高铝粉煤灰中部分主微量元素的分布规律研究

本文旨在研究部分主微量元素在高铝粉煤灰中的分布规律,从而为其资源化利用提供科学依据。首先根据高铝粉煤灰的物相组成特点采用新的分离方法将之分离为三个相(或相组合):铁质微珠、莫来石-刚玉相以及玻璃相;然后分别用化学分析和ICP-MS测试主微量元素在高铝粉煤灰、铁质微珠以及莫来石-刚玉相中的含量,并结合相关数据计算出这些元素在玻璃相中的含量。结果表明,除Al、Mn外,其他元素均在玻璃相中有不同程度的富集;除Al外,其他元素则在莫来石-刚玉相中有不同程度的贫化;除Ti以外的铁族元素以及除Ga、Pb以外的金属成矿元素均在铁质微珠中富集,其他元素则在其中贫化。     

Long-term brine impacted fly ash,Part II: Mobility of major species in the ash residues

The leaching of major species from fly ash is a function of the pH of the solution in contact with the fly ash. The aim of this study was to determine the effect of the pH of the leachant on the leaching of species from the ash residues recovered after the long-term fly ash–brine interactions. Acid neutralization capacity (ANC) tests using solutions of different pH values ranging from the initial pH of the ash residues (11–12) to pH 4 were employed in the leaching experiments. The ANC tests revealed that the release of major species from the ash residues depended on the pH of the leachants except for Na and Cl, where the significant concentrations leached were independent of the solution pH. The concentrations of Al and Si in the ANC leachates were very high at pH below 6 while Ca, K, Sr, Mg and B were immediately mobilized from the brine impacted fly ash when in contact with de-ionized water, and leaching increased as the pH decreased. The concentration of SO₄ leached from the brine impacted ash residues at high pH was high, and the leaching increased with decrease in the pH of the leachant. This study shows that most of the major elements captured in the ash residues could be mobilized when in contact with aqueous solutions of various pH. This reveals that the co-disposal of fly ash and brine may not be the best practice as the major elements captured in the ash residues could leach over time.     

An evaluation of trace element release associated with acid mine drainage

The determination of trace element release from geologic materials, such as oil shale and coal overburden, is important for proper solid waste management planning. The objective of this study was to determine a correlation between trace element residency and concentration to trace element release using the following methods: (1) sequential selective dissolution for determining trace element residencies, (2) toxicity characteristic leaching procedure (TCLP), and (3) humidity cell weathering study simulating maximum trace element release. Two eastern oil shales were used, a New albany shale that contains 4.6 percent pyrite, and a Chattanooga shale that contains 1.5 percent pyrite. Each shale was analyzed for elemental concentrations by soluble, adsorbed, organic, carbonate, and sulfide phases. All leachates were analyzed to determine total trace element concentrations. The results of the selective dissolution studies show that each trace element has a unique distribution between the various phases. Thus, it is possible to predict trace element release based on trace element residency. The TCLP results show that this method is suitable for assessing soluble trace element release but does not realistically assess potential hazards. The results of the humidity cell studies do demonstrate a more reasonable method for predicting trace element release and potential water quality hazards. The humidity cell methods, however, require months to obtain the required data with a large number of analytical measurements. When the selective dissolution data are compared to the trace element concentrations in the TCLP and humidity cell leachates, it is shown that leachate concentrations are predicted by the selective dissolution data. Therefore, selective dissolution may represent a rapid method to assess trace element release associated with acid mine drainage.     

Distribution of reduced inorganic sulfur compounds in lake sediments receiving acid mine drainage

The sediments of Lake Anna, Virginia, act as a major sink for incoming acid mine drainage (AMD) pollutants (Fe, SO₄²⁻, H⁺) due to bacterial sulfate reduction (SR). Acid-volatile sulfide (AVS), elemental S, and pyrite concentrations in the sediments of the polluted arm of the lake are significantly greater than those in unpolluted sections of the lake. Measurements of SR using ³⁵SSO₄²⁻ showed that AVS and S⁰ are the major short-term (48 h) products of SR in these sediments. Inorganic forms of S(AVS, S⁰, and FeS₂) made up from 60 to 100% of the total sediment S concentration. Pyrite concentrations in the sediment were high but decreased exponentially with distance from the AMD source, suggesting that the pyrite was deposited as stream detritus from the abandoned mines. Iron monosulfide and elemental S concentrations were highest at a station 1 km away from the AMD inflow, indicating formation in situ. There was no evidence for the formation of organic S species. The results suggest that in Fe- and S-rich locations such as those contaminated with acid mine drainage, the distribution of end products of SR may vary substantially from those reported for more moderate environments.     

