黄铁矿含金机理探讨   总被引：2，自引：0，他引：2  

李国华  王大伟  黄志良 《地质与资源》2001,10(2):102-105

在大多数金矿床中,黄铁矿是金的主要载体矿物之一.本文从黄铁矿的晶体结构化学角度出发,分析了黄铁矿的晶体结构特点;探讨了金以An⁺和An^-离子形式分别替代Fe²⁺离子和S^2-离子的形成机理以及以可见金方式在黄铁矿中的赋存机制.通过分析,认为金在黄铁矿中的富集主要与黄铁矿的晶体结构有关,特别是与黄铁矿中的Fe-S、S-S、An-S和Fe-Au键的电子结构特点有关.  相似文献   

高盐强酸性地下水中复合苯系污染物原位芬顿氧化实验研究   总被引：1，自引：0，他引：1       下载免费PDF全文

郭威  袁放  张佳  谢斌  冯学洋  陈鸿汉 《水文地质工程地质》2021,48(2):182-189

在原位氧化过程中,实际场地地下水和含水介质的物化特征是影响氧化效果的重要因素,而目前对此影响的研究较少。以某场地实际高盐强酸性复合苯系污染地下水为研究对象,以地下水中2-硝基-4-甲氧基苯胺(2-nitro-4-methoxyaniline,2-N)和3-硝基-4-甲氧基苯胺(3-nitro-4-methoxyaniline,3-N)为特征污染物,探究芬顿(Fenton)试剂原位氧化特征,并研究液相环境因素(初始H2O2浓度、初始Fe2+浓度、初始pH值、初始醋酸(Acetic acid,HAc)浓度、初始SO4^2-浓度)以及含水层介质对Fenton法去除2-N和3-N的影响。结果显示:(1)Fenton法去除2-N和3-N效果显著,且在初始液相条件为c(H2O2)=7 mmol/L、c(Fe²⁺)=4 mmol/L、pH=4、c(HAc)=0 mg/L和c(SO4^2-)=0 mmol/L时去除效果最佳;(2)各因素对Fenton法氧化2-N和3-N的影响不同,加入H₂O₂和Fe²⁺使2-N和3-N去除率上升,增大HAc浓度使2-N和3-N去除率下降;(3)含水层介质对2-N和3-N具有一定吸附性,且对3-N的吸附性强于2-N,二者在本实验中最大吸附态占比分别为29%和42%,而吸附态的存在会抑制Fenton法对2-N和3-N的去除;(4)矿物分析结果显示介质含有少量黄铁矿,在硫酸环境下,介质腐蚀溶解释放Fe²⁺,在达到一定浓度后,无需额外添加Fe²⁺即可完成Fenton反应进而去除2-N和3-N。  相似文献   

重金属污染土壤修复的Pb2+钝化产物稳定性     

赵玉岩  姜伟明  臧利斌  孙文  汤肖丹 《吉林大学学报(地球科学版)》2020,50(3):875-882

自然状态下土壤中重金属元素是否稳定存在是重金属污染固化修复技术中的核心问题。本文以常见重金属离子Pb²⁺为例,分析土壤中重金属离子与常见离子基团结合的稳定性。将第一性原理应用于Pb的存在形态和稳定性的分析,计算了PbCO₃、PbSO₄、PbCl₂、Pb₃（PO₄）₂、PbAl₂O₄和Pb₃Fe₂（PO₄）₄的自由能、能带和态密度。首先推断Pb²⁺和CO₃^2-、SO₄^2-、Cl^-、PO₄^3-等土壤中常见阴离子的结合稳定性,再判断加入金属阳离子Al³⁺和Fe³⁺对体系稳定性的影响。结果表明：铅化合物自由能从高到低趋势为PbCl₂、PbAl₂O₄、PbCO₃、PbSO₄、Pb₃（PO₄）₂、Pb₃Fe₂（PO₄）₄,其相应的结构稳定性顺序从大到小为Pb₃Fe₂（PO₄）₄、Pb₃（PO₄）₂、PbSO₄、PbCO₃、PbAl₂O₄、PbCl₂。通过对能带和态密度的分析,首先确定了SO₄^2-和PO₄^3-的引入能够增强含Pb体系的稳定性,进一步加入金属阳离子Fe³⁺会使体系更稳定。推测SO₄^2-、PO₄^3-为治理Pb²⁺污染合适的官能团,应选择容易释放SO₄^2-、PO₄^3-的物质作为合适的钝化剂。在实际应用中可选择磷酸二氢钠、无水硫酸钠、脱硫石膏等作为钝化剂。  相似文献   

