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1.
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   

2.
Major uncertainties exist with respect to the aqueous geochemical evolution of the Martian surface. Considering the prevailing cryogenic climates and the abundance of salts and iron minerals on Mars, any attempt at comprehensive modeling of Martian aqueous chemistry should include iron chemistry and be valid at low temperatures and high solution concentrations. The objectives of this paper were to (1) estimate ferrous iron Pitzer-equation parameters and iron mineral solubility products at low temperatures (from < 0 °C to 25 °C), (2) incorporate these parameters and solubility products into the FREZCHEM model, and (3) use the model to simulate the surficial aqueous geochemical evolution of Mars.Ferrous iron Pitzer-equation parameters were derived in this work or taken from the literature. Six new iron minerals [FeCl2·4H2O, FeCl2·6H2O, FeSO4·H2O, FeSO4·7H2O, FeCO3, and Fe(OH)3] were added to the FREZCHEM model bringing the total solid phases to 56. Agreement between model predictions and experimental data are fair to excellent for the ferrous systems: Fe-Cl, Fe-SO4, Fe-HCO3, H-Fe-Cl, and H-Fe-SO4.We quantified a conceptual model for the aqueous geochemical evolution of the Martian surface. The five stages of the conceptual model are: (1) carbonic acid weathering of primary ferromagnesian minerals to form an initial magnesium-iron-bicarbonate-rich solution; (2) evaporation and precipitation of carbonates, including siderite (FeCO3), with evolution of the brine to a concentrated NaCl solution; (3) ferrous/ferric iron oxidation; (4) either evaporation or freezing of the brine to dryness; and (5) surface acidification.What began as a dilute Mg-Fe-HCO3 dominated leachate representing ferromagnesian weathering evolved into an Earth-like seawater composition dominated by NaCl, and finally into a hypersaline Mg-Na-SO4-Cl brine. Weathering appears to have taken place initially under conditions that allowed solution of ferrous iron [low O2(g)], but later caused oxidation of iron [high O2(g)]. Surface acidification and/or sediment burial can account for the minor amounts of Martian surface carbonates. This model rests on a large number of assumptions and is therefore speculative. Nevertheless, the model is consistent with current understanding concerning surficial salts and minerals based on Martian meteorites, Mars lander data, and remotely-sensed spectral analyses.  相似文献   

3.
Various iron-bearing primary phases and rocks have been weathered experimentally to simulate possible present and past weathering processes occurring on Mars. We used magnetite, monoclinic and hexagonal pyrrhotites, and metallic iron as it is suggested that meteoritic input to the martian surface may account for an important source of reduced iron. The phases were weathered in two different atmospheres: one composed of CO2 + H2O, to model the present and primary martian atmosphere, and a CO2 + H2O + H2O2 atmosphere to simulate the effect of strong oxidizing agents. Experiments were conducted at room temperature and a pressure of 0.75 atm. Magnetite is the only stable phase in the experiments and is thus likely to be released on the surface of Mars from primary rocks during weathering processes. Siderite, elemental sulfur, ferrous sulfates and ferric (oxy)hydroxides (goethite and lepidocrocite) are the main products in a water-bearing atmosphere, depending on the substrate. In the peroxide atmosphere, weathering products are dominated by ferric sulfates and goethite. A kinetic model was then developed for iron weathering in a water atmosphere, using the shrinking core model (SCM). This model includes competition between chemical reaction and diffusion of reactants through porous layers of secondary products. The results indicate that for short time scales, the mechanism is dominated by a chemical reaction with second order kinetics (k = 7.75 × 10−5 g−1/h), whereas for longer time scales, the mechanism is diffusion-controlled (DeA = 2.71 × 10−10 m2/h). The results indicate that a primary CO2- and H2O-rich atmosphere should favour sulfur, ferrous phases such as siderite or Fe2+-sulfates, associated with ferric (oxy)hydroxides (goethite and lepidocrocite). Further evolution to more oxidizing conditions may have forced these precursors to evolve into ferric sulfates and goethite/hematite.  相似文献   

