Geochemical and mineralogical study of bauxite deposit of Mainpat Plateau,Surguja District,Central India

Bauxite deposits of Mainpat Plateau Surguja District, India, are composed of kaolinite, gibbsite, goethite, anatase, and bohemite. Quartz and micas are absent in the samples. The presence of boehmite and goethite are evidences of intense weathering during the formation of the bauxite deposits. The Mainpat Plateau is a mesa landform, at an elevation of around 1,060 m from msl in comparison to the general elevation of 580, consisting of Archaeans (granite?gneisses, phyllite, etc.) at the base, Gondwanas and Deccan basalt, and at the top having a cover of laterite and bauxite. The extremely high values of the chemical index of alteration, and the low values of the alkali metals and alkali earth metals, support an intense weathering origin for the bauxite deposit. There is evidence of deposition in the deposits based on the presence of pisoids in the bauxite samples and the composition of the parent rock. Kaolin minerals were first produced by the hydrolytic weathering of aluminous sediments and then gibbsite was formed as early kaolin was desilicated. The bauxite is having high TiO₂ up to 17 %. The Mainpat laterite/bauxite deposits are characterized by having 50?58 % average Al₂O₃ and 10?30 % Fe₂O₃.     

Equation of state of hexagonal aluminous phase in basaltic composition to 63 GPa at 300 K

A laser-heated diamond-anvil cell that is capable of operating up to a pressure of 63 GPa, with X-ray diffraction facilities using a synchrotron radiation source at the SPring-8, has been developed to observe the compressibility of a hexagonal aluminous phase, [K_0.15Na_1.66Ca_0.11Mg_1.29Fe²⁺ _0.86Al_3.13Ti_0.09Si_1.98] _Σ9.27O₁₂. The hexagonal aluminous phase is a potassium host mineral from the subducted oceanic crust in the Earth's lower mantle. A sample was heated using a YAG laser at each pressure increment to relax the deviatoric stress in the sample. X-ray diffraction measurements were carried out at 300 K using an angle-dispersive technique. Pressure was measured using an internal platinum pressure calibrant. The observed unit-cell volumes were used to obtain a third-order Birch–Murnaghan equation of state: unit-cell volume V _o=185.94(±16) ų, density ρ _o=4.145 g/cm³, and bulk modulus K _o=198(±3) GPa when the first pressure is derivative of the bulk modulus K ^′ _o is fixed to 4. The density of hexagonal aluminous phase is lower than that of coexisting Mg-perovskite in the subducted oceanic crust.     

The mineralogy and geochemistry of a nickeliferous laterite profile (Greenvale,Queensland, Australia)

A laterite profile on serpentinite at Greenvale, Australia, has been investigated in order to elucidate the formation of the secondary minerals and the trace element behaviour during tropical weathering. Mineralogical and chemical studies indicate that the serpentine alters to montmorillonite, aluminous goethite, and quartz. Chromiferous chlorite, a stable component, becomes concentrated in the weathering profile. No members of the kaolin group or bauxite group were identified, and the alumina occurs chiefly in solid solution with the goethite. In the upper levels of the profile serpentine and mont-morillonite disappear completely, and the amount of alumina substituting in the goethite increases. With increasing depth the Fe₂O₃ and Al₂O₃ content falls, whereas SiO₂ and MgO increase. This is in accordance with the usual trends of lateritic weathering. The trace elements Ni, Co, Mn, Cu and Cr are all concentrated during the weathering process. Evidence suggests that Ni is associated with goethite, and possibly is incorporated in the lattice of this mineral. No appreciable nickel is associated with the manganese minerals. The concentration of Cr takes place mainly through the increase of the stable chromiferous chlorite.

