Mine drainage from the weathering of sulfide minerals and magnetite

Pyrite and pyrrhotite are the principal minerals that generate acid drainage in mine wastes. Low-pH conditions derived from Fe-sulfide oxidation result in the mobilization of contaminant metals (such as Zn, Cd, Ni and Cr) and metalloids (such as As) which are of environmental concern. This paper uses data from detailed mineralogical and geochemical studies conducted at two Canadian tailings impoundments to examine the mineralogical changes that pyrite, pyrrhotite, sphalerite and magnetite undergo during and after sulfide oxidation, and the subsequent release and attenuation of associated trace elements. The stability of sphalerite in tailings impoundments generally is greater than that of pyrrhotite, but less than pyrite. Dissolved Ni and Co derived from Fe sulfides, and to a lesser extent, dissolved Zn and Cd from sphalerite, are commonly attenuated by early-formed Fe oxyhydroxides. As oxidation progresses, a recycling occurs due to continued leaching from low-pH pore waters and because the crystallinity of Fe oxyhydroxides gradually increases which decreases their sorptive capacity. Unlike many other elements, such as Cu, Pb and Cr, which form secondary minerals or remain incorporated into mature Fe oxyhydroxides, Zn and Ni become mobile. Magnetite, which is a potential source of Cr, is relatively stable except under extremely low-pH conditions. A conceptual model for the sequence of events that typically occurs in an oxidizing tailings impoundment is developed outlining the progressive oxidation of a unit of mine waste containing a mixed assemblage of pyrrhotite and pyrite.     

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.     

Modelling natural attenuation of heavy-metal groundwater contamination in the Selebi-Phikwe mining area,Botswana

Seepage from a tailings dam is the major source of groundwater pollution in the Selebi-Phikwe area, where mining of sulphidic nickel–copper–cobalt ore started in 1973 and will continue until 2014. The seepage water has a pH in the range of 1.7–2.8 and is strongly enriched in SO₄ ²⁻ (5,680 g/L) and heavy metals (6,230 μg/L Ni, 1,860 μg/L Cu and 410 μg/L Co). The fracture aquifer affected by pollution from the dam exhibits a remarkable capacity of heavy-metal sorption. Most of the Ni, Cu and Co is scavenged at less than 500 m distance downgradient from the polluting source, whereas SO₄ ²⁻ is not immobilized significantly. The heavy-metal sorption process is assumed to be due to surface complexation, which is supported by a relatively high groundwater pH (in the range of 6.2–7.8 at >200 m distance from the tailings dam). The objective of this study is to demonstrate that the sorption process can be incorporated into a realistic three-dimensional reactive-transport groundwater model that is implicitly charge-balanced. The simulations are performed with the PHAST1.2 program, which is based on the HST3D flow and transport code and the hydrochemical PHREEQC2.12 code.     

Mineralogical and geochemical characterization of the Old Tailings Dam,Australia: Evaluating the effectiveness of a water cover for long-term AMD control

Establishing a shallow water cover over tailings deposited in a designated storage facility is one option to limit oxygen diffusion and retard oxidation of sulfides which have the potential to form acid mine drainage (AMD). The Old Tailings Dam (OTD) located at the Savage River mine, western Tasmania contains 38 million tonnes of pyritic tailings deposited from 1967 to 1982, and is actively generating AMD. The OTD was constructed on a natural gradient, resulting in sub-aerial exposure of the southern area, with the northern area under a natural water cover. This physical contrast allowed for the examination of tailings mineralogy and geochemistry as a function of water cover depth across the OTD. Tailings samples (n = 144, depth: ≤ 1.5 m) were collected and subjected to a range of geochemical and mineralogical evaluations. Tailings from the southern and northern extents of the OTD showed similar AMD potential based on geochemical (NAG pH range: 2.1 to 4.2) and bulk mineralogical parameters, particularly at depth. However, sulfide alteration index (SAI) assessments highlighted the microscale contrast in oxidation. In the sub-aerial zone pyrite grains are moderately oxidized to a depth of 0.3 m (maximum SAI of 6/10), under both gravel fill and oxidized covers, with secondary minerals (e.g., ferrihydrite and goethite) developed along rims and fractures. Beneath this, mildly oxidized pyrite is seen in fresh tailings (SAI = 2.9/10 to 5.8/10). In the sub-aqueous zone, the degree of pyrite oxidation demonstrates a direct relationship with cover depth, with unoxidized, potentially reactive tailings identified from 2.5 m, directly beneath an organic-rich sediment layer (SAI = 0 to 1/10). These findings are broadly similar to other tailings storage facilities e.g., Fox Lake, Sherritt-Gordon ZnCu mine, Canada and Stekenjokk mine, Sweden where water covers up to 2 m have successfully reduced AMD. Whilst geotechnical properties of the OTD restrict the extension of the water cover, pyrite is enriched in cobalt (up to 2.6 wt%) indicating reprocessing of tailings as an alternative management option. Through adoption of an integrated mineralogical and geochemical characterization approach for tailings assessment robust management strategies after mine closure can be developed.     

