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.     

Investigation of zinc extraction from different leach residues by acid leaching

With different properties, zinc is one of the most important non-ferrous metals and it is used in various application areas, especially as an anti-corrosion agent. In Turkey, zinc production was based on zinc carbonate ores (ZnCO₃), at Çinkur plant from establishment to 1997 due to high reserves of zinc carbonate. After that, zinc concentrate coming from Iran was used in this plant over the last two decades. Thus, two different leach residues called as Turkish leach residue (TLR) and Iranian leach residue (ILR) were accumulated more than one million ton in Çinkur stock piles. In this study, it is aimed to investigate zinc recovery for each leach residue by use of sulphuric acid (H₂SO₄) and to compare the TLR and the ILR. Initially, detailed chemical, mineralogical and thermal analyses of these different leach residues were carried out. In order to investigate the effect of acid concentration and reaction duration on zinc recovery, leaching experiments were carried out at following conditions: 95 °C, 100 g/L pulp density and 600 rpm stirring rate. According to the characterization results, the chemical compositions for both residues are nearly similar; however, experimental results show that zinc recovery per cent of the ILR was higher than that of TLR for all experimental durations and acid concentrations. This may be due to the presence of Zn-containing compounds in the both residues at different percentages.     

Influence of the natural organic matter in the removal of caffeine from water by fixed-bed column adsorption

The removal of caffeine from tap water by F-400 granular activated carbon in fixed-bed adsorption experiments was carried out. Textural and chemical characterization of the adsorbent through N₂ adsorption–desorption isotherms, Fourier transform infrared spectrometry, isoelectric point determination and scanning electron microscopy studies was developed in studies previously reported. Caffeine breakthrough curves and total organic carbon profiles at different operation conditions (inlet concentration, volumetric flow rate and mass of adsorbent) were obtained. These experimental results showed a displacement of the natural organic matter from the active sites exerted by caffeine molecules due to their higher affinity to the surface carbon. This behavior led to an overshooting, a local outlet natural organic matter concentration higher than the feed quantity. A competitive effect seems to be observed in the removal of the target compound, decreasing the efficiency of the process. Axial dispersion coefficients and dimensionless numbers were estimated for the caffeine removal onto F-400 activated carbon. Therefore, the regeneration of the adsorbent by adsorption–desorption cycles was studied.     

Alkalinity production as an indicator of failure in steel slag leach beds treating acid mine drainage

Acid mine drainage is a serious environmental problem throughout mining regions of the US and around the world. In Appalachia, reuse of steel slag from steel production as a source of alkalinity for treatment of acid mine drainage has become a common practice. In these systems, dubbed steel slag leach beds, relatively clean surface water is percolated through a bed of steel slag to add large amounts of alkalinity to the water before mixing it with acidic, metalliferous mine water. These beds do not operate consistently and their failure mechanisms are poorly understood. Using the experience of Raccoon Creek watershed in southern Ohio, the alkalinity distribution of the discharge of six steel slag leach beds is compared. Two of these beds are still functional, one has been abandoned and three are operating poorly. The difference in alkalinity distribution between these beds suggests that a carbonate-dominated alkalinity system is an indicator of a poorly performing steel slag leach bed, while a more even distribution between hydroxide, carbonate and bicarbonate may point to more ideal operating conditions. In eight laboratory column experiments, this evidence was then expanded upon by testing different mixed media substrates (differing mixes of steel slag, wood chips and river gravel) to see which provided the most ideal alkalinity distributions. The columns that had steel slag mixed either with wood chips or wood chips and river gravel outperformed the column with slag only in terms of alkalinity distribution, perhaps due to microbial processes or increased hydraulic conductivity without significant added calcium or carbon that could drive calcium carbonate precipitation within the beds and causing them to fail.     