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Ein Lateritprofil des Serpenitis von Greenvale, Australien, wurde hinsichtlich seines Mineral- und Spurengehaltes untersucht. Ausschlaggebend waren die durch die tropische Verwitterung entstandenen Sekundärmineralien. Mineralogische und chemische Untersuchungen lassen erkennen, daß aufgrund der Verwitterung die Serpentingesteine Umwandlungen in Montmorillonit, aluminiumhaltigen Goethit und Quarz zeigen. Minerale der Kaolin- oder Bauxitgruppen ließen sich nicht feststellen, da Aluminiumgehalte in Form fester Lösung im Goethit gebunden wurden; in höher gelegenen Profilen kommen Serpentine und Montmorillonit zum völligen Verschwinden. Mit zunehmender Tiefe nehmen Fe₂O₃- und Al₂O₃-Gehalte ab, während SiO₂ und MgO ansteigen, analog zu Beobachtungen an bekannten lateritischen Verwitterungsprofilen. Im Zuge der Entstehung neuer Verwitterungsmineralien erfahren Elemente wie Nickel, Kobalt, Mangan, Kupfer und Chrom eine partielle Anreicherung. Z. B. wird Nickel in Eisenmineralien gebunden (Goethit), während chromhaltige Chlorite sich als stabil erweisen und sich bei der Verwitterung anreichern.

     

The effect of sulfate on aluminum concentrations in natural waters: some stability relations in the system Al2O3-SO3-H2O at 298 K

While gibbsite and kaolinite solubilities usually regulate aluminum concentrations in natural waters, the presence of sulfate can dramatically alter these solubilities under acidic conditions, where other, less soluble minerals can control the aqueous geochemistry of aluminum. The likely candidates include alunogen, Al₂(SO₄)₃ · 17H₂O, alunite, KAl₃(SO₄)₂(OH)₆, jurbanite, Al(SO₄)(OH) · 5H₂O, and basaluminite, Al₄(SO₄)(OH)₁₀ · 5H₂O. An examination of literature values shows that the log $\text{K}{}_{\mathrm{sp}}\text{= ?85.4}$ for alunite and log $\text{K}{}_{\mathrm{sp}}\text{= ?117.7}$ for basaluminite. In this report the log $\text{K}{}_{\mathrm{sp}}\text{= ?7.0}$ is estimated for alunogen and log $\text{K}{}_{\mathrm{sp}}\text{= ?17.8}$ is estimated for jurbanite. The solubility and stability relations among these four minerals and gibbsite are plotted as a function of pH and sulfate activity at 298 K. Alunogen is stable only at pH values too low for any natural waters (<0) and probably only forms as efflorescences from capillary films. Jurbanite is stable from $\text{pH < 0}$ up to the range of 3–5 depending on sulfate activity. Alunite is stable at higher pH values than jurbanite, up to 4–7 depending on sulfate activity. Above these pH limits gibbsite is the most stable phase. Basaluminite, although kinetically favored to precipitate, is metastable for all values of pH and sulfate activity. These equilibrium calculations predict that both sulfate and aluminum can be immobilized in acid waters by the precipitation of aluminum hydroxysulfate minerals.Considerable evidence supports the conclusion that the formation of insoluble aluminum hydroxy-sulfate minerals may be the cause of sulfate retention in soils and sediments, as suggested by Adams and Rawajfih (1977), instead of adsorption.     

Origin of zoned spinel by coupled dissolution–precipitation and inter-crystalline diffusion: evidence from serpentinized wehrlite, Bangriposi, Eastern India

