Thermodynamic properties of tooeleite,Fe63+(As3+O3)4(SO4)(OH)4·4H2O     

《Chemie der Erde / Geochemistry》2016,76(3):419-428

Tooeleite, nominally Fe₆³⁺(As³⁺O₃)₄(SO₄)(OH)₄·4H₂O, is a relatively uncommon mineral of some acid-mine drainage systems. Yet, if it does occur, it does so in large quantities, indicating that some specific conditions favor the formation of this mineral in the system Fe-As-S-O-H. In this contribution, we report the thermodynamic properties of synthetic tooeleite. The sample was characterized by powder X-ray diffraction, scanning electron microscopy, extended X-ray absorption fine-structure spectroscopy, and Mössbauer spectroscopy. These methods confirmed that the sample is pure, devoid of amorphous impurities of iron oxides, and that the oxidation state of arsenic is 3+. Using acid-solution calorimetry, the enthalpy of formation of this mineral from the elements at the standard conditions was determined as −6196.6 ± 8.6 kJ mol⁻¹. The entropy of tooeleite, calculated from low-temperature heat capacity data measured by relaxation calorimetry, is 899.0 ± 10.8 J mol⁻¹ K⁻¹. The calculated standard Gibbs free energy of formation is −5396.3 ± 9.3 kJ mol⁻¹. The log K_sp value, calculated for the reaction Fe₆(AsO₃)₄(SO₄)(OH)₄·4H₂O + 16H⁺ = 6Fe³⁺ + 4H₃AsO₃ + SO₄²⁻ + 8H₂O, is −17.25 ± 1.80. Tooeleite has stability field only at very high activities of aqueous sulfate and arsenate. As such, it does not appear to be a good candidate for arsenic immobilization at polluted sites. An inspection of speciation diagrams shows that the predominance field of Fe³⁺ and As³⁺ overlap only at strongly basic conditions. The formation of tooeleite, therefore, requires strictly selective oxidation of Fe²⁺ to Fe³⁺ and, at the same time, firm conservation of the trivalent oxidation state of arsenic. Such conditions can be realized only by biological systems (microorganisms) which can selectively oxidize one redox-active element but leave the other ones untouched. Hence, tooeleite is the first example of an “obligatory” biomineral under the conditions prevailing at or near the Earth's surface because its formation under these conditions necessitates the action of microorganisms.  相似文献   

Deciphering As and Cu cycling in sediment pore waters in a large marina (Port Camargue,southern France) using a multi-tracer (Fe,Mn, U,Mo) approach     

《Applied Geochemistry》2016

The sediments of the Port Camargue marina (South of France) are highly polluted by Cu and As (Briant et al., 2013). The dynamics of these pollutants in pore waters was investigated using redox tracers (sulfides, Fe, Mn, U, Mo) to better constrain the redox conditions.In summer, pore water profiles showed a steep redox gradient in the top 24 cm with the reduction of Fe and Mn oxy-hydroxides at the sediment water interface (SWI) and of sulfate immediately below. Below a depth of 24 cm, the Fe, Mn, Mo and U profiles in pore waters reflected Fe and Mn reducing conditions and, unlike in the overlying levels, sulfidic conditions were not observed. This unusual redox zonation was attributed to the occurrence of two distinct sediment layers: an upper layer comprising muddy organic-rich sediments underlain by a layer of relatively sandy and organic-poor sediments. The sandy sediments were in place before the building of the marina, whereas the muddy layer was deposited later. In the muddy layer, large quantities of Fe and Mo were removed in summer linked to the formation of insoluble sulfide phases. Mn, which can adsorb on Fe-sulfides or precipitate with carbonates, was also removed from pore waters. Uranium was removed probably through reduction and adsorption onto particles. In winter, in the absence of detectable pore water sulfides, removal of Mo was moderate compared to summer.Cu was released into solution at the sediment water interface but was efficiently trapped by the muddy layer, probably by precipitation with sulfides. Due to efficient trapping, today the Cu sediment profile reflects the increase in its use as a biocide in antifouling paints over the last 40 years.In the sandy layer, Fe, Mn, Mo and As were released into solution and diffused toward the top of the profile. They precipitated at the boundary between the muddy and sandy layers. This precipitation accounts for the high (75 μg g⁻¹) As concentrations measured in the sediments at a depth of 24 cm.  相似文献   

Reactivity of micas and cap-rock in wet supercritical CO2 with SO2 and O2 at CO2 storage conditions     