4.
Although iron isotopes provide a new powerful tool for tracing a variety of geochemical processes, the unambiguous interpretation of iron isotope ratios in natural systems and the development of predictive theoretical models require accurate data on equilibrium isotope fractionation between fluids and minerals. We investigated Fe isotope fractionation between hematite (Fe2O3) and aqueous acidic NaCl fluids via hematite dissolution and precipitation experiments at temperatures from 200 to 450 °C and pressures from saturated vapor pressure (Psat) to 600 bar. Precipitation experiments at 200 °C and Psat from aqueous solution, in which Fe aqueous speciation is dominated by ferric iron (FeIII) chloride complexes, show no detectable Fe isotope fractionation between hematite and fluid, Δ57Fefluid-hematite = δ57Fefluid − δ57Fehematite = 0.01 ± 0.08‰ (2 × standard error, 2SE). In contrast, experiments at 300 °C and Psat, where ferrous iron chloride species (FeCl2 and FeCl+) dominate in the fluid, yield significant fluid enrichment in the light isotope, with identical values of Δ57Fefluid-hematite = −0.54 ± 0.15‰ (2SE) both for dissolution and precipitation runs. Hematite dissolution experiments at 450 °C and 600 bar, in which Fe speciation is also dominated by ferrous chloride species, yield Δ57Fefluid-hematite values close to zero within errors, 0.15 ± 0.17‰ (2SE). In most experiments, chemical, redox, and isotopic equilibrium was attained, as shown by constancy over time of total dissolved Fe concentrations, aqueous FeII and FeIII fractions, and Fe isotope ratios in solution, and identical Δ57Fe values from dissolution and precipitation runs. Our measured equilibrium Δ57Fefluid-hematite values at different temperatures, fluid compositions and iron redox state are within the range of fractionations in the system fluid-hematite estimated using reported theoretical β-factors for hematite and aqueous Fe species and the distribution of Fe aqueous complexes in solution. These theoretical predictions are however affected by large discrepancies among different studies, typically ±1‰ for the Δ57Fe Fe(aq)-hematite value at 200 °C. Our data may thus help to refine theoretical models for β-factors of aqueous iron species. This study provides the first experimental calibration of Fe isotope fractionation in the system hematite-saline aqueous fluid at elevated temperatures; it demonstrates the importance of redox control on Fe isotope fractionation at hydrothermal conditions.  相似文献   

5.
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   

6.
Using a simple ionic model with polarizable oxygen ions and dissociating water molecules, we have calculated the energetics governing the distribution of Fe(II)/Fe(III) ions at the reduced (2 × 1) surface of α-Fe2O3 (hematite) (0 1 2) under dry and hydrated conditions. The results show that systems with Fe(II) ions located in the near-surface region have lower potential energy for both dry and hydrated surfaces. The distribution is governed by coupling of the ferrous iron centers to positive charge associated with missing oxygen atoms on the dry reduced (2 × 1) (0 2 1) surface. As the surface is hydroxylated, the missing oxygen rows are filled and protons from dissociated water molecules become the positive charge centers, which couple more weakly to the ferrous iron centers. At the same time, the first-layer iron centers change from fourfold or fivefold coordination to sixfold coordination lowering the potential energy of ferric iron in the first layer and favoring migration of ferrous iron from the immediate surface sites. This effect can also be understood as reflecting stronger solvation of Fe(III) by the adsorbed water molecules and by hydrolysis reactions favoring Fe(III) ions at the immediate surface. The balance between these two driving forces, which changes as a function of hydration, provides a compelling explanation for the anomalous coverage dependence of water desorption in ultra-high vacuum experiments.  相似文献   

