马兰煤矿矿井水水质变化特征及成因

通过对山西省马兰煤矿2号煤层采掘面在开采和封闭时期的矿井水和沉积物的研究,揭示采掘面封闭前后对矿井水水质和沉积物的影响机理。研究结果表明:马兰煤矿矿井水均为SO4—Ca型水质,矿井水均富含SO24-和Fe离子;随着上部煤层的不断开采,3处矿井水呈现相同的变化规律,矿井水的pH值升高,Eh值降低,SO24-、Fe、Mn和Zn离子浓度随之下降,其中北一暗斜井处的矿井水水质变化最显著;矿井水水质指标和流速变化能够控制其沉积物的矿物组成和结晶程度,北一暗斜井处的沉积物在两次采样中由斯沃特曼铁矿变为针铁矿,而其他两处的矿井水沉积物矿物组分没有发生变化,主要由针铁矿组成。研究结果能够提高对老空区积水水质的预测精度,并对煤矿突水水源判识具有重要意义。     

在我国发现的Schwertmannite矿物及其特征

采用X射线衍射(XRD)、扫描电镜与能谱(SEM-EDX)、X射线荧光(XRF)、傅立叶红外光谱(FT-IR)、热分析(DTA-TG)等分析方法,在我国山西马兰煤矿的酸性矿坑排水(AMD)沉淀物中首次发现了“斯沃特曼铁矿”(Schwertmannite)。研究表明,山西马兰煤矿酸性矿坑排水沉淀物中的Schwertmannite矿物的粒径为0.3~70μm,且分布比较均匀,其BET表面积为44.065 0 m2/g;SEM二次电子像显示为球形或椭圆形(聚集体)结构,颗粒大小比较均匀,球的表面有针状毛刺;该矿物的化学式为Fe8O8(OH)4.52(SO4)1.74.4.73H2O。     

马兰煤矿矿井水水质变化特征及成因

通过对山西省马兰煤矿2号煤层采掘面在开采和封闭时期的矿井水和沉积物的研究,揭示采掘面封闭前后对矿井水水质和沉积物的影响机理。研究结果表明:马兰煤矿矿井水均为SO₄-Ca型水质,矿井水均富含SO₄2-和Fe离子;随着上部煤层的不断开采,3处矿井水呈现相同的变化规律,矿井水的pH值升高,Eh值降低,SO₄2-、Fe、Mn和Zn离子浓度随之下降,其中北一暗斜井处的矿井水水质变化最显著;矿井水水质指标和流速变化能够控制其沉积物的矿物组成和结晶程度,北一暗斜井处的沉积物在两次采样中由斯沃特曼铁矿变为针铁矿,而其他两处的矿井水沉积物矿物组分没有发生变化,主要由针铁矿组成。研究结果能够提高对老空区积水水质的预测精度,并对煤矿突水水源判识具有重要意义。      

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.     

煤矿酸性水水化学特征及其环境地球化学信息研究

以水化学数据为依据,应用相关分析,结合地质、水文勘探资料,对煤矿酸性矿排水 (AMD)的水化学特点及其成因进行了研究。煤矿AMD在一定的物质条件和环境条件下形成,只要条件适宜,不管是高硫煤还是低硫煤均可产生酸性水;低pH、高Eh、高TDS及高硬度是煤矿AMD的重要特征,水中的SO₃2-与其EC之间以及Fe3+/Fe2+比值与其Eh值走势具有良好的一致性,水中微量元素及重金属来源较复杂,如Ni、Cu、Co、Zn等来源于黄铁矿的氧化溶解,但Pb、Sr等主要来自AMD对煤系地层中煤及岩石中矿物的淋滤作用。      

硫化矿原电池效应研究现状

硫化矿原电池效应普遍存在于金属硫化物矿山、硫化矿的人工开采与利用过程中,在浮选、湿法冶金、生物冶金、地球化学过程、重金属离子污染和酸性矿山排水的污染治理方面有重要作用,已引起高度重视。本文综述了硫化矿原电池反应原理、电化学研究方法及其在浮选、湿法冶金、生物冶金、地球化学过程、重金属离子污染和酸性矿山排水的污染与治理上的影响和应用现状。指出建立天然硫化物矿物原电池地球化学,从源头上实现消除或减弱硫化矿原电池效应导致的重金属离子和酸性矿山排水环境污染,将成为今后原电池效应在地学的重要研究方向。     

安徽淮北朔里煤矿硬质高岭土矿石特征及自然类型划分

朔里煤矿共生硬质高岭土矿赋存在下石盒子组底部的铝土泥岩中;其主要矿物为高岭石,次要矿物软水铝石,另有少量赤铁矿、金红石、锐钛矿等铁钛矿物;化学成分以Al2O3、SiO2为主,Fe2O3＋TiO2含量超过2％则不能圈定为矿体。朔里煤矿共生硬质高岭土矿共划分四种自然类型：①灰白-浅灰色高岭土矿,②深灰-灰黑色高岭土矿,③花斑状高岭土矿,④灰色含黄铁矿或少量鲕状菱铁矿高岭土矿。     

山西省中条山铜矿田电气石与电气石岩的研究

本文通过对中条山铜矿田电气石和电气石岩地质产状、岩相学和矿物学、矿物化学等特征的研究，指出本区有三种成因类型的电气石：（１）北峪酸性侵入体岩浆期后热液成因电气石；（２）中条群地层中变质热液形成的电气石；（３）赋矿岩石和近矿围岩中热液蚀变电气石。第（３）类电气石具有特征的产状、矿物化学和矿物共生组合标型，是重要的找矿标志     

鄂尔多斯盆地镇原地区洛河组黏土矿物特征及找铀意义

近年经过深入的铀矿勘查工作,在鄂尔多斯盆地西南部洛河组发现了具有工业意义的铀矿体,实现了深部铀矿勘查的重要突破。通过薄片鉴定、扫描电镜、X射线衍射、蚀变矿物光谱扫描等分析手段,对镇原地区洛河组黏土矿物的组成、含量及特征进行了系统研究。结果表明,洛河组赋矿砂岩与盆地东北部、西南部最重要的含铀岩系——直罗组具有较明显的差别。洛河组赋矿砂岩中黏土矿物总量较低,不同类型砂体中黏土矿物组合略有差异,其中泥岩、氧化砂岩、钙质砂岩、矿化砂岩中主要黏土矿物为伊蒙混层和伊利石,其次为高岭石和绿泥石。富矿砂岩和灰绿色围岩中的黏土矿物则主要是高岭石和伊蒙混层,其次为伊利石和绿泥石。扫描电镜下可见绿泥石、伊蒙混层、高岭石、少量伊利石与沥青铀矿伴生现象,但黏土矿物与铀矿物相关性不明显,表明在洛河组成矿过程中,黏土矿物可以吸附铀,但不是铀矿富集最主要的影响因素。通过对洛河组砂岩中黏土矿物赋存关系的研究,提出研究区至少存在两期绿泥石和一期高岭石的生成,揭示了由碱性→酸性→碱性流体的作用过程。黏土矿物特征可以作为铀成矿过程中后生流体示踪的重要标志。     

对矿物包裹体溶液性质的新认识——兼论含矿溶液是酸性溶液的地质证据

对金属矿床成矿溶液的性质 ,特别是 pH值 (酸碱度 )的确定 ,是认识含矿溶液的成因、成矿条件和成矿机理的关键。目前对成矿溶液性质的研究主要局限在对围岩蚀变矿物包裹体的测定方面 ,并得出近中性热卤水成矿的结论。作者认为 ,多数围岩蚀变矿物的包裹体溶液不能代表原成矿溶液的性质 ,“近中性的热卤水成矿”的认识有误 ,应是酸性水形成的含矿溶液成矿 ,并从矿物包裹体溶液的特征、Roedder的高金属含量的矿物包裹体溶液的发现、氢氧同位素资料、矿物包裹体中高卤水溶液的起源以及成矿溶液的演化机理等方面论述了酸性金属含矿溶液的成因及成矿演化过程。     

合成施威特曼石吸附Cu^2＋和Pb^2＋的实验研究

施威特曼石普遍存在于含大量SO42-的酸矿水中,其表面吸附的SO42-使得该矿物具有强吸附重金属离子的能力,可用于处理重金属离子污染。实验通过在不同浓度Cu2＋溶液中合成施威特曼石时发现,Cu2＋与施威特曼石的共沉淀量较低,FTIR分析表明Cu2＋与施威特曼石的羟基发生反应。开展施威特曼石吸附Pb2＋的实验,结果表明施威特曼石对Pb2＋的吸附符合Langmuir模型,施威特曼石吸附Cu2＋和Pb2＋后出现1545.4 cm-1和1435.0 cm-1（Cu2＋）两个吸收峰,可能是施威特曼石孔道表面形成了三元配合物。在241×10-6的初始浓度（与尾矿孔隙水的Pb2＋含量相近）下有61.4%的Pb2＋去除率,显示了较好的环境修复价值。     

The behavior of trace elements during schwertmannite precipitation and subsequent transformation into goethite and jarosite

Schwertmannite is a ubiquitous mineral formed from acid rock drainage (ARD), and plays a major role in controlling the water chemistry of many acid streams. The formation of schwertmannite was investigated in the acid discharge of the Monte Romero abandoned mine (Iberian Pyrite Belt, SW, Spain). Schwertmannite precipitated from supersaturated solutions mainly owing to the oxidation of Fe(II) to Fe(III) and transformed with time into goethite and jarosite. In a few hours, schwertmannite precipitation removed more than half of the arsenic load from solution, whereas the concentration of divalent trace metals (Zn, Cu, Pb, Cd, Ni, and Co) remained almost unchanged. In the laboratory, natural schwertmannite was kept in contact with its coexisting acid water in a flask with a solid-liquid mass ratio of 1:5 for 353 days. During this time, the pH of the solution dropped from 3.07 to 1.74 and the concentrations of sulfate and Fe increased. During the first 164 days, schwertmannite transformed into goethite plus H₃O-jarosite but, subsequently, goethite was the only mineral to form. Some of the trace elements, such as Al, Cu, Pb, and As were depleted in solution during the first stage as schwertmannite transformed into goethite plus H₃O-jarosite. On the contrary, the transformation of schwertmannite to goethite (with no jarosite) during the second stage released Al, Cu, and As to the solution. Despite the variation in their concentrations in solution, approximately 80% of the total Al and Cu inventories and more than 99% As and Pb remained in the solid phase throughout the entire aging process.     

A natural attenuation of arsenic in drainage from an abandoned arsenic mine dump

At the abandoned As mine in Nishinomaki, Japan, discharged water from the mining and waste dump area is acidic and rich in As. However, the As concentration in the drainage has been decreased to below the maximum contaminant level (0.01 mg/l for drinking water, Japan) without any artificial treatments before mixing with a tributary to populated areas. This implies that the As concentration in water from the waste dump area has been naturally attenuated. To elucidate the reaction mechanisms of the natural attenuation, analysis of water quality and characterization of the precipitates from the stream floor were performed by measuring pH, ORP and electric conductivity on-site, as well as X-ray diffraction, ICP-mass spectrometry and ion-chromatography. Selective extractions and mineral alteration experiments were also conducted to estimate the distribution of As in constituent phases of the precipitates and to understand the stability of As-bearing phases, respectively. The water contamination resulted from oxidation of sulfide minerals in the waste rocks, i.e., the oxidation of pyrite and realgar and subsequent release of Fe, SO₄, As(V) and proton. The released Fe(II) transformed to Fe(III) by bacterial oxidation; schwertmannite then formed immediately. While the As concentrations in the stream were lowered nearly to background level downstream, those in the ochreous precipitates were up to several tens of mg/g. The As(V) was effectively removed by the formed schwertmannite and had been naturally attenuated. Although schwertmannite is metastable with respect to goethite, the experiments show that the transformation of schwertmannite to goethite may be retarded by the presence of absorbed As(V) in the structure. Therefore, the attenuation of As in the drainage and the retention of As by schwertmannite are expected to be maintained for the long term.     

尾矿酸浸液制备氢氧化铁过程中施威特曼石的形成与转变

尾矿酸浸液在制备氢氧化铁的过程中,由于逐渐滴加碱液正好形成了pH值为2.8～3.8的高SO2-4、高Fe环境,因而生成了施威特曼石.施威特曼石是一种亚稳定矿物,随着时间的延长和体系状态改变,它可以转变为更稳定的针铁矿(氢氧化铁).考查了pH值、温度及时间对施威特曼石相转变的影响.结果表明,在60℃条件下,在pH值为12的碱溶液中转化36 h,施威特曼石可完全转变为Fe(OH)3.     

Schwertmannite stability in acidified coastal environments

A combination of analytical and field measurements has been used to probe the speciation and cycling of iron in coastal lowland acid sulfate soils. Iron K-edge EXAFS spectroscopy demonstrated that schwertmannite dominated (43-77%) secondary iron mineralization throughout the oxidized and acidified soil profile, while pyrite and illite were the major iron-bearing minerals in the reduced potential acid sulfate soil layers. Analyses of contemporary precipitates from shallow acid sulfate soil groundwaters indicated that 2-line ferrihydrite, in addition to schwertmannite, is presently controlling secondary Fe(III) mineralization. Although aqueous pH values and concentrations of Fe(II) were seasonally high, no evidence was obtained for the Fe(II)-catalyzed crystallization of either mineral to goethite. The results of this study indicate that: (a) schwertmannite is likely to persist in coastal lowland acid sulfate soils on a much longer time-scale than predicted by laboratory experiments; (b) this mineral is less reactive in these types of soils due to surface-site coverage by components such as silicate and possibly, to a lesser extent, natural organic matter and phosphate and; (c) active water table management to promote oxic/anoxic cycles around the Fe(II)-Fe(III) redox couple, or reflooding of these soils, will be ineffective in promoting the Fe(II)-catalyzed transformation of either schwertmannite or 2-line ferrihydrite to crystalline iron oxyhydroxides.     

Chemistry of acid production in black coal mine washery wastes

Column leaching tests on black coal mine washery wastes were performed, to determine the chemistry of acid generation. Coal mine coarse rejects and tailings were subjected to wet and dry cycle dissolution and subsequently column leached. The rates of iron sulphide oxidation and carbonate mineral dissolution were determined based on the drainage chemistry. The kinetic data from column leach experiments are used to predict the time required to deplete the acid producing and acid consuming minerals in the mine wastes. The acid production in the mine rejects was found to depend upon iron chemistry, carbonate chemistry, diffusion of oxygen, and permeability. The chemistry of the drainage from two different coal mines is compared.     

Spatial variability of arsenic in some iron-rich deposits generated by acid mine drainage

Potential contamination of rivers by trace elements can be controlled, among others, by the precipitation of oxyhydroxides. The streambed of the studied area, located in “La Châtaigneraie” district (Lot River Basin, France), is characterised by iron-rich ochreous deposits, acidic pH (2.7–4.8) and SO₄–Mg waters. Beyond the acid mine drainage, the presence of As both in the dissolved fraction and in the deposits is also a problem. Upstream, at the gallery outlet, As concentrations are high (As_max = 2.6 μmol/l and up to 5 wt% locally, respectively, in the dissolved and in the solid fractions). Downstream, As concentrations decrease below 0.1 μmol/l in the dissolved fraction and to 1327 mg/kg in the solid fraction. This natural attenuation is related to the As retention within ochreous precipitates (amorphous to poorly crystalline Fe oxyhydroxides, schwertmannite and goethite), which have great affinities for this metalloid. Upstream, schwertmannite is dominant while downstream, goethite becomes the main mineral. The transformation of schwertmannite into goethite is observed in the upstream deposits as schwertmannite is unstable relative to goethite. Furthermore, thermodynamic calculations indicate that the downstream goethite is not able to precipitate in situ according to the water chemistry. Goethite mainly results from the transformation of schwertmannite and its solid transport downstream.Moreover, as highlighted by leaching experiments carried out on the ochreous precipitates, this transformation does not seem to affect the As-retention in solids as no release of As was observed in the solution. Arsenic may either be strongly trapped by co-precipitation in the present minerals or it may be quickly released and re-adsorbed on the precipitate surface.     

Arsenate and chromate incorporation in schwertmannite

High concentrations of Cr (up to 812 ppm) and As (up to 6740 ppm) were detected in precipitates of the mineral schwertmannite in areas influenced by acid mine drainage. Schwertmannite may act as well as a natural filter for these elements in water as well as their source by releasing the previously bound elements during its dissolution or mineral-transformation. The mechanisms of uptake and potential release for the species arsenate and chromate were investigated by performing synthesis and stability experiments with schwertmannite.Schwertmannite, synthesized in solutions containing arsenate in addition to sulphate, was enriched by up to 10.3 wt% arsenate without detectable structural changes as demonstrated by powder X-ray diffraction (XRD). In contrast to arsenate, a total substitution of sulphate by chromate was possible in sulphate-free solutions. Thereby, the chromate content in schwertmannite could reach 15.3 wt%.To determine the release of oxyanions from schwertmannite over time, synthetic schwertmannite samples containing varying amounts of sulphate, chromate and arsenate were kept at a stable pH of either 2 or 4 over 1 year in suspension. At several time intervals Fe and the oxyanions were measured in solution and alterations of the solid part were observed by XRD and Fourier-Transform infrared (FT-IR) spectroscopy. At pH 2 schwertmannite partly dissolved and the total release of arsenate (24%) was low in contrast to chromate (35.4–57.5%) and sulphate (67–76%). Accordingly, the ionic activity product (log IAP) of arsenated schwertmannite was lowest (13.5), followed by the log IAP for chromated schwertmannite (16.2–18.5) and the log IAP for regular (=non-substituted) schwertmannite (18). At pH 4 schwertmannite transformed to goethite, an effect which occurred at the fastest rate for regular schwertmannite (=arsenate- and chromate-free), followed by chromate and arsenate containing schwertmannite. Both chromate and more evidently arsenate have a stabilizing effect on the schwertmannite structure, because they retarded the dissolution and transformation reactions.These kinetic investigations as well as crystallographic considerations demonstrated that the strength of the Fe(III) complexes with the anions controls the formation process and the stability of schwertmannite: with increasing affinity of the oxyanions to form complexes with Fe(III), the strength of the resulting binding and thus the stability and substitution preference increases.     

Formation and stability of schwertmannite in acidic mining lakes

Schwertmannite (ideal formula: Fe₈O₈(OH)₆SO₄) is typically found as a secondary iron mineral in pyrite oxidizing environments. In this study, geochemical constraints upon its formation are established and its role in the geochemical cycling of iron between reducing and oxidizing conditions are discussed. The composition of surface waters was analyzed and sediments characterized by X-ray diffraction, FTIR spectroscopy and determination of the Fe:S ratio in the oxalate extractable fraction from 18 acidic mining lakes. The lakes are exposed to a permanent supply of pyritegenous ferrous iron from adjacent ground water. In 3 of the lakes the suspended matter was fractionated using ultra filtration and analyzed with respect to their mineral composition. In addition, stability experiments with synthetic schwertmannite were performed. The examined lake surface waters were O₂-saturated and have sulfate concentrations (10.3 ± 5.5 mM) and pH values (3.0 ± 0.6) that are characteristic for the stability window of schwertmannite. Geochemical modeling implied that i) the waters were saturated with respect to schwertmannite, which controlled the activity of Fe³⁺ and sulfate, and ii) a redox equilibrium exists between Fe²⁺ and schwertmannite. In the uppermost sediment layers (1 to 5 cm depth), schwertmannite was detectable in 16 lakes—in 5 of them by all three methods. FTIR spectroscopy also proved its occurrence in the colloidal fraction (1-10 kDa) in all of the 3 investigated lake surface waters. The stability of synthetic schwertmannite was examined as a function of pH (2-7) by a 1-yr experiment. The transformation rate into goethite increased with increasing pH. Our study suggests that schwertmannite is the first mineral formed after oxidation and hydrolysis of a slightly acidic (pH 5-6), Fe(II)-SO₄ solution, a process that directly affects the pH of the receiving water. Its occurrence is transient and restricted to environments, such as acidic mining lakes, where the coordination chemistry of Fe³⁺ is controlled by the competition between sulfate and hydroxy ions (i.e. mildly acidic).