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1.
The importance of the discovery of jarosite at the Meridiani Planum region of Mars is discussed. Terrestrial studies demonstrate that jarosite requires a unique environment for its formation, crystallizing from highly acidic (pH < 4) S-rich brines under highly oxidizing conditions. A likely scenario for jarosite formation on Mars is that degassing of shallow magmas likely released SO2 that reacted with aqueous solutions in shallow aquifers or on the martian surface. This interaction forms both H2SO4 and H2S. A martian oxidant must be identified to both oxidize H2S to produce the required acidity of the fluid, and to oxidize Fe2+ to Fe3+. We suggest that reactions involving both sulfur and the reduction of CO2 to CO may provide part of the answer. The jarosite crystal structure is truly remarkable in terms of its tolerance for the substitution of a large number of different cations with different ionic radii and charges. The structure accommodates hydrogen, oxygen, and sulfur, the stable isotope systematics of which are strong recorders of low-temperature fluid-rock-atmosphere interactions. Jarosite has been proven to be a robust chronometer for Ar-Ar and K-Ar dating techniques, and there is every reason to believe that U-Pb, Rb-Sr, and Nd-Sm techniques for older jarosite from Mars will also be robust. Although the discovery of jarosite on Mars alone, with no other analytical measurements on the phase, has given us insights to martian surficial processes, the true power of jarosite can not be exploited until jarosite is sampled and returned from Mars. Mars sample return is a long way off but, until then, we should be vigilant about examining martian meteorites for alteration assemblages that contain jarosite. A suite of jarosite samples representing a significant time span on Mars may hold the key to reading the record of martian atmospheric evolution.  相似文献   

2.
火星次生含水蚀变矿物是火星地质历史时期水环境和气候演变历史的真实记录,一直以来都是火星探测、火星陨石研究的重点,是认识火星环境特征和气候演化的重要研究对象。文中对比研究了表土角砾岩NWA7034、火成堆晶岩MIL03346等两块最富蚀变矿物火星陨石,以及Gale撞击坑出露的Sheepbed泥岩3种岩石类型的蚀变程度及其蚀变矿物类型和组合,分析了层状硅酸盐、铁氧化物/氢氧化物、钙硫酸盐等蚀变矿物的成因及环境指示意义。发现这3类岩石的蚀变作用各不相同。火星陨石NWA7034的蚀变作用以氧化和加热作用为主,无蒸发盐类矿物。火星陨石MIL03346的蚀变程度最低,为后期水溶液进入缝隙而引发的,蚀变作用以橄榄石的伊利石化、裂隙和缝隙中填充次生矿物细脉为主。而火星Sheepbed泥岩经历了后期的等化学风化过程(isochemical weathering),次生过程包括成岩蚀变和成岩后蚀变两个阶段。其中,成岩过程中的蚀变以橄榄石蚀变为铁氧化物和蒙皂石矿物为主,成岩后以形成蒸发盐类矿物硫酸钙为主。以上3种岩石蚀变矿物组成差异反映了火星上不同地质背景中、不同气候条件下蚀变过程的复杂性。文中对火星含水矿物及部分典型矿物的形成条件和过程进行系统总结,这对于理解未来火星探测任务、识别含水矿物的形成、揭示火星水环境和地质历史具有重要指导意义。  相似文献   

3.
The paper discusses the formation conditions of the Ary-Bulak ongonite massif (eastern Transbaikalia). Studies of melt and fluid inclusions have shown that, along with crystalline phases and a silicate melt, ongonitic magma contained aqueous–saline fluids of different types, fluoride melts compositionally similar to fluorite, sellaite, cryolite, chiolite, and more complex aluminum fluorides as well as silicate melts with abnormal Cs and As contents. An ongonite melt crystallized with the participation of P–Q fluids as vapor solutions, presumably NaF-containing and slightly admixed with chlorides. We studied the properties and composition of brine inclusions from Ca- and F-rich rocks on the margin of the massif. Depending on the thermophysical properties of the host rocks and ongonite melt, the duration of its crystallization has been estimated for a magma chamber of the size and shape of the Ary-Bulak massif. Magma chamber cooling has been modeled, and the density, viscosity, and Rayleigh number of the ongonite melt have been estimated from the composition of silicate glasses in melt inclusions. These data strongly suggest intense convection in the residual magma chamber lasting for centuries. We have calculated possible fluid overpressure during the crystallization and degassing of the ongonite melt in a closed magma chamber.Calcium- and fluorine-rich aphyric and porphyritic rocks on the southwestern margin of the massif might have formed by the following mechanism. Local decompression in the magma chamber quenched an oxygen-containing calcium fluoride melt accumulated at the crystallization front, and then these rocks altered during the interaction with fluids. When penetrating the marginal zone, a P–Q magmatic fluid which coexisted with the melt in the residual chamber cooled and changed its composition and properties. This caused the fluid to boil and segregate into immiscible phases: a vapor solution and a brine extremely rich in Cl, F, K, Cs, Mn, Fe, and Al. The fluoride and silicate liquids were immiscible; the silicate melts had abnormal Cs and As contents; changes in the composition and properties of the magmatic fluids caused them to boil and produce brines. All this is evidence for complex fluid–magma interaction and heterogeneous ongonitic magma during the crystallization of the Ary-Bulak rocks. These processes were favored by the low viscosity and high mobility of the F- and water-rich ongonite melt, intense melt convection in the residual chamber, and rising fluid pressure during its degassing.  相似文献   