7.
Computer modelling techniques were used to elucidate the hydration behaviour of three iron (hydr)oxide minerals at the atomic level: white rust, goethite and hematite. A potential model was first adapted and tested against the bulk structures and properties of eight different iron oxides, oxyhydroxides and hydroxides, followed by surface simulations of Fe(OH)2, α-FeO(OH) and α-Fe2O3. The major interaction between the adsorbing water molecules and the surface is through interaction of their oxygen ions with surface iron ions, followed by hydrogen-bonding to surface oxygen ions. The energies released upon the associative adsorption of water range from 1 to 17 kJ mol−1 for Fe(OH)2, 26 to 80 kJ mol−1 for goethite and 40 to 85 kJ mol−1 for hematite, reflecting the increasing oxidation of the iron mineral. Dissociative adsorption at goethite and hematite surfaces releases larger hydration energies, ranging from 120 to 208 kJ mol−1 for goethite and 76 to 190 kJ mol−1 for hematite.The thermodynamic morphologies of the minerals, based on the calculated surface energies, agree well with experimental morphologies, where these are available. When the partial pressures required for adsorption of water from the gas phase are plotted against temperature for the goethite and hematite surfaces, taking into account experimental entropies for water, it appears that these minerals may well be instrumental in the retention of water during the cyclic variations in the atmosphere of Mars.  相似文献   

8.
In addition to equilibrium isotopic fractionation factors experimentally derived, theoretical predictions are needed for interpreting isotopic compositions measured on natural samples because they allow exploring more easily a broader range of temperature and composition. For iron isotopes, only aqueous species were studied by first-principles methods and the combination of these data with those obtained by different methods for minerals leads to discrepancies between theoretical and experimental isotopic fractionation factors. In this paper, equilibrium iron isotope fractionation factors for the common minerals pyrite, hematite, and siderite were determined as a function of temperature, using first-principles methods based on the density functional theory (DFT). In these minerals belonging to the sulfide, oxide and carbonate class, iron is present under two different oxidation states and is involved in contrasted types of interatomic bonds. Equilibrium fractionation factors calculated between hematite and siderite compare well with the one estimated from experimental data (ln α57Fe/54Fe = 4.59 ± 0.30‰ and 5.46 ± 0.63‰ at 20 °C for theoretical and experimental data, respectively) while those for Fe(III)aq-hematite and Fe(II)aq-siderite are significantly higher that experimental values. This suggests that the absolute values of the reduced partition functions (β-factors) of aqueous species are not accurate enough to be combined with those calculated for minerals. When compared to previous predictions derived from Mössbauer or INRXS data [Polyakov V. B., Clayton R. N., Horita J. and Mineev S. D. (2007) Equilibrium iron isotope fractionation factors of minerals: reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mössbauer spectroscopy. Geochim. Cosmochim. Acta71, 3833-3846], our iron β-factors are in good agreement for siderite and hematite while a discrepancy is observed for pyrite. However, the detailed investigation of the structural, electronic and vibrational properties of pyrite as well as the study of sulfur isotope fractionation between pyrite and two other sulfides (sphalerite and galena) indicate that DFT-derived β-factors of pyrite are as accurate as for hematite and siderite. We thus suggest that experimental vibrational density of states of pyrite should be re-examined.  相似文献   

9.
Combining analytical data from hot spring samples with thermodynamic calculations permits a quantitative assessment of the availability and ranking of various potential sources of inorganic chemical energy that may support microbial life in hydrothermal ecosystems. Yellowstone hot springs of diverse geochemical composition, ranging in pH from <2 to >9 were chosen for this study, and dozens of samples were collected during three field seasons. Field measurements of dissolved oxygen, nitrate, nitrite, total ammonia, total sulfide, alkalinity, and ferrous iron were combined with laboratory analyses of sulfate and other major ions from water samples, and carbon dioxide, hydrogen, methane, and carbon monoxide in gas samples to evaluate activity products for ∼300 coupled oxidation-reduction reactions. Comparison of activity products and independently calculated equilibrium constants leads to values of the chemical affinity for each of the reactions, which quantifies how far each reaction is from equilibrium. Affinities, in turn, show systematic behavior that is independent of temperature but can be correlated with pH of the hot springs as a proxy for the full spectrum of geochemical variability. Many affinities are slightly to somewhat dependent on pH, while others are dramatically influenced by changes in chemical composition. All reactions involving dissolved oxygen as the electron acceptor are potential energy sources in all hot spring samples collected, but the ranking of dominant electron donors changes from ferrous iron, and sulfur at high pH to carbon monoxide, hydrogen, and magnetite as pH decreases. There is a general trend of decreasing energy yields depending on electron acceptors that follows the sequence: O2(aq) > NO3− ≈ NO2− ≈ S > pyrite ≈ SO4−2 ≈ CO(g) ≈ CO2(g) at high pH, and O2(aq) ≈ magnetite > hematite ≈ goethite > NO3− ≈ NO2− ≈ S ≈ pyrite ≈ SO4−2 at low pH. Many reactions that are favorable sources of chemical energy at one set of geochemical conditions fail to provide energy at other conditions, and vice versa. This results in energy profiles supplied by geochemical processes that provide fundamentally different foundations for chemotrophic microbial communities as composition changes.  相似文献   

10.
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   

11.
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   

12.
Sedimentary basins in general, and deep saline aquifers in particular, are being investigated as possible repositories for large volumes of anthropogenic CO2 that must be sequestered to mitigate global warming and related climate changes. To investigate the potential for the long-term storage of CO2 in such aquifers, 1600 t of CO2 were injected at 1500 m depth into a 24-m-thick “C” sandstone unit of the Frio Formation, a regional aquifer in the US Gulf Coast. Fluid samples obtained before CO2 injection from the injection well and an observation well 30 m updip showed a Na–Ca–Cl type brine with ∼93,000 mg/L TDS at saturation with CH4 at reservoir conditions; gas analyses showed that CH4 comprised ∼95% of dissolved gas, but CO2 was low at 0.3%. Following CO2 breakthrough, 51 h after injection, samples showed sharp drops in pH (6.5–5.7), pronounced increases in alkalinity (100–3000 mg/L as HCO3) and in Fe (30–1100 mg/L), a slug of very high DOC values, and significant shifts in the isotopic compositions of H2O, DIC, and CH4. These data, coupled with geochemical modeling, indicate corrosion of pipe and well casing as well as rapid dissolution of minerals, especially calcite and iron oxyhydroxides, both caused by lowered pH (initially ∼3.0 at subsurface conditions) of the brine in contact with supercritical CO2.  相似文献   

13.
Iron isotopes fractionate during hydrothermal processes. Therefore, the Fe isotope composition of ore-forming minerals characterizes either iron sources or fluid histories. The former potentially serves to distinguish between sedimentary, magmatic or metamorphic iron sources, and the latter allows the reconstruction of precipitation and redox processes. These processes take place during ore formation or alteration. The aim of this contribution is to investigate the suitability of this new isotope method as a probe of ore-related processes. For this purpose 51 samples of iron ores and iron mineral separates from the Schwarzwald region, southwest Germany, were analyzed for their iron isotope composition using multicollector ICP-MS. Further, the ore-forming and ore-altering processes were quantitatively modeled using reaction path calculations. The Schwarzwald mining district hosts mineralizations that formed discontinuously over almost 300 Ma of hydrothermal activity. Primary hematite, siderite and sulfides formed from mixing of meteoric fluids with deeper crustal brines. Later, these minerals were partly dissolved and oxidized, and secondary hematite, goethite and iron arsenates were precipitated. Two types of alteration products formed: (1) primary and high-temperature secondary Fe minerals formed between 120 and 300 °C, and (2) low-temperature secondary Fe minerals formed under supergene conditions (<100 °C). Measured iron isotope compositions are variable and cover a range in δ56Fe between −2.3‰ and +1.3‰. Primary hematite (δ56Fe: −0.5‰ to +0.5‰) precipitated by mixing oxidizing surface waters with a hydrothermal fluid that contained moderately light Fe (δ56Fe: −0.5‰) leached from the crystalline basement. Occasional input of CO2-rich waters resulted in precipitation of isotopically light siderite (δ56Fe: −1.4 to −0.7‰). The difference between hematite and siderite is compatible with published Fe isotope fractionation factors. The observed range in isotopic compositions can be accounted for by variable fractions of Fe precipitating from the fluid. Therefore, both fluid processes and mass balance can be inferred from Fe isotopes. Supergene weathering of siderite by oxidizing surface waters led to replacement of isotopically light primary siderite by similarly light secondary hematite and goethite, respectively. Because this replacement entails quantitative transfer of iron from precursor mineral to product, no significant isotope fractionation is produced. Hence, Fe isotopes potentially serve to identify precursors in ore alteration products. Goethites from oolitic sedimentary iron ores were also analyzed. Their compositional range appears to indicate oxidative precipitation from relatively uniform Fe dissolved in coastal water. This comprehensive iron isotope study illustrates the potential of the new technique in deciphering ore formation and alteration processes. Isotope ratios are strongly dependent on and highly characteristic of fluid and precipitation histories. Therefore, they are less suitable to provide information on Fe sources. However, it will be possible to unravel the physico-chemical processes leading to the formation, dissolution and redeposition of ores in great detail.  相似文献   