Mineralogical and geochemical alteration of Hitura sulphide mine tailings with emphasis on nickel mobility and retention

Weathering of Hitura (W Finland) nickel sulphide mine tailings and release of heavy metals into pore water was studied with mineralogical (optical and electron microscopy, X-ray diffraction) and geochemical methods (selective extractions). Tailings were composed largely of serpentine, micas and amphiboles with only minor carbonates and sulphides. Sulphides, especially pyrrhotite, have oxidized intensively in the shallow tailings in 10–15 years, but a majority of the tailings have remained unchanged. Oxidation has resulted in depletion of carbonates, slightly decreased pH, and heavy metal (Ni, Zn) release in pore water as well as in the precipitation of secondary Fe precipitates. Nevertheless, in the middle of the tailings area, where the oxidation front moves primarily downward, released heavy metals have been adsorbed and immobilized with these precipitates deeper in the oxidation zone. In contrast to what was seen in pore water pH, but in accordance with static tests of the previous studies, the neutralisation potential ratio (NPR) calculated based on the mineralogical composition and the total sulphur content suggested that tailings are ‘not potentially acid mine drainage (AMD) generating’. However, the calculated buffering capacity of the tailings resulted largely from the abundant serpentine because of the low carbonate content. Despite its slow weathering rate, serpentine may buffer the acidity to some extent through ion exchange processes in fine ground tailings. Nevertheless, in practice, acid production capacity of the tailings depends primarily on the balance between Ca–Mg carbonates and iron sulphides. NPR calculation based on carbonate and sulphur contents suggested, that the Hitura tailings are ‘likely AMD generating’. The study shows that sulphide oxidation can be significant in mobilisation of heavy metals even in apparently non-acid producing, low sulphide tailings. Therefore, prevention of oxygen diffusion into tailings is also essential in this type of sulphide tailings.     

Reactive transport modelling of mine tailings columns with capillarity-induced high water saturation for preventing sulfide oxidation

A series of laboratory column tests on reactive mine tailings was numerically simulated to study the effect of high water saturation on preventing sulfide mineral oxidation and acid mine drainage (AMD). The approach, also known as an elevated water table (EWT), is a promising alternative to full water covers for the management and closure of sulfidic tailings impoundments and for the long term control of acid mine drainage. The instrumented columns contained reactive tailings from the Louvicourt mine, Quebec, and were overlain by a protective sand cover. Over a 13–19 month period, the columns were exposed to atmospheric O₂ and flushed approximately every month with demineralized water. A free draining control column with no sand cover was also used. During each cycle, water table elevations were controlled by fixing the pressure at the column base and drainage water was collected and analyzed for pH and Eh, major ions, and dissolved metals (Fe, Zn, Cu, Pb, and Mg). The columns were simulated using the multi-component reactive transport model MIN3P which solves the coupled nonlinear equations for transient water flow, O₂ diffusion, advective–dispersive transport and kinetic geochemical reactions. Physical properties and mineralogical compositions for the material layers were obtained from independent laboratory data. The simulated and observed data showed that as the water table elevation increased, the effluent pH became more neutral and SO₄ and dissolved metal concentrations decreased by factors on the order of 10²–10³. It is concluded that water table depths less than or equal to one-half of the air entry value (AEV) can keep mine tailings sufficiently saturated over the long term, thus reducing sulfide oxidation and AMD production.     

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.     