《Applied Geochemistry》2016

Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO₂, O₂, and NOx, may be present in CO₂ streams from coal combustion sources. SO₂ and O₂ have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO₂ fluid may also come into contact with the base of cap-rock after CO₂ injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation.The first observation of mineral dissolution and precipitation on phyllosilicates and CO₂ storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO₂ reactions with industrial impurities SO₂ and O₂ at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO₂ containing SO₂, or SO₂ and O₂, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO₂ dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO₂ containing SO₂ or in pure supercritical CO₂. In the presence of SO₂, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was buffered by carbonate dissolution. Ca-sulfate, and Fe-bearing precipitates were observed post SO₂-CO₂ reaction, mainly centered on surface cracks and an illite rich illite-smectite precipitate quantified. Water saturated impure supercritical CO₂ was observed to have reactivity to rock-forming biotite, muscovite and phlogopite mineral separates. In the cap-rock core however carbonates and chlorite were the main reacting minerals showing the importance of assessing actual whole core.  相似文献   

长江中下游成矿带庐枞盆地小包庄铁矿床地质特征研究   总被引：3，自引：0，他引：3  

刘一男  范裕  高昌生  张千明  张乐骏 《岩石学报》2016,32(2):319-333

罗河铁矿床位于长江中下游成矿带内庐枞火山岩盆地的西北部,是成矿带内已发现规模最大的铁矿床。2013年在罗河铁矿床深部又勘探新发现了小包庄大型铁矿床,这是长江中下游成矿带内近年来重大找矿突破之一,具有重要的理论研究意义和勘探应用价值。本文在前人工作基础上,基于详细的钻孔观察和系统的岩相学、矿相学工作并结合电子探针测试分析,研究了小包庄铁矿床的矿化蚀变特征,厘定了矿床的成矿阶段,分析了成矿作用过程,并初步探讨了矿床成因。研究表明,罗河铁矿床和小包庄铁矿床为同一成矿系统在不同深度成矿作用的产物。小包庄铁矿床主矿体矿呈厚大的透镜状、似层状产于砖桥组地层中,位于罗河铁矿床主矿体之下约800~1000m,主要由浸染状矿体组成。矿床中金属矿物主要为磁铁矿和黄铁矿,非金属矿物主要为硬石膏、透辉石和碳酸盐,矿石的代表性矿物组合为磁铁矿-硬石膏-透辉石。矿石的结构构造主要有浸染状构造、脉状构造、块状构造、自形-半自形粒状结构、他形粒状结构和筛状结构等。矿床围岩蚀变强烈,主要蚀变类型有碱性长石化、透辉石化、绿泥石化、绿帘石化、碳酸盐化和硬石膏化。小包庄铁矿床形成经历了热液期的四个阶段,即碱性长石阶段、透辉石-硬石膏-磁铁矿阶段、绿泥石-绿帘石-碳酸盐阶段和硬石膏-黄铁矿-碳酸盐-石英阶段,其中,铁矿化主要发育于透辉石-硬石膏-磁铁矿阶段。通过矿床地质特征的分析以及与宁芜地区铁矿床的对比研究,本文认为小包庄铁矿床成矿物质和成矿流体来源于深部的闪长质侵入岩(?),而矿化发育在远离侵入岩或次火山岩之上的火山岩中,明显有别于宁芜地区玢岩铁矿床,类似于智利安第斯成矿带中部分产于安山质火山岩中的磁铁矿-磷灰石型矿床,是长江中下游成矿带中产于火山岩中的一类特殊类型的玢岩型铁矿。  相似文献   

姚家岭锌金多金属矿床围岩蚀变三维空间定量分析研究   总被引：2，自引：1，他引：1  

李晓晖  袁峰  张明明  蒋其胜  韩长生  黄建满  张淑虹  钟国雄 《岩石学报》2016,32(2):390-398

姚家岭锌金多金属矿床是近年来在长江中下游成矿带铜陵矿集区新发现的大型多金属矿床。姚家岭锌金多金属矿床的成矿作用具有多阶段性的特点,矿床范围内围岩蚀变强烈,蚀变类型复杂多样。三维地质信息技术及三维空间分析方法为定量化分析围岩蚀变的空间分布以及与矿化之间的相关关系提供了有利工具。本文基于上述方法,有效地对姚家岭锌金多金属矿床的围岩蚀变的分带性及其与不同矿化之间的关联性行了定量分析。较之于传统研究方法,不仅能快速地对蚀变与矿化的分布特征进行分析,还能从定量的角度获取不同信息之间的规律性和相关性。本文采用的相关方法不但有助于更准确的判定蚀变分带及规律,还可为矿床的成矿模式及找矿模型的建立提供定量化的数据支持。  相似文献   