14.
Low-temperature aqueous processes have been implicated in the generation of jarosite and hematite on the martian surface, but little is known regarding the role that high-temperature magmatic fluids may have played in producing similar assemblages on Mars. We have identified jarosite and hematite in a clinopyroxene-hosted melt inclusion in martian meteorite MIL 03346 that shows evidence of having been hydrothermally precipitated. In addition to jarosite and hematite, the melt inclusion contains titanomagnetite, pyrrhotite, potassic-chlorohastingsite, an iron-rich silicate glass and possibly goethite. These phases were identified and characterized using scanning electron microscopy (SEM), con-focal Raman-spectroscopy and electron probe microanalysis (EPMA).Based on observed textural relationships and the compositions of the hosted phases, we report that the jarosite-bearing melt inclusion in MIL 03346 has recorded a fluid-rich history that began in the magmatic stage and continued to low-temperatures. This history begins at entrapment of a volatile-rich silicate melt that likely reached fluid-saturation after only minor crystallization within the melt inclusion. This fluid, rich in chlorine, reacted with surrounding silicate material to produce the potassic-chlorohastingsite. As cooling proceeded, the liquid phase eventually became more oxidized and reacted with the pyrrhotite. Sulfide oxidation resulted in SO42− formation and concomitant acid production, setting the stage for jarosite formation once the fluid cooled beyond the upper thermal stability of jarosite (∼200 °C). As the fluid cooled below 200 °C, jarosite continued to precipitate with hematite and/or goethite until equilibrium was established or reactions became kinetically unfavorable.This work suggests an additional jarosite-hematite formation pathway on Mars; one that may be important wherever magmatic-hydrothermal fluids come into contact with primary sulfide grains at the martian surface or subsurface. Moreover, hydrothermal fluids rich in chlorine, sulfur, and iron are important for ore-forming processes on Earth, and their indirect identification on Mars may have important implications for ore-formation on Mars.  相似文献   

15.
In order to improve our understanding of HSE geochemistry, we evaluate the effect of Fe on the solubility of Pd in silicate melts. To date, experimentally determined Pd solubilities in silicate melt are only available for Fe-free anorthite-diopside eutectic compositions. Here we report experiments to study the solubility of Pd in a natural picritic melt as a function of pO2 at 1300 °C in a one atm furnace. Palladium concentrations in the run products were determined by laser-ablation-ICP-MS. Palladium increases from 1.07 ± 0.26 ppm at FMQ-2, to 306 ± 19 ppm at FMQ+6.6. At a relative pO2 of FMQ the slope in log Pd concentration vs. log pO2 space increases considerably, and Pd concentrations are elevated over those established for AnDi melt compositions. In the same pO2 range, ferric iron significantly increases relative to ferrous iron. Furthermore, at constant pO2 (FMQ+0.5) Pd concentrations significantly increase with increasing XFeO-total in the melt. Therefore, we consider ferric Fe to promote the formation of Pd2+ enhancing the solubility of Pd in the picrite melt significantly.The presence of FeO in the silicate melt has proven to be an important melt compositional parameter, and should be included and systematically investigated in future experimental studies, since most natural compositions have substantial FeO contents.  相似文献   

16.
Mössbauer spectroscopy has been used widely to characterize the ferric (Fe3+) and ferrous (Fe2+) proportions and coordination of solid materials. To obtain these accurately, the recoilless fraction is indispensible. The recoilless fractions (f) of iron-bearing minerals, including oxides, oxyhydroxides, silicates, carbonates, phosphates and dichalcogenides, and silicate glasses were evaluated from the temperature dependence of their center shifts or absorption area with the Debye model approximation. Generally, the resolved Debye temperature (θD) of ferric iron in minerals, except dichalcogenides, through their center shifts ranging from 400 to 550 K, is significantly larger than ferrous iron ranging from 300 to 400 K, which is consistent with the conclusion from previous work. The resolved f (Fe3+)RT with the center shift model (CSM) ranges from 0.825 to 0.925, which is larger than that obtained for f(Fe2+)RT, which ranges from 0.675 to 0.750. Meanwhile, the θD and f resolved from temperature-dependence of absorption are generally lower than from center shifts, especially for ferric iron. The significant difference between f(Fe3+) and f(Fe2+) indicates the necessity of recoilless fraction correction on the Fe3+/(Fe3++Fe2+) resolved from Mössbauer spectra.  相似文献   

17.
Neutrophilic iron oxidizing bacteria (FeOB) must actively compete with rapid abiotic processes governing Fe(II) oxidation and as a result have adapted to primarily inhabit low-O2 environments where they can more successfully compete with abiotic Fe(II) oxidation. The spatial distribution of these microorganisms can be observed through the chemical gradients they affect, as measured using in situ voltammetric analysis for dissolved Fe(II), Fe(III), O2, and FeS(aq). Field and laboratory determination of the chemical environments inhabited by the FeOB were coupled with detailed kinetic competition studies for abiotic and biotic oxidation processes using a pure culture of FeOB to quantify the geochemical niche these organisms inhabit. In gradient culture tubes, the maximum oxygen levels, which were associated with growth bands of Sideroxydans lithotrophicus (ES-1, a novel FeOB), were 15-50 μM. Kinetic measurements made on S. lithotrophicus compared biotic/abiotic (killed control) Fe oxidation rates. The biotic rate can be a significant and measurable fraction of the total Fe oxidation rate below O2 concentrations of approximately 50 μM, but biotic Fe(II) oxidation (via the biotic/abiotic rate comparison) becomes difficult to detect at higher O2 levels. These results are further supported by observations of conditions supporting FeOB communities in field settings. Variablity in cell densities and cellular activity as well as variations in hydrous ferrous oxide mineral quantities significantly affect the laboratory kinetic rates. The microbial habitat (or geochemical niche) where FeOB are active is thus largely controlled by the competition between abiotic and biotic kinetics, which are dependent on Fe(II) concentration, PO2, temperature and pH in addition to the surface area of hydrous ferric oxide minerals and the cell density/activity of FeOB. Additional field and lab culture observations suggest a potentially important role for the iron-sulfide aqueous molecular cluster, FeS(aq), in the overall cycling of iron associated with the environments these microorganisms inhabit.  相似文献   