祁连山老虎沟地区夏季大气颗粒物中水溶性离子的变化特征     

张艳阁  徐建中  余光明 《冰川冻土》2017,39(5):1022-1028

为了研究青藏高原东北缘老虎沟地区大气颗粒物中水溶性无机离子组分的变化特征,于2016年7月16日至8月11日共采集13个PM_2.5样品和4套粒径分级样品。研究结果显示：非沙尘期间,水溶性离子总质量浓度为2.35 μg·m^-3,主要离子SO₄^2-、Ca²⁺、NH₄⁺和NO₃^-的浓度分别为1.28、0.33、0.32和0.28 μg·m^-3,约占水溶性离子浓度总和的94%;沙尘期间,水溶性无机离子总质量浓度为12.63 μg·m^-3,是非沙尘期间浓度的5倍,主要离子SO₄^2-、Ca²⁺、Cl^-、Na⁺和NO₃^-的浓度依次为5.36、4.77、0.80、0.62和0.61 μg·m^-3,约占水溶性离子浓度总和的96%。分级样品分析结果表明,NO₃^-主要分布在粗颗粒模态,可能是前体物在粉尘表面发生非均相反应产生。在沙尘时期,SO₄^2-主要为粉尘贡献,集中分布在粗颗粒模态。在非沙尘时期,SO₄^2-在粗颗粒模态和积聚模态都有较多的分布。积聚模态的SO₄^2-主要是通过前体物与NH₃发生均相反应产生。据估算,非沙尘时期的二次反应对PM_2.5中SO₄^2-的贡献约为80%。  相似文献   

洮河流域水化学特征及其时空变化研究     

朱朝霞 《地下水》2023,(4):108-111

以洮河流域河水为研究对象,通过对2018年每隔1月洮河干流及支流博拉河和广通河采样点的河水进行水化学研究,揭示了洮河流域河水的水化学组成,探讨了其水化学性质时空变化。结果表明：洮河流域水质偏碱性,干流上游pH值小于下游,并在枯水期都比丰水期为大;矿化度呈枯水期比丰水期小,河水属于中等矿化度水和适度硬水;总硬度、电导率呈枯水期比丰水期大;HCO₃^-、Ca²⁺、Na⁺、Cl^-、SO₄^2-、CO₃^2-含量呈枯水期比丰水期大;干流上游HCO₃^-、Ca²⁺、CO₃^2-含量大于下游,干流上游Mg²⁺、K⁺、Na⁺、Cl^-、SO₄^2-、MnO₄<...  相似文献   

鄂尔多斯盆地南部旬邑-宜君地区直罗组古层间氧化带地球化学特征及水-岩作用探讨     

张良 《地质与勘探》2023,59(6):1250-1259

鄂尔多斯盆地南部旬邑-宜君地区直罗组古层间氧化带具有明显分带特征,通过对不同分带砂岩主量、微量、稀土元素及环境敏感参数特征对比研究,将旬邑-宜君地区古层间氧化带发育的水-岩作用过程划分成两个阶段：古层间氧化带形成和大规模成矿阶段、二次还原改造阶段。(1)古层间氧化带形成和大规模成矿阶段：含氧水进入目的层砂体,使砂体中Fe²⁺氧化成Fe³⁺(Fe²⁺含量最低,Fe³⁺最高);砂体中的U被氧化为U⁶⁺,形成铀酰腐殖酸盐络合物发生迁移(U、Corg、S含量最低、Th/U比值最高);长石高岭土化使Si发生流失(SiO₂含量降低);携带大量U的氧化流体运移至氧化还原过渡带(Corg、∑S含量最高、Fe²⁺含量仅低于灰绿色砂体),还原剂(有机质和黄铁矿等)将U⁶⁺还原成U⁴⁺,形成沥青铀矿;U⁴⁺与SiO₄^4-发生反应形成铀石(Th/U比...  相似文献   

