Modeling aqueous ferrous iron chemistry at low temperatures with application to Mars

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.     

Nontronite synthesis at low temperatures

The low-temperature synthesis of clay minerals is possible through the aging of freshly prepared hydroxide—silica precipitates. The rapid synthesis of nontronite is only possible at surface temperatures under reducing conditions. Under oxidizing conditions, pure Fe(III)- or pure Al-smectite minerals could not be synthesized at low temperatures. It is only from Fe(II)-containing solutions that nontronite and lembergite, the di-[Fe(III)] and tri-[Fe(II)] octahedral three-layer silicates, are built up in several days at low temperatures. The presence of Fe(II) enables an octahedral layer of the brucite—gibbsite type to be formed. These are necessary for the bidimensional orientation of SiO₄ tetrahedrons, leading to clay-mineral formation. The Fe²⁺ and/or Mg²⁺ ions are necessary for the formation of the Al³⁺- and Fe³⁺-containing three-layer silicate minerals.Under reducing diagenetic conditions, the Fe contents in recent sediments are sufficient to build up Al-rich three-layer minerals under both fresh-water and salt-water conditions.     

Dislocations in olivine indented at low temperatures

Microhardness experiments have been performed on faces of olivine single crystals oriented at 45° to the [100] and [001] axis. Experiments have been performed between 20°C and 900°C in order to follow the evolution of the slip systems and the evolution of the nature of dislocations with temperature. Slip systems were identified using interferential contrast, decoration and transmission electron microscopy (TEM). Although the two possible Burgers vectors [001] and [100] are acted upon symmetrically, the only activated slip systems are (100) [001] and {110} [001]. The latter system is less developed and appears only at 600°C and above. Dislocations are mainly [001] screws, which are always very straight. Microcracks are observed together with dislocations. Above 600°C there is a clear relationship between both as a narrow plastic zone is developed around the cracks.     

A molal-based model for strong acid chemistry at low temperatures (<200 to 298 K)

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.     

Genesis of cristobalite and tridymite at low temperatures

It is suggested that an explanation of the observed metastable formation of cristobalite and tridymite in the stability field of quartz lies in the topology of these silica polymorphs and the resulting energies at the time of formation.     

An XPS and SEM study of gold deposition at low temperatures on sulphide mineral surfaces: Concentration of gold by adsorption/reduction

Using X-ray photoelectron spectroscopy (XPS or ESCA) and scanning electron microscopy (SEM), we have examined the mechanism of adsorption and reduction of gold solutions on sulphides. KAu^IIICl₄ solutions are quickly adsorbed on the sulphide surfaces, and the Au(III) is quickly reduced to Au(0). Monolayer Au coverage is attained within one minute. The reduction is auto-catalyzed and Au metal grows on the surface. SEM photographs clearly show agglomerates of gold unevenly distributed on the surface. Specific sites of abnormally high Au concentration are found. We propose possible mechanisms for the adsorption and reduction. Our results suggest that adsorption of Au(III) and Au(I) by sulphide minerals, followed by reduction, could play an important role in the deposition of gold in natural systems especially at low temperature and low gold solution concentrations.     

Natural fluid phases at high temperatures and low pressures

Gas phases at low pressures and high (magmatic) temperatures have certain peculiar properties. The fluid is mainly water vapour, which is usually observed during discharging of crystal magmatic melts. At >700°C and <100 bar these peculiar properties include: formation of near ‘dry' salt melts as second fluid phase, very strong fractionation of hydrolysis products between vapour and melts, subvalence state of metals during transport processes, and high sensitivity of the gas to conditions of sublimate precipitation. Phase diagram analysis as well as results of field and laboratory experiments are presented in this article. The processes could be a model for industrial technologies to clean wastes from toxic, rare and heavy metals. Transport forms of some elements in volcanic gases are very similar to the species which were formed first in the protosolar nebula.     