采空区大掺量粉煤灰无机固化泡沫制备及特性研究

煤矿采空区漏风是引发煤火灾害的重要原因,传统充填堵漏材料易干裂,流动性差,成本高,因此研发出有效充填封堵漏风通道的新型材料十分必要。通过单因素变量法,以材料流动度、初凝时间、抗压强度为指标进行配比优选,研发出大掺量粉煤灰无机固化泡沫充填堵漏新材料。同时,利用红外光谱、X射线衍射仪、扫描电镜表征材料的水化过程。结果表明∶基于泡沫均匀度、发泡倍数、半衰期及析水率等参数,优选出十二烷基硫酸钠(SDS)∶辛癸基葡糖苷(APG)=1∶1,黄原胶(XG)∶瓜尔胶(GG)=1∶1的水基泡沫。研发的大掺量粉煤灰无机固化泡沫,其初凝时间与粉煤灰掺量、水灰比、泡沫掺量成正比;流动度与水灰比成正比,与粉煤灰掺量成反比,随泡沫掺量增加先上升后缓慢降低;抗压强度随粉煤灰掺量增加呈先增加后减小趋势,与水灰比和泡沫掺量呈反比关系。综合评价指标确定粉煤灰掺量为60%、水灰比为0.6、泡沫与复合浆液体积比为1∶1时,材料流动度好,为15.9 cm,初凝时间适中,为5 h,抗压强度高,28 d达到1.5 MPa。该材料的水化产物是钙矾石(AFT)以及C-S-H凝胶,由水泥先发生水化反应生成Ca(OH)2,后与粉煤灰反应生...     

Geotechnical characterization of fly ash composites for backfilling mine voids

Backfilling of mine voids is mandatory to avoid subsequent ground stability problems in the form of subsidence. River sand and mill tailings have been widely used since a long time as backfilling materials. However, with a strict regulation banning river sand mining in India, research for developing alternative engineering materials substituting sand has gained importance. In the present study four fly ash composite materials (FCMs) was developed from the fly ash obtained from a captive thermal unit of Rourkela Steel Plant (RSP). The main constituent of the composite were fly ash, lime and gypsum. Detailed physical, and engineering properties were determined for the FCMs. Significant increases in the compressive strength were obtained after 56 days of curing time. A detailed SEM studies was undertaken to account for the increase in strength with time. The fly ash composite developed from RSP has potential to be used as substitute to sand for backfilling the mine voids.     

Origin of acid mine drainage in Enugu

Mine flooding is a serious problem in the Enugu Coal Mines and has led to the abandonment of two of the four mines. About 1800 m³ of water is pumped out daily from the mines into the nearby streams. The source of this enormous volume of water has been established based on the hydrodynamics and hydrology of the area. It is shown that although two prolific aquifers—an unconfined and a confined system—overlie the mines, the mine water is derived principally from the unconfined aquifer. The pathway of flow is, however, provided by the numerous fractures connecting the two aquifers and the mine tunnel.The major hydrochemical activity resulting in pollution of the mine water occurs within the sumps in the floor of the longwalls. These sumps act as oxidation chambers where groundwater from the fractures is mixed and subsequently reacted with sulfur-rich solutes released by coal mining.Contrary to general belief, the mine drainage has not seriously degraded the chemistry of receiving streams. The pH, electric conductivity and, thus, the dissolved ions were increased less than 10% of the values in the unaffected region.     

The occurrence of gold in fly ash derived from high-Ge coal

We present the first data on the mode of occurrence of Au in fly ashes from the Wulantuga and Lincang power plants in China, which burn high-Ge coal. Gold occurs as fine-grained drop-like particles with a size of n*0.01–0.2 μm on the surface of the glass globules. These features of the Au particles are proof for Au condensation from the gas phase and deposition on the surface of fly ash in the cooler zone of the electrostatic precipitator and baghouse filter.     