秦岭主峰太白山北麓降水化学特征分析     

王少安  卢爱刚  康世昌 《冰川冻土》2015,37(3):676-684

利用太白山北麓2011年12月-2013年7月共39次降水样品数据资料, 定量分析了该区域降水化学的特征和时间变化规律. 结果表明: 太白山北麓地区降水中, 除常量离子Na⁺、NH₄⁺、K⁺、Mg²⁺、Ca²⁺、F^-、Cl^-、SO₄^2-、NO₃^-外, CO₃^2-、HCO₃^-、PO₄^3-及低分子有机酸也占有相当比例. 研究区降水常量离子浓度的顺序依次为: NH₄⁺ > SO₄^2- > Ca²⁺ > NO₃^- > Na⁺ > Cl^- > Mg²⁺ > K⁺ > F^-, 离子总浓度表现出明显的季节变化: 夏季(轻度污染) < 秋季(中等污染) < 春季(严重污染) < 冬季(极重污染). 利用因子分析法得出太白山北麓地区降水组分主要有三种来源; Na⁺、Cl^-、Mg²⁺、Ca²⁺主要来自地壳源, SO₄^2-、NO₃^-、NH₄⁺主要来自人为源, K⁺和F^-主要由海盐源和人为源共同贡献. 根据Hysplit 后向气流轨迹分析, 得出不同路径气团降水离子组分不同: 受地形等因素影响, 北方路径的气团比南方路径气团离子总浓度较高; 受土壤类型影响, 西北方向气团降水Na⁺、Mg²⁺、Ca²⁺浓度较高; 受人为活动影响, 东北方向SO₄^2-、NO₃^-、NH₄⁺浓度较高.  相似文献   

氟对磷酸盐矿物形成影响的试验研究——Ca²⁺-HPO₄^2--HCO₃^1--F^1--H₂O体系          下载免费PDF全文

姜善春  陈友明  潘均 《地质科学》1964,5(4):341-352

我們在前一篇文章里曾討論了Ca²⁺-HPO₄^2--F^1--H₂O体系中氟对磷酸盐矿物形成影响的若干方面。为了使該項模拟試驗工作更符合于表生作用条件,我們在叶連俊教授的指导下,在上述实驗体系中增加了一个組分--HCO₃^1-,进行了Ca²⁺-HPO₄^2--HCO₃^1-F^1--H₂O体系的試驗研究。其目的为进一步探索在合有HCO₃^1-組分的体系中氟对磷酸盐矿物形成的影响,以及CO₃^2-能否进入磷灰石晶格和磷酸盐矿物与碳酸盐矿物的沉积分异順序等問題。  相似文献   

膏盐层在矽卡岩型铁矿成矿中的作用   总被引：11，自引：0，他引：11  

李延河  谢桂青  段超  韩丹  王成玉 《地质学报》2013,87(9):1324-1334

矽卡岩型铁矿是我国富铁矿的重要类型,约占全国富铁矿总储量的60%。虽然膏盐层与矽卡岩型铁矿的关系已引起部分矿床学家的关注,但膏盐层的控矿机制尚不清楚。本文以我国最重要的大冶式和邯邢式矽卡岩型铁矿为例,探讨了膏盐层在矽卡岩型铁矿成矿中的作用。膏盐层富含碳酸盐、石膏和石盐等,不仅可以为成矿提供大量Na⁺、Cl^-、CO3²⁺等矿化剂,使围岩发生钠长石化、方柱石化（氯化）和矽卡岩化等蚀变,使Fe²⁺以NaFe-Cl等络合物形式搬运,膏盐层还是地壳深处最重要的氧化障,能够将硅酸盐熔体和成矿溶液中的Fe²⁺氧化成Fe³⁺,富集形成铁矿床,是矽卡岩型铁矿成矿的关键因素。大冶地区的膏盐层属于中三叠统下部的嘉陵江组,邯邢地区的膏盐层属于中奥陶统马家沟组—峰峰组。大冶和邯邢式矽卡岩型铁矿中硫化物的δ³⁴S_V-CDT值异常高,计算结果表明矿床中约80%的硫来自膏盐层硫酸盐的还原,还原温度多在500℃以上,但硫化物的沉淀温度相对较低,就位时间稍晚;硫酸盐的δ³⁴S_V-CDT值和还原温度越高,硫化物的δ³⁴S_V-CDT值越高,原始岩浆硫所占比例越高,硫化物的δ³⁴S_V-CDT值越低。当炽热的岩浆与膏盐层（CaSO₄）发生同化混染时,SO₄^2-将硅酸盐熔体中的Fe²⁺氧化成Fe³⁺,Fe³⁺无法进入硅酸盐矿物晶格,而形成Fe₃O₄/Fe₂O₃进入熔体,铁氧化物在磷、氯化钠、水等挥发分和盐类物质的作用下在岩浆房中与硅酸盐熔体发生不混熔,形成铁矿浆,沿构造有利部位贯入,形成矿浆型铁矿床。在矽卡岩型铁矿床中,矿浆充填型和热液交代型矿体同时存在,二者在空间上具有一定的分带性,有时渐变过渡,矿浆充填型铁矿体通常位于深部靠近成矿岩体的部位,而热液交代型铁矿体位于成矿流体运移的前方。在SO₄^2-氧化Fe²⁺的同时自身被还原为S^2-,与Fe²⁺结合形成硫铁矿,分布在铁矿的上部或边部。  相似文献   

中国第二次北极科学考察沿线气溶胶成分分析   总被引：7，自引：2，他引：5  

徐建中  孙俊英  任贾文  秦大河 《冰川冻土》2005,27(2):205-212

对2003年7月15~9月28日间中国第二次北极科学考察沿线所采集的气溶胶样品进行分析,获得了Na⁺、NH₄⁺ 、Ca²⁺、Cl^-、MSA、SO₄^2- 等11种离子的浓度数据(文中使用当量浓度).根据相关分析, 可将11种离子分为3类: 海盐源离子, 包括Na⁺、Mg²⁺、K⁺、Ca²⁺、Cl^-、SO₄^2-; 人为源, 包括NH₄⁺ 、NO₃^-; 其它源, 包括 CH₃COO^-、MSA、C₂O₄^2-. 气溶胶以海盐气溶胶为主, Cl^-、Na⁺ 离子分别是阴阳离子中含量最大的离子, (Na⁺ +Cl^-)对气溶胶载量(所测定的阴阳离子的总和)的贡献平均为60.2%, 占气溶胶总量的一半以上. NH₄⁺ /SO₄^2- 的比值的平均为0.45, 根据当地的大气环境和气溶胶的离子平衡, 认为气溶胶样品中NH₄⁺ 和 SO₄^2- 主要是以 NH4HSO4的形式结合. 根据考察沿线 NO₃^- 浓度的变化, 把考察沿线大致分为3个区: 日本海区, 中值为15.2 neq·m^-3; 鄂霍次克海及白令海区, 中值为1.8 neq·m^-3; 北冰洋区, 其浓度较低, 中值为0.4 neq·m^-3. 考察沿线白令海是MSA的高产区.  相似文献   

Pyrite oxidation in the tertiary sands of the London Basin aquifer     

《Applied Geochemistry》1994,9(2):161-173

Possible groundwater quality changes related to pyrite oxidation during artificial groundwater recharge and its storage in the Tertiary sands of the London Basin are investigated. Pyrite textures in the Tertiary sands are examined by scanning electron microscopy while an experimental approach is used to study mechanisms of pyrite oxidation and of some associated chemical reactions. In the Tertiary sands of the London Basin aquifer, pyrite occurs as aggregates made of discrete individual crystals 0.5–5 μm in size or, in a cryptocrystalline form, often as pseudomorphs of biogenic debris. It can expose a very large specific surface area to porefluids. Although ferric iron, which can be an oxidising agent of pyrite, is abundant in the solid phase of the Tertiary sands, it does not appear to take a significant part in this case. Pyrite oxidation seems to rely on a supply of oxygen. Leaching experiments using a 0.001 M H₂SO₄ solution were carried out to examine interactions between mildly acidic groundwater resulting from pyrite oxidation at a moderate rate and the host-sediment. In the presence of CaCO₃ in the solid phase, H⁺ is rapidly buffered by CaCO₃ dissolution. Oscillations of this reaction around equilibrium appear to trigger cation-exchange reactions on clay mineral surfaces, resulting in the release of major cations (e.g. K and Mg) into solution. In the absence of CaCO₃ in the solid phase, H⁺ buffering occurs less efficiently solely through exchange of cations for H⁺ on clay minerals surfaces. If the rate of pyrite oxidation in the Tertiary sands becomes high enough for the buffering capacity of the system to be exceeded, the groundwater pH begins to fall. Interactions between low pH (2) groundwaters and the host sediments were examined by leaching solid material in 0.01 M and 0.1 M H₂SO₄ solutions. Concentrations of Fe, Mg and K increase in solution throughout the experiment, indicating partial dissolution of clay minerals. The composition of the porefluid thus depends on the geochemical composition and surface area of the different clay minerals present.  相似文献   

胶东金矿床Au迁移富集的地球化学探讨          下载免费PDF全文

张言  杨凤筠 《地质科学》1992,(2):193-197

本文编制了系统 Fe²⁺—Fe³⁺—∑S—∑CO₂—[SO₁^2-]和 Fe²⁺—FeS—FeCO—Fe(OH)₂的相图,以及溶液中络合物 Au—s 和 Au—Cl 在不同温度下的 C_Au—PH 图。有证据表明,金可能是以 Au—S 络合物形式迁移的,控制金沉淀的主要因素是溶液的 Eh 和∑S 的活度。  相似文献   

Botanical constraints on pyrite formation     

《Chemical Geology》2007,236(3-4):228-246

  相似文献   

Pyrite (FeS₂) oxidation: A sub-micron synchrotron investigation of the initial steps   总被引：1，自引：0，他引：1  

Anand P. Chandra 《Geochimica et cosmochimica acta》2011,75(20):6239-6254

Pyrite is an environmentally significant mineral being the major contributor to acid rock drainage. Synchrotron based SPEM (scanning photoelectron microscopy) and micro-XPS (X-ray photoelectron spectroscopy) have been used to characterise fresh and oxidised pyrite (FeS₂) with a view to understanding the initial oxidation steps that take place during natural weathering processes. Localised regions of the pyrite surface containing Fe species of reduced coordination have been found to play a critical role. Such sites not only initiate the oxidation process but also facilitate the formation of highly reactive hydroxyl radical species, which then lead the S oxidation process.Four different S species are found to be present on fresh fractured pyrite surfaces: S₂²⁻_(bulk) (4-fold coordination), S₂²⁻_(surface) (3-fold coordination), S²⁻ and S⁰/S_n²⁻ (metal deficient sulfide and polysulfide respectively). These species were found to be heterogeneously distributed on the fractured pyrite surface. Both O₂ and H₂O gases are needed for effective oxidation of the pyrite surface. The process is initiated when O₂ dissociatively and H₂O molecularly adsorb onto the surface Fe sites where high dangling bond densities exist. H₂O may then dissociate to produce OH radicals. The adsorption of these species leads to the formation of Fe-oxy species prior to the formation of sulfoxy species. Evidence suggests that Fe-O bonds form prior to Fe-OH bonds. S oxidation occurs through interactions of OH radicals formed at the Fe sites, with formation of SO₄²⁻ occurring via S₂O₃²⁻/SO₃²⁻ intermediates. The pyrite oxidation process is electrochemical in nature and was found to occur in patches, where site specific adsorption of O₂ and H₂O has occurred. Fe and S oxidation was found to occur within the same area of oxidation probably in atomic scale proximity. Furthermore, the O in SO₄²⁻ arises largely from H₂O; however, depending on the surface history, SO₄²⁻ formed early in the oxidation process may also contain O from O₂.  相似文献   

Theoretical studies on metal thioarsenites and thioantimonides: synergistic interactions between transition metals and heavy metalloids     

JA Tossell 《Geochemical transactions》2000,1(1):16-7

Recently we established that the ternary complex, CuAsS(SH)(OH) has an unusually high stability and makes a large contribution to the total concentrations of both Cu and As in sulfidic solutions equilibrated with Cu and As sulfide minerals. This ternary complex has an unusual structure, containing a bond which is formally Cu(I)–As(III), along with a broken As–S bond. We have now found that complexes with similar structures exist for Au⁺ and Tl⁺ coordinated to AsS(SH)(OH)^-. However, such a direct metal–metalloid bond is not a requirement for stability. In fact, TlAsS(SH)(OH) is unstable while AuAsS(SH)(OH) is highly stable (compared to the aquo ion). Zn²⁺, Cd²⁺, Hg²⁺ and Pb²⁺ also form bonds to the As of AsS(SH)(OH), but without breaking any As–S bonds, and HgAsS(SH)(OH)⁺ and PbAsS(SH)(OH)⁺ are particularly stable complexes. Calculated structures are shown for these complexes, gas-phase energies are calculated, and formation constants in aqueous solution are estimated. The SbS(SH)(OH)^- ion forms analogous complexes, with similar stabilities. However, the Au⁺ complex of SbS(SH)(OH)^- is slightly less stable than the Cu⁺ complex, opposite to the order found for the AsS(SH)(OH)^- ligand. The Au⁺ and AuSH complexes of AsSSHOH^- or AsS(SH)₂ ^- may be implicated in "invisible gold" in arsenian pyrites. Vibrational frequencies are given for the AuAsS(SH)₃ ^- complex and the XANES energies of this complex and Au(SH)₂ ^- are compared. The existence of such strong complexes may explain the many correlations observed between the concentrations of coinage metals and metalloids.  相似文献   

Redox potential (Eh) and anion effects of pyrite (FeS₂) leaching at pH 1     

Anand P. Chandra  Andrea R. Gerson 《Geochimica et cosmochimica acta》2011,75(22):6893-6911

Pyrite plays the central role in the environmental issue of acid rock drainage. Natural weathering of pyrite results in the release of sulphuric acid which can lead to further leaching of heavy and toxic metals from other associated minerals. Understanding how pyrite reacts in aqueous solution is critical to understanding the natural weathering processes undergone by this mineral. To this end an investigation of the effect of solution redox potential (Eh) and various anions on the rate of pyrite leaching under carefully controlled conditions has been undertaken.Leaching of pyrite has been shown to proceed significantly faster at solution Eh of 900 mV (SHE) than at 700 mV, at pH 1, for the leach media of HCl, H₂SO₄ and HClO₄. The predominant effect of Eh suggests electrochemical control of pyrite leaching with similar mechanism(s) at Eh of 700 and 900 mV albeit with different kinetics. Leach rates at 700 mV were found to decrease according to HClO₄ > HCl > H₂SO₄ while at 900 mV the leach rate order was HCl > HClO₄ > H₂SO₄. Solution Fe³⁺ activity is found to continually increase during all leaches; however, this is not accompanied by an increase in leach rate.Synchrotron based photoemission electron microscopy (PEEM) measurements showed a localised distribution of adsorbed and oxidised surface species highlighting that pyrite oxidation and leaching is a highly site specific process mediated by adsorption of oxidants onto specific surface sites. It appears that rates may be controlled, in part, by the propensity of acidic anions to bind to the surface, which varies according to , thus reducing the reactive or effective surface area. However, anions may also be involved in specific reactions with surface leach products. Stoichiometric dissolution data (Fe/S ratio), XPS and XRD data indicate that the highest leach rates (in HCl media at 900 mV Eh) correlate with relatively lower surface S abundance. Furthermore, there are indications that solution Cl⁻ assists oxidation especially at higher Eh through the prevention of surface S⁰ buildup at reactive surface sites.  相似文献   

Geochemical Styudy of Gold and Arsenic Mineralization of the Carlin-Type Gold Deposits,Qinling Region,China     