Textural and mineral–chemical characteristics in the Bangriposi wehrlites (Eastern India) provide insight into metamorphic processes that morphologically and chemically modified magmatic spinel during serpentinization of wehrlite. Aluminous chromite included in unaltered magmatic olivine is chemically homogenous. In sub-cm to 10s-of-micron-wide veins, magnetite associated with antigorite and clinochlore comprising the serpentine matrix is near-stoichiometric. But Al–Cr–Fe³⁺ spinels in the chlorite–magnetite veins are invariably zoned, e.g., chemically homogenous Al-rich chromite interior successively mantled by ferritchromite/Cr-rich magnetite zone and magnetite continuous with vein magnetite in the serpentine matrix. In aluminous chromite, ferritchromite/Cr-rich magnetite zones are symmetrically disposed adjacent to fracture-controlled magnetite veins that are physically continuous with magnetite rim. The morphology of ferritchromite–Cr-rich magnetite mimics the morphology of aluminous chromite interior but is incongruous with the exterior margin of magnetite mantle. Micropores are abundant in magnetite veins, but are fewer in and do not appear to be integral to the adjacent ferritchromite–Cr-rich magnetite zones. Sandwiched between chemically homogenous aluminous chromite interior and magnetite mantle, ferritchromite–Cr-rich magnetite zones show rim-ward decrease in Cr₂O₃, Al₂O₃ and MgO and complementary increase in Fe₂O₃ at constant FeO. In diffusion profiles, Fe₂O₃–Cr₂O₃ crossover coincides with Al₂O₃ decrease to values <0.5 wt% in ferritchromite zone, with Cr₂O₃ continuing to decrease within magnetite mantle. Following fluid-mediated (hydrous) dissolution of magmatic olivine and olivine + Al–chromite aggregates, antigorite + magnetite and chlorite + magnetite were transported in 10s-of-microns to sub-cm-wide veins and precipitated along porosity networks during serpentinization (T: 550–600 °C, f(O₂): ?19 to ?22 log units). These veins acted as conduits for precipitation of magnetite as mantles and veins apophytic in chemically/morphologically modified magmatic Al-rich chromite. Inter-crystalline diffusion induced by chemical gradient at interfaces separating aluminous chromite interiors and magnetite mantles/veins led to the growth of ferritchromite/Cr-rich magnetite zones, mimicking the morphology of chemically modified Al–Cr–Fe–Mg spinel interiors. Inter-crystalline diffusion outlasted fluid-mediated aluminous chromite dissolution, mass transfer and magnetite precipitation.     

Reflectance spectroradiometry applied to a semi-quantitative analysis of the mineralogy of the N4ws deposit,Carajás Mineral Province,Pará, Brazil

Quantifying the abundance and physicochemical properties of minerals using reflectance spectroradiometry in the visible, near infrared and shortwave infrared (400–2500 nm) regions is an important tool in mineral exploration. In this study, the reflectance spectra of drill cores from the world-class N4WS iron deposit located in the Carajás Mineral Province, Brazil, were obtained. These spectra were validated using X-ray fluorescence (XRF) geochemical analyses and thin sections. The reflectance spectra were collected using a FieldSpec 3 spectroradiometer (ASD, Boulder, Colorado, USA) in 10 drill cores. The mineralogy of the deposit is mainly hematite, with lesser amounts of magnetite, goethite, quartz, kaolinite, gibbsite, smectite, talc, carbonate and chlorite. The mineralogy of the iron deposit was extracted from the spectral data using the geometry (depth and wavelength) of absorption features across the reflectance spectrum removed from the continuum. The depth of the absorption features is proportional to the mineral abundance, and the wavelength is proportional to the mineral chemical composition. The diagnostic absorption features of each mineral were used to determine the mineral abundance and composition. The final products include the abundance of iron (hydro) oxide (11.6% root-mean-square error [RMSE] Fe₂O₃); abundance of aluminous clays (RMSE 6% Al₂O₃); abundance of talc (8% RMSE MgO); identification of clay type (kaolinite, montmorillonite or gibbsite); composition of carbonate (dolomite vs. calcite); and composition of chlorite (Mg vs. Fe). The mineral abundance and composition results provided an effective characterisation of the ore, protore and host rocks and showed variations within the ore body.     