4.
金属矿床的成矿流体成分和流体包裹体   总被引:7,自引:1,他引:6  
卢焕章  单强 《岩石学报》2015,31(4):1108-1116
自然界中的成矿流体按其主要成分,可分为:(1)岩浆,即形成岩浆矿床的岩浆;(2)以H2O为主的流体(含Na Cl);(3)以CO2为主的流体。地壳中的流体类型很多,只有含一定金属元素含量的,并且达到一定浓度时才称为金属矿床的成矿流体。基于对矿床中流体包裹体和天然成矿流体中金属种类和含量的测定,这些金属矿床的成矿流体按金属元素含量可以分为五组,成矿流体可以来自岩浆、岩浆热液、大气降水、盆地卤水和变质流体等地质环境。  相似文献   

5.
本文从江西德兴斑岩铜矿铜厂矿床的流体包裹体研究出发,讨论了矿床成矿物质来源与矿床成因。矿床中流体包裹体分为6类,即富液包裹体、富气包裹体、含石盐多相包裹体、含CO2多相包裹体以及熔体包裹体和熔体-流体包裹体。富气包裹体、含石盐多相包裹体和熔体与熔体-流体包裹体代表了成矿早期岩浆热液的特征。在这些包裹体中发现黄铜矿等金属矿物,表明成矿金属主要源自岩浆。含石盐多相包裹体和富气包裹体与矿体关系不甚密切,但其中所含有的金属矿物特别是黄铜矿,暗示早期来自岩浆的热液流体金属含量较高,形成于大气降水与岩浆热液混合之前。成矿中晚期大气降水流体在冷却和稀释岩浆流体方面对于矿床的形成作出了一定贡献,但是来自围岩的大气降水可能并没有向成矿体系提供大量金属。  相似文献   

6.
ABSTRACT Despite the close association with volcanic activity, the source of metals and ligands in the epithermal ore deposits is still controversial. In order to explore the magmatic–hydrothermal connection further, silicate melt, saline- and water-rich fluids, and CO2 vapours are documented that are trapped as inclusions in quartz phenocrysts from dacitic dykes associated with epithermal gold/base metal mineralization in the Shila district (Peru). Melt inclusion characteristics, and microthermometric and laser Raman fluid inclusion data are presented. The investigation of melt and fluid inclusions reveals that the volatile phase of magmas might represent the precursors to the early chlorine-rich ore-forming epithermal solutions. Microthermometric investigations in magmatic quartz crystals and data on quartz mineralized veins suggest that the fluid evolution and ore deposition may be the result of several processes including: release of an evolving magmatic fluid, and/or boiling, and/or mixing.  相似文献   

7.
Whether water has played a role in the petrogenesis of martian basalts remains a subject of significant debate. Estimates of pre-eruptive water concentrations in martian magmas are impeded by the effects of degassing and shock. However, zoning trends of light lithophile elements (LLE) in pyroxene have been interpreted as evidence for the degassing of magmatic water, on the basis of the soluble behavior of these elements in hydrothermal fluids. We provide ion microprobe analyses of LLE in pyroxene in the Zagami and Shergotty martian basalts, complemented by detailed electron microprobe analyses and major-element X-ray maps, to independently verify the zoning of LLE and its relationship to texture and major-element variations. Our results corroborate previous results; specifically, that Li concentrations are lower in rims than cores of Shergotty and Zagami pyroxene. In contrast, we see no evidence for a core-to-rim decrease in B. In the absence of further data, we interpret the decrease in Li as reflecting either loss after crystallization of pyroxene cores, consistent with magmatic degassing, or the diffusive preferential loss of Li from pyroxene rims, possibly as a result of shock. Because the partitioning behavior of Li between hydrous fluid, minerals, and melt under relevant conditions of pressure, temperature, and melt composition is unknown, the viability of the water degassing hypothesis depends on experiments establishing the compatibility of Li in hydrous fluid associated with martian basaltic melt and the incompatibility of Li in pyroxene at elevated pressures.  相似文献   

