Investigation of pyrite oxidation and acid mine drainage characterization associated with Razi active coal mine and coal washing waste dumps in the Azad shahr–Ramian region,northeast Iran

Acid mine drainage (AMD) pollution is considered to be the most serious water pollution problem in mining areas. AMD containing iron sulfates and other components can affect the receiving water bodies. Pyrite oxidation and AMD generation can be considered as important processes that may take place in the wastes produced by coal mining and coal washing operations in the Golestan province (northeast Iran). The study area is characterized by appropriate atmospheric conditions that favor pyrite oxidation and the presence of a large amount of water bodies. This study attempts to consider pyrite oxidation and AMD generation in the Azad shahr–Ramian region. The impact of AMD on the quality of the surface water bodies was investigated by taking samples and analyzing them for hydro-geochemical parameters. Stiff and Piper diagrams were used to represent chemical analyses of water samples. The coal samples taken from different depths at four points on two different coal waste dumps were analyzed to find the fraction of pyrite that remained in the waste particles to investigate the pyrite oxidation process. A computational fluid dynamic package called PHOENICS was used to model pyrite oxidation process numerically. The results obtained from the geochemical analyses of water and coal samples and numerical simulation show pyrite oxidation and acid generation in the region. However, the presence of carbonate rocks raised the pH of the water samples. The drainages of the Razi mine may be recognized as natural alkaline mine drainages.     

Experimental study on prevention of acid mine drainage by silica coating of pyrite waste rocks with amorphous silica solution

Acid mine drainage (AMD) is a widespread environmental problem associated with working and abandoned mining operations. It results from the microbial oxidation of pyrite in the presence of water and air, affording an acidic solution that contains toxic metal ions. Pyrite microencapsulation, utilizing silica coating, is a novel approach for controlling AMD that has been shown to be very effective in controlling pyrite oxidation. The roles of the solution pH and silica concentration in the formation mechanism for the AMD-preventing coating were investigated. A silica coating can be formed from silica solution at pH 7, at which the amount of Fe eluted from pyrite into the solution is small. No coating was formed at other pH values, and the amounts of eluted Fe were larger than at pH 7, especially at pH 11. The silica coating forms from 2,500 to 5,000 mg/L silica solutions, but not from 0 or 1,000 mg/L silica solutions. The coating formation rate was slower in the 2,500 mg/L silica solution than in the 5,000 mg/L silica solution. The formation of silica coating on pyrite surfaces depends on three main steps: formation of Fe(OH)₃ on the surface of pyrite, reaction between Fe(OH)₃ and silicate in the solution on the pyrite surface, and growth of the silica layer on the first layer of silica. The best pH condition to enable these steps was around 7, and the silica coating formation rate can be controlled by the concentration of silica.     

Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As−1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O₂), hypoxic (2% O₂, 98% N₂), and anoxic (5% H₂, 95% N₂) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (−1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations.     

Immobilization of toxic elements in mine residues derived from mining activities in the Iberian Pyrite Belt (SW Spain): Laboratory experiments

In the mining environments of the Iberian Pyrite Belt (IPB), the oxidation of sulphide wastes generates acid drainage with high concentrations of SO₄, metals and metalloids (Acid Mine Drainage, AMD). These acid and extremely contaminated discharges are drained by the fluvial courses of the Huelva province (SW Spain) which deliver high concentrations of potentially toxic elements into the Gulf of Cádiz. In this work, the oxidation process of mine tailings in the IPB, the generation of AMD and the potential use of coal combustion fly ash as a possible alkaline treatment for neutralization of and metal removal from AMD, was studied in non-saturated column experiments. The laboratory column tests were conducted on a mine residue (71.6 wt% pyrite) with artificial rainfall or irrigation. A non-saturated column filled solely with the pyrite residue leached solutions with an acid pH (approx. 2) and high concentrations of SO₄ and metals. These leachates have the same composition as typical AMD, and the oxidation process can be compared with the natural oxidation of mine tailings in the IPB. However, the application of fly ash to the same amount of mine residue in another two non-saturated columns significantly increased the pH and decreased the SO₄ and metal concentrations in the leaching solutions. The improvement in the quality of leachates by fly ash addition in the laboratory was so effective that the leachate reached the pre-potability requirements of water for human consumption under EU regulations. The extrapolation of these experiments to the field is a promising solution for the decontamination of the fluvial courses of the IPB, and therefore, the decrease of pollutant loads discharging to the Gulf of Cádiz.     

Study of galvanic interactions between pyrite and chalcopyrite in a flowing system: implications for the environment

When galvanic interactions between pyrite and chalcopyrite occur in solution, pyrite, with the higher rest potential, acts as a cathode and is protected whereas chalcopyrite, with the lower rest potential, acts as an anode and its oxidation is increased. In this work a three-electrode system was used to investigate the corrosion current density and mixed potential of a galvanic cell comprising a pyrite cathode and a chalcopyrite anode in a flowing system. The results showed that with increasing concentration of ferric ion in the solution, with increasing acidity, and with increasing flow rate of the solution, the corrosion current density increased and the mixed potential of the galvanic cell became more positive. These experimental results are of direct significance to the control of environmental pollution in mining activity. By using the galvanic model, mixed potential theory, and the Butler–Volmer equation, the experimental results were explained theoretically.     

Hydrogeologic and environmental impact of amjhore pyrite mines,India

Drainage from active and inactive pyrite mines has produced chemical and physical pollution of both ground- and surface water in Amjhore region. In the present case, chemical pollution is caused by exposing pyrite minerals to oxidation or leaching, resulting in undesirable concentrations of dissolved materials. Pyrite mining suddenly exposed large quantities of sulfides to direct contact with oxygen, and oxidation proceeds rapidly, resulting in acidity and release of metal (Fe) and sulfates to the water system, eventually resulting in water pollution in the region. The magnitude and impact of the problem is just being recognized and, as the present and the future projected demand for clean water is of top priority, the present studies were undertaken.Mine drainage includes water flowing from the surface and underground mines and runoff or seepage from the pyrite mines. This article describes the various hydrologic factors that control acid water formation and its transport. The mine drainage is obviously a continuing source of pollution and, therefore, remedial measures mainly consisting of a double-stage limestone-lime treatment technique have been suggested. The present results will be used to develop an alternative and more effective abatement technology to mitigate acid production at the source, namely, the technique of revegetation of the soil cover applied to the waste mine dump material.Water quality change is discussed in detail, with emphasis on acidity formed from exposed pyrite material and on increase in dissolved solids. Preventive and treatment measures are recommended.     

A combined mathematical geophysical model for prediction of pyrite oxidation and pollutant leaching associated with a coal washing waste dump

The waste produced by coal washing process produces many environmental problems. In this study, the pollution problems associated with the waste produced by Alborz Sharghi Coal Washing Plant was investigated by mathematical modeling. The study area is located at 11 km. to Razmjah coal region and 45 km. to Tehran-Mashhad road in the north part od Iran. To achieve the goal, a few samples were taken from different depths at three points on the waste dump in order to investigate pyrite oxidation and pollution generation. The samples were then analysed, using an AA-670 Shimadzu atomic absorption to determine the fraction of pyrite remained within the waste particles. A numerical finite volume model using Phoenics package has been developed to simulate pyrite oxidation and pollution generation from the Alborz Sharghi coal washing waste dump. The pyrite oxidation reaction is described by the shrinking-core model. Gaseous diffusion is the main mechanism for the transport of oxygen through the waste. The results of numerical modelling were compared with the field observations and close agreement was achieved. A simple mathematical model incorporating advection and hydrodynamic dispersion processes was also presented in order to verify the results of geophysical time-laps method showing transportation of the pollutants through the downstream of the waste dump. Both mathematical model and geophysical time-laps method are agreed in the identification of pollutant transport emanated from the waste dump. The results of such investigations can be used for designing an effective environmental management program.     

常见硫化物的氧化作用及其环境效应

自然或人为采矿活动暴露的硫化物矿物的氧化作用，常产生一定范围的次生地球化学异常和严重的环境污染，在黄铁矿，方铅矿，闪锌矿，毒砂等硫化物矿物氧化过程中，S，Pb,Cd,As等有害元素将被有效释放而进入水体，并通过大气－水－土壤－植物－动物等途径危害人类。     

Pyrite oxidation related to pyritic minesite spoils and its controls: A review

Pyrite oxidation is considered to be a main contribution to the acidification of minesite spoils and the generation of the Acid Mine Drainage (AMD) which has become the greatest threat to the ecological environment. In this paper, pyrite oxidation and its controls are reviewed with respect to the latest literature. Conceptual model and empirical rate law model with reference to indoor experiments are classified and presented to describe pyrite oxidation in heterogeneous minesite spoil piles. The influences of Thiobacillus (T) ferrooxidans on pyrite oxidation are simply summarized. In order to prevent the generation of the AMD, three approaches including the addition of alkali to minesite spoil, use of dry covers, and coating on the minesite spoil surface, are discussed.     

The effect of As, Co, and Ni impurities on pyrite oxidation kinetics: An electrochemical study of synthetic pyrite

Synthetic pyrite crystals doped with As, Co, or Ni, undoped pyrite, and natural arsenian pyrite from Leadville, Colorado were investigated with electrochemical techniques and solid-state measurements of semiconducting properties to determine the effect of impurity content on pyrite’s oxidation behavior. Potential step experiments, cyclic voltammetry, and AC voltammetry were performed in a standard three-electrode electrochemical cell setup. A pH 1.78 sulfuric acid solution containing 1 mM ferric iron, open to atmospheric oxygen, was chosen to approximate water affected by acid drainage. Van der Pauw/Hall effect measurements determined resistivity, carrier concentration and carrier mobility.The anodic dissolution of pyrite and the reduction of ferric iron half-reactions are taken as proxies for natural pyrite oxidation. Pyrite containing no impurities is least reactive. Pyrite with As is more reactive than pyrite with either Ni or Co despite lower dopant concentration. As, Co, and Ni impurities introduce bulk defect states at different energy levels within the band gap. Higher reactivity of impure pyrite suggests that introduced defect levels lead to higher density of occupied surface states at the solid-solution interface and increased metallic behavior. The current density generated from potential step experiments increased with increasing As concentration. The higher reactivity of As-doped pyrite may be related to p-type conductivity and corrosion by holes. The results of this study suggest that considering the impurity content of pyrite in mining waste may lead to more accurate risk assessment of acid producing potential.     

Origin of nickel in water solution of the chalk aquifer in the north of France and influence of geochemical factors

In the north of France, high registers of nickel are sometimes recorded within the chalk aquifer. In a confined context, the presence of pyrite in the covering clays or in the marcasite nodules encrusted in the clay may constitute a natural source of trace metals. With an objective of sanitary control, the limits of chemical contents regulating the quality of water destined for human consumption have been lowered by the European Framework Directive in the field of water policy (2000/60/EC). As a result, nickel limits have been reduced from 50 to 20 μg/l. The analyses, carried out on three water catchment fields in our area of study, were centred on variable parameters (Eh, O₂(d), pH, Conductivity, T°), major elements (SO₄, NO₃) and metals (Fe, Ni, Mn, Co). The acquired data enabled us to identify from one hand, the conditions which are presented within the site, special thanks to the evolution of nitrate and iron contents and on the other hand, the natural origin (geological) of nickel for two of the three sites studied based essentially on the evaluation of the Nickel/Cobalt ratio. Thus, on the first site, the evolution of nickel content and nitrate content showed the influence of the phenomenon of denitrification on the re-mobilisation of the nickel. Whereas on the second site, a high variation of total iron content and oxygen dissolved in solution highlighted a particular phenomenon of oxidation of the pyrite through molecular oxygen. Finally, the correlation with the sulphates clearly showed behaviour of the nickel, once released, that was entirely dependent on the phenomenon of adsorption on the iron and manganese hydroxides.     

富镉铅锌矿床开采过程中水质污染特征——以贵州都匀牛角塘富镉锌矿床为例

铅锌矿的开采和选冶使含锌和镉等有害物质的尾矿暴露于地表,这些有毒元素通过自然风化淋滤作用进入地表水,进而污染矿区水体,对矿区生态环境破坏性极大。本文通过对贵州都匀牛角塘富镉锌矿区河流、选矿厂排放的污水、坑道水进行采样分析,发现矿区水体呈弱碱性,水体重金属污染并不严重,其中Cd等重金属有毒元素的含量大多没有超过生活用水国家标准和农业灌溉水国家标准。结合已有研究成果,认为碳酸岩地区碱性环境限制了镉等重金属有毒元素的活化迁移,使其就近富集在矿区土壤、植物及河流沉积物中。更重要的是由于碳酸盐岩对矿山酸性排水的中和缓冲作用,降低了矿石的风化淋滤速度,减轻了因铅锌矿开采和选冶活动导致的Zn、Cd等有毒重金属元素对矿区环境的污染,为非碳酸岩地区铅锌矿山环境污染和治理提供了一些借鉴。     

Environmental geochemistry of Zarshuran Au-As deposit, NW Iran

Zarshuran deposit is the most famous and important As-Au mine in Iran. However, there is no information on the impact of mining activity on the surrounding environment, especially on water systems. This paper attempts to document the concentration of arsenic and associated elements in waters and sediments resulting from the mining history of Zarshuran, a period covering hundreds of years. Water and sediment samples collected from Zarshuran Stream indicate high content of some potentially toxic elements, especially of As which ranges from 0.028 to 40 ng/l in water and 182 to 36,000 mg/kg in sediment samples. Mining activity, exposure of a large volume of mining wastes to weathering, and the anomalously high background of trace metals in the mining area are considered to be the main sources of heavy metal pollution.     

Geochemical effects of oxidation products and framboidal pyrite oxidation in acid mine drainage prediction techniques

Acid mine drainage predictive testwork associated with the Australian Mineral Industries Research Association (AMIRA) P387A Project: Prediction and Kinetic Control of Acid Mine Drainage (AMD) has critically examined static acid assessment and kinetic information from acid–base accounting techniques, including net acid production potential (NAPP), net acid generation (NAG) and column leach tests. This paper compares results on two waste rock samples that were obtained from the Kaltim Prima Coal mine (KPC) containing significant quantities of fine-grained framboidal pyrite. In agreement with other research, the authors' results indicated that framboidal pyrite is more reactive than euhedral forms due to the greater specific surface area of framboidal pyrite. This is evidenced by optical microscopy of reacted samples. Importantly, the results showed that NAPP testing is biased by the rapid acid generating oxidation of framboidal pyrite prior to, and during the acid neutralisation capacity (ANC) test. This can result in negative ANC values for samples containing significant framboidal pyrite (often “corrected” to zero kg H₂SO₄/t) when significant ANC is actually present in the sample. NAG testing using H₂O₂ indicated that samples containing a significant quantity of framboidal pyrite can result in the catalytic decomposition of the H₂O₂ prior to complete oxidation of the sulfide minerals present, requiring sequential addition of H₂O₂ for completion. A benefit of the NAG test, however, is that it assesses the net acid generation capacity of the sample without bias towards acid generation as is observed using NAPP methods. The kinetic NAG test also gives information on the reaction sequence of framboidal and euhedral pyrite. Periodic (kinetic) analysis of sub-samples from column leach tests indicated rapid oxidation of the framboidal pyrite compared to the euhedral pyrite, which was correlated with the greater framboidal pyrite surface area.Calculations to determine the sulfide/sulfate acidity derived from the oxidation of framboidal pyrite prior to; and during the ANC test have been developed to provide a better indication of the actual ANC (ANC_Actual) of the sample. Paste pH values of <pH 4–5 may be one suitable trigger mechanism for the implementation of this new method. This has led to an improved NAPP estimation of total acid production. Together with NAG and column leach testing this improved methodology has resulted in accurate AMD characterisation of samples containing acidic oxidation products and framboidal pyrite.     

Effect of acid mine drainage on a karst basin: a case study on the high-As coal mining area in Guizhou province,China

Acid mine drainage (AMD) is a common pollution in mining areas due to the oxidation of pyrite and associated sulfide minerals at mines, tailings and mine dumps. Elevated metals (Fe, Mn, Al) and metalloids (As, Hg) in AMD would deteriorate the local aquatic environment and influence the water supply. A carbonate basin with deposits of high-arsenic coal in Xingren County, southwestern China, was chosen to study the behavior of As and other chemical constituents along a river receiving AMD. Heavy metals (Fe, Mn) and major ions such as (Ca²⁺, Mg²⁺, Cl⁻, SO₄ ²⁻) in surface water, and As in sediment and surface water were analyzed. It was found that high concentrations of SO₄ ²⁻ (1,324–7,560 mg/L) and Fe (369–1,472 mg/L) in surface water were mainly controlled by the interactions between water and rocks such as the oxidation of pyrite in the local coal seams, precipitation and adsorption of iron minerals. Although ubiquitous carbonate minerals in the bedrock and the riverbeds, low pH (<3) water was maintained until 2 km downstream from the AMD source due to the Fe(hydro)oxide minerals coating on the surface of carbonate minerals to restrain the neutralization of acidic water. Moreover, the formation of Fe(hydro)oxide precipitations absorbed As was dominated the attenuation of As from water to sediment. Whereas, the dilution also played an important role in decrease of As in river water.     

Processes controlling the composition of acid sulfate solutions evolved from coal

Leaching of a series of Appalachian coals by distilled water has been studied in laboratory reactors. From columns open to air at 25°C, leachates were produced containing typically about 0.2 M SO₄²⁻, 0.1 M total Fe and having pH < 2. Leachates contained high concentrations of toxic trace metals, including Be, Al, Cu and Cd. Concentrations of sulfate and Fe in leachates from different coals were similar and were not related to concentrations of total S in the coals. Saturation with respect to melanterite (FeSO₄·7H₂O) and a ferric oxyhydroxide phase was observed in most solutions. Leachates were undersaturated with respect to anhydrous ferric sulfate and Na-jarosite, but supersaturated with respect to K-jarosite, suggesting that none of these phases controlled solution composition. The ratio of total ferric Fe to total ferrous Fe normally exceeded unity. Accumulation of ferric Fe indicates either that its reaction with pyrite is inhibited in weathered coals, or that the coals contain pockets of oxidized pore fluid that are out of contact with pyrite. Release of Be correlated with release of Al, and release of Cu correlated with release of Fe. Reducing the temperature, lowering the partial pressure of oxygen or adding limestone retarded the release of pyrite oxidation products from the coals. Addition of limestone should be considered if it is necessary to control release of acid leachates from coal piles.     

Copper, nickel and zinc contamination in soils within the precincts of mining and landfilling environments

This study determined copper, nickel and zinc concentrations in soils within the precincts of a copper-nickel mining and urban landfilling environments, and used obtained values to appraise the degree of soil contamination and pollution based on geoaccumulation index, contamination factor and pollution load index. Mean concentrations of copper (252.4?mg/kg), nickel (153.0?mg/kg) and zinc (30.4?mg/kg) in soils around the mining area were considerably higher than those around the landfill (4.3, 0.91, and 13.7?mg/kg, respectively, for copper, nickel and zinc). The mining area was moderate to heavily contaminated with copper, nickel and zinc (1?<?I _geo?<?4), whereas the landfill area was moderately contaminated (1?<?I _geo?<?3). In both areas, the level of copper contamination was higher than that of nickel and zinc. Contamination around the mining environment was attributed to mining activities whereas around the landfill area, migration of leachate from the disposed waste could have been responsible.     

Estimation of potential pollution of waste mining dumps at Peña del Hierro (Pyrite Belt,SW Spain) as a base for future mitigation actions

Peña del Hierro is an abandoned mine site located in the catchment area of the Tinto river (Pyrite Belt, SW Spain). As leaching from the spoils affect the quality of the stream water, the waste dumps have been characterized for mineralogy, geochemistry and granulometry to obtain an estimate of the potential pollution. Waste rock dumps in Peña del Hierro are very heterogeneous and are mainly composed of acid volcanic tuffs > gossan > shales > roasted pyrite ashes > floated pyrite. The volcanic tuffs, the gossan and the shales coexist in the same piles. The roasted pyrite ashes and the floated pyrite form more homogeneous dumps. The dissolution of pyrite concentrated in pyrite ashes and floated pyrite units can generate acid mine drainage. Nevertheless, acid volcanic tuffs, which are rich in pyrite and have no neutralizing minerals, are the main source of these acidic effluents. Only muscovite might partially neutralize the acidity, but the dissolution of this mineral is too slow to compensate for acidity. The occurrence of jarosite in the <2 mm fraction indicates that extreme acid mine drainage occurs. The gossan and roasted pyrite ashes have high contents of trace elements. According to their concentration, As (46–1710 ppm), Pb (113–3455 ppm) and Hg (0–53) are some of the most important toxic trace elements in these wastes. In dumps mainly composed of volcanic tuffs most of the trace elements derive from the gossan mixed in the piles. Gossan is stable in an oxidizing environment, but acidic effluents (pH < 2) can dissolve Fe oxyhydroxides from them and release high amounts of trace elements to the stream water. This research contributes to estimating the production of acid mine drainage and the actual contamination risk of potentially toxic elements in soils and waters of this area, and could be the base for possible future mitigation actions in other areas affected by mining wastes.     

Intense pyrite formation under low-sulfate conditions in the Achterwasser lagoon, SW Baltic Sea

In comparison to similar low-sulfate coastal environments with anoxic-sulfidic sediments, the Achterwasser lagoon, which is part of the Oder estuary in the SW Baltic Sea, reveals unexpectedly high pyrite concentrations of up to 7.5 wt%. Pyrite occurs mainly as framboidal grains variable in size with diameters between 1 and 20 μm. Pyritization is not uniform down to the investigated sediment depth of 50 cm. The consumption of reactive-Fe is most efficient in the upper 20 cm of the sediment column, leading to degrees of pyritization (DOP) as high as 80 to 95%.Sediment accumulation in the Achterwasser takes place in high productivity waters. The content of organic carbon reaches values of up to 10 wt%, indicating that pyrite formation is not limited by the availability of organic matter. Although dissolved sulfate concentration is relatively low (<2 mmol/L) in the Achterwasser, the presence of H₂S in the pore water suggests that sulfate is unlikely to limit pyrite authigenesis. The lack of free Fe(II) in the pore waters combined with the possibility of a very efficient transformation of Fe-monosulfides to pyrite near the sediment/water interface suggests that pyrite formation is rather controlled by (i) the availability of reactive-Fe, which limits the FeS formation, and by (ii) the availability of an oxidant, which limits the transformation of FeS into pyrite. The ultimate source for reactive-Fe is the river Oder, which provides a high portion of reactive-Fe (∼65% of the total-Fe) in the form of suspended particulate matter. The surficial sediments of the Achterwasser are reduced, but are subject to oxidation from the overlying water by resuspension. Oxidation of the sediments produces sulfur species with oxidation states intermediate between sulfide and sulfate (e.g., thiosulfate and polysulfides), which transform FeS to FeS₂ at a significant rate. This process of FeS-recycling is suggested to be responsible for the formation of pyrite in high concentrations near the sediment surface, with DOP values between 80 and 95% even under low sulfate conditions.A postdepositional sulfidization takes place in the deeper part of the sediment column, at ∼22 cm depth, where the downward diffusion of H₂S is balanced by the upward migration of Fe(II). The vertical fluctuation of the diffusion front intensifies the pyritization of sediments. We suggest that the processes described may occur preferentially in shallow water lagoons with average net-sedimentation rates close to zero. Such environments are prone to surficial sediment resuspension, initiating oxidation of Fe-sulfides near the sediment/water interface. Subsequent FeS₂ formation as well as postdepositional sulfidization leads to a major pyrite spike at depth within the sediment profile.     

Geochemical modeling of arsenic sulfide oxidation kinetics in a mining environment

Arsenic sulfide (AsS (am), As₂S₃ (am), orpiment, and realgar) oxidation rates increase with increasing pH values. The rates of arsenic sulfide oxidation at higher pH values relative to those at pH∼2 are in the range of 26-4478, 3-17, 8-182, and 4-10 times for As₂S₃ (am), orpiment, AsS (am), and realgar, respectively.Numerical simulations of orpiment and realgar oxidation kinetics were conducted using the geochemical reaction path code EQ3/6 to evaluate the effects of variable DO concentrations and mineral reactivity factors on water chemistry evolution during orpiment and realgar oxidation. The results show that total As concentrations increase by ∼1.14 to 13 times and that pH values decrease by ∼0.6 to 4.2 U over a range of mineral reactivity factors from 1% to 50% after 2000 days (5.5 yr). The As release from orpiment and realgar oxidation exceeds the current U.S. National Drinking Water Standard (0.05 ppm) approximately in 200-300 days at the lowest initial dissolved oxygen concentration (3 ppm) and a reactivity factor of 1%. The results of simulations of orpiment oxidation in the presence of albite and calcite show that calcite can act as an effective buffer to the acid water produced from orpiment oxidation within relatively short periods (days/months), but the release of As continues to increase.Pyrite oxidation rates are faster than orpiment and realgar from pH 2.3 to 8; however, pyrite oxidation rates are slower than As₂S₃ (am) and AsS (am) at pH 8. The activation energies of arsenic sulfide oxidation range from 16 to 124 kJ/mol at pH∼8 and temperature 25 to 40°C, and pyrite activation energies are ∼52 to 88 kJ/mol, depending on pH and temperature range. The magnitude of activation energies for both pyrite and arsenic sulfide solids indicates that the oxidation of these minerals is dominated by surface reactions, except for As₂S₃ (am). Low activation energies of As₂S₃ (am) indicate that diffusion may be rate controlling.Limestone is commonly mixed with sulfide minerals in a mining environment to prevent acid water formation. However, the oxidation rates of arsenic sulfides increase as solution pH rises and result in a greater release of As. Furthermore, the lifetimes of carbonate minerals (i.e., calcite, aragonite, and dolomite) are much shorter than those of arsenic sulfide and silicate minerals. Thus, within a geologic frame time, carbonate minerals may not be present to act as a pH buffer for acid mine waters. Additionally, the presence of silicate minerals such as pyroxenes (wollastonite, jadeite, and spodumene) and Ca-feldspars (labradorite, anorthite, and nepheline) may not be important for buffering acid solutions because these minerals dissolve faster than and have shorter lifetimes than sulfide minerals. However, other silicate minerals such as Na and K-feldspars (albite, sanidine, and microcline), quartz, pyroxenes (augite, enstatite, diopsite, and MnSiO₃) that have much longer lifetimes than arsenic sulfide minerals may be present in a system. The results of our modeling of arsenic sulfide mineral oxidation show that these minerals potentially can release significant concentrations of dissolved As to natural waters, and the factors and mechanisms involved in arsenic sulfide oxidation warrant further study.