Release,transport and attenuation of metals from an old tailings impoundment

The oxidation of sulfide minerals from mine wastes results in the release of oxidation products to groundwater and surface water. The abandoned high-sulfide Camp tailings impoundment at Sherridon, Manitoba, wherein the tailings have undergone oxidation for more than 70 a, was investigated by hydrogeological, geochemical, and mineralogical techniques. Mineralogical analysis indicates that the unoxidized tailings contain nearly equal proportions of pyrite and pyrrhotite, which make up to 60 wt% of the total tailings, and which are accompanied by minor amounts of chalcopyrite and sphalerite, and minute amounts of galena and arsenopyrite. Extensive oxidation in the upper 50 cm of the tailings has resulted in extremely high concentrations of dissolved SO₄ and metals and As in the tailings pore water (pH < 1, 129,000 mg L⁻¹ Fe, 280,000 mg L⁻¹ SO₄, 55,000 mg L⁻¹ Zn, 7200 mg L⁻¹ Al, 1600 mg L⁻¹ Cu, 260 mg L⁻¹ Mn, 110 mg L⁻¹ Co, 97 mg L⁻¹ Cd, 40 mg L⁻¹ As, 15 mg L⁻¹ Ni, 8 mg L⁻¹ Pb, and 3 mg L⁻¹ Cr). The acid released from sulfide oxidation has been extensive enough to deplete carbonate minerals to 6 m depth and to partly deplete Al-silicate minerals to a 1 m depth. Below 1 m, sulfide oxidation has resulted in the formation of a continuous hardpan layer that is >1 m thick. Geochemical modeling and mineralogical analysis indicate that the hardpan layer consists of secondary melanterite, rozenite, gypsum, jarosite, and goethite. The minerals indicated mainly control the dissolved concentrations of SO₄, Fe, Ca and K. The highest concentrations of dissolved metals are observed directly above and within the massive hardpan layer. Near the water table at a depth of 4 m, most metals and SO₄ sharply decline in concentration. Although dissolved concentrations of metals and SO₄ decrease below the water table, these concentrations remain elevated throughout the tailings, with up to 60,600 mg L⁻¹ Fe and 91,600 mg L⁻¹ SO₄ observed in the deeper groundwater. During precipitation events, surface seeps develop along the flanks of the impoundment and discharge pore water with a geochemical composition that is similar to the composition of water directly above the hardpan. These results suggest that shallow lateral flow of water from a transient perched water table is resulting in higher contaminant loadings than would be predicted if it were assumed that discharge is derived solely from the deeper primary water table. The abundance of residual sulfide minerals, the depletion of aluminosilicate minerals in the upper meter of the tailings and the presence of a significant mass of residual sulfide minerals in this zone after 70 a of oxidation suggest that sulfide oxidation will continue to release acid, metals, and SO₄ to the environment for decades to centuries.     

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.     

Geological analogue for circumneutral pH mine tailings: implications for long-term storage,Macraes Mine,Otago, New Zealand

Tailings from the Macraes Au mine cyanidation process are stored in an impoundment about 0.6 km² and 80 m deep whose pH is maintained near 8 by the neutralizing capacity of the gangue minerals. The tailings are sandy (>50 μm particles), have a hydraulic conductivity of about 10⁻² m/day, and contain 0.1–1.0 wt.% S and 0.1–1.5 wt.% graphitic C from the primary deposit. Concentrations of As in the pore water of the mixed tailings, which are a combination of various tailings types, range from 0.1 to 20 ppm, HCO₃^- is 100 to 200 ppm, and dissolved SO₄ is 100–1700 ppm. The mixed tailings will be stored in this impoundment in perpetuity after mining ceases. Confidence in the long-term pH stability of these tailings can be gained from examination of mineralogically and chemically similar geological analogues in the immediate vicinity. A sequence, typically about 5 m thick, of sands and gravels derived from the Macraes mineralized zone 12–28 ka ago contains rounded detrital sulfide mineral grains which are unoxidized despite their close proximity to the surface and the occasional incursion of oxygenated waters. These sediments have a hydraulic conductivity of about 10⁻⁴ m/day. Saturating water pH is currently 7–8. Sands with 0.2–0.8 wt.% organic C host SO₄-reducing bacteria (SRB), and local cementation by authigenic framboidal pyrite has occurred. SRB were found in water-saturated sediments with decreased hydraulic conductivity and alkaline and anoxic conditions. These bacteria are involved in the formation of authigenic framboidal pyrite, reducing the cycling of dissolved Fe in the sediments. Carbon is not a limiting factor in this process as organic matter is present in the sandstone and ground water contains up to 180 ppm HCO₃^-. Comparison of the 28 ka old sediments with the modern tailings suggests that the chemical behaviour of the two will be similar, possibly with the crystallization of authigenic pyrite in the tailings over the long term. As long as the present slightly anoxic and circumneutral pH environmental conditions are maintained in the mixed tailings impoundment, sulfide decomposition and acidification are unlikely.     

Estimation of groundwater recharge using the soil moisture budget method and the base-flow model

A detailed characterization of the site is crucial to designing an efficient method of managing the risks associated with tailings from abandoned mines. Therefore, samples collected from various depths within tailings in Guryong mine, Korea, were analyzed for their chemical, physical and mineralogical characteristics. All samples of the Guryong tailings had acid-generating potential. However, in the oxidation zone, the net acid generation (NAG) was low (30 kg H₂SO₄ t⁻¹) although the acid neutralization potential (ANP) was less than zero. The ANP values in the unoxidation zone were higher (> −56.0 kg CaCO₃ t⁻¹) than in the other zones. As a result, the amount of alkali ions that are needed to neutralize the acid needs to be considered. In this experiment G3, G4 and G6 drill cores containing fine tailings particles near the unoxidation zone were observed to contain calcite (CaCO₃) with acid-neutralizing capacity. A low pH (2−4) in the oxidation zone of the tailings changed to a neutral pH in the unoxidation zone of the tailings. These results suggest that the acid-neutralizing capacity of the tailings was controlled by particle and mineral composition of tailings.     

Surface oxidation of pyrite under ambient atmospheric and aqueous (pH = 2 to 10) conditions: electronic structure and mineralogy from X-ray absorption spectroscopy

The nature of the surface oxidation phase on pyrite, FeS₂, reacted in aqueous electrolytes at pH = 2 to 10 and with air under ambient atmospheric conditions was studied using synchrotron-based oxygen K edge, sulfur L_III edge, and iron L_II,III edge X-ray absorption spectroscopy. We demonstrate that O K edge X-ray absorption spectra provide a sensitive probe of sulfide surface oxidation that is complementary to X-ray photoelectron spectroscopy. Using total electron yield detection, the top 20 to 50 Å of the pyrite surface is characterized. In air, pyrite oxidizes to form predominantly ferric sulfate. In aqueous air-saturated solutions, the surface oxidation products of pyrite vary with pH, with a marked transition occurring around pH 4. Below pH = 4, a ferric (hydroxy)sulfate is the main oxidation product on the pyrite surface. At higher pH, we find iron(III) oxyhydroxide in addition to ferric (hydroxy)sulfate on the surface. Under the most alkaline conditions, the O K edge spectrum closely resembles that of goethite, FeOOH, and the surface is oxidized to the extent that no FeS₂ can be detected in the X-ray absorption spectra. In a 1.667 × 10⁻³ mol/L Fe³⁺ solution with ferric iron present as FeCl₃ in NaCl, the oxidation of pyrite is autocatalyzed, and formation of the surface iron(III) oxyhydroxide phase is promoted at low pH.     

Supergene mineralization in mining residues of the Matchless cupreous pyrite deposit (Namibia)—a clue to the origin of modern and fossil duricrusts in semiarid climates

Mineralogical, geochemical, sedimentological and microbiological investigations of the evolution of supergene mineralization of mining residues at Matchless chalcopyrite–pyrite deposit (Namibia) have delineated what may be called “the minero-stratigraphy of tailings”. The encrustations of the supergene or secondary mineralization have originated from alteration of sulfides and carbonates of the primary mineralization and from chemical agents (e.g. lime, phosphate) added during processing of ore. The variation in tailings discharge and the early diagenetic alteration led to a pronounced bedding and the development of distinct layers within the tailings impoundment: (1) gypsum–carbonate (e.g. huntite), (2) gypsum–sulfate (e.g. melanterite), (3) gypsum–phosphate (e.g. brushite), (4) gypsum–chloride (e.g. halite), (5) sulfate–gypsum efflorescence (e.g. copiapite).Deposition and early diagenesis of tailings may be described as follows: During deposition of tailings, oxidation began because of relocations of the discharge point. Phyllosilicate-rich layers form local aquatards and minimize solution homogenization in the succeeding cycles of deposition. The whole impoundment is a series of paleo-oxidation zones on which the current oxidation in the vadose zone is being superimposed. Low-pH zones, even though some are now in the saturated part of the impoundment, owe their low pH to low dolomite content, reflecting variations in the input of primary minerals. Excess pyrite and Fe hydrolysis is still generating acidity and the formation of a typical “gossan-type” profile is in progress. The modern hardpans in the tailings may, during late diagenesis, eventually evolve to duricrusts analogous to those duricrusts that have largely been studied in geological series prevalently of Cenozoic age.     