8.
Exsolution (unmixing) of the volatile element-rich phases from cooling and crystallising silicate magmas is critical for element transport from the Earth’s interior into the atmosphere, hydrosphere, crustal hydrothermal systems, and the formation of orthomagmatic ore deposits. Unmixing is an inherently fugitive phenomenon and melt inclusions (droplets of melt trapped by minerals) provide robust evidence of this process. In this study, melt inclusions in phenocrystic and miarolitic quartz were studied to better understand immiscibility in the final stages of cooling of, and volatile exsolution from, granitic magmas, using the tin-bearing Omsukchan Granite (NE Russia) as an example.

Primary magmatic inclusions in quartz phenocrysts demonstrate the coexistence of silicate melt and magma-derived Cl-rich fluids (brine and vapour), and emulsions of these, during crystallisation of the granite magma. Microthermometric experiments, in conjunction with PIXE and other analytical techniques, disclose extreme heterogeneity in the composition of the non-silicate phases, even in fluid globules within the same silicate melt inclusion. We suggest that the observed variability is a consequence of strong chemical heterogeneity in the residual silicate-melt/brine/vapour system on a local scale, owing to crystallisation, immiscibility and failure of individual phases to re-equilibrate. The possible evolution of non-silicate volatile magmatic phases into more typical “hydrothermal” chloride solutions was examined using inclusions in quartz from associated miarolitic cavities.  相似文献   


9.
中酸性岩浆体系成矿流体及微量元素地球化学特征   总被引:5,自引:0,他引:5       下载免费PDF全文
从流体成矿作用角度出发,与酸性岩浆体系有关的成矿流体可以分为:酸性岩浆硅酸盐熔融体,岩浆一热液过渡阶段硅酸盐熔融体及其分异的流体,酸性岩浆熔体分异形成的热水成矿溶液。酸性岩浆体系主要提供热源和部分矿质,其提供的热源驱动地下水淋滤、萃取围岩中的成矿物质形成地下水热液成矿流体。变质岩混合岩化形成花岗质岩浆过程中所形成的混合岩化成矿流体。在此基础上,讨论了上述不同成矿流体的微量元素地球化学特征及其对成矿的控制作用。  相似文献   

10.
Silicate-melt inclusions in magmatic rocks: applications to petrology   总被引:20,自引:0,他引:20  
Maria-Luce Frezzotti   《Lithos》2001,55(1-4):273-299
Silicate-melt inclusions in igneous rocks provide important information on the composition and evolution of magmatic systems. Such inclusions represent accidentally trapped silicate melt (±immiscible H2O and/or CO2 fluids) that allow one to follow the evolution of magmas through snapshots, corresponding to specific evolution steps. This information is available on condition that they remained isolated from the enclosing magma after their entrapment. The following steps of investigation are discussed: (a) detailed petrographic studies to characterise silicate-melt inclusion primary characters and posttrapping evolution, including melt crystallisation; (b) high temperature studies to rehomogenise the inclusion content and select chemically representative inclusions: chemical compositions should be compared to relevant phase diagrams.

Silicate-melt inclusion studies allow us to concentrate on specific topics; inclusion studies in early crystallising phases allow the characterisation of primary magmas, while in more differentiated rocks, they unravel the subsequent chemical evolution. The distribution of volatile species (i.e., H2O, CO2, S, Cl) in inclusion glass can provide information on the degassing processes and on recycling of subducted material. In intrusive rocks, silicate melt inclusions may preserve direct evidence of magmatic stage evolution (e.g., immiscibility phenomena). Melt inclusions in mantle xenoliths indicate that high-silica melts can coexist with mantle peridotites and give information on the presence of carbonate melt within the upper mantle. Thus, combining silicate-melt inclusion data with conventional petrological and geochemical information and experimental petrology can increase our ability to model magmatic processes.  相似文献   


11.
吉伯特铁矿是新疆阿勒泰地区产于泥盆纪海相火山岩中的小型矿床。本文对吉伯特铁矿床的包裹体开展了研究,识别了熔体包裹体、熔体-流体包裹体以及富晶体的流体包裹体,并对其进行了初步的显微测温、激光拉曼光谱和电子探针等研究。熔体包裹体中含有富Si玻璃质、贫Si富Fe熔体、石英、萤石、方解石、磁铁矿等多种成分,它们分别组成不同的包裹体组合。熔体包裹体、熔体-流体包裹体和流体包裹体的存在表明它们被捕获时是一种熔体与流体共存的不混溶状态,这充分说明了吉伯特铁矿床的形成与岩浆熔体、岩浆-热液过渡性流体有直接的成因联系。吉伯特铁矿床中Fe的矿化是一个熔体相逐渐减少,流体相逐渐增加的连续演化过程,它受岩浆作用、岩浆-热液过渡性流体以及矽卡岩作用的共同制约。  相似文献   

12.
Basalts and basaltic cumulates from Mars (delivered to Earth as meteorites) carry a record of the history of that planet - from accretion to initial differentiation and subsequent volcanism, up to recent times. We provide new microprobe data for plagioclase, olivine, and pyroxene from 19 of the martian meteorites that are representative of the six types of martian rocks. We also provide a comprehensive WDS map dataset for each sample studied, collected at a common magnification for easy comparison of composition and texture. The silicate data shows that plagioclase from each of the rock types shares similar trends in Ca-Na-K, and that K2O/Na2O wt% of plagioclase multiplied by the Al content of the bulk rock can be used to determine whether a rock is “enriched” or “depleted” in nature. Olivine data show that meteorite Y 980459 is a primitive melt from the martian mantle as its olivine crystals are in equilibrium with its bulk rock composition; all other olivine-bearing Shergottites have been affected by fractional crystallization. Pyroxene quadrilateral compositions can be used to isolate the type of melt from which the grains crystallized, and minor element concentrations in pyroxene can lend insight into parent melt compositions.In a comparative planetary mineralogy context, plagioclase from Mars is richer in Na than terrestrial and lunar plagioclase. The two most important factors contributing to this are the low activity of Al in martian melts and the resulting delayed nucleation of plagioclase in the crystallizing rock. Olivine from martian rocks shows distinct trends in Ni-Co and Cr systematics compared with olivine from Earth and Moon. The trends are due to several factors including oxygen fugacity, melt compositions and melt structures, properties which show variability among the planets. Finally, Fe-Mn ratios in both olivine and pyroxene can be used as a fingerprint of planetary parentage, where minerals show distinct planetary trends that may have been set at the time of planetary accretion.Although the silicate mineralogical data alone cannot support one specific model of martian magmatism over another, the data does support the basic igneous reservoirs proposed for Mars, and may also be used to constrain some aspects of specific petrogenetic models. Examples include enriched and depleted reservoirs that can be identified by plagioclase K, Na and Al composition, multivalent element partitioning in olivine and pyroxene (V, Cr) elucidates oxygen fugacity conditions of the reservoirs, and minor element concentrations (i.e., Cr in pyx) show that proposed fractional crystallization models linking Y 980459 to QUE 94201 will not work.  相似文献   

13.
Dynamic crystallization experiments have been performed on synthetic glasses representative of shock-generated melts observed in Los Angeles, Sayh al Uhaymir 150 and Dar al Gani 476 martian basalts. On the basis of qualitative (texture) and quantitative (fractal analysis) results, we show that melt pockets in Los Angeles cooled at a rate of 1040-1560 °C/h. Sayh al Uhaymir 150 and Dar al Gani 476 melt pockets cooled at 780 °C/h. Conductive cooling models, for a range of meteoroid diameters (10-50 cm), indicate that the minimum meteoroid diameter was small, on the order of 10-15 cm and that melt pockets cooled from post-shock temperatures within minutes. Our results also have bearing on shock implanted martian atmospheric components because it is during cooling that the melt pockets have the potential to lose gases. Modeling of argon diffusion in a spherical melt pocket indicates that during cooling and quench crystallization ∼4-60% of trapped martian atmospheric argon may be lost from the melt pocket through diffusive transport.  相似文献   

