首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
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   

2.
Recent Mars missions have stimulated considerable thinking about the surficial geochemical evolution of Mars. Among the major relevant findings are the presence in Meridiani Planum sediments of the mineral jarosite (a ferric sulfate salt) and related minerals that require formation from an acid-salt brine and oxidizing environment. Similar mineralogies have been observed in acidic saline lake sediments in Western Australia (WA), and these lakes have been proposed as analogues for acidic sedimentary environments on Mars. The prior version of the equilibrium chemical thermodynamic FREZCHEM model lacked Al and Si chemistries that are needed to appropriately model acidic aqueous geochemistries on Earth and Mars. The objectives of this work were to (1) add Al and Si chemistries to the FREZCHEM model, (2) extend these chemistries to low temperatures (<0 °C), if possible, and (3) use the reformulated model to investigate parallels in the mineral precipitation behavior of acidic Australian lakes and hypothetical Martian brines.FREZCHEM 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. Aluminum chloride and sulfate mineral parameterizations were based on experimental data. Aluminum hydroxide and silicon mineral parameterizations were based on Gibbs free energy and enthalpy data. New aluminum and silicon parameterizations added 12 new aluminum/silicon minerals to this Na-K-Mg-Ca-Fe(II)-Fe(III)-Al-H-Cl-Br-SO4-NO3-OH-HCO3-CO3-CO2-O2-CH4-Si-H2O system that now contain 95 solid phases.There were similarities, differences, and uncertainties between Australian acidic, saline playa lakes and waters that likely led to the Burns formation salt accumulations on Mars. Both systems are similar in that they are dominated by (1) acidic, saline ground waters and sediments, (2) Ca and/or Mg sulfates, and (3) iron precipitates such as jarosite and hematite. Differences include: (1) the dominance of NaCl in many WA lakes, versus the dominance of Fe-Mg-Ca-SO4 in Meridiani Planum, (2) excessively low K+ concentrations in Meridiani Planum due to jarosite precipitation, (3) higher acid production in the presence of high iron concentrations in Meridiani Planum, and probably lower rates of acid neutralization and hence, higher acidities on Mars owing to colder temperatures, and (4) lateral salt patterns in WA lakes. The WA playa lakes display significant lateral variations in mineralogy and water chemistry over short distances, reflecting the interaction of acid ground waters with neutral to alkaline lake waters derived from ponded surface runoff. Meridiani Planum observations indicate that such lateral variations are much less pronounced, pointing to the dominant influence of ground water chemistry, vertical ground water movements, and aeolian processes on the Martian surface mineralogy.  相似文献   

3.
Geochemical processes occurring in cold environments on Earth, Mars, and Europa have elicited considerable interest in the application of geochemical models to subzero temperatures. Few existing geochemical models explicitly include acid chemistry and those that do are largely restricted to temperatures ≥0°C or rely on the mole-fraction scale rather than the more common molal scale. This paper describes (1) use of the Clegg mole-fraction acid models to develop a molal-based model for hydrochloric, nitric, and sulfuric acids at low temperatures; (2) incorporation of acid chemistry and nitrate minerals into the FREZCHEM model; (3) validation and limitations of the derived acid model; and (4) simulation of hypothetical acidic brines for Europa.The Clegg mole-fraction acid models were used to estimate activities of water and mean ionic activity coefficients that serve as the database for estimating molal Pitzer-equation parameters for HCl (188 to 298 K), HNO3 (228 to 298 K), and H2SO4 (208 to 298 K). Model eutectics for HNO3 and H2SO4 agree with experimental measurements to within ± 0.2°C. In agreement with previous work, the experimental freezing point depression (fpd) data for pure HCl at subzero temperatures were judged to be flawed and unreliable. Three alternatives are discussed for handling HCl chemistry at subzero temperatures. In addition to defining the solubility of solid-phase acids, this work also adds three new nitrate minerals and six new acid salts to the FREZCHEM model and refines equilibria among water ice, liquid water, and water vapor over the temperature range from 180 to 298 K. The final system is parameterized for Na-K-Mg-Ca-H-Cl-SO4-NO3-OH-HCO3-CO3-CO2-H2O.Simulations of hypothetical MgSO4-H2SO4-H2O and Na2SO4-MgSO4-H2SO4-H2O brines for Europa demonstrate how freezing can convert a predominantly salt solution into a predominantly acid solution at subzero temperatures. This result has consequences for the effects of salinity, acidity, and temperature as limiting factors for potential life on Europa. Strong acidity would limit life-forms to highly acidophilic organisms.  相似文献   