Oxide and sulphide minerals in highly oxidized, Rb-depleted, Archaean granulites of the Shevaroy Hills Massif, South India: Oxidation states and the role of metamorphic fluids

The Shevaroy Hills of northern Tamil Nadu, southern India, expose the highest-grade granulites of a prograde amphibolite facies to granulite facies deep-crustal section of Late Archaean age. These highly oxidized quartzofeldspathic garnet charnockites generally show minor high-TiO₂ biotite and amphibole as the only hydrous minerals and are greatly depleted in the incompatible elements Rb and Th. Peak metamorphic temperatures (garnet–orthopyroxene) and pressures (garnet–orthopyroxene–plagioclase–quartz) are near 750 °C and 8 kbar, respectively. Pervasive veinlets of K-feldspar exist throughout dominant plagioclase in each sample and show clean contact with orthopyroxene. They are suggested to have been produced by a low H₂O activity, migrating fluid phase under granulite facies conditions, most likely a concentrated chloride/carbonate brine with high alkali mobility accompanied by an immiscible CO₂-rich fluid. Silicate, oxide and sulphide mineral assemblages record high oxygen fugacity. Pyroxenes in the felsic rocks have high Mg/(Mg+Fe) (0.5–0.7). The major oxide mineral is ilmenite with up to 60 mole per cent exsolved hematite. Utilizing three independent oxygen barometers (ferrosilite–magnetite–quartz, ferrosilite–hematite–quartz and magnetite–hematite) in conjunction with garnet–orthopyroxene exchange temperatures, samples with XIlmHm>0.1 yield a consistent oxygen fugacity about two log units above fayalite stability. Less oxidized samples (XIlmHm<0.1) show some scatter with indications of having equilibrated under more reducing conditions. Temperature-f (O₂ ) arrays result in self consistent conditions ranging from 660 °C and 10^?16 bar to 820 °C and 10^?11.5 bar. These trends are confirmed by calculations based on the assemblage clinopyroxene–orthopyroxene–magnetite–ilmenite using the QUIlF program. In the most oxidized granulite samples (XIlmHm>0.4) pyrite is the dominant sulphide and pyrrhotite is absent. Pyrite grains in these samples have marginal alteration to magnetite along the rims, signifying a high-temperature oxidation event. Moderately oxidized samples (0.1no coexisting magnetite. Chalcopyrite is a common accessory mineral of pyrite and pyrrhotite in all the samples. Textures in some samples suggest that it formed as an exsolution product from pyrrhotite. Extensive vein networks of magnetite and pyrite, associated principally with the pyroxene and amphibole, give evidence for a pervasive, highly oxidizing fluid phase. Thermodynamic analysis of the assemblage pyrrhotite, pyrite and magnetite yields consistent high oxidation states at 700–800 °C and 8 kbar. The oxygen fugacity in our most oxidized pyrrhotite-bearing sample is 10^?12.65 bar at 770 °C. There are strong indications that the Shevaroy Hills granulites recrystallized in the presence of an alkali-rich, low H₂O-activity fluid, probably a concentrated brine. It cannot be demonstrated at present whether the high oxidation states were set by initially oxidized protoliths or effected by the postulated fluids. The high correspondence of maximally Rb-depleted samples with the highest recorded oxidation states suggests that the Rb depletion event coincided with the oxidation event, probably during breakdown of biotite to orthopyroxene+K-feldspar. We speculate that these alterations were effected by exhalations from deep-seated alkali basalts, which provided both heat and high oxygen fugacity, low a_H2O fluids. It will be of interest to determine whether greatly Rb-depleted granulites in other Precambrian terranes show similar highly-oxidizing signatures.     

Kinetics of pyrite to pyrrhotite reduction by hydrogen in calcite buffered solutions between 90 and 180 °C: Implications for nuclear waste disposal

The kinetics of abiotic redox reactions induced by hydrogen are poorly documented although it represents a growing area of interest in terms of both nuclear waste storage assessment and the comprehensive study of hydrogen-rich fluid in mid-ocean ridge hydrothermal systems. We present an experimental kinetics study of pyrite reduction into pyrrhotite under significant H₂ pressure and mid-hydrothermal conditions. We describe the mechanism and kinetic behavior of this reaction by combining textural and solution analyses under various conditions of temperature, pyrite particles size, H₂ pressure and pH. When pH is controlled by calcite, the reaction presents all the characteristics of a coupled dissolution-precipitation mechanism occurring at the pyrite-pyrrhotite interface. By considering the chemical affinity of the coupled reaction as a function of reaction extent, we demonstrate that the spatial coupling is induced both by pyrite as a substrate for pyrrhotite nucleation and by the role of fluid chemistry at the reaction front. Far from equilibrium with respect to pyrite, the kinetics of sulfide production associated with the reaction are linearly related to the square root of time with an activation energy of 53 kJ/mol. This value is higher than what is expected for a diffusion-controlled kinetic regime. We suggest that the reaction rate is controlled both by pyrite reductive dissolution and by sulfide diffusion through the porous pyrrhotite microstructure. We provide a simple sulfide production-rate expression on the basis of our measured rate constants that can be used in geochemical modeling to further evaluate the impact of hydrogen on pyrite under nuclear waste disposal conditions.     

Le système hydrothermal actuel de Los Humeros (Mexique): Etat du système SO −− 4 —SH2 à 300°C,origine du soufre et phénomènes d'oxydation associés à l'ébullition du fluide ascendant

In the geothermal system of Los Humeros, hydrothermal fluids are low in sulfur (7.7 mM/kg) and are slightly alkaline (pH of ca. 8.5) at depth. Nevertheless, the aqueous sulfate-sulfide species are in isotopic and chemical equilibrium. The “freezing” of these equilibria at 290 °C is tentatively related to boiling of water at this temperature. In the LH1 borehole δ³⁴S values for pyrite (ca. 0‰) and present aqueous SH₂ (ca. ?12‰) are very different. Measured δ³⁴S value of the bulk aqueous sulfur is close to ?11‰ These data suggest a possible magmatic origin of pyrite (ca. 0‰) and, in contrast, a sedimentary source for the present hydrothermal sulfur. The CO₂/CH₄ molar ratio of 58 determined in the fluid from this well is much lower than the ratio calculated for 300° and 350 °C. This divergence is eliminated when the equilibrium constant is reestimated (log K_G=?7.9 at 300 °C). Based on fluid inclusion study the boiling of hydrothermal fluid before the geothermal area was opened by drilling is proven in neoformed minerals sampled at different levels of the volcanic sequence. In this way, the pervasive oxidation of the primary reduced paragenesis (pyrite + pyrrhotite + magnetite) can be explained. The boiling of the ascending water does induce a H₂ loss from the liquid and creates more oxidizing conditions in the ascending liquid. Moreover, the continuous vaporization of liquid water induces its gradual cooling and increases the ascension speed. Furthermore, a persistence of chemical equilibrium between primary paragenesis and the hydrothermal fluid at different levels would require a very fast and unrealistic adjustment of the fO₂-fH₂ parameters to the local equilibrium conditions. This expected disequilibrium induces the afore mentioned oxidation processes under steady-state conditions.     

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。     

Grass cover density and metal speciation in profiles of a tailings-pile from a mining zones in Zacatecas,North-Central Mexico

The 7-year-old mine tailings pile P2 from Concepción del Oro has been revegetated spontaneously by xerophyte grasses, covering about the 30% of its surface. To elucidate the effect of the grass cover in the geochemical behavior of the sulfide minerals (SM) and metals, the strata of four selected profiles (P2-I, P2-II, P2-III and P2-IV, with high, middle, low, and null grass cover, respectively) were analyzed mineralogically and chemically, using scanner electron microscopy, X-ray diffractometer and performing a six-step sequential extraction method. An older (50-year-old) and uncovered (without grass cover) profile of the tailings pile P3 was also analyzed. In all the profiles from P2, the SM oxidation is not yet an extended process; however, the samples from the uncovered profile P2-IV showed evidences of SM (pyrite and chalcocite) oxidation, as well as the presence of gypsum and Fe oxides, as the major secondary phases resulted from the SM oxidation. Additionally, the carbonate content and pH values in P2-IV were lower than in the covered profiles from P2. The oldest and uncovered P3-I profile showed an extensive oxidation of sulfurs which resulted in the depletion of carbonates and a pH 2. Another distinctive characteristics of the covered profiles was that Pb, Cu, and Zn were mainly associated with the reducible fractions (carbonates and/or amorphous oxides); meanwhile, in the uncovered (P2-IV and P3-I) such metals were mainly associated with the oxidizable fraction (crystalline oxides). The results suggest that the mineralogical transformations control metal stability in plant-covered impoundments (phytostabilization): the occurrence of a thick grass cover, with an efficient water usage and retention, seems to shun both the acidic dissolution of carbonates and the reductive dissociation of the formerly present oxyhydroxides, which is desired for remediation tasks. This is the first report about the effects of grass cover for a carbonaceous and unsaturated mine tailings from a semiarid region, that can help in a better understanding of the scope of phytoremediation in such conditions.     

Geochemical,mineralogical and microbiological characterization of a sulphide-bearing carbonate-rich gold-mine tailings impoundment,Joutel, Québec

The results of an integrated geochemical and mineralogical study conducted at the Agnico-Eagle gold-mine tailings impoundment, Joutel, Québec, are correlated with bacterial populations determined from an enumeration of 3 groups of Thiobacilli. The tailings were determined to contain approximately 5 wt.% sulphide–S, predominantly as pyrite, and up to 30 wt.% carbonate minerals, chiefly as dolomite–ankerite and siderite. The objective of the study was to evaluate the potential for the development of acidic drainage and dissolved-metal migration in carbonate-rich tailings impoundments, and to compare the results of the geochemical and microbiological characterization of the tailings. Sulphide-oxidation reactions have proceeded to a depth of 20–100 cm below the tailings surface. Pyrrhotite consistently shows more alteration than pyrite and arsenopyrite. Pyrrhotite is altered mainly through the replacement by goethite. The most abundant Thiobacilli are neutrophilic bacteria of the Thiobacillus thioparus type. The maximum most probable number values for these bacteria occur 20–40 cm below the tailings surface, a depth that coincides with the disappearance of oxide coatings. This observation, coupled with the sharp decline in gas-phase O₂ concentration, suggests that rapid bacterially-mediated S–oxidation is occurring at this depth. The pore-water pH throughout the tailings varies between 6.5 and 8.5; no low-pH waters were observed in the impoundment. These neutral pH conditions are attributed to the effect of acid-consuming carbonate-mineral dissolution reactions, which are also indicated by increased concentrations of Mg and Ca and alkalinity in the shallow zone of the tailings. As a result of these acid-neutralization reactions, dissolved metal concentrations are low.     

Metal and metalloid leaching from tailings into streamwater and sediments in the old Ag–Pb–Zn Terramonte mine,northern Portugal

Tailings deposited over the Castanheira, a stream which flows through the old Ag–Pb–Zn Terramonte mine area, showed a great potential environmental risk due to sulphide weathering, facilitated by the tailings–water interaction. The high concentrations of Al, Fe, Pb and Zn in the tailings are associated with the exchangeable, reducible and sulphide fractions and suggest sphalerite and pyrite occurrences. Oxidation of pyrite is responsible for the low pH values (3.38–4.89) of the tailings. The water from the Castanheira stream is not suitable for human consumption due to high concentrations of SO₄ ^2?, Mn, Al, Cd, Ni, and Pb. The lowest concentrations of metals and metalloids were detected in downstream stretches of the Castanheira. However, As, Fe and Zn in deeper sediments tend to increase downstream. Significant concentrations of trivalent forms of arsenic were detected in water samples. In downstream stretches of the Castanheira, some free ions (Fe²⁺, Mn²⁺ and Zn²⁺) also predominate and the water is saturated with ferrihydrite, goethite, hematite, lepidocrosite and magnetite.