郯庐断裂带张八岭隆起段晚中生代岩浆岩继承锆石U-Pb年代学:源区属性及构造意义   总被引：1，自引：0，他引：1  

谢成龙  陈娟  刘友勤  朱晓超  牛漫兰  向必伟 《岩石学报》2016,32(4):976-1000

大别与苏鲁造山带之间的郯庐断裂带张八岭隆起段,构成了华北与扬子板块之间的断裂边界。该边界带的深部结构状态长期以来存在着不同的认识。本文利用张八岭隆起带沿线出露的晚中生代岩浆岩中继承锆石U-Pb年代学信息,结合地球物理资料及Nd、Pb、Hf同位素资料,分析了其深部的岩浆源区属性及结构状态。张八岭隆起带北段晚中生代岩浆岩继承锆石年龄以1.9~2.7Ga为主,最大峰值年龄为2.5Ga;南段继承锆石年龄以2.2~2.6Ga为主,峰值年龄也为2.5Ga;郯庐断裂带庐江段则以含大量新元古代锆石为特征,在0.7Ga形成显著的分布峰值,并有早元古和少量太古代年龄信息。分析结果表明,张八岭隆起带北段的晚中生代岩浆岩源区为华北下地壳,南段的源区兼有华北和扬子陆壳的信息,而更南部庐江段则以扬子地壳源区为特征。电法剖面揭示,郯庐断裂主边界在张八岭隆起带下向南东倾斜,从而深部存在华北地壳;而南部庐江段转变为向北西陡倾,从而深部皆为扬子地壳。郯庐断裂深部产状特征支持其印支期应为斜向汇聚边界。而其中三叠纪继承锆石的缺失指示隆起带上变质岩应为原地岩石,而非来自大别造山带。  相似文献   

广东省典型铜矿床区域地球化学异常特征     

张伟  陈陵康  朱进守 《物探与化探》2016,(4):728-731

广东省铜矿床具产地分散、类型多样、储量集中的特点。以八个典型铜矿床为例,探讨铜异常及其元素组合特征,得出:1铜富集部位对已知矿的反映较好;2规模相似的不同类型铜矿床,其铜异常面积相近,但铜平均含量差异较大;3斑岩型铜矿的Cu、Mo、Sb组合,岩浆热液型、矽卡岩型、复成因型铜矿的Cu、Pb、Zn、Ag、Cd、Bi、Mo、W、Sn、Mn组合,火山岩型铜矿的Cu、Pb、Zn、Cd、Ag、As组合较稳定。这些结论为进一步了解广东省铜矿的成矿规律及开展地质勘查、地质评价工作提供了一定的科学依据。  相似文献   

Early Cretaceous Climate Changes Recorded in Magnetic Susceptibility and Color Index Variations of the Lower Liupanshan Group, Central China     

DAI Shuang  ZHU Qiang  HUANG Yongbo  DA SILVA A. Christine  ZHAO Jie  LIU Junwei  KONG Li  PENG Dongxiang  LUO Lingling  YAN Ningyun  WANG Wenjie  ZHANG Xiang 《《地质学报》英文版》2016,90(3):1011-1023

This study carried out comprehensive analysis on sedimentology, magnetic susceptibility(χlf) and color data of the continental sediments of the Liupanshan Group in Central China so as to obtain climatic change information during the 129.14–122.98 Ma interval. Based on the results of the ?lf and of the redness(a*), the section can be divided into two segments:(1) 129.14–126.3 Ma, with the lowest ?lf values and strongly variable relatively high values of redness and(2) 126.3–122.98 Ma, with high ?lf values and relatively low redness. Analysis of the lithology and facies as well as the magnetic minerals and their contents points to a detrital origin of the magnetic minerals and this allow us to interpret the relationship between magnetic susceptibility variations and climate changes. Our study shows that the climate was significantly dry and hot during the whole studied interval although the interval between 126.3 Ma and 122.98 was a little bit cooler with increased humidity.  相似文献   

Triterpenols as Proxies for Tracking the Mangrove Evolution in China     

ZHANG Daolai  LIU N  YIN Ping  ZHU Zhigang  LU Jingfang  LIN Xuehui  ZHANG Yuanyuan  MENG Xianwei 《《地质学报》英文版》2016,90(5):1926-1926

正Objective Located at the interface of terrestrial and marine ecosystems,mangroves are particularly sensitive to environmental changes.They provide a sedimentary sink for organic carbon,whereby core samples could provide detailed records of mangrove evolution.Human induced,rapid environmental changes in recent years require a better understanding of the mangrove ecosystems evolution in the past,by reconstructing the past mangrove  相似文献   

Identification of Greigite in the Pliocene Sediments of Qinghai Lake and Its Geological Significance     

FU Chaofeng  Jan BLOEMENDAL  QIANG Xiaoke  Mimi J. HILL  AN Zhisheng 《《地质学报》英文版》2016,90(6):2261-2262

正Objective The Qinghai Lake in North China is the largest interior plateau lake in Central Asia,and is sensitive to climate change and the environmental effects of Tibetan Plateau uplift.An almost continuous 626 m long sediment core was drilled in an in-filled part of the southern lake basin in the Scientific Drilling at Qinghai Lake.Previous  相似文献