Neutralisation of acid mine drainage with alkaline industrial residues: laboratory investigation using batch-leaching tests

This study constitutes a first stage of the elaboration of a concept for setting up capillary barriers composed of reactive tailings and alkaline industrial wastes. The aim of this barrier is (1) short-term mitigation by neutralising acid produced by Fe sulfides and (2) long-term mitigation by stabilisation of secondary products. The alkaline industrial wastes, cement kiln dust (CKD) and red mud bauxite (RMB), are used to produce neutral conditions. A series of time-controlled static leaching experiments were performed. Samples of reactive tailings were prepared containing 0, 2, 5, and 10% alkaline material. The water:solid ratios were also varied (3:1, 6:1, and 20:1) in order to characterise the geochemical balance between liquid and solid phases. The data are used to discern whether mineral solubility controls exist for particular ions. The pH results show that the use of 5% CKD, 10% CKD and 10% (CKD+RMB) allows neutral pH conditions to be maintained in the reactive layer. At these percentages, the concentrations of Al, Fe, Cu, Zn and SO₄ in solution are significantly reduced compared with those obtained with the reactive tailings only. Aluminum concentrations are principally controlled by secondary phases like boehmite and gibbsite; Fe, by goethite and ferrihydrite; Cu and Zn, by hydroxides. Calcium and SO₄ concentrations are controlled by precipitation of gypsum. The concentrations of Na and K are found not to be controlled by mineral solubility.     

Copper isotope fractionation in acid mine drainage

We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The δ⁶⁵Cu values (based on ⁶⁵Cu/⁶³Cu) of enargite (δ⁶⁵Cu = −0.01 ± 0.10‰; 2σ) and chalcopyrite (δ⁶⁵Cu = 0.16 ± 0.10‰) are within the range of reported values for terrestrial primary Cu sulfides (−1‰ < δ⁶⁵Cu < 1‰). These mineral samples show lower δ⁶⁵Cu values than stream waters (1.38‰ ? δ⁶⁵Cu ? 1.69‰). The average isotopic fractionation (Δ_aq-min = δ⁶⁵Cu_aq − δ⁶⁵Cu_min, where the latter is measured on mineral samples from the field system), equals 1.43 ± 0.14‰ and 1.60 ± 0.14‰ for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in ⁶⁵Cu relative to chalcopyrite (1.37 ± 0.14‰) and enargite (0.98 ± 0.14‰) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (Δ_aq-min^o=-0.57±0.14‰, where min^o refers to the starting mineral) and no apparent fractionation for enargite (Δ_aq-min^o=0.14±0.14‰). Abiotic fractionation is attributed to preferential oxidation of ⁶⁵Cu⁺ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of ⁶⁵Cu_aq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of δ⁶⁵Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage remediation and ore prospecting purposes.     

Mineralogy and trace element association in an acid mine drainage iron oxide precipitate; comparison of selective extractions

Mineral and trace element characterization of an Fe-rich precipitate from an acid mine system was accomplished by X-ray diffraction (XRD), differential X-ray diffraction, and ICP chemical analysis. A primary objective was to evaluate the effectiveness of common selective dissolution treatments in determining the association of minerals with potentially toxic trace elements. The precipitate consisted primarily of goethite, a poorly crystalline phase resembling synthetic ferrihydrite, dolomite and gypsum in clay-size fractions. The ammonium oxalate and EDTA treatments, which are thought by some workers to dissolve only poorly crystalline phases, were found to dissolve a significant amount of crystalline goethite. However, the oxalate extraction did dissolve more ferrihydrite than the other treatments tested. A solution of 0.1 M hydroxylamine hydrochloride in 0.1 M HNO₃, which is thought by some to dissolve mostly the highly soluble Mn-oxides was found to also dissolve goethite, as did 0.25 M hydroxylamine hydrochloride in 25% (v/v) acetic acid, 0.25 M hydroxylamine hydrochloride in 0.25 M HCI, 0.5 M HCI, and Na-dithionite buffered with Na-citrate and 1.0 M NaHCO₃. Both trace and major elements that were extracted with the various treatments were found to vary significantly and non-systematically when compared to the proportion of total extractable Fe. These selective extractions cannot be used to make reliable conclusions about trace metal and mineral associations. Gypsum was identified by XRD in claysize separations from the sample, but this phase was not detected in diffraction scans of the bulk sample. This finding indicates that individual phases can be segregated by particle size.     

