆] to one sample. The progress of sulfide oxidation and the rates of solute release were determined to evaluate the extent of mineral dissolution. These processes were influenced strongly by the capacity of the material to generate acidity, which was enhanced by the presence of hydronium-bearing natrojarosite. Acid-neutralization processes occurring during the laboratory tests were affected by reaction kinetics, consistent with field observations. In particular, the extent of carbonate-mineral dissolution appears to be different in the laboratory than in the field, where more prolonged rock–water interaction allowed more complete chemical equilibration. As a consequence, the capacity of this test procedure to predict weathering reactions in mine tailings is limited by its inability to reproduce the weathering sequence observed in the field. The results of the microbiological study showed that distinct groups of sulfur-oxidizing bacteria operate at different stages of the oxidative process, as was observed in field studies where tailings oxidation occurred under natural conditions, suggesting that microbiological tests performed for laboratory studies are reflective of field conditions.