开放流动体系中黄铁矿-黄铜矿原电池反应实验研究

采用双电极体系对黄铁矿-黄铜矿组成原电池反应的腐蚀电流密度研究表明,原电池的腐蚀电流密度随体系中氧化性离子(如Fe3+)浓度的增加而增大;随溶液流速的加快而增大.实验结果对矿山环境污染治理有指导意义.结合原电池模型、混合电位理论和Butler-Volmer方程从理论上对实验结果进行了解释.     

硫化物矿物原电池反应的实验研究进展

自然界中大多数硫化物矿物都有良好的导电性,具有半导体的性质.当具有不同电极电位的矿物在溶液中接触在一起,就会形成原电池发生电化学腐蚀,其中电极电位低的矿物作为原电池的阳极发生氧化反应,其溶解会加剧,而电极电位高的矿物作为原电池的阴极发生还原反应,其溶解会受到抑制.     

尾矿中硫化物风化氧化模拟实验研究

为防治矿山尾矿造成环境污染，对方铅矿，闪锌矿，磁黄铁矿、黄铜矿，黄铁矿进行了风化氧化实验研究，结果显示，硫化物的氧化速率顺序为：方铅矿＞闪锌矿＞磁黄铁矿＞黄铜矿＞黄铁矿，侵蚀液pH值越低，硫化物氧化速率越大，有机物存在对硫化物氧化起缓冲和抑制作用。     

嗜酸性氧化亚铁硫杆菌与硫化物矿石相互作用的实验研究

实验研究了嗜酸性氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans,简称A.f)与硫化物矿石之间的相互作用,以观察不同矿石矿物发生微生物氧化和形成次生矿物的差异。采用ICP-OES分析了反应前后溶液成分变化,利用扫描电子显微镜(SEM)、能谱分析(EDS)和X射线衍射(XRD)等分析手段研究了矿石表面形貌的变化和沉淀物的矿物组成。分析结果表明,A.f对同一矿石中不同矿物作用强度存在明显差异,方铅矿、闪锌矿发生强烈氧化分解,而与黄铁矿的相互作用则较弱。这种差异可能与矿物晶体结构有关,在多种矿物并存的情况下,可能发生了原电池反应,作为阴极的黄铁矿受到保护,而作为阳极的闪锌矿、方铅矿的氧化作用得到促进,总体上表现为A.f对矿石硫化矿物的选择性作用。     

硫化物固—液界面电化学效应实验探讨

硫化物作为一类重要的常见矿物，目前国内外对其表面矿物学特征研究有限。具体到硫化物固－液界面处的行为机理，前人的研究程度就更低了。笔者自行设计了一个Fe1-xS-Cr^6 原电池，通过实测电动势（E），t-E关系曲线，溶液可见光吸收谱及其λ－A关系曲线，阐明硫化物与Cr^6＋溶液间的界面行为机理。认为其界面行为过程为；硫化物溶解→离子反应（氧化还原）→吸附Cr^3 。该原电池与一般原电池结构不同，其主要差别在于将反应电极和测量电极分开，从而解决电极反应过程中的浓度极化问题，提高了电化学实验的精度。该研究成果有助于揭示矿物－液体相互作用机理，完善和丰富表面矿物学研究内容，深化化界面成矿理论，并对环境治理，矿物材料应用等开发领域具有重要的参考价值。     

黄铁矿在不同pH值硫酸钠溶液中的电化学腐蚀研究

溶液的pH值对黄铁矿的电化学腐蚀行为有着重要的影响。本文运用开路电位测量、Tafel扫描、循环伏安扫描以及电化学阻抗谱等电化学测试技术,研究黄铁矿在pH值分别为2.0、6.5、11.0的0.1mol/L Na2SO4溶液中的电化学腐蚀行为。结果表明:溶液中pH值升高时,黄铁矿的开路电位降低,腐蚀电流升高,阻抗谱中圆弧半径减小,这些变化说明了黄铁矿变得更加容易被腐蚀。分析其原因为当溶液中pH值升高时,黄铁矿氧化过程产生的中间产物S2O2-3变得比较稳定,因此,由其分解产生的单质硫的量减少,继而因单质硫在黄铁矿表面吸附造成的钝化作用也随之减弱,黄铁矿的腐蚀速率增加。     

塔西南缘铅锌矿硫同位素特征及硫的来源探讨

通过塔西南缘铅锌矿带金属硫化物(方铅矿、黄铁矿、黄铜矿、闪锌矿)的硫同位素测试研究,结果显示δ34S值范围在-38.3‰～24.0‰,具双峰式分布,推测两种或两种以上流体相混合是导致矿床硫同位素组成变化的主要原因,一类硫化物的δ34S值集中在-6‰～6‰,组成的矿石呈细粒、草莓状结构及浸染状构造;另一类硫化物的δ34S值集中在-32‰～-24‰,组成的矿石呈粗粒、脉状或角砾状构造。两种流体受构造应力和压实作用的影响,沿着断裂或岩石的裂隙运移并相混合,发生热化学硫酸盐还原反应,产生的HS-与Zn2+、Pb2+结合形成闪锌矿、方铅矿,在有利部位沉淀成矿。硫主要来源于海水硫酸盐。     

低温平衡ZnS-PbS-FeS-H_2S四组分体系的热力学分析

本文介绍了热力学相图在浅成低温热液硫化物矿床中的应用,并以三江地区金顶铅锌矿床中的矿物含量为例进行定量分析。一方面在相同温度下,浓度与矿物(组合)之间存在对应关系,并且一些矿物(组合)对应特定的酸碱条件,例如在400K和105Pa条件下,黄铁矿与方铅矿的组合在碱性环境下稳定,而方铅矿与闪锌矿的组合在酸性环境中稳定,且酸性条件下当lg[Pb2+]≥-11.29时,才开始出现方铅矿;另一方面对比了298.15K和400K条件下矿物共生组合的及介质pH值的变化情况,并得到400K条件下形成矿物或矿物组合所需离子的浓度更高。     

相山西部牛头山铅锌矿化体成矿物质来源:原位硫同位素的制约

近年来,在相山铀矿田的西部牛头山地区深部发现了铅锌矿化体,其成因机制不明.为探讨牛头山铅锌矿化体物质来源,开展了硫化物原位硫同位素分析研究.根据硫化物矿物之间的充填和包裹关系判断,铅锌矿化体金属硫化物形成的先后顺序是:黄铁矿形成最早,方铅矿和闪锌矿次之,细脉状黄铜矿形成最晚.利用LA-MC-ICP-MS技术对矿化体中几种金属硫化物分别进行了系统的原位硫同位素分析.结果显示:黄铁矿、闪锌矿、方铅矿、细脉状黄铜矿的δ34S值介于-4.8‰~+5.4‰之间,各硫化物矿物之间硫同位素未达到完全平衡分馏,利用黄铁矿δ34S值得到的矿化流体δ34S_ΣS值（总硫同位素组成）近似为+3.7‰,与共生矿物对（闪锌矿-方铅矿）图解法得到的闪锌矿和方铅矿沉淀时矿化流体的δ34S_ΣS值（+3.2‰）相近,表明形成牛头山铅锌矿化体的矿化流体δ34S_ΣS值大约为+3.7‰,为岩浆硫.结合前人的岩浆岩年龄数据,我们判断该铅锌矿化体金属硫化物的硫可能主要来自次火山岩相花岗斑岩岩浆热液.同一薄片中闪锌矿δ34S值高于共生的方铅矿,表明两者硫同位素基本平衡,利用共生矿物对（闪锌矿-方铅矿）硫同位素温度计计算得出平衡温度为197~476℃,与前人通过脉石矿物流体包裹体得到的铅锌矿化流体温度基本一致.相山火山盆地与相邻的北武夷黄岗山、梨子坑等产铅锌矿的火山盆地具有相似的成矿条件及成矿物质来源,使相山火山盆地具有良好的铅锌多金属找矿前景.      

地壳浅部导电性矿物的一种新的压溶机制：应力原电池过程

以黄铁矿为例,通过导电性矿物的力学-电化学相互作用实验,得出：导电性矿物的电极电位与弹性轴压应力是较好的负线性相关关系。以此为基础,通过电化学理论分析,得出：地壳浅部与溶液接触的导电性矿物颗粒内部存在各种各样的应力原电池,通过应力原电池过程,压溶作用得以实现。导电性矿物应力原电池引起压涛作用的发现,无疑对诸如构造地球化学、地电化学甚至湿法冶金等领域的有关研究具有重要意义。     

Galvanic interaction between galena and pyrite in an open system

1IntroductionMost sulfide minerals in nature have perfect con-ductivity and possess semiconducting properties.Gal-vanic corrosion may occur when two sulfide mineralswith different potentials are connected together in thesolution.The mineral with the highe…     

Galvanic interactions between metal sulfide minerals in a flowing system: Implications for mines environmental restoration

Managing mine water that has been contaminated with metal sulfide minerals due to galvanic corrosion is becoming an increasingly important environmental problem. Here, galvanic corrosion was investigated by studying galvanic interactions between pyrite–chalcopyrite and pyrite–galena in flowing mediums such as mine discharge water and flowing rainwater. The results showed that the corrosion current density of pyrite–galena is greater than that of pyrite–chalcopyrite under identical conditions. The corrosion current density of the galvanic cell tends to increase with increasing concentrations of strongly oxidizing ions (e.g., Fe³⁺) in the flowing medium, whereas the existence of non-oxidizing and non-reducing ions (e.g., Na⁺) have no obvious influence on the galvanic cell. In addition, the corrosion current density increases with increasing flow rate. Using the galvanic model, mixed potential theory and Butler–Volmer equation, the experimental results were explained theoretically. Because these experiments were performed under conditions very similar to those seen in mine discharge water and flowing rainwater, these results have direct implications for the future management and control of environmental pollution from mining operations.     

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.     

Onboard experiment investigating metal leaching of fresh hydrothermal sulfide cores into seawater

We observed the initial release rate of metals from four fresh (i.e., without long time exposure to the atmosphere) hydrothermal sulfide cores into artificial seawater. The sulfide samples were collected by seafloor drilling from the Okinawa Trough by D/V Chikyu, powdered under inert gas, and immediately subjected to onboard metal-leaching experiments at different temperatures (5 °C and 20 °C), and under different redox conditions (oxic and anoxic), for 1–30 h. Zinc and Pb were preferentially released from sulfide samples containing various metals (i.e., Mn, Fe, Cu, Zn, Cd, and Pb) into seawater. Under oxic experimental conditions, Zn and Pb dissolution rates from two sulfide samples composed mainly of iron disulfide minerals (pyrite and marcasite) were higher than those from two other sulfide samples with abundant sphalerite, galena, and/or silicate minerals. Scanning electron microscopy confirmed that the high metal-releasing sample contained several galvanic couples of iron disulfide with other sulfide minerals, whereas the low metal-releasing sample contained fewer galvanic couples or were coated by a silicate mineral. The experiments overall confirmed that the galvanic effects with iron disulfide minerals greatly induce the initial release of Zn and Pb from hydrothermal sulfides into seawater, especially under warm oxic conditions.     

硫化物矿物氧化反应动力学实验研究

硫化物矿床和含硫化物矿床（如中高硫煤）在开发过程中由于氧化作用向环境释放大量的酸、硫酸盐、重金属及其它有害物质,造成一定范围内的次生地球化学异常和环境污染;而中国大陆硫化物的排放量2010年将达到39．1×10 6 t。因此,人们对硫化物矿物在表生环境下的氧化行为日益重视。硫化物矿物的氧化速率受矿物本身物理化学特性（组成、结构、表面性质）和介质条件（溶解氧DO、Fe 3＋浓度、pH、Eh、温度及微生物）等多种因素的控制。在全面分析近年来国内外文献的基础上,系统介绍了硫化物矿物氧化动力学实验研究方法、实验参数的选择、反应机理、反应产物及反应速率等的研究现状。指出今后应加强对初始阶段的氧化反应速率、反应中间产物、多因素的综合作用、分子水平上的反应机理解释等方面的研究。     

Galvanic interactions between galena–sphalerite and their reactivity

The galvanic effect between the main associated mineralogical phases in a mineral sphalerite concentrate was evaluated using an alternative methodology. Comparative voltammetric studies were performed between high purity galena mineral (94.65%) and sphalerite concentrate (content of 78.11% sphalerite, ZnS; 13.64% galena, PbS; 0.57% chalcopyrite, CuFeS₂; 0.41% cadmium sulfide, CdS; and 0.11% arsenopyrite, FeAsS) using carbon paste electrodes (CPE) in order to identify galvanic interactions that affect their reactivity. The electrolyte was an aqueous solution of 0.1 M NaNO₃ (pH 6.5). The results showed that, in sphalerite concentrate, the electrochemical reactivity of the galena was diminished and displaced to more positive potentials with respect to the high purity galena mineral response. This behavior can be attributed to the galvanic protection offered by the sphalerite on the galena, thereby avoiding its free oxidation. On the other hand, sphalerite oxidation was diminished by the formation of a passive products film that is dissolved to more positive potentials which provokes oxidation of other minerals like CuFeS₂, (Zn,Cd)S and FeAsS present in a minor proportion in the sphalerite concentrate.     

四川平武县金洞沟金矿地质特征及其成因探讨

金洞沟金矿床是位于四川省北部平武县境内的小型岩金矿床。在详细研究矿床地质特征的基础上,测试了石英包裹体均一温度、盐度、化学成分及H、O同位素组成,分析了金属硫化物（黄铁矿、方铅矿、闪锌矿)的S同位素组成,对金的成矿作用进行了深入探讨。研究结果表明：金洞沟金矿床为低温热液型金矿床,其成矿物源主要是志留系茂县群浅变质碎屑岩系,矿石中硫化物以黄铁矿为主,硫化物含量约1%,为少硫化物型矿石。流体包裹体及S、H、O同位素研究显示成矿流体是主要由大气降水组成的热液,成矿温度为125～185 ℃,平均温度为148.7 ℃,属低温热液型金矿床。在此基础上,提出金洞沟金矿床的成矿作用经历了原始含矿岩系（矿源层)的形成、区域变质作用衍生矿源层的形成、热液成矿作用及表生氧化富集等4个阶段,韧性剪切构造活动是引起金活化、迁移和富集的主要因素。该成果为该矿床成因的认识和找矿工作提供了参考。     

Interaction of thionocarbamate and thiourea collectors with sulphide minerals: a flotation and adsorption study

The ability of O-isopropyl-N-ethyl thionocarbamate (IPETC), O-isobutyl-N-ethoxycarbonyl thionocarbamate (IBECTC) and butyl ethoxycarbonyl thiourea (BECTU) collectors to increase the flotation of the sulphide minerals, chalcopyrite, galena and pyrite, has been studied. For each collector, the flotation characteristics of these minerals, flotation rate constant and flotation recovery maximum, have been calculated from the flotation data and compared as a function of pH and collector concentration. Overall, the flotation performance of these collectors is stronger for chalcopyrite than for galena and pyrite. Flotation increases with collector concentration and decreasing pH values. For chalcopyrite, the collector performances of BECTU are slightly better than those of IPETC but far superior to those of IBECTC, especially at high pH values or at low collector concentrations. The flotation performance of these collectors has been shown to be in good agreement with the amount of collector adsorbed at the mineral surface. The affinity of BECTU for the various minerals has been calculated using a multilayer adsorption model.     

Re–Os isotope evidence for mixed source components in carbonate-replacement Pb–Zn–Ag deposits in the Lavrion district,Attica, Greece

The Lavrion ore district contains carbonate-replacement and vein-type Pb–Zn–Ag deposits as well as low-grade porphyry Mo, Cu–Fe skarn, and minor breccia-hosted Pb–Zn–Cu sulfide mineralization. These ore types are spatially related to a Late Miocene granodiorite intrusion (7 to 10 Ma), and various sills and dikes of mafic to felsic composition. Samples of sphalerite and pyrite from the Ilarion carbonate replacement deposit, and galena from Vein 80 (vein-type mineralization) in the Adami deposit show heterogeneous Re–Os values. These values were partially disturbed by hydrothermal activity associated with the formation of hydrothermal veins (e.g., Vein 80). A plot of initial ¹⁸⁷Os/¹⁸⁸Os versus 1/Os_common ratios for pyrite and sphalerite from the Ilarion deposit form a mixing line (r²?=?0.78) between high concentration crustal-like and low concentration mantle-like end-members, or two crustal end-members one of which was more radiogenic than the other. Based on the Re–Os systematics and previously published geological and geochemical evidence, the most plausible explanation for the Re–Os isotope data is that ore-forming components were derived from mixed sources, one of which was a radiogenic crustal source from schists and carbonates probably near intrusion centers and the other, intrusive rocks in the district that are less radiogenic. Although the Re and Os concentrations of galena from Vein 80 are above background values they cannot be used as a chronometer. However, the results of the current study suggest that although pyrite, sphalerite, and galena are poor geochronometers in this ore deposit, due to partial open-system behavior, they still yield valuable information on the origin of the source rocks in the formation of bedded replacement and vein mineralization in the Lavrion district.