14.
The Middle–Lower Yangtze River Valley is one of the most important metallogenic belts in China, hosting numerous Cu–Fe–Au–Mo deposits. The Taochong deposit is located in the northern part of the Fanchang iron ore district of the Middle–Lower Yangtze River metallogenic belt. The Fe-orebody is hosted by Middle Carboniferous to Lower Permian limestones. Skarns and Fe-orebodies occur as tabular bodies along interlayer-gliding faults, at some distance from the inferred granitic intrusions. Field evidence and petrographic observations indicate that the three stages of hydrothermal activity—the skarn, iron oxide (main mineralization stage), and carbonate stages—all contributed to the formation of the Taochong iron deposit. The skarn stage is characterized by the formation of garnet and pyroxene, with high-temperature, hypersaline hydrothermal fluids with isotopic compositions similar to those of typical magmatic fluids. These fluids were probably generated by the separation of brine from a silicate melt instead of the product of aqueous fluid immiscibility. The iron oxide stage coincides with the replacement of garnet and pyroxene by actinolite, chlorite, quartz, calcite and hematite. The hydrothermal fluids at this stage are represented by saline fluid inclusions that coexist with vapor-rich inclusions with anomalously low δD values (− 66‰ to − 94‰). The decrease in ore fluid δ18Owater with time and decreasing depth is consistent with the decreases in fluid salinity and temperature. The fluid δD values also show a decreasing trend with decreasing depth. Both fluid inclusion and stable isotopic data suggest that the ore fluid during the main period of mineralization was evolved by the boiling of various mixtures of magmatic brine and meteoric water. This process was probably induced by a drop in pressure from lithostatic to hydrostatic. The carbonate stage is represented by calcite veins that cut across the skarn and orebody, locally producing a dense stockwork. This observation indicates the veins formed during the waning stages of hydrothermal activity. The fluids from this stage are mainly represented by a variety of low-salinity fluid inclusions, as well as fewer high-salinity inclusions. These particular fluids have the lowest δ18Owater values (− 2.2‰ to 0.4‰) and a wide of range of δD values (− 40‰ to − 81‰), which indicate that they were originated from a mixture of residual fluids from the oxide stage, various amounts of meteoric water, and possibly condensed vapor. Low-temperature boiling probably occurred during this stage.We also discuss the reasons behind the anomalously low δD values in fluid inclusion water extracted by thermal decrepitation from quartz at high temperatures, and suggest that calcite data provide a possible benchmark for adjusting low δD values found in quartz intergrown with calcite.  相似文献   