4.
碳酸盐矿物的阴极发光性与微量元素的关系   总被引：7，自引：0，他引：7       下载免费PDF全文
碳酸盐矿物的阴极发光特征与其成分有关。笔者用阴极发光与电子探针微区分析法对砂岩中碳酸盐矿物进行测试分析 ,其结果表明碳酸盐矿物的阴极发光与微量元素含量有如下规律 :①碳酸盐矿物在铁含量高于猝灭下限或锰含量低于激活下限时 ,不具有阴极发光性 ;②铁的猝灭下限约为 0 0 4mol,锰的激活下限为小于 7× 10 - 5mol;③铁 /锰比值越高 ,越不利于碳酸盐矿物阴极发光 ;但是铁 /锰比值小于 1的碳酸盐一定具有阴极发光 ;④铁或锰二者之一含量很少时不利于碳酸盐矿物的阴极发光。  相似文献   

5.
Perennial ice covers on many Antarctic lakes have resulted in high lake inorganic carbon contents. The objective of this paper was to evaluate and compare the brine and CO2 chemistries of Lake Vida (Victoria Valley) and West Lake Bonney (Taylor Valley), two lakes of the McMurdo Dry Valleys (East Antarctica), and their potential consequences during global warming. An existing geochemical model (FREZCHEM-15) was used to convert measured molarity into molality needed for the FREZCHEM model, and this model added a new algorithm that converts measured DIC into carbonate alkalinity needed for the FREZCHEM model. While quite extensive geochemical information exists for ice-covered Taylor Valley lakes, such as West Lake Bonney, only limited information exists for the recently sampled brine of >25 m ice-thick Lake Vida. Lake Vida brine had a model-calculated pCO2 = 0.60 bars at the field pH (6.20); West Lake Bonney had a model-calculated pCO2 = 5.23 bars at the field pH (5.46). Despite the high degree of atmospheric CO2 supersaturation in West Lake Bonney, it remains significantly undersaturated with the gas hydrate, CO2·6H2O, unless these gas hydrates are deep in the sediment layer or are metastable having formed under colder temperatures or greater pressures. Because of lower temperatures, Lake Vida could start forming CO2·6H2O at lower pCO2 values than West Lake Bonney; but both lakes are significantly undersaturated with the gas hydrate, CO2·6H2O. For both lakes, simulation of global warming from current subzero temperatures (?13.4 °C in Lake Vida and ?4.7 °C in West Lake Bonney) to 10 °C has shown that a major loss of solution-phase carbon as CO2 gases and carbonate minerals occurred when the temperatures rose above 0 °C and perennial ice covers would disappear. How important these Antarctic CO2 sources will be for future global warming remains to be seen. But a recent paper has shown that methane increased in atmospheric concentration due to deglaciation about 10,000 years ago. So, CO2 release from ice lakes might contribute to atmospheric gases in the future.  相似文献   

6.
The assemblage clinopyroxene + magnesite was observed in Earth’s high-pressure metamorphic samples, and its stability in subducting slabs was confirmed by experiments. Recent studies also suggested that the fO2 variations observed in SNC meteorites can be explained by polybaric graphite-CO-CO2 equilibria in the Martian mantle. Although there is no direct evidence for the stability of the cpx + mc assemblage in Mars mantle, its high-pressure–high-temperature decomposition to cpx + fo + CO2 makes it a good analogue for the source of carbon metasomatism, in particular, to study nakhlites formation. Iron, which is present in the Earth’s and Martian mantles, may, however, influence the speciation of carbon. We performed experiments on a clinopyroxene + magnesite assemblage at 1.8 and 3.0 GPa and temperatures corresponding to the Earth’s and Martian mantles. The role of iron and of fO2 was investigated by (1) replacing all or part of the magnesite by siderite FeCO3, (2) adding Fe0 and (3) using graphite C capsules. A carbonate-silicate melt forms at both Earth and Mars conditions. Clinopyroxene and olivine are the main solid phases in the iron-free experiments. Fe2+ and Fe0 decrease their melting temperatures and increase the silicate fraction in the melt. The produced carbonate-silicate melts may be involved in the formation of some carbon-rich lavas on Earth (e.g., carbonatites, ultramafic lamprophyres, or kamafugites). Our results may also be used to interpret ophiolite samples or inclusions. In particular, we show that wüstite may form in equilibrium with carbonate-silicate melt in opx-(and silica-) poor regions of the mantle below 3 GPa. Our results also confirm the hypothesis of carbon metasomatism in the Martian nakhlites source. Immiscibility or reduction could explain the absence or rarity of C in Martian lavas.  相似文献   

7.
We examine the possibility that crystalline hematite (α-Fe2O3) deposits on Mars were derived from the precursor iron oxyhydroxide minerals akaganéite (β-FeOOH) or lepidocrocite (γ-FeOOH) and compare them to an earlier study of goethite (α-FeOOH) and magnetite (Fe3O4) precursors. Both the mid-infrared and visible/near infrared spectra of hematite are dependent upon the hematite precursor mineral and the temperature of transformation. Laboratory spectra are compared to spectra from the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) and the Mars Exploration Rover (MER) Opportunity Mini-TES and Pancam experiments, allowing us to infer the formation environment of Martian crystalline hematite deposits. Akaganéite and lepidocrocite readily transform to hematite at temperatures of 300 and 500°C, respectively. The visible/near-infrared and mid-infrared spectra of akaganéite-derived hematite are poor matches to data returned from TES, Mini-TES, and Pancam. The spectra of lepidocrocite-derived hematite are slightly better fits, but previously published spectra of goethite-derived hematite still represent the best match to MGS and MER spectral data. The experiments demonstrate that hematite precursor mineralogy, temperature of formation, and crystal shape exert a strong control on the hematite spectra.  相似文献   

8.
Early (>3 Gy) wetter climate conditions on Mars have been proposed, and it is thus likely that pedogenic processes have occurred there at some point in the past. Soil and rock chemistry of the Martian landing sites were evaluated to test the hypothesis that in situ aqueous alteration and downward movement of solutes have been among the processes that have transformed these portions of the Mars regolith. A geochemical mass balance shows that Martian soils at three landing sites have lost significant quantities of major rock-forming elements and have gained elements that are likely present as soluble ions. The loss of elements is interpreted to have occurred during an earlier stage(s) of weathering that may have been accompanied by the downward transport of weathering products, and the salts are interpreted to be emplaced later in a drier Mars history. Chemical differences exist among the sites, indicating regional differences in soil composition. Shallow soil profile excavations at Gusev crater are consistent with late stage downward migration of salts, implying the presence of small amounts of liquid water even in relatively recent Martian history. While the mechanisms for chemical weathering and salt additions on Mars remain unclear, the soil chemistry appears to record a decline in leaching efficiency. A deep sedimentary exposure at Endurance crater contains complex depth profiles of SO4, Cl, and Br, trends generally consistent with downward aqueous transport accompanied by drying. While no model for the origin of Martian soils can be fully constrained with the currently available data, a pedogenic origin is consistent with observed Martian geology and geochemistry, and provides a testable hypothesis that can be evaluated with present and future data from the Mars surface.  相似文献   

9.
Chert has formed from two sodium-silicate minerals, magadiite (NaSi7,O13(OH)3·3H2O) and kenyaite (NaSi11O20.5(OH)4·3H2O), in uppermost Pleistocene deposits of lakes Magadi and Natron in Kenya and Tanzania. The chert consists of finely crystalline quartz and characteristically forms nodules of irregular shape with white coatings having reticulate surface patterns. Similar nodules are widespread in lower and middle Pleistocene lacustrine deposits in the vicinity of Lake Magadi, Lake Natron, and Olduvai Gorge. Although magadiite and kenyaite are absent in the lower and middle Pleistocene deposits, the chert in these beds probably formed from a sodium-silicate precursor. All of the chert-bearing sediments were deposited in saline, alkaline lakes rich in dissolved sodium carbonate-bicarbonate.Magadiite (and chert) may form either thin, widespread deposits or localized masses which may be cross-cutting. Thin, widespread layers of magadiite have been precipitated by mixing of silica-rich brine with fresh water in a chemically stratified lake; localized masses may have been formed by interaction of brine with fresher water entering the floor or margin of the lake. Magadiite and kenyaite can alter to chert in contact with sodium-carbonate brine and possibly by leaching with relatively fresh water over a period of 20,000 years or less.The siliceous zeolites clinoptilolite and erionite predominate in trachyte tuffs associated with magadiite and chert; less-siliceous phillipsite predominates in trachyte tuffs of chert-free sequences.  相似文献   

10.
Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 · 10−8 to 1 · 10−5 M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca2+, Mg2+, HCO3−, SO42−, H4SiO4, and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters.  相似文献   

11.
The suggestion that radon could be used as a radioactive tracer of regolith-atmosphere exchanges and as a proxy for subsurface water on Mars, as well as its indirect detection in the Martian atmosphere by the rover Opportunity, have raised the need for a better characterization of its production process and transport efficiency in the Martian soil. More specifically, a proper estimation of radon exhalation rate on Mars requires its emanation factor and diffusion length to be determined. The dependence of the emanation factor as a function of pore water content (at 267 and 293 K) and the dependence of the adsorption coefficient on temperature, specific surface area and nature of the carrier gas (He, He + CO2) have been measured on a Martian soil analogue (Hawaiian palagonitized volcanic ash, JSC Mars-1), whose radiometric analysis has been performed. An estimation of radon diffusion lengths on Mars is provided and is used to derive a global average emanation factor (2-6.5%) that accounts for the exhalation rate inferred from the 210Po surface concentration detected on Martian dust and from the 214Bi signal measured by the Mars Odyssey Gamma Ray Spectrometer. It is found to be much larger than emanation factors characterizing lunar samples, but lower than the emanation factor of the palagonite samples obtained under dry conditions. This result probably reflects different degrees of aqueous alteration and could indicate that the emanation factor is also affected by the current presence of pore water in the Martian soil. The rationale of the “radon method” as a technique to probe subsurface water on Mars, and its sensitivity to soil parameters are discussed. These experimental data are useful to perform more detailed studies of radon transport in the Martian atmosphere using Global Climate Models and to interpret neutron and gamma data from Mars Odyssey Gamma Ray Spectrometer.  相似文献   

12.
The magnetites and sulfides located in the rims of carbonate globules in the Martian meteorite ALH84001 have been claimed as evidence of past life on Mars. Here, we consider the possibility that the rims were formed by dissolution and reprecipitation of the primary carbonate by the action of water. To estimate the rate of these solution-precipitation reactions, a kinetic model of magnesite-siderite carbonate dissolution was applied and used to examine the physicochemical conditions under which these rims might have formed. The results indicate that the formation of the rims could have taken place in < 50 yr of exposure to small amounts of aqueous fluids at ambient temperatures. Plausible conditions pertaining to reactions under a hypothetical ancient Martian atmosphere (1 bar CO2), the modern Martian atmosphere (8 mbar CO2), and the present terrestrial atmosphere (0.35 mbar CO2) were explored to constrain the site of the process. The results indicated that such reactions likely occurred under the latter two conditions. The possibility of Antarctic weathering must be entertained, which, if correct, would imply that the plausibly biogenic minerals (single-domain magnetite of characteristic morphology and sulfide) reported from the rims may be the products of terrestrial microbial activity. This model is discussed in terms of the available isotope data and found to be compatible with the formation of ALH84001 rims. Particularly, anticorrelated variations of radiocarbon with δ13C indicate that carbonate in ALH84001 was affected by solution-precipitation reactions immediately after its initial fall (∼13,000 yr ago) and then again during its recent exposure prior to collection.  相似文献   

13.
Isothermal evaporation experiments were carried out on an acidic (pH 2), partially oxidized (Fe2+/FeT ∼0.5) brine with a cation composition consistent with derivation from the chemical weathering of martian basalt. During evaporation, the brine composition evolved to a highly acidic (un-scaled pH −1.3) Mg-Fe-SO4-Cl brine depleted in Ca, Al and K. Evaporite minerals identified throughout the course of the experiment include (in order of crystallization): gypsum, Mg-rich voltaite, (Mg0.7, )SO4·7H2O and rhomboclase. The solid solution compositions of voltaite and (Mg0.7, )SO4·7H2O, although uncommon in analogous environments on Earth, result from the distinct chemistry of evaporating martian surface fluids. Analysis of brine compositions with available thermodynamic models indicates that, although gypsum and rhomboclase precipitate at equilibrium saturation, kinetic controls on the precipitation of copiapite-group minerals affect the subsequent sulfate mineralogy and evolving chemistry of the entire system. In addition, geochemical simulations of the experimental evaporation process suggest that the appearance of voltaite and rhomboclase indicate a “metastable” evaporation pathway for martian fluids whereby bilinite and copiapite-group minerals did not form despite thermodynamic saturation. Comparison of the experimentally-produced assemblage to available observations of saline minerals at the martian surface represents a step toward systematically characterizing evaporite mineralogy as a function of Fe-oxidation in the initially dilute fluid. Deconvolving the complexity of Fe-sulfate formation in martian environments ultimately will help to exploit the sensitivity of these minerals to pH and redox conditions present at the ancient martian surface.  相似文献   

14.
We report new measurements of equilibrium relative humidities for stable and metastable hydration-dehydration equilibria involving several magnesium sulfates in the MgSO4·nH2O series. We also report a comprehensive thermodynamic treatment of the system including solution properties and experimental data from the published literature, i.e. solubilities, heat capacities and additional decomposition humidities. While for some magnesium sulfate hydrates solubility data in the binary system MgSO4-H2O are sparse, there is a reasonable database of solubility measurements of these hydrates in the ternary MgCl2-MgSO4-H2O and the quaternary reciprocal Na+-Mg2+-Cl−-SO42−-H2O systems. To make these data suitable for the determination of solubility products, we parameterized a Pitzer ion interaction model for the calculation of activity coefficients and water activities in mixed solutions of these systems and report the ion interaction parameters for the Na+-Mg2+-Cl−-SO42−-H2O system. The model predicted solubilities in the reciprocal system are in very good agreement with experimental data. Using all available experimental data and the solution model an updated phase diagram of the MgSO4-H2O system covering the whole temperature range from about 170 to 473 K is established. This treatment includes MgSO4·H2O (kieserite), MgSO4·4H2O (starkeyite), MgSO4·5H2O (pentahydrite), MgSO4·6H2O (hexahydrite), MgSO4·7H2O (epsomite) and MgSO4·11H2O (meridianiite). It is shown that only kieserite, hexahydrite, epsomite and meridianiite show fields of stable existence while starkeyite and pentahydrite are always metastable. Due to sluggish kinetics of kieserite formation, however, there is a rather extended field of metastable existence of starkeyite which makes this solid a major product in dehydration reactions. The model predicted behavior of the magnesium sulfates is in excellent agreement with observations reported in the literature under terrestrial temperature and relative humidity conditions. We also discuss the implications of the new phase diagram for sulfates on Mars.  相似文献   

15.
Apatite preserves a record of the halogen and water fugacities that existed during the waning stages of crystallization of planetary magmas, when they became saturated in phosphates. We develop a thermodynamic formalism based on apatite-merrillite equilibria that makes it possible to compare the relative values of halogen and water fugacities in Martian, lunar and terrestrial basalts, accounting for possible differences in pressure, temperature and oxygen fugacities among the planets. We show that each of these planetary bodies has distinctive ratios among volatile fugacities at apatite saturation and that these fugacities are in some cases related in a consistent way to volatile fugacities in the mantle magma sources. Our analysis shows that the Martian mantle parental to basaltic SNC meteorites was dry and poor in both fluorine and chlorine compared to the terrestrial mantle. The limited data available from Mars show no secular variation in mantle halogen and water fugacities from ∼4 Ga to ∼180 Ma. The water and halogens found in present-day Martian surface rocks have thus resided in the planet’s surficial systems since at least 4 Ga, and may have been degassed from the planet’s interior during a primordial crust-forming event. In comparison to the Earth and Mars, the Moon, and possibly the eucrite parent body too, appear to be strongly depleted not only in H2O but also in Cl2 relative to H2O. Chlorine depletion is strongest in mare basalts, perhaps reflecting an eruptive process characteristic of large-scale lunar magmatism.  相似文献   

16.
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   

17.
At T > 100°C development of thermodynamic models suffers from missing experimental data, particularly for solubilities of sulfate minerals in mixed solutions. Solubilities in Na+-K+-Ca2+-Cl−-SO42−/H2O subsystems were investigated at 150, 200°C and at selected compositions at 100°C. The apparatus used to examine solid-liquid phase equilibria under hydrothermal conditions has been described.In the system NaCl-CaSO4-H2O the missing anhydrite (CaSO4) solubilities at high NaCl concentrations up to halite saturation have been determined. In the system Na2SO4-CaSO4-H2O the observed glauberite (Na2SO4 · CaSO4) solubility is higher than that predicted by the high temperature model of Greenberg and Møller (1989), especially at 200°C. At high salt concentrations, solubilities of both anhydrite and glauberite increase with increasing temperature. Stability fields of the minerals syngenite (K2SO4 · CaSO4 · H2O) and goergeyite (K2SO4 · 5 CaSO4 · H2O) were determined, and a new phase was found at 200°C in the K2SO4-CaSO4-H2O system. Chemical and single crystal structure analysis give the formula K2SO4 · CaSO4. The structure is isostructural with palmierite (K2SO4 · PbSO4). The glaserite (“3 K2SO4 · Na2SO4”) appears as solid solution in the system Na2SO4-K2SO4-H2O. Its solubility and stoichiometry was determined as a function of solution composition.  相似文献   

18.
Boltwoodite and uranophane are uranyl silicates common in oxidized zones of uranium ore deposits. An understanding of processes that impact uranium transport in the environment, especially pertaining to the distribution of uranium between solid phases and aqueous solutions, ultimately requires determination of thermodynamic parameters for such crystalline materials. We measured formation enthalpies of synthetic boltwoodites, K(UO2)(HSiO4)·H2O and Na(UO2)(HSiO4)·H2O, and uranophane, Ca(UO2)2(HSiO4)2·5H2O, by high temperature oxide melt solution calorimetry. We also studied the aqueous solubility of these phases from both saturated and undersaturated conditions at a variety of pH. The combined data permit the determination of standard enthalpies, entropies and Gibbs free energies of formation for each phase and analysis of its potential geological impact from a thermodynamic point of view.  相似文献   

19.
The solubility of Fe-ettringite (Ca6[Fe(OH)6]2(SO4)3 · 26H2O) was measured in a series of precipitation and dissolution experiments at 20 °C and at pH-values between 11.0 and 14.0 using synthesised material. A time-series study showed that equilibrium was reached within 180 days of ageing. After equilibrating, the solid phases were analysed by XRD and TGA while the aqueous solutions were analysed by ICP-OES (calcium, sulphur) and ICP-MS (iron). Fe-ettringite was found to be stable up to pH 13.0. At higher pH-values Fe-monosulphate (Ca4[Fe(OH)6]2(SO4) · 6H2O) and Fe-monocarbonate (Ca4[Fe(OH)6]2(CO3) · 6H2O) are formed. The solubilities of these hydrates at 25 °C are:   相似文献   

20.
The magnitude of equilibrium iron isotope fractionation between Fe(H2O)63+ and Fe(H2O)62+ is calculated using density functional theory (DFT) and compared to prior theoretical and experimental results. DFT is a quantum chemical approach that permits a priori estimation of all vibrational modes and frequencies of these complexes and the effects of isotopic substitution. This information is used to calculate reduced partition function ratios of the complexes (103 · ln(β)), and hence, the equilibrium isotope fractionation factor (103 · ln(α)). Solvent effects are considered using the polarization continuum model (PCM). DFT calculations predict fractionations of several per mil in 56Fe/54Fe favoring partitioning of heavy isotopes in the ferric complex. Quantitatively, 103 · ln(α) predicted at 22°C, ∼ 3 ‰, agrees with experimental determinations but is roughly half the size predicted by prior theoretical results using the Modified Urey-Bradley Force Field (MUBFF) model. Similar comparisons are seen at other temperatures. MUBFF makes a number of simplifying assumptions about molecular geometry and requires as input IR spectroscopic data. The difference between DFT and MUBFF results is primarily due to the difference between the DFT-predicted frequency for the ν4 mode (O-Fe-O deformation) of Fe(H2O)63+ and spectroscopic determinations of this frequency used as input for MUBFF models (185-190 cm−1 vs. 304 cm−1, respectively). Hence, DFT-PCM estimates of 103 · ln(β) for this complex are ∼ 20% smaller than MUBFF estimates. The DFT derived values can be used to refine predictions of equilibrium fractionation between ferric minerals and dissolved ferric iron, important for the interpretation of Fe isotope variations in ancient sediments. Our findings increase confidence in experimental determinations of the Fe(H2O)63+ − Fe(H2O)62+ fractionation factor and demonstrate the utility of DFT for applications in “heavy” stable isotope geochemistry.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号