Kinetics of chromate reduction by pyrite and biotite under acidic conditions

The removal of chromate from aqueous solutions, using finely ground pyrite and biotite, was investigated by batch experiments. The kinetics and mechanism of chromate reduction are discussed here. Chromate reduction by pyrite was about 100 times faster than that by biotite, and was also faster at pH 3 than 4. When pyrite was used, more than 90% of the initial chromate was reduced within 4 h at pH 4, and within 40 min. at pH 3. However, with biotite more than 400 h was required for the reduction of 90% of the initial chromate. The results indicate that the rate of chromate reduction was strongly depending on the amount and dissolution rate of the Fe(II) in the minerals. The reduction of chromate at pH 4 resulted in the precipitation of (Cr, Fe)(OH)_3(s), which is believed to have limited the concentrations of dissolved Cr(III) and Fe(III) to less than the expected values. When biotite was used, the amounts of decreased Fe(II) and reduced Cr(VI) showed no stoichiometric relationship, which implies that not only was there chromate reduction by Fe(II) ions in the acidic solution, but also heterogeneous reduction of Fe(III) ions by structural Fe(II) in biotite. However, the results from a series of the experiments using pyrite showed that the concentrations of the decreased Fe(II) and the reduced Cr(VI) were close to the stoichiometric ratio of 3:1. This was because the oxidation of pyrite rapidly created Fe(II) ions, even in oxygenated solutions, and the chromate reduction by the Fe(II) ions was significantly faster than the Fe(II) ion oxygenation. When compared with the experimental sets controlled at an initial pH of 3, the pH of the biotite batch, which was not controlled, increased to 3.4. Because of the increase in the pH, Cr(VI) was not completely removed, and 25% (1.2–1.3 mg/L Cr(VI)) of the initial concentration remained for up to 1000 h. The pH increase is, in most cases, caused by the hydrolysis of clay minerals. However, in the pyrite batches, there was no difference in the variations of the chromate reduction in relation to the pH control. There was also no difference in the capacity and rate of Cr(VI) reduction in 0.01 M NaCl or Na₂SO₄ solutions. In the 0.01 M NaH₂PO₄ solution pyrite experiment, the Cr(VI) was not completely removed, despite the maintenance of the pH at 3. The dominant Fe species was about 10 mg/L Fe(III) and few Fe(II) ions existed in solution. The Fe phosphate (Fe₃(PO₄)₂ or FePO₄) coatings on the surface of pyrite prevented access of O₂ or Cr(VI). Therefore, the surface coatings are likely to have caused the deterioration of the Cr(VI) reduction capacity in the NaH₂PO₄ solution.     

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

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

硫代硫酸钠沉淀法富集铜冶炼废酸中铼的实验研究

白银有色集团铜业公司冶炼废酸量每年约为1×105m3,其中铼含量为5~70 mg/L,为综合利用废酸中的铼,采用硫代硫酸钠作为特效沉淀剂,对该沉淀剂加入量、反应时间、反应温度以及废酸中铼含量对铼沉淀率的影响做了较系统的实验研究,得到较优化的沉淀条件。进一步的中试放大实验取得了良好的技术指标:富铼渣泥中含铼达1.66%,铼的回收率达到99.8%。在此基础上,对沉淀剂的氧化还原反应机理进行了探讨。本方法工艺简单,铼沉淀率高,环境友好,较适用于废酸中铼的高效提取。     

Potential for the formation and migration of colloidal material from a near-surface waste disposal site

Organic material typically constitutes a substantial volume (∼ 90%) of the low-level radioactive wastes (LLRW) intended for near-surface disposal at Chalk River Laboratories (CRL), Ontario, Canada. These wastes can contain a large variety of organic materials, including paper, cardboard, plastic bags, used clothing, and mop heads. After emplacement in a disposal facility, leaching of the LLRW by water can mobilize inorganic and organic substances, ranging from small molecules such as acetic acid to unidentifiable material of colloidal size range. This study determined the potential for colloid formation produced by LLRW degradation, because colloid-facilitated transport of contaminants could affect the safety performance of a disposal facility.The decomposition of compacted LLRW was simulated by recirculating water in a closed system over several compacted bales of waste to determine the potential composition and colloid content of leachates. Size fractionation of organic matter was performed on leachate samples that had been aged for 18 months to simulate the microbial degradation of organic matter within leachates during migration out of the LLRW disposal facility. The aged leachates contained high concentrations of dissolved organic matter, ranging between 74 and 5074 mg/l as C. In most of the leachates, volatile fatty acids accounted for a significant fraction (up to 81%) of the dissolved organic carbon. Although 5–110 mg/l of organic colloids were observed in leachates, in most cases, the organic colloids made up a very small fraction of the total leached organic carbon. Therefore, since the complexation properties of dissolved and colloidal organics are probably similar, contaminants complexed to organics are most likely to be dissolved and not affected by colloid transport. The leachates also contained significant quantities of Fe and Al, which could potentially precipitate Fe and Al as colloids after oxidation. Although a significant portion of the dissolved Fe may have been produced by the corrosion of the ☐es used to contain the bales, the high Fe concentrations could be representative of leachates from LLRW that contain metallic Fe components. If Fe and Al colloids are stable, stable concentrations in LLRW leachates could be high enough to affect contaminant transport. Therefore, the Fe and Al content of LLRW should be minimized. The concentrations of natural colloids in sandy aquifers, such as those found at CRL are too low to affect contaminant migration significantly.     

络合剂淋洗Cu污染粉土的土柱试验研究

以当前我国备受关注的土体污染为背景,通过土柱试验研究了不同络合剂对Cu的淋洗效果,结果表明:乙二胺四乙酸二钠二水合物（ethylenediaminetetraacetic acid disodium saltdihydrate,EDTA）淋洗效果最佳,柠檬酸（citric acid,CIT）次之,氨三乙酸三钠盐单水合物（nitrilotriacetic acid trisodium salt monohydrate, NTA）淋洗效果相对最差;使用不同浓度的EDTA淋洗负载量为150 mg/kg的Cu污染土,浓度增大并未有效促进Cu的解吸,而较小浓度（0.005 mol/L）的EDTA是有效且经济的浓度,其对Cu的去除率达84%;0.015 mol/L的EDTA淋洗不同负载量的Cu污染土,随负载量增加,淋洗率下降,最高去除率为84%,但去除量增加;研究结果可为重金属污染土的淋洗修复工艺提供理论参考依据。     

Immobilization of phosphorus,copper, zinc and arsenic in swine manure by activated red mud

Red mud (RM), the solid waste of alumina industry, is high in silicon, calcium, aluminum and iron oxides. In this study, RM was activated by heat treatment at different temperatures and characterized with BET nitrogen gas sorption, scanning electron microscopy analysis and X-ray diffraction analysis. Immobilization of phosphorus, copper, zinc, and arsenic in swine manure by activated RM was studied as a function of RM dosage, pH and time. The immobilization efficiency of phosphorus, copper, zinc and arsenic increased with the increase in RM dosage, reaching 77, 39, 42, and 78 % when the proportion of RM to swine manure was 20 %. The pH of the solution had a significant impact on the immobilization and it was found that the efficiency increased with the increase in pH. During the 24-h immobilization, the efficiency increased with time and achieved equilibrium after 12 h. Chemical variations of phosphorus, copper, zinc, and arsenic during the immobilization process were investigated with sequential chemical extraction method and the results showed that the contents of non-labile fractions of phosphorus, heavy metals and arsenic increased obviously, whereas the contents of labile fractions decreased.     

辽东地区前寒武纪变质岩中黄铁矿特征分析

利用电镜能谱分析技术对董家沟组片麻岩和辽河群板岩、大理岩样品中10个黄铁矿主量元素进行分析,检测结果表明,以辽河群板岩样品为主的6个黄铁矿w(Fe)=56.30%～65.42%、w(S)=34.58%～43.70%,属于硫亏损性黄铁矿,形成于富铁贫硫环境;董家沟组片麻岩和辽河群大理岩的4个黄铁矿样品w(Fe)=40.61%～45.11%、w(S)=54.74%～59.39%,属于硫饱和性黄铁矿,形成于贫铁富硫环境。     

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.     

A demonstration of an affinity between pyrite and organic matter in a hydrothermal setting

One of the key-principles of the iron-sulphur world theory is to bring organic molecules close enough to interact with each other, using the surface of pyrite as a substrate in a hydrothermal setting. The present paper explores the relationship of pyrite and organic matter in a hydrothermal setting from the geological record; in hydrothermal calcite veins from Carboniferous limestones in central Ireland. Here, the organic matter is accumulated as coatings around, and through, pyrite grains. Most of the pyrite grains are euhedral-subhedral crystals, ranging in size from ca 0.1-0.5 mm in diameter, and they are scattered throughout the matrix of the vein calcite. The organic matter was deposited from a hydrothermal fluid at a temperature of at least 200°C, and gives a Raman signature of disordered carbon. This study points to an example from a hydrothermal setting in the geological record, demonstrating that pyrite can have a high potential for the concentration and accumulation of organic materials.     

Removal of dissolved selenium by siderite,pyrite, and sphalerite: Implications to selenium sequestration in water-saturated,anoxic coal waste rock

The mechanisms of abiotic sequestration of Se(VI) and Se(IV) on a sample of coal waste rock collected from the Elk Valley, Canada and on three pure mineral species (i.e., siderite, pyrite, and sphalerite) present in coal waste rock were assessed using sterile batch testing under water-saturated, anoxic conditions. Only siderite removed measurable Se(VI) from the test solutions with ~90% removal after 100 d attributed to initial adsorption to the siderite surface as Se(VI) and subsequent reduction to Se(IV) and Se(0). In contrast to Se(VI), all samples removed Se(IV) from the aqueous solutions. The rate of Se(IV) removal was pyrite > siderite > waste rock > sphalerite. The waste rock sample removed Se(IV) from solution in two stages: up to ~40% of the aqueous Se(IV) was rapidly removed (by day 1) followed by slower removal of Se(IV) with up to ~97% removal after 99 d. Se(IV) removal is attributed to the adsorption of Se(IV) and subsequent reduction to Se(0) onto the siderite and pyrite phases of the waste rock. The initial (1 d) removal of Se(IV) by waste rock was characterized using a distribution coefficient (K_d) of 15.5 L/kg. Longer-term Se(IV) removal was fitted with zero and first order removal rates. The removal of Se(IV) by sphalerite was minor and deemed to have a minimal effect on Se sequestration in the waste rock. Desorption tests on waste rock showed that the fraction of sequestered Se susceptible to desorption decreased with time as adsorbed Se(IV) was reduced to insoluble Se(0). These findings show that abiotic Se sequestration can occur in saturated, anoxic zones in coal waste rock dumps.     

硫酸和硝酸对桂林毛村碳酸盐岩溶蚀的室内模拟

硫酸和硝酸对碳酸盐岩的溶蚀会减少岩溶碳汇量,但其定量关系有待进一步研究。文章根据野外水体中SO42-、NO3-浓度,在室内封闭条件下分别设计了碳酸（0.033 mol?L-1）、硫酸和硝酸（0.1~1.7 mmol?L-1）（CSN酸）及硫酸、硝酸（0.1~1.7 mmol?L-1）（SN酸）对碳酸盐岩的溶蚀实验,实验历时144 h。结果表明:CSN酸中泥晶灰岩和白云岩的溶蚀速率均大于SN酸的。CSN酸中,泥晶灰岩溶蚀速率总体均高于白云岩,平均值分别为1.34 mg?（cm2?d）-1和1.21 mg?（cm2?d）-1。而在SN酸中,二者溶蚀速率差别不大,平均值分别为0.92 mg·（cm2?d）-1和0.93 mg·（cm2?d）-1;HCO3-浓度与溶蚀速率结果对应,泥晶灰岩和白云岩在CSN酸溶蚀液中HCO3-平均值分别为1.43 mmol?L-1和1.33 mmol?L-1,而在SN酸中泥晶灰岩的HCO3-低于白云岩,平均值分别为0.33 mmol?L-1和0.39 mmol?L-1。CSN酸中HCO3-浓度随酸浓度的增大而减小,而SN酸中其浓度随酸浓度的增大而增大。当SO42-、NO3-浓度为0.1~0.3 mmol?L-1时,碳酸对白云岩的溶蚀作用占75.89%~58.64%,对泥晶灰岩的溶蚀作用占80.21%~59.06%,当SO42-、NO3-浓度大于0.44 mmol?L-1时,其溶蚀作用小于50%。当SO42-、NO3-浓度为0.0~0.2 mmol?L-1时,野外实测数据与模拟数据基本吻合;当浓度>0.2 mmol?L-1时,野外实测碳酸对碳酸盐岩的溶蚀比例高于模拟实验。研究结果进一步说明了硝酸和硫酸对碳酸盐岩溶蚀作用的显著影响,可为其他酸对岩溶碳汇影响提供参考。