15.
The BIF-hosted iron ore system represents the world's largest and highest grade iron ore districts and deposits. BIF, the precursor to low- and high-grade BIF hosted iron ore, consists of Archean and Paleoproterozoic Algoma-type BIF (e.g., Serra Norte iron ore district in the Carajás Mineral Province), Proterozoic Lake Superior-type BIF (e.g., deposits in the Hamersley Province and craton), and Neoproterozoic Rapitan-type BIF (e.g., the Urucum iron ore district).The BIF-hosted iron ore system is structurally controlled, mostly via km-scale normal and strike-slips fault systems, which allow large volumes of ascending and descending hydrothermal fluids to circulate during Archean or Proterozoic deformation or early extensional events. Structures are also (passively) accessed via downward flowing supergene fluids during Cenozoic times.At the depositional site the transformation of BIF to low- and high-grade iron ore is controlled by: (1) structural permeability, (2) hypogene alteration caused by ascending deep fluids (largely magmatic or basinal brines), and descending ancient meteoric water, and (3) supergene enrichment via weathering processes. Hematite- and magnetite-based iron ores include a combination of microplaty hematite–martite, microplaty hematite with little or no goethite, martite–goethite, granoblastic hematite, specular hematite and magnetite, magnetite–martite, magnetite-specular hematite and magnetite–amphibole, respectively. Goethite ores with variable amounts of hematite and magnetite are mainly encountered in the weathering zone.In most large deposits, three major hypogene and one supergene ore stages are observed: (1) silica leaching and formation of magnetite and locally carbonate, (2) oxidation of magnetite to hematite (martitisation), further dissolution of quartz and formation of carbonate, (3) further martitisation, replacement of Fe silicates by hematite, new microplaty hematite and specular hematite formation and dissolution of carbonates, and (4) replacement of magnetite and any remaining carbonate by goethite and magnetite and formation of fibrous quartz and clay minerals.Hypogene alteration of BIF and surrounding country rocks is characterised by: (1) changes in the oxide mineralogy and textures, (2) development of distinct vertical and lateral distal, intermediate and proximal alteration zones defined by distinct oxide–silicate–carbonate assemblages, and (3) mass negative reactions such as de-silicification and de-carbonatisation, which significantly increase the porosity of high-grade iron ore, or lead to volume reduction by textural collapse or layer-compaction. Supergene alteration, up to depths of 200 m, is characterised by leaching of hypogene silica and carbonates, and dissolution precipitation of the iron oxyhydroxides.Carbonates in ore stages 2 and 3 are sourced from external fluids with respect to BIF. In the case of basin-related deposits, carbon is interpreted to be derived from deposits underlying carbonate sequences, whereas in the case of greenstone belt deposits carbonate is interpreted to be of magmatic origin. There is only limited mass balance analyses conducted, but those provide evidence for variable mobilization of Fe and depletion of SiO2. In the high-grade ore zone a volume reduction of up to 25% is observed.Mass balance calculations for proximal alteration zones in mafic wall rocks relative to least altered examples at Beebyn display enrichment in LOI, F, MgO, Ni, Fe2O3total, C, Zn, Cr and P2O5 and depletions of CaO, S, K2O, Rb, Ba, Sr and Na2O. The Y/Ho and Sm/Yb ratios of mineralised BIF at Windarling and Koolyanobbing reflect distinct carbonate generations derived from substantial fluid–rock reactions between hydrothermal fluids and igneous country rocks, and a chemical carbonate-inheritance preserved in supergene goethite.Hypogene and supergene fluids are paramount for the formation of high-grade BIF-hosted iron ore because of the enormous amount of: (1) warm (100–200 °C) silica-undersaturated alkaline fluids necessary to dissolve quartz in BIF, (2) oxidized fluids that cause the oxidation of magnetite to hematite, (3) weakly acid (with moderate CO2 content) to alkaline fluids that are necessary to form widespread metasomatic carbonate, (4) carbonate-undersaturated fluids that dissolve the diagenetic and metasomatic carbonates, and (5) oxidized fluids to form hematite species in the hypogene- and supergene-enriched zone and hydroxides in the supergene zone.Four discrete end-member models for Archean and Proterozoic hypogene and supergene-only BIF hosted iron ore are proposed: (1) granite–greenstone belt hosted, strike-slip fault zone controlled Carajás-type model, sourced by early magmatic (± metamorphic) fluids and ancient “warm” meteoric water; (2) sedimentary basin, normal fault zone controlled Hamersley-type model, sourced by early basinal (± evaporitic) brines and ancient “warm” meteoric water. A variation of the latter is the metamorphosed basin model, where BIF (ore) is significantly metamorphosed and deformed during distinct orogenic events (e.g., deposits in the Quadrilátero Ferrífero and Simandou Range). It is during the orogenic event that the upgrade of BIF to medium- and high-grade hypogene iron took place; (3) sedimentary basin hosted, early graben structure controlled Urucum-type model, where glaciomarine BIF and subsequent diagenesis to very low-grade metamorphism is responsible for variable gangue leaching and hematite mineralisation. All of these hypogene iron ore models do not preclude a stage of supergene modification, including iron hydroxide mineralisation, phosphorous, and additional gangue leaching during substantial weathering in ancient or Recent times; and (4) supergene enriched BIF Capanema-type model, which comprises goethitic iron ore deposits with no evidence for deep hypogene roots. A variation of this model is ancient supergene iron ores of the Sishen-type, where blocks of BIF slumped into underlying karstic carbonate units and subsequently experienced Fe upgrade during deep lateritic weathering.  相似文献   

16.
The Mars Global Surveyor, Mars Exploration Rover, and Mars Express missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major recent mission findings are the presence of jarosite (a ferric sulfate salt), which requires formation from an acid-sulfate brine, and the occurrence of hematite and goethite on Mars. Recent ferric iron models have largely focused on 25 °C, which is a major limitation for models exploring the geochemical history of cold bodies such as Mars. Until recently, our work on low-temperature iron-bearing brines involved ferrous but not ferric iron, also obviously a limitation. The objectives of this work were to (1) add ferric iron chemistry to an existing ferrous iron model (FREZCHEM), (2) extend this ferrous/ferric iron geochemical model to lower temperatures (<0 °C), and (3) use the reformulated model to explore ferrous/ferric iron chemistries on Mars.The FREZCHEM model is an equilibrium chemical thermodynamic model parameterized for concentrated electrolyte solutions using the Pitzer approach for the temperature range from <−70 to 25 °C and the pressure range from 1 to 1000 bars. Ferric chloride and sulfate mineral parameterizations were based, in part, on experimental data. Ferric oxide/hydroxide mineral parameterizations were based exclusively on Gibbs free energy and enthalpy data. New iron parameterizations added 23 new ferrous/ferric minerals to the model for this Na-K-Mg-Ca-Fe(II)-Fe(III)-H-Cl-SO4-NO3-OH-HCO3-CO3-CO2-O2-CH4-H2O system.The model was used to develop paragenetic sequences for Rio Tinto waters on Earth and a hypothetical Martian brine derived from acid weathering of basaltic minerals. In general, model simulations were in agreement with field evidence on Earth and Mars in predicting precipitation of stable iron minerals such as jarosites, goethite, and hematite. In addition, paragenetic simulations for Mars suggest that other iron minerals such as lepidocrocite, schwertmannite, ferricopiapite, copiapite, and bilinite may also be present on the surface of Mars. Evaporation or freezing of the Martian brine led to similar mineral precipitates. However, in freezing, compared to evaporation, the following key differences were found: (1) magnesium sulfates had higher hydration states; (2) there was greater total aqueous sulfate (SO4T = SO4 + HSO4) removal; and (3) there was a significantly higher aqueous Cl/SO4T ratio in the residual Na-Mg-Cl brine. Given the similarities of model results to observations, alternating dry/wet and freeze/thaw cycles and brine migration could have played major roles in vug formation, Cl stratification, and hematite concretion formation on Mars.  相似文献   

17.
Three types of fluid inclusions have been identified in olivine porphyroclasts in the spinel harzburgite and lherzolite xenoliths from Tenerife: pure CO2 (Type A); carbonate-rich CO2–SO2 mixtures (Type B); and polyphase inclusions dominated by silicate glass±fluid±sp±silicate±sulfide±carbonate (Type C). Type A inclusions commonly exhibit a “coating” (a few microns thick) consisting of an aggregate of a platy, hydrous Mg–Fe–Si phase, most likely talc, together with very small amounts of halite, dolomite and other phases. Larger crystals (e.g. (Na,K)Cl, dolomite, spinel, sulfide and phlogopite) may be found on either side of the “coating”, towards the wall of the host mineral or towards the inclusion center. These different fluids were formed through the immiscible separations and fluid–wall-rock reactions from a common, volatile-rich, siliceous, alkaline carbonatite melt infiltrating the upper mantle beneath the Tenerife. First, the original siliceous carbonatite melt is separated from a mixed CO2–H2O–NaCl fluid and a silicate/silicocarbonatite melt (preserved in Type A inclusions). The reaction of the carbonaceous silicate melt with the wall-rock minerals gave rise to large poikilitic orthopyroxene and clinopyroxene grains, and smaller neoblasts. During the metasomatic processes, the consumption of the silicate part of the melt produced carbonate-enriched Type B CO2–SO2 fluids which were trapped in exsolved orthopyroxene porphyroclasts. At the later stages, the interstitial silicate/silicocarbonatite fluids were trapped as Type C inclusions. At a temperature above 650 °C, the mixed CO2–H2O–NaCl fluid inside the Type A inclusions were separated into CO2-rich fluid and H2O–NaCl brine. At T<650 °C, the residual silicate melt reacted with the host olivine, forming a reaction rim or “coating” along the inclusion walls consisting of talc (or possibly serpentine) together with minute crystals of NaCl, KCl, carbonates and sulfides, leaving a residual CO2 fluid. The homogenization temperatures of +2 to +25 °C obtained from the Type A CO2 inclusions reflect the densities of the residual CO2 after its reactions with the olivine host, and are unrelated to the initial fluid density or the external pressure at the time of trapping. The latter are restricted by the estimated crystallization temperatures of 1000–1200 °C, and the spinel lherzolite phase assemblage of the xenolith, which is 0.7–1.7 GPa.  相似文献   

18.
Twelve massive sulphide deposits from the Iberian Pyrite Belt (IPB) show well-preserved iron caps, some of which were mined during the last century to recover precious metals (e.g., Tharsis, Rio Tinto, San Miguel). Field observations and correlation assays between the distinct mineral sequences at different deposits suggest that all the gossans were developed under similar conditions and have undergone the same geological events. All the gossans have a mushroom-like morphology in sharp contact with the underlying massive sulphide orebodies. In most cases these are located over an apparent supergene enrichment zone rich in secondary sulphides. Some gossans extend into tongues of alluvial heterolithic breccias consisting of eroded transported gossans displaced as far as several hundred meters away from their sources. The distribution of major minerals throughout the gossan profiles (goethite, hematite, quartz and jarosite) and the statistical analysis of the geochemical data distinguish three separate zones, with gradual contacts roughly parallel to the current topography: (1) the lower zone dominated by goethite and subordinate jarosite, with significant enrichment in S, As, P, Pb, Sn, Sb, Ag and Au; (2) the middle or principal zone dominated by goethite and lacking jarosite, which is depleted in S, and As, as well as heavy and precious metals; and (3) the upper zone near the surface, mainly composed of hematite and quartz with only weak anomalies in P, Pb and Sn. The origin and variations occurred in the profiles are explained by a three-stage process. This involves an initial acidic stage of gossan development centred on the oxidation of sulphides that lead to the formation of the first Fe-rich oxyhydroxides and sulphates (mainly goethite and jarosite, respectively). Over time, a progressive stage of maturity is reached progressively downwards through the gossan profile due to the intensification of the oxidation and leaching processes. The ongoing gossan formation produced alteration and reprecipitation of pre-existing oxyhydroxides, the loss of the majority of the previously sorbed heavy metals, and a major dilution of trace elements especially in the zones near the surface. The main results of this stage of formation are the production of heavy metal-depleted oxyhydroxides, most commonly goethite and hematite, and the disappearance of jarosite. Subsequently, local uplift of the gossanous rocks by neotectonic movements facilitated the rejuvenation of the oxidation of the ores. This final stage complicated the previously developed zonation with the formation of jarosite in mature areas. Possible major breaks in this gossan development ocurred in Messinian times (7–8 Ma) and at the beginning of the Early Quaternary (1–2 Ma?).  相似文献   

19.
A first experimental study was conducted to determine the equilibrium iron isotope fractionation between pyrrhotite and silicate melt at magmatic conditions. Experiments were performed in an internally heated gas pressure vessel at 500 MPa and temperatures between 840 and 1000 °C for 120-168 h. Three different types of experiments were conducted and after phase separation the iron isotope composition of the run products was measured by MC-ICP-MS. (i) Kinetic experiments using 57Fe-enriched glass and natural pyrrhotite revealed that a close approach to equilibrium is attained already after 48 h. (ii) Isotope exchange experiments—using mixtures of hydrous peralkaline rhyolitic glass powder (∼4 wt% H2O) and natural pyrrhotites (Fe1 − xS) as starting materials— and (iii) crystallisation experiments, in which pyrrhotite was formed by reaction between elemental sulphur and rhyolitic melt, consistently showed that pyrrhotite preferentially incorporates light iron. No temperature dependence of the fractionation factor was found between 840 and 1000 °C, within experimental and analytical precision. An average fractionation factor of Δ 56Fe/54Fepyrrhotite-melt = −0. 35 ± 0.04‰ (2SE, n = 13) was determined for this temperature range. Predictions of Fe isotope fractionation between FeS and ferric iron-dominated silicate minerals are consistent with our experimental results, indicating that the marked contrast in both ligand and redox state of iron control the isotope fractionation between pyrrhotite and silicate melt. Consequently, the fractionation factor determined in this study is representative for the specific Fe2+/ΣFe ratio of our peralkaline rhyolitic melt of 0.38 ± 0.02. At higher Fe2+/ΣFe ratios a smaller fractionation factor is expected. Further investigation on Fe isotope fractionation between other mineral phases and silicate melts is needed, but the presented experimental results already suggest that even at high temperatures resolvable variations in the Fe isotope composition can be generated by equilibrium isotope fractionation in natural magmatic systems.  相似文献   

20.
Giant iron-ore deposits, such as those in the Hamersley Province of northwestern Australia, may contain more than a billion tonnes of almost pure iron oxides and are the world's major source of iron. It is generally accepted that these deposits result from supergene oxidation of host banded iron formation (BIF), accompanied by leaching of silicate and carbonate minerals. New textural evidence however, shows that formation of iron ore at one of those deposits, Mount Tom Price, involved initial high temperature crystallisation of magnetite-siderite-iron silicate assemblages. This was followed by development of hematite- and ferroan dolomite-bearing assemblages with subsequent oxidation of magnetite, leaching of carbonates and silicates and crystallisation of further hematite. Preliminary fluid inclusion studies indicate both low and high salinity aqueous fluids as well as complex salt-rich inclusions with the range of fluid types most likely reflecting interaction of hydrothermal brines with descending meteoric fluids. Initial hematite crystallisation occurred at about 250 °C and high fluid pressures and continued as temperatures decreased. Although the largely hydrothermal origin for mineralisation at Mount Tom Price is in conflict with previously proposed supergene models, it remains consistent with interpretations that the biosphere contained significant oxygen at the time of mineralisation. Received: 16 February 1999 / Accepted: 14 May 1999  相似文献   

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