Fuxin Zhang  Jianqin Ma  Yanjing Chen 《中国地球化学学报》2001,20(4):333-342

Element geochemistry of gold arsenic and mineralogical features of their sulfides in the Carlin-type gold depostis of the Qinling region are discussed in this paper.The initial contents of ore-forming elements such as glod and arsenic are high the ore-bearing rock series in the Qinling region.Furthermore,both the metals are concentrated mainly in the diagenetic pyrite.Study on the mineralogy of arsenic-bearing sulfide minerals in the ores demonstrated that there is a poistive correlation between gold and arsenic in the sulfide minerals.Available evidence suggests that gold in the As-bearing sulfide minerals in likely to be presented as a charge species(Au ),and it is most possible for it to replace the exxcess arsenic at the site of iron and war probably deposited together with arsenic as solid in the sulfide minerals. Pyrite is composed of(Aux^3 ,Fe1-2^2 )([AsS]x^3-[S2]1-x^2-),and arenopyrite of (Aux^3 ,Fe1-x^3 )([AsS]x^3-[AsS2]1-x^3-).The occurrence of glod in the As-sulfied minerals from the Carlin-type gold depostis in the Qinling region has been confirmed by electron probe and transmission electron microscopic studies.The results show that gold was probably depostied together with arsenicas coupled solid solutions in sulfide minerals in the early stage of mineralization.Metallogenic chemical reactions concerning gold deposition in the Carlin-type As-rich gold deposits would involve oxidation of glod and concurrent reduction of arsenic.Later,the deposited gold as solid was remobilized and redistributed as exsolutions,as a result of increasing hydrothermal alteration and crystallization,and decreasing resistance to refractoriness of the host minerals.Gold occurs as sub-microscopic grains(ranging from 0.04tp 0.16μm in diameter)of native gold along micro factures in and crystalline grains of the sulfiedes.  相似文献   

O and S isotopic composition of dissolved and attached oxidation products of pyrite by Acidithiobacillus ferrooxidans: Comparison with abiotic oxidations     

Céline Pisapia  M. Chaussidon  B. Humbert 《Geochimica et cosmochimica acta》2007,71(10):2474-2490

The acidophilic iron-oxidizing bacterium, Acidithiobacillus ferrooxidans, plays a part in the pyrite oxidation process and has been widely studied in order to determine the kinetics of the reactions and the isotopic composition of dissolved product sulphates, but the details of the oxidation processes at the surface of pyrite are still poorly known. In this study, oxygen and sulphur isotopic compositions (δ¹⁸O and δ³⁴S) were analyzed for dissolved sulphates and water from experimental aerobic acidic (pH < 2) pyrite oxidation by A. ferrooxidans. The oxidation products attached to the pyrite surfaces were studied for their morphology (SEM), their chemistry (Raman spectroscopy) and for their δ¹⁸O (ion microprobe). They were compared to abiotically (Fe³⁺, H₂O₂, O₂) oxidized pyrite surface compounds in order to constrain the oxidation pathways and to look for the existence of potential biosignatures for this system.The pyrite dissolution evolved from non-stoichiometric (during the first days) to stoichiometric (with increasing time) resulting in dissolved sulphates having distinct δ¹⁸O (e.g. +11.0‰ and −2.0‰, respectively) and δ³⁴S (+4.5‰ and +2.8‰, respectively) values. The “oxidation layer” at the surface of pyrite is complex and made of iron oxides, sulphate, polysulphide, elemental sulphur and polythionates. Bio- and Fe³⁺-oxidation favour the development of monophased micrometric bumps made of hematite or sulphate while other abiotic oxidation processes result in more variable oxidation products. The δ¹⁸O of these oxidation products at the surface of oxidized pyrites are strongly variable (from ≈−40‰ to ≈+30‰) for all experiments.Isotopic fractionation between sulphates and pyrite, Δ³⁴S_SO4-pyrite, is equal to −1.3‰ and +0.4‰ for sulphates formed by stoichiometric and non-stoichiometric processes, respectively. These two values likely reflect either a S-S or a Fe-S bond breaking process. The Δ¹⁸O_SO4-H2O and Δ¹⁸O_SO4-O2 are estimated to be ≈+16‰ and ≈−25‰, respectively. These values are higher than previously published data and may reflect biological effects. The large δ¹⁸O heterogeneity measured at the surfaces of oxidized pyrites, whatever the oxidant, may be related (i) to the existence of local surface environments isolated from the solution in which the oxidation processes are different and (ii) to the stabilization at the pyrite surface of reaction intermediates that are not in isotopic equilibrium with the solution. Though the oxygen isotopic composition of surface oxidation products cannot be taken as a direct biosignature, the combined morphological, chemical and isotopic characterization of the surfaces of oxidized pyrites may furnish clues about a biological activity on a mineral surface.  相似文献   