Impacts of acid mine drainage on a stream in subtropical China during a major flood event

Field and laboratory work was carded out to investigate the chemistry and ecotoxicity of stream water affected by acid mine drainage in a tributary catchment of the Pearl River in subtropical China during a major flood event that corresponded to a return period of 100 years occurred in the study area. The results indicate that stream water was affected by acid mine drainage from the Dabaoshan Mine at least to a distance of 25 km downstream of the mine water discharge point. It appears that sulfide-H^＋ from the waste rock dumps was readily available for discharging and the amount of H^＋ being transported outwards depended on the volume of out-flowing waters. However, there was a lag time for the discharge of the metals. This may be attributed to the slower release of metals, relative to H^＋, because it might take more time for the dissolution of heavy metal-bearing compounds. Fe, Zn and Al were the major metals of potential toxicity contained in the AMD-affected stream water, followed by Mn, Cu, Pb, As, Cd and Ni. Acute toxicity tests show that the AMD-affected stream water at 3.5 km downstream of the discharge point was highly toxic to the test organisms.     

Effects of coal fly ash amended soils on trace element uptake in plants

Variations in As, Ba, Bi, Cd, Co, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, Sn, Th, Tl, U, W, and Zn uptake were evaluated in young, middle-aged, and mature basil, tomato, zucchini, and sunflower plants grown in soils amended with 5, 10, and 20% by weight fly ash. Elements susceptible to uptake with increasing fly ash were As and Tl, with As exceeding potentially toxic levels in basil and zucchini. Temporal variations in element uptake included (1) increasing Ba and Cd concentrations in tomato and As, Ba, Cd, and Tl in zucchini, (2) decreasing Co concentrations in tomato, zucchini, and sunflower, Ni in zucchini, and Tl in basil, and (3) increasing As and Ni concentrations in basil and Pb in zucchini and sunflower during early growth followed by decreasing concentrations at maturity. Although most of the trace elements were below reported toxic levels, the elevated concentrations of As in plant tissue suggests that fly ash treatment programs can lead to potentially toxic accumulations of As, and thus, should be carefully monitored.     

Spatial variations and controls of acid mine drainage generation

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

煤矿酸性矿井水成因及其处理方法

煤矿酸性矿井水是煤矿开采中由于硫铁矿与空气、水接触,在微生物作用下经过一系列地球化学反应产生的一种危害矿井生产、破坏生态环境的有害矿井排水.本文结合酸性矿井水的危害、形成原因,阐述了酸性矿井水的处理方法.     

铜陵矿山酸性排水及固体废弃物中的重金属元素

在调查中国铜陵凤凰山铜矿和新桥硫铁矿两种不同类型矿山固体废弃物特征的基础上,研究了矿山尾矿和废石产生酸性排水的可能性及其差异以及矿山固体废弃物中重金属元素的赋存形式。结果表明,凤凰山铜矿的尾矿基本不产生矿山酸性排水,而新桥硫铁矿采矿废石产生矿山酸性排水,并且凤凰山铜矿的尾矿和新桥硫铁矿采矿废石中重金属元素的赋存形式也有差异,前者重金属Cu、Pb、Zn、Cd、As、Hg主要赋存于硅酸盐态中,而后者在还原态中有较高的含量,这反映了在地表条件下尾矿中大量重金属元素已经发生了迁移,而采矿废石已经开始氧化,且酸性排水的存在更有利于废石中重金属元素的迁移和扩散,进而导致矿区周围环境的污染。     

Municipal solid waste incineration fly ash sintered lightweight aggregates and kinetics model establishment

Municipal solid waste incineration fly ash blended with pine sawdust and shale, using a neotype trefoil rotary kiln to form lightweight aggregates, is an effective and a potential means method of fly ash disposal. The optimum sintering conditions of Trefoil rotary kiln were determined in terms of an orthogonal test by measuring the pellets’ bulk density, granule strength, 1 h water absorption. As far as the kinetics is concerned, an integral method of Coats–Redfern was introduced to analyze the kinetics characteristics of the mixture samples. Also, the kinetic triplets (apparent activation energy, pre-exponential factor and reaction order) were estimated by the reaction of kinetics model functions. It is shown that the optimum sintering conditions are as follows: (a) preheating temperature of 500 °C, (b) sintering temperature of 1130 °C, (c) holding time of 4 min. The optimum reaction models of the four stages are Avrami–Erofeev, Mample, Avrami–Erofeev and There-dimensional diffusion (Jander), respectively.