18.
The redox conditions during frictional melting provide information on the physical and chemical conditions during seismic slip in the crust. Here we examine frictional melts from five localities by analyzing host rocks and corresponding pseudotachylytes using Mössbauer spectroscopy. The faults examined are located at South Mountain, Arizona; Fort Foster, Maine (two localities); Long Ridge fault, North Carolina; and the Homestake shear zone, Colorado. The main iron-bearing phases in the pseudotachylytes are phyllosilicates (biotite, muscovite and clays) and iron oxides (magnetite and hematite) and minor pyrite. The ferrous/ferric ratios of the phyllosilicates in the host rocks are the same as those in the pseudotachylytes, except for the hematite-bearing pseudotachylyte from the Long Ridge fault, which is more oxidized. The magnetites in the host rocks and the corresponding pseudotachylytes have different ferric and ferrous iron distributions, which is attributed to different cation chemistry, rather than redox conditions. With the exception of the South Mountain locality, the ferric/ferrous ratios of the micas are interpreted to record the primary redox state of the pseudotachylyte melt as the calculated oxygen fugacities are consistent with magnetite and hematite equilibria. Pyrite-bearing pseudotachylytes plot ~0–1 log10 units above the fayalite-magnetite-quartz (FMQ) buffer. Magnetite-bearing pseudotachylytes plot ~2–4 log10 units above the FMQ buffer, and hematite-bearing pseudotachylytes plot 3.5 log10 units above the hematite-magnetite (HM) buffer. Hematite-bearing pseudotachylytes, together with previous oxygen isotope data, are inferred to represent melting in the presence of externally derived pressurized water. Other localities are inferred to represent melting under rock-buffered, closed system, conditions. If the localities studied are representative of seismogenic faulting, the calculated oxygen fugacities indicate that, in the system C–O–H–S, H2O and CO2 should be the dominant fluid species. This is the first detailed study of the redox state of pseudotachylytes.  相似文献   

19.
The distribution of iron in a 6-m core of post-glacial sediment from an oligotrophic lake (Connistonwater, England) was determined, principally by Mossbauer spectroscopy on dried samples. The immediate post-glacial deposits contain 4.8 wt. % of iron, with a Fe2+; Fe3+ ratio ～- 4. The iron there is predominantly in the form of chlorite, but there are small amounts in hematite and illite. The distribution of iron is different, and very variable in the recent sediments (~ < 13,000 BP), which contain 25–35 per cent organic matter and 5.2 wt. % of iron relative to the inorganic fraction. Typically half the iron is present there as chlorite, and the rest is ferric, mostly in the form of an amorphous gel which is also present in undried samples. To explain the observed ferrous:ferric profile, it is proposed that the latter includes iron which was once mobile, having been leached from the Fe2+-bearing clays under reducing conditions in the soils of the drainage basin, or in the sediment itself. It was subsequently precipitated as ferric hydroxide on contact with the oxic lake water. In contrast, the ferrous iron in the sediments is immobile iron, which remained locked in the chlorite phase of the clay particles as they were carried from soil to sediment intact.All the sediments are rather inhomogeneous. Chlorite, and especially hematite, are mechanically concentrated in pink varves in the immediate post-glacial deposits. In the partly inorganic sediments, the concentration of ferrous iron (chlorite) is approximately uniform, but the ferric content may differ by a factor of five between regions only a few millimeters apart.  相似文献   

20.
The purpose of this study was to examine structural alterations of finely ground phlogopite, a trioctahedral mica, when exposed to acid, iron- and sulfate-rich solutions typical of bioleaching systems. Phlogopite suspensions were supplemented with ferrous sulfate and incubated with iron- and sulfur-oxidizing bacteria (Acidithiobacillus ferrooxidans) at 22 °C. As bacteria oxidized ferrous iron, ferric iron thus formed partially precipitated as K-jarosite. K-jarosite precipitation was contingent on the preceding ferrous iron oxidation by bacteria and the release of interlayer-K from phlogopite. This chemically and microbially induced weathering involved alteration of phlogopite to a mixed layer structure that included expansible vermiculite. The extent of phlogopite weathering and structure expansion varied with duration of the contact, concentration of ferrous iron and phlogopite, and the presence of monovalent cations (NH4+, K+, or Na+) in the culture solution. NH4+ and K+ ions (100 mM) added to culture suspensions precipitated as jarosite and thereby effectively prevented the loss of interlayer-K and structural alteration of phlogopite. Additional Na+ (100 mM) was insufficient to precipitate ferric iron as natrojarosite and therefore the precipitation was coupled with interlayer-K released from phlogopite. When ferrous iron was replaced with elemental sulfur as the substrate for A. ferrooxidans, the weathering of phlogopite was based on chemical dissolution without structural interstratification. The results demonstrate that iron oxidation and the concentration and composition of monovalent ions can have an effect on mineral weathering in leaching systems that involve contact of phlogopite and other mica minerals with acid leach solutions.  相似文献   

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