The role of carbonate ions in pyrite oxidation in aqueous systems     

Claudia L. Caldeira  Virginia S.T. Ciminelli  Kwadwo Osseo-Asare 《Geochimica et cosmochimica acta》2010,74(6):1777-1789

The mechanism of pyrite oxidation in carbonate-containing alkaline solutions at 80 °C was investigated with the help of rate experiments, thermodynamic modeling and diffuse reflectance infrared spectroscopy (DRIFTS). Pyrite oxidation rate increased with pH and was enhanced by addition of bicarbonate/carbonate ions. The carbonate effect was found to be limited to moderately alkaline conditions (pH 8-11). Metastable Eh-pH diagrams, at 25 °C, indicate that soluble iron-carbonate complexes (FeHCO₃⁻, FeCO₃⁰, Fe(CO₃)(OH)⁻ and FeCO₃²⁻) may coexist with pyrite in the pH range of 6-12.5. Above pH 11 and 13, the Fe(II) and Fe(III) hydroxocomplexes, respectively, become stable, even in the presence of carbonate/bicarbonate ions. Surface-bound carbonate complexes on iron were also identified with DRIFTS as products of pyrite oxidation in addition to iron oxyhydroxides and soluble sulfate species. The conditions under which thermodynamic and DRIFTS analyses indicate the presence of carbonate compounds also correspond to those in which the fastest rate of pyrite oxidation in carbonate solutions was observed. Following the Singer-Stumm model for pyrite oxidation in acidic solutions, it is assumed that Fe(III) is the preferred pyrite oxidant under alkaline conditions. We propose that carbonate ions facilitate the electron transfer from soluble iron(II)-carbonate to O₂, increase the iron solubility, and provide buffered, favorable alkaline conditions at the reaction front, which in turn favors the overall kinetics of pyrite oxidation. Therefore, the electron transfer from sulfur atoms to O₂ is facilitated by the formation of the cycle of Fe(II)-pyrite/Fe(III)-carbonate redox couple at the pyrite surface.  相似文献   

Compounds with mixed and intermediate sulfur valences as precursors of banded sulfides in carbonate-hosted Zn-Pb deposits in Belgium and Poland     

H. Kucha  W. Viaene 《Mineralium Deposita》1993,28(1):13-21

Compounds of Fe, Pb and Zn with mixed and intermediate sulfur valences form ubiquitous inclusions and relics in banded sphalerite, pyrite-melnikovite and galena. Banded sulfides continuously grade into banded compounds with mixed and intermediate sulfur valences, the latter with a fibrous microtexture. A fibrous microtexture is also shown by banded sphalerite and pyrite from Zn-Pb deposits of Belgium and Poland. It is therefore suggested that the fibrous sphalerite inherited such a microtexture, unusual for cubic ZnS, by direct replacement of a fibrous precursor with mixed and/or intermediate sulfur valences. The last band of banded sphalerite is often overgrown by idiomorphic, isometric sphalerite precipitated directly from the solution as ZnS. The following Fe, Pb and Zn compounds with mixed and intermediate sulfur valences were found in carbonate-hosted Zn-Pb deposits of Belgium and Poland: sulfoxylanes (M²⁺SO₂; S²⁺), subsulfites (M²⁺S₂O₄; S³⁺), sulfites (M²⁺SO₃; S⁴⁺), pyrosulfites (M²⁺S₂O₅; S⁴⁺) and thiosulphates(M²⁺S₂O₃; S^2– and S⁶⁺).  相似文献