The mobility of thorium in natural waters at low temperatures

Thermodynamic properties of 32 dissolved thorium species and 9 thorium-bearing solid phases have been collected from the literature, critically evaluated and estimated where necessary for 25°C and 1 atm pressure. Although the data are incomplete, especially for thorium minerals and organic complexes, some tentative conclusions can be drawn. Dissolved thorium is almost invariably complexed in natural waters. For example, based on ligand concentrations typical of ground water (ΣCl = 10 ppm, ΣF = 0.3 ppm, ΣSO₄ = 100 ppm, andΣPO₄ = 0.1 ppm), the predominant thorium species are Th(SO₄)⁰₂, ThF²⁺₂, and Th(HPO₄)₂⁰below pH ≈ 4.5; Th(HPO₄)^2?₃ from about pH 4.5 to 7.5; and Th(OH)⁰₄ above pH 7.5. Based on stability constants for thorium citrate, oxalate and EDTA complexes, it seems likely that organic complexes predominate over inorganic complexes of thorium in organic-rich stream waters, swamp waters, soil horizons, and waterlogged recent sediments. The thorium dissolved in seawater is probably present in organic complexes and as Th(OH)⁰₄. The tendency for thorium to form strong complexes enhances its potential for transport in natural waters by many orders of magnitude below pH 7 in the case of inorganic complexing, and below about pH 8 when organic complexing is important. The existence of complexes in addition to those formed with hydroxyl, is apparent from the fact that measured dissolved thorium in fresh surface waters (pH values generally 5–8) usually ranges from about 0.01 to 1 ppb and in surface seawater (pH = 8.1) is about 0.00064 ppb. This may be contrasted with the computed solubility of thorianite in pure water which is only 0.00001 ppb Th as Th(OH)⁰₄ above pH 5. Although complexing increases the solubility of thorium-bearing heavy minerals below pH 8, maximum thorium concentrations in natural waters are probably limited in general by the paucity and slow solution rate of these minerals and by sorption processes, rather than by mineral-solution equilibria.     

Brine substitute liquids for soil freezing at very low temperatures

The strength of a frozen soil increases with decreasing temperature. Furthermore, the speed it takes to form a frozen wall increases on lowering the temperature of the freezing liquid.

With the traditional freezing systems using brine it is difficult to work with temperatures below −30°C. To go lower than this limit, it is necessary to substitute the brine by using freezing liquids that maintain good hydraulic and thermal characteristics at much lower temperatures.

Different organic liquids have been tested and good results have been obtained with some aromatic hydrocarbon mixes from the terpene family.

As a result of the research, for practical purposes a by-product ofa distilling citrus fruit skins has been selected. This liquid solidifies at −100°C approx. and maintains a low viscosity rate below −30°C.

The present paper describes the thermal and hydraulic properties of this product as a function of the temperature concerned and compares them to the same properties of classic brines of CaCl₂.     

Fractionation of sulfur isotopes during laboratory synthesis of pyrite at low temperatures

The reaction products and the accompanying sulfur isotope fractionations during the reaction of H₂S with goethite in aqueous media at 22–24°C for periods from 0.5 hr to 65 days were studied. Fine-grained pyrite formed within two days and was isotopically 0.8‰ lighter than the H₂S source. After 65 days reaction time the pyrite had nearly the same isotopic value as the H₂S. Aqueous precipitation of pyrite from H₂S and goethite at room temperature involved three major steps, namely: (1) the rapid oxidation of H₂S and reduction of Fe³⁺ during which elemental S is formed; (2) the formation of acid-volatile sulfides and the disappearance of elemental S; and (3) the formation of pyrite at the expense of acid-volatile sulfides.     

塔里木盆地塔中低凸起地层水化学特征对不整合的响应

对塔中低凸起地层水化学特征与不整合之间关系的研究结果表明,地层水化学特征对不整合具有很好的响应。在遭受强烈抬升和剥蚀、之间形成不整合的奥陶系和志留系,以及紧靠不整合面附近的石炭系CⅢ油组,其地层水具有矿化度、Cl-含量、K Na 含量和r(Cl-Na)/rMg值相对较小,而HCO3-含量、rNa/rCl值和rSO42-×100/rCl值相对较大的特点,反映出地质历史时期大气降水的影响。在志留系与石炭系之间以及志留系与奥陶系之间的不整合面附近,地层水的矿化度、r(Cl-Na)/rMg值和B3 含量变小,而rNa/rCl值和rSO24-×100/rCl值变大,具有典型的遭受大气淋滤的地层水化学基本特征。     

Magnetites from a sulphide bearing iron ore formation in Sweden

Magnetite coexisting with sulphides from an iron ore formation in northern Sweden has been investigated with micro-probe and X-ray methods. The Mg/Mg + Fe ratio in magnetite can be correlated with the presence or absence of coexisting pyrite, indicating varying sulphur pressure in the rocks. Sulphurization of magnetite is assumed to be responsible for the introduction of Mg into the magnetite structure.

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Zusammenfassung Magnetit aus einem Eisenerz Nordschwedens, der zusammen mit Eisensulfiden vorkommt, wurde mittels Elektronen-Mikrosonde und Röntgenbeugung untersucht. Das Mg/Mg + Fe Verhältnis des Magnetits wurde zu der Anwesenheit oder dem Fehlen von Pyrit in Beziehung gesetzt. Es zeigt sich, daß unterschiedliche Schwefeldampfdrucke in den Gesteinen geherrscht haben müssen. Die Sulfidisierung des Magnetits wird für den Einbau des Mg in die Magnetit-Struktur verantwortlich gemacht.

     

Interactions between sulphide minerals and xanthates,I. The formation of monothiocarbonate at galena and pyrite surfaces

The rate of decomposition of potassium ethyl monothiocarbonate has been determined at pH values between 5 and 10, and its molar absorptivity at 221 nm determined to be 1.24 · 10⁴mol/cm.A novel apparatus for use in the study of reactions between sulphide minerals, oxygen and thiol reagents has been developed, and applied to the reactions of potassium ethyl xanthate with galena and pyrite. It has been shown that both minerals react with ethyl xanthate in the presence of oxygen or oxidation products to form soluble as well as adsorbed xanthate derivatives. The soluble derivative has been identified to be ethyl monothiocarbonate. The adsorbed xanthate at a galena surface, unlike that at a pyrite surface, is gradually converted to a soluble monothiocarbonate under the action of dissolved oxygen. The effect of variables such as pH, the initial xanthate and oxygen concentrations, and the initial state of oxidation of the mineral on the formation of monothiocarbonate has been studied. It is tentatively proposed that an intermediate adsorbed mixed xanthate-hydroxide species is involved in the formation of monothiocarbonate at both galena and pyrite surfaces.The significance of the formation of monothiocarbonate to flotation practice is discussed briefly. The formation of monothiocarbonate represents a wastage of reagent, and could lead to a decrease in flotability of xanthated galena with time of exposure to aerated solutions.     

低温条件下有机酸对铁、铜的淋滤实验研究

水／岩作用实验研究表明，在低温条件下柠檬酸、草酸和酒石酸对岩石中的铁、铜都有很高的淋滤率。这表明，在表生地质作用过程中有机酸对成矿元素有很强的活化能力。实验研究同时发现，有机酸对成矿元素的活化能力受其分解温度的限制，由于大部分有机酸的分解温度都在２５０℃以下，因而有机酸对成矿元素的活化仅限于低温条件。本次研究还显示，判断一种岩石能否成为矿源层，不能简单的以其中成矿元素的含量高低作为标准，其中更关键的因素是元素在岩石中的存在形式，如果成矿元素在岩石中难以活化的形式存在，那么含量再高也无法提供成矿物质     

Unexpected phase assemblages in inclusions with ternary H2O-salt fluids at low temperatures

Phase assemblages and temperatures of phase changes provide important information about the bulk properties of fluid inclusions, and are typically obtained by microthermometry. Inclusions are synthesized in natural quartz containing an aqueous fluid with a composition in the ternary systems of H₂O-NaCl₂-CaCl₂, H₂O-NaCl-MgCl₂, and H₂O-CaCl₂-MgCl₂. This study reveals that these fluid inclusions may behave highly unpredictably at low temperatures due to the formation of metastable phase assemblages. Eutectic temperatures cannot be detected in most of the fluid inclusions containing these ternary systems. Nucleation of a variety of solid ice and salt-hydrate phases in single fluid inclusions is often partly inhibited. Raman spectroscopy at low temperatures provides an important tool for interpreting and understanding microthermometric experiments, and visualizing stable and metastable phase assemblages. Final dissolution temperatures of ice, salt-hydrates, and salt must be treated with care, as they can only be interpreted by purely empirical or thermodynamic models at stable conditions.     

Constraints on core formation from Pt partitioning in mafic silicate liquids at high temperatures

A new high temperature piston cylinder design has enabled the measurement of platinum solubility in mafic melts at temperatures up to 2500 °C, 2.2 GPa pressure, and under reducing conditions for 1-10 h. These high temperature and low f_O2 conditions may mimic a magma ocean during planetary core formation. Under these conditions, we measured tens to hundreds of ppm Pt in the quenched silicate glass corresponding to , 4-12 orders of magnitude lower than extrapolations from high f_O2 experiments at 1 bar and at temperatures no higher than 1550 °C. Moreover, the new experiments provide coupled textural and compositional evidence that noble metal micro-nuggets, ubiquitous in experimental studies of the highly siderophile elements, can be produced on quench: we measure equally high Pt concentrations in the rapidly quenched nugget-free peripheral margin of the silicate as we do in the more slowly quenched nugget-bearing interior region. We find that both temperature and melt composition exercise strong control on and that Pt⁰ and Pt¹⁺ may contribute significantly to the total dissolved Pt such that low f_O2 does not imply low Pt solubility. Equilibration of metal alloy with liquid silicate in a hot primitive magma might not have depleted platinum to the extent previously believed.     

针铁矿-四方纤铁矿-水体系氧同位素分馏的实验研究

针铁矿是非常重要的三价铁氧化物之一,其氧同位素组成对于古环境再造具有很大的价值。以4种不同的铁化合物作为Fe3+离子的源物质,于30～120℃范围内,采用强迫水解方法,在不同同位素组成的水中分别实验合成针铁矿和四方纤铁矿。结果表明,以Fe(NO3)3·9H2O、NH4Fe(SO4)2·12H2O、Fe(SO4)3·7H2O为Fe3+源物质合成的是纯针铁矿,而以FeCl3·6H2O为Fe3+源物质合成的是四方纤铁矿。氧同位素分析显示,在30～120℃范围内实验测定的针铁矿-水体系和四方纤铁矿-水体系氧同位素分馏几乎不可区分,并且满足下列分馏关系:103lnα针铁矿-水=9.59×103/T-26.39103lnα四方纤铁矿-水=8.85×103/T-24.44实验测定的针铁矿-水体系氧同位素分馏不仅与前人实验结果一致,而且与增量方法理论计算相近。由于实验采用不同反应途径得到了一致的分馏结果,因此所测定的针铁矿-水体系氧同位素分馏代表了热力学平衡。     

Relationship between primary iron sulphide species,sulphur source,depth of formation and age of submarine exhalative sulphide deposits

Older and deeper-water submarine exhalative ore deposits tend to be pyrrhotite-bearing whereas pyrite is favoured in recent and shallow-water deposits. It is proposed that increases in sea water sulphur concentrations and Eh through geologic time and at shallower sea water depths, and also the tendency for solutions exhaled at greater water depths to be hotter may account for this observed relationship. Available sulphur isotope data for submarine exhalative deposits are compatible with this hypothesis. Many exceptions are noted to the commonly held view that pyrite breaks down to pyrrhotite at higher grades of metamorphism. Pyrrhotite bearing deposits tend to be older and formed in deep water tectonically active zones and are therefore more often metamorphosed. A loose correlation between metamorphism and pyrrhotite occurrence has thus resulted.