Mineralogy,geochemistry, and ore formation of Nuwaifa bauxite deposit,western desert of Iraq

Nuwaifa Formation is a part of sequence stratigraphy that belongs to the Jurassic system exposed in the western desert of Iraq. The Jurassic system consists of Ubaid, Hussainiyat, Amij, Muhaiwir, and Najmah formations. Each formation is composed of basal clastic unit overlain by upper carbonate unit. Nuwaifa karst bauxite was developed in fossil karsts within the Ubaid Formation in areas where maximum intersection of fractures and faults exist. This bauxitization process affected the upper surface of the Ubaid limestone formation, which directly underlies the Nuwaifa bauxite Formation. Nuwaifa Formation represents karst-filling deposit that consists of a mixture of allochthonous (sandstone, claystone, and mudstone) and autochthonous lithofacies (bauxite kaolinite, kaolinitic bauxite, iron-rich bauxite, and flint clay). Most bauxite bodies occur within the autochthonous lithofacies and are lenticular in shape with maximum thickness ranges from few meters to 35 m and in some place up to 100 m. Petrographically, the bauxite deposit exhibits collomorphic-fluidal, pisolitic, oolitic, nodular, brecciated, and skeletal textures indicative of authigenic origin. Mineralogy boehmite and gibbsite are the only bauxite minerals; the former is dominant in the upper parts of the bauxite profiles, whereas the latter is dominant throughout the lower and middle part of the bauxite. Kaolinite, hematite, goethite, calcite, and anatase occur to a lesser extent. The study bauxites are mainly composed of Al₂O₃ (33–69.6 wt.%), SiO₂ (8.4–42 wt.%), Fe₂O₃ (0.5–15.9 wt.%), and TiO₂ (0.7–6.1 wt.%) with LOI ranging from 13.5 to 19.1 wt.%. Geochemical investigations indicate that the immobile elements like Al₂O₃, TiO₂, Cr, Zr, and Ni were obviously enriched, while SiO₂, Fe₂O₃, CaO, MgO, Zn, Co, Ba, Mn, Cu, and Sr were depleted during bauxitization process. The results of this study strongly suggest that the bauxite deposits of the Nuwaifa Formation are derived from the kaolinite of the Lower Hussainiyat Formation.     

Oxygen isotope fractionation between hydroxide minerals and water

The modified increment method has been applied to the calculation of oxygen isotope fractionation factors for hydroxide minerals. The results suggest the following sequence of ¹⁸O-enrichment in the common hydroxides: limonite > gibbsite > goethite > brucite > diaspore. The hydroxides are significantly enriched in ¹⁸O relative to the corresponding oxides. The sequence of ¹⁸O-enrichment in the hydroxides and oxides of trivalent cations is as follows: M(OH)₃ > MO(OH) > M₂O₃. There are also considerable fractionations within the polymorphos of Al(OH)₃. The internally consistent fractionation factors for hydroxide–water systems are obtained for the temperature range of 0 to 1200 °C, which are comparable with the data derived from synthesis experiments and natural samples at surficial temperatures. Temperature dependence of oxygen isotope fractionations between goethite, gibbsite, boehmite and diaspore and water are significant enough for the purpose of geothermometry. Thus the hydroxide–water pairs hold great promise of serving as reliable paleothermometers in surficial geological environments. Received: 22 January 1997 / Revised, accepted: 2 June 1997     

Gibbs energy of aluminous minerals

The discrepancy between the tabulated Gibbs Energies of Formation for Al₂SiO₅ and corundum relative to muscovite and kaolinite is considered to lie principally with the latter two minerals. New values for heat of formation of gibbsite [Gbs] will affect the tabulated H _f ⁰ , G _f(298,1) ⁰ for the other aluminous minerals which are referred to gibbsite as calorimetric aluminum reference. Gibbs Energy Difference Functions, calculated from phase equilibria in the system CaO-Al₂O₃-SiO₂-(H₂O-CO₂), can be used to estimate consistent H _f ⁰ , G _f(298,1) ⁰ values for aluminous minerals. A self consistent data set is presented referred to G _f(298,1) ⁰ [Corundum]=–378.08 kcal mol^–1. Two independent values for G _f(298,1) ⁰ [Anorthite]=–961.52 and –960.29 kcal, from a recalculation of the H _f ⁰ [Anor] based upon the revised H _f(298,1) ⁰ [Gbs]=–309.325 kcal mol^–1 and from measurement of silica activity on the anorthite-saturated part of the CaO-Al₂O₃-SiO₂ liquidus, respectively, are considered to show the magnitude of the discrepancy and are used in the calculations.     

Kinetics of Fe2+-Mg distribution in aluminous orthopyroxenes

Kinetic studies of isothermal heating experiments (600–800° C) on aluminous pyroxenes (Mg_0.942Fe _0.880 ²⁺ Fe _0.068 ³⁺ Mn_0.016Ca_0.010Al_0.084) (Si_1.848Al_0.152) permit the determination of rate constant of isothermal disordering as 2.5457 E13(±1.4 E13) min^?1. The activation energy is determined as 278 (±23) kJ/mol. Data on two other aluminous pyroxenes at 700° C indicate that the rate constant decreases significantly with increasing amount of trivalent cations. There is a similar but reverse correlation between the concentration of trivalent cations and the Fe²⁺-Mg equilibrium distribution between sites. The site distribution coefficient increases with increasing concentration of trivalent cations at constant temperature.     

Loss of metals from pelites during regional metamorphism

In aluminous metapelites the ratio H₂O⁺/K₂O decreases with increasing metamorphic grade and degree of reaction. This ratio is a very practical indicator for the progress of the mineral reconstitution during progressive metamorphism. With decreasing values of the ratio H₂O⁺/ K₂O the Cu concentration and the following element ratios also decrease either continuously or in stepwise fashion: Tl/K₂O, Ba/K₂O, Pb/K₂O, Bi/K₂O, Hg/K₂O, Sr/Na₂O, Zn/(Fe²⁺+Mg), Cd/(Fe²⁺+Mg); Rb/K₂O remains approximately constant. In the aluminous metapelites of the Damara Orogen in Namibia the following losses occur between the biotite isograd and anatexis: 61% Cu, 20% Tl, 34% Ba, 59% Pb, 86% Bi, 46% Hg, 30% Sr, 25% Zn, 31% Cd. Thus the potential of regional metamorphism to form hydrothermal deposits in the low grade environment should not be neglected.     

Amphibolites with staurolite and other aluminous minerals: calculated mineral equilibria in NCFMASH

Amphibolite facies mafic rocks that consist mainly of hornblende, plagioclase and quartz may also contain combinations of chlorite, garnet, epidote, and, more unusually, staurolite, kyanite, sillimanite, cordierite and orthoamphiboles. Such assemblages can provide tighter constraints on the pressure and temperature evolution of metamorphic terranes than is usually possible from metabasites. Because of the high variance of most of the assemblages, the phase relationships in amphibolites depend on rock composition, in addition to pressure, temperature and fluid composition. The mineral equilibria in the Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCFMASH) model system demonstrate that aluminium content is critical in controlling the occurrence of assemblages involving hornblende with aluminous minerals such as sillimanite, kyanite, staurolite and cordierite. Except in aluminous compositions, these assemblages are restricted to higher pressures. The iron to magnesium ratio (X_Fe), and to a lesser extent, sodium to calcium ratio, have important roles in determining which (if any) of the aluminous minerals occur under particular pressure–temperature conditions. Where aluminous minerals occur in amphibolites, the P–T–X dependence of their phase relationships is remarkably similar to that in metapelitic rocks. The mineral assemblages of Fe‐rich amphibolites are typically dominated by garnet‐ and staurolite‐bearing assemblages, whereas their more Mg‐rich counterparts contain chlorite and cordierite. Assemblages involving staurolite–hornblende can occur over a wide range of pressures (4–10 kbar) at temperatures of 560–650 °C; however, except in the more aluminous, iron‐rich compositions, they occupy a narrow pressure–temperature window. Thus, although their occurrence in ‘typical’ amphibolites may be indicative of relatively high pressure metamorphism, in more aluminous compositions their interpretation is less straightforward.     

The effect of TiO2 and Fe2O3 on metapelitic assemblages at greenschist and amphibolite facies conditions: mineral equilibria calculations in the system K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–Fe2O3

Mineral equilibria calculations in the system K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–Fe₂O₃ (KFMASHTO) using thermocalc and its internally consistent thermodynamic dataset constrain the effect of TiO₂ and Fe₂O₃ on greenschist and amphibolite facies mineral equilibria in metapelites. The end‐member data and activity–composition relationships for biotite and chloritoid, calibrated with natural rock data, and activity–composition data for garnet, calibrated using experimental data, provide new constraints on the effects of TiO₂ and Fe₂O₃ on the stability of these minerals. Thermodynamic models for ilmenite–hematite and magnetite–ulvospinel solid solutions accounting for order–disorder in these phases allow the distribution of TiO₂ and Fe₂O₃ between oxide minerals and silicate minerals to be calculated. The calculations indicate that small to moderate amounts of TiO₂ and Fe₂O₃ in typical metapelitic bulk compositions have little effect on silicate mineral equilibria in metapelites at greenschist to amphibolite facies, compared with those calculated in KFMASH. The addition of large amounts of TiO₂ to typical pelitic bulk compositions has little effect on the stability of silicate assemblages; in contrast, rocks rich in Fe₂O₃ develop a markedly different metamorphic succession from that of common Barrovian sequences. In particular, Fe₂O₃‐rich metapelites show a marked reduction in the stability fields of staurolite and garnet to higher pressures, in comparison to those predicted by KFMASH grids.     

Configurational thermodynamics of aluminous pyroxenes: A generalized pair approximation

A pair approximation is used to estimate the effects of short-range order on the thermodynamic properties of aluminous clinopyroxenes on the joins diopside (CaMg-Si₂O₆)-jadeite (NaAlSi₂O₆) and diopside-CaTs (CaAl₂SiO₆). The generalized pair approximation is the simplest model for concentrated solutions which includes short-range order. Short-range order is expected to be especially significant in coupled solid solutions, such as aluminous pyroxenes, since atoms of different valence substitute for each other. The calculations show that the random model, in which the configurational entropy is calculated as if atoms on each crystallographic site mix randomly, is appropriate as a first approximation. The excess entropy relative to the random model behaves regularly, is always negative, and becomes more negative as temperature decreases or the ordering energies increase. The excess entropy relative to the random model can be modeled reasonably well with a simple power series, or Margules-type, formulation. In contrast, the excess entropy relative to a molecular model, in which the ideal activity is assumed to be equal to some mole fraction, is irregular, can be positive or negative, and even changes in sign with variations in temperature and composition. The configurational enthalpy is positive at high temperatures, and becomes negative with decreasing temperature or increasing ordering energy. The mixing enthalpy can have non-configurational contributions, in addition to the effective short-range configurational contributions considered explicitly. The pair approximation predicts an ordering transition from C2/c to P2₁/n for CaTs and diopside-CaTs solutions at moderate to low temperatures, respectively. A field where C2/c orders to C2 is also found. A higher order approximation, different relative ordering energies, or quantitative consideration of strain contributions is required to account for the C2/c to P2/n transition in omphacites. There is no justification for molecular models, in which the configurational entropy is calculated as if endmember “molecules” were mixing in the crystal, in either concentrated or dilute solutions. Molecular models do not represent limiting ordered states for coupled solid solutions.     

The effect of Tschermak's substitution on assemblages in aluminous dolomites

A calculated petrogenetic grid for the system CaO-MgO-Al₂O₃-SiO₂-CO₂-H₂O (CaMASCH), incorporating Tschermak's substitutions in amphibole, chlorite, talc and clinopyroxene, is used to examine phase relationships in aluminous marbles. A series of diagrams illustrating the effect upon stable mineral assemblages of increasing the aluminium content of a bulk composition is used to show the way aluminous minerals enter mineral assemblages in progressively more aluminous rocks. The effects of changing pressure and the incorporation of Fe into the bulk composition on the stable mineral assemblages are also examined. The calculated equilibria are shown to be in reasonable agreement with natural assemblages, and the incorporation of new experimental data on amphiboles into the existing dataset is shown to improve the agreement between observed and natural amphibole compositions.     

Iron control by equilibria between hydroxy-Green Rusts and solutions in hydromorphic soils

In order to verify Fe control by solution - mineral equilibria, soil solutions were sampled in hydromorphic soils on granites and shales, where the occurrence of Green Rusts had been demonstrated by Mössbauer and Raman spectroscopies. Eh and pH were measured in situ, and Fe(II) analyzed by colorimetry. Ionic Activity Products were computed from aqueous Fe(II) rather than total Fe in an attempt to avoid overestimation by including colloidal particles. Solid phases considered are Fe(II) and Fe(III) hydroxides and oxides, and the Green Rusts whose general formula is [Fe^II_1−xFe^III_x(OH)₂]^+x· [x/z A^−z]^−x, where compensating interlayer anions, A⁻, can be Cl⁻, SO₄²⁻, CO₃²⁻ or OH⁻, and where x ranges a priori from 0 to 1. In large ranges of variation of pH, pe and Fe(II) concentration, soil solutions are (i) oversaturated with respect to Fe(III) oxides; (ii) undersaturated with respect to Fe(II) oxides, chloride-, sulphate- and carbonate-Green Rusts; (iii) in equilibrium with hydroxy-Green Rusts, i.e., Fe(II)-Fe(III) mixed hydroxides. The ratios, x = Fe(III)/Fe_t, derived from the best fits for equilibrium between minerals and soil solutions are 1/3, 1/2 and 2/3, depending on the sampling site, and are in every case identical to the same ratios directly measured by Mössbauer spectroscopy. This implies reversible equilibrium between Green Rust and solution. Solubility products are proposed for the various hydroxy-Green Rusts as follows: log K_sp = 28.2 ± 0.8 for the reaction Fe₃(OH)₇ + e⁻ + 7 H⁺ = 3 Fe²⁺ + 7 H₂O; log K_sp = 25.4 ± 0.7 for the reaction Fe₂(OH)₅ + e⁻ + 5 H⁺ = 2 Fe²⁺ + 5 H₂O; log K_sp = 45.8 ± 0.9 for the reaction Fe₃(OH)₈ + 2e⁻ + 8 H⁺ = 3 Fe²⁺ + 8 H₂O at an average temperature of 9 ± 1°C, and 1 atm. pressure. Tentative values for the Gibbs free energies of formation of hydroxy-Green Rusts obtained are: Δ_fG° (Fe₃(OH)₇, cr, 282.15 K) = −1799.7 ± 6 kJ mol⁻¹, Δ_fG° (Fe₂(OH)₅, cr, 282.15 K) = −1244.1 ± 6 kJ mol⁻¹ and Δ_fG° (Fe₃(OH)₈, cr, 282.15 K) = −1944.3 ± 6 kJ mol⁻¹.     

Oxidation modes and thermodynamics of Fe oxyhydroxycarbonate green rust: Dissolution-precipitation versus in situ deprotonation

Fe^II-III hydroxycarbonate green rust GR(CO₃²⁻), Fe^II₄ Fe^III₂ (OH)₁₂ CO₃·3H₂O, is oxidized in aqueous solutions with varying reaction kinetics. Rