Weathering of phlogopite in simulated bioleaching solutions

The purpose of this study was to examine structural alterations of finely ground phlogopite, a trioctahedral mica, when exposed to acid, iron- and sulfate-rich solutions typical of bioleaching systems. Phlogopite suspensions were supplemented with ferrous sulfate and incubated with iron- and sulfur-oxidizing bacteria (Acidithiobacillus ferrooxidans) at 22 °C. As bacteria oxidized ferrous iron, ferric iron thus formed partially precipitated as K-jarosite. K-jarosite precipitation was contingent on the preceding ferrous iron oxidation by bacteria and the release of interlayer-K from phlogopite. This chemically and microbially induced weathering involved alteration of phlogopite to a mixed layer structure that included expansible vermiculite. The extent of phlogopite weathering and structure expansion varied with duration of the contact, concentration of ferrous iron and phlogopite, and the presence of monovalent cations (NH₄⁺, K⁺, or Na⁺) in the culture solution. NH₄⁺ and K⁺ ions (100 mM) added to culture suspensions precipitated as jarosite and thereby effectively prevented the loss of interlayer-K and structural alteration of phlogopite. Additional Na⁺ (100 mM) was insufficient to precipitate ferric iron as natrojarosite and therefore the precipitation was coupled with interlayer-K released from phlogopite. When ferrous iron was replaced with elemental sulfur as the substrate for A. ferrooxidans, the weathering of phlogopite was based on chemical dissolution without structural interstratification. The results demonstrate that iron oxidation and the concentration and composition of monovalent ions can have an effect on mineral weathering in leaching systems that involve contact of phlogopite and other mica minerals with acid leach solutions.     

Quantification of mineral dissolution rates and applicability of rate laws: Laboratory studies of mill tailings

Reliable quantification of mineral weathering rates is a key to assess many environmental problems. In this study, the authors address the applicability of pure mineral laboratory rate laws for dissolution of mill tailings samples. Mass-normalised sulfide and aluminosilicate mineral dissolution rates, determined in oxygenated batch experiments, were found to be different between two samples from the same ∼50-year-old, carbonate-depleted mill tailings deposit. Consideration of difference in particle surface area and mineralogy between the samples resolved most of this discrepancy in rates. While the mineral surface area normalised dissolution rates of pyrite in a freshly crushed pure pyrite specimen and a sulfide concentrate derived from the tailings were within the range of abiotic literature rates of oxidation by dissolved molecular O₂, as were rates of sphalerite and chalcopyrite dissolution in the tailings, dissolution rates of pyrite and aluminosilicates in the tailings generally differed from literature values. This discrepancy, obtained using a consistent experimental method and scale, is suggested to be related to difficulties in quantifying individual mineral reactive surface area in a mixture of minerals of greatly varying particle size, possibly due to factors such as dependence of surface area-normalised mineral dissolution rates on particle size and time, or to non-proportionality between rates and BET surface area.     

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.     

The dissolution of olivine added to soil: Implications for enhanced weathering

Chemical weathering of silicate minerals consumes atmospheric CO₂ and is a fundamental component of geochemical cycles and of the climate system on long timescales. Artificial acceleration of such weathering (“enhanced weathering”) has recently been proposed as a method of mitigating anthropogenic climate change, by adding fine-grained silicate materials to continental surfaces. The efficacy of such intervention in the carbon cycle strongly depends on the mineral dissolution rates that occur, but these rates remain uncertain. Dissolution rates determined from catchment scale investigations are generally several orders of magnitude slower than those predicted from kinetic information derived from laboratory studies. Here we present results from laboratory flow-through dissolution experiments which seek to bridge this observational discrepancy by using columns of soil returned to the laboratory from a field site. We constrain the dissolution rate of olivine added to the top of one of these columns, while maintaining much of the complexity inherent in the soil environment. Continual addition of water to the top of the soil columns, and analysis of elemental composition of waters exiting at the base was conducted for a period of five months, and the solid and leachable composition of the soils was also assessed before and after the experiments. Chemical results indicate clear release of Mg²⁺ from the dissolution of olivine and, by comparison with a control case, allow the rate of olivine dissolution to be estimated between 10^−16.4 and 10^−15.5 moles(Mg) cm⁻² s⁻¹. Measurements also allow secondary mineral formation in the soil to be assessed, and suggest that no significant secondary uptake of Mg²⁺ has occurred. The olivine dissolution rates are intermediate between those of pure laboratory and field studies and provide a useful constraint on weathering processes in natural environments, such as during soil profile deepening or the addition of mineral dust or volcanic ash to soils surfaces. The dissolution rates also provide critical information for the assessment of enhanced weathering including the expected surface-area and energy requirements.     

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.     

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.     

Mineralogical, chemical, and crystallographic properties of supergene jarosite-group minerals from the Xitieshan Pb-Zn sulfide deposit, northern Tibetan Plateau, China

Supergene jarosite-group minerals are widespread in weathering profiles overlying Pb-Zn sulfide ores at Xitieshan, northern Tibetan Plateau, China. They consist predominantly of K-deficient natrojarosite, with lesser amounts of K-rich natrojarosite and plumbojarosite. Electron microprobe (EMP) analyses, scanning electron microcopy (SEM) investigation, and X-ray mapping reveal that the jarosite-group minerals are characterized by spectacular oscillatory zoning composed of alternating growth bands of K-deficient and K-bearing natrojarosite (K₂O >1 wt.%). Plumbojarosite, whenever present, occurs as an overgrowth in the outermost bands, and its composition can be best represented by K_0.29Na_0.19Pb_0.31Fe_2.66Al_0.22(SO₄)_1.65(PO₄)_0.31(AsO₄)_0.04(OH)_7.37. The substitution of monovalent for divalent cations at the A site of plumbojarosite is charge balanced by the substitution of five-valent for six-valent anions in XO₄ at the X site. Thermogravimetric analysis (TGA) of representative samples reveal mass losses of 11.46 wt.% at 446.6 °C and 21.42 wt.% at 683.4 °C due to dehydroxylation and desulfidation, respectively. TGA data also indicate that the natrojarosite structure collapses at 446.6 °C, resulting in the formation of NaFe(SO₄)₂ and minor hematite. The decomposition products of NaFe(SO₄)₂ are hematite and Na₂SO₄. Powder X-ray diffraction (XRD) analyses show that the jarosite-group minerals have mean unit-cell parameters of a?=?7.315 Å and c?=?016.598 Å. XRD and EMP data support the view that substitutions of Na for K in the A site and full Fe occupancy in the B site can considerably decrease the unit-cell parameter c, but only slightly increase a. The results from this study suggest that the observed oscillatory zoning of jarosite-group minerals at Xitieshan resulted mainly from substitutions of K for Na at the A site and P for S at the X site.     

Dissolution rates of phyllosilicates as a function of bacterial metabolic diversity

Weathering experiments using biotite and phlogopite in the presence of bacteria were conducted to better understand biotic dissolution kinetics and processes (proton- and ligand-promoted dissolution) under aerobic conditions. Miniature batch reactors (300 μl in microplate wells) were used at 24 °C for 3 days with and without bacterial strains. Abiotic experiments were performed with organic and nitric acids in order to calibrate the biotite-phlogopite chemical dissolution. An empirical model was used to fit the pH dependence for iron release rate (r_Fe) considering the influence of both protons and ligands from acidic to neutral conditions (pH ranging from 3 to 7): r_Fe=k_H(a_H+)^m+k_L(a_L)¹ where k is the apparent rate constant, a_H+ and a_L are the activities of protons and ligands, and m and l are the reaction orders. For both minerals in most cases at a given pH, the iron release rates in the presence of bacteria were in good agreement with rates determined by the chemical model and could be explained by a combination of proton- and ligand-promoted processes. Bacteria affect mineral dissolution and iron release rates through the quantities and nature of the organic acids they produce. Three domains were differentiated and proposed as biochemical models of mica dissolution: (1) below pH 3, only proton-promoted dissolution occurred, (2) in weakly acidic solutions both ligand- and proton-promoted mechanisms were involved, and (3) iron immobilization occured, at pH values greater than 4 for biotite and greater than 5 for phlogopite. This model allows us to distinguish the “weathering pattern phenotypes” of strains. Bacteria that are isolated from horizons poor in carbon appear more efficient at weathering micas than bacterial strains isolated from environments rich in carbon. Moreover, our results suggest that the mineral could exert a control on the release of organic acids and the “weathering pattern phenotypes” of bacteria.     

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.     

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

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

Mineralogical and chemical characteristics of some natural jarosites

This paper presents a detailed study of the mineralogical, microscopic, thermal, and spectral characteristics of jarosite and natrojarosite minerals. Systematic mineralogic and chemical examination of a suite of 32 natural stoichiometric jarosite and natrojarosite samples from diverse supergene and hydrothermal environments indicates that there is only limited solid solution between Na and K at low temperatures, which suggests the presence of a solvus in the jarosite-natrojarosite system at temperatures below about 140 °C. The samples examined in this study consist of either end members or coexisting end-member pairs of jarosite and natrojarosite. Quantitative electron-probe microanalysis data for several natural hydrothermal samples show only end-member compositions for individual grains or zones, and no detectable alkali-site deficiencies, which indicates that there is no hydronium substitution within the analytical uncertainty of the method. In addition, there is no evidence of Fe deficiencies in the natural hydrothermal samples. Hydronium-bearing jarosite was detected in only one relatively young supergene sample suggesting that terrestrial hydronium-bearing jarosites generally are unstable over geologic timescales.Unit-cell parameters of the 20 natural stoichiometric jarosites and 12 natural stoichiometric natrojarosites examined in this study have distinct and narrow ranges in the a- and c-cell dimensions. There is no overlap of these parameters at the 1σ level for the two end-member compositions. Several hydrothermal samples consist of fine-scale (2-10 μm) intimate intergrowths of jarosite and natrojarosite, which could have resulted from solid-state diffusion segregation or growth zoning due to variations in the Na/K activity ratio of hydrothermal solutions.     

Microbial activity and chemical weathering in the Middendorf aquifer,South Carolina

We use reactive transport modeling to better understand the kinetics of chemical weathering in the Cretaceous Middendorf aquifer of South Carolina, USA, and the relationship of this process to subsurface microbial activity. We constructed a model accounting for the kinetics of mineral dissolution and precipitation, ion exchange, and the CO₂ and bicarbonate produced by iron reducing and sulfate reducing bacteria in the aquifer. We then fit the model to observed trends in the chemical composition of groundwater along the aquifer by adjusting the rate constants for the kinetic reactions considered. The modeling portrays weathering in the Middendorf as a slow process by which groundwater gradually reacts toward equilibrium with minerals in the aquifer. The rate constants predicted are 6 to 7 orders of magnitude smaller than measured in laboratory experiments and 3 to 4 orders of magnitude less than those inferred from weathering rates in soils. The rate constants are smaller even than expected by projecting observed trends with the duration of weathering to the geologic age of the Middendorf. Weathering is driven largely by biological activity: about half the acid consumed is CO₂ derived from the recharge area, and about half is supplied by iron reducing bacteria in the aquifer; only about 1% of the acid is of atmospheric origin, from CO₂ dissolved in rainwater.     

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.     

Effects of a proline solution cover on the geochemical and mineralogical characteristics of high-sulfur coal gangue

Batch experiments were conducted to comparatively evaluate the inhibition effects and mechanisms of a low-concentration (1%) proline solution cover on the release of pollutants from high-sulfur coal gangue. High-sulfur coal gangue was continuously immersed in a proline solution and in deionized water (as a control treatment) for 540 days. The results showed that the coal gangue in the control treatment was oxidized and generated leachate with poor water qualities, i.e., the leachate exhibited lower pH values, higher redox potential values, higher pollutant concentrations (SO₄^2?, Fe, Mn, Cu, and Zn), and high levels of acidophilic sulfur-oxidizing bacteria. However, compared to the control treatment, the addition of the proline solution (1%) significantly improved the water quality of the leachate by significantly reducing the Eh values, the pollutant concentrations (SO₄^2?, Fe²⁺, Fe, Mn, Cu, and Zn), and the activity of acidophilic sulfur-oxidizing bacteria and by significantly increasing the pH value to neutral. The proline treatment significantly inhibited the oxidation of coal gangue and the release of pollutants, mainly by inhibiting the activity of acidophilic sulfur-oxidizing bacteria and by altering the heavy metal fractions and the mineralogical characteristics. Therefore, in engineering practice, workers should consider using an environmental friendly aqueous proline solution cover to achieve the in-situ control of pollutant releases from coal gangue dumps.     

Influence of hardpan layers on arsenic mobility in historical gold mine tailings

Hardpans, or cemented layers, form by precipitation and cementation of secondary minerals in mine tailings and may act as both physical and chemical barriers. Precipitation of secondary minerals during weathering of tailings can sequester metal(loid)s, thereby limiting their release to the environment. At Montague Gold Mines in Nova Scotia, tailings are partially cemented by the Fe arsenate mineral scorodite (FeAsO₄·2H₂O). Previous studies have shown that the formation of scorodite can effectively limit aqueous As concentrations due to its relatively low solubility (<1 mg/L at pH 3–4) and high As content (43–52 wt.% As₂O₅, this study). Co-existing waters and solids were sampled at Montague Gold Mines to identify present-day field conditions influencing scorodite precipitation and dissolution, and to better understand the mineralogical and chemical relationship between hardpan and tailings. In addition to scorodite, hardpan cements were found to include amorphous Fe arsenate and Fe oxyhydroxide. Nearly all hardpan is associated with historical arsenopyrite-bearing concentrate which provides a source of acidity, As⁵⁺ and Fe³⁺ for secondary mineral precipitation. Pore waters sampled from the hardpan have pH values ranging from 2.43 to 7.06. Waters with the lowest pH values also have the highest As concentrations (up to 35.8 mg/L) and are associated with the most extensive hardpan and greatest amount of weathered sulfide. Samples from areas with discontinuous hardpan and less sulfide have near-neutral pH and lower As concentrations. Detailed petrographic observations indicate that the identity and stability of As-bearing secondary minerals depends on the continued availability of sulfide concentrate. The results of this study are being used to develop remediation strategies for highly weathered, hardpan-bearing tailings that consider the stability of both primary and secondary minerals under various cover scenarios.     

Kinetic modelling of geochemical processes at the Aitik mining waste rock site in northern Sweden

A steady-state geochemical model has been developed to study water-rock interactions controlling metal release from waste rock heaps at the Aitik Cu mine in northern Sweden. The Cu release in drainage waters from the site is of environmental concern. The waste rock heaps are treated as single completely mixed flow-through reactors. The geochemical model includes kinetices of sulphide and primary silicate mineral weathering, heterogeneous equilibrium with secondary mineral phases and speciation equilibrium. Field monitoring of drainage water composition provides a basis for evaluation of model performance.The relative rate of oxidative weathering of sulphides and dissolution of primary silicate minerals, using published kinetic data, are consistent with net proton and base cation fluxes at the site. The overall rate of Fe²⁺ oxidation within the heap is three orders of magnitude faster than that which could be explained by surface-catalysed reaction kinetics. This suggests significant activity of iron-oxidizing bacteria. The absolute weathering rates of sulphides and silicate minerals, normalized to a measured BET surface area, are approximately two orders of magnitude lower at field scale than published rates from laboratory experiments. Because of the relative absence of carbonate minerals, the weathering of biotite and plagioclase feldspar are important sources of alkalinity.     

The waste sulfuric acid lake of the TiO2-plant at Armyansk,Crimea, Ukraine. Part II. Modelling the chemical evolution with PHRQPITZ

The past and future evolution of a salt lake near Armyansk (Crimea, Ukraine), in which waste sulfuric acid has been discharged since 1969, is modelled using the equilibrium aqueous chemistry model PHRQPITZ. The initial lake is represented by a simplified salt solution, about 1.4 times concentrated average seawater. Since the waste acid contains iron and other metals, the effluent is modelled by an FeSO₄ solution of pH 1.04, containing minor amounts of Na and Mg. The PHRQPITZ model is adapted to describe precipitation of the trivalent Fe minerals natrojarosite and ferrihydrite. The yearly input of effluent constituents is assumed constant, and the input of water from the effluent is compensated by the yearly excess of evaporation over rainfall.According to the model, calcite dissolution from the underlying calcareous clays nearly buffers the increase in acidity of the lake by the effluent, maintaining pH at a value around 1.7, up to 16 a of operation (1986). Increase of Fe, Na, and SO₄ is buffered by precipitation of natrojarosite and gypsum. At the direct contact with the sediments a relatively impervious Fe (hydr)oxide layer develops. This hampers further reaction with the sediments, which effectively stops around 1992, when pH has reached a value of 0.85.It is predicted that with further increase in concentration, either through continued acid input or by evaporation of the acid lake, dissolution of previously precipitated natrojarosite first acts as a relative H buffer, followed by resumed precipitation of natrojarosite when the potential H increase is counterbalanced by the SO_4/HSO₄ association equilibrium. The concept of buffering in its strict sense does not apply, as conditional equilibrium constants for the extremely acid and concentrated conditions in the lake are far from constant and may differ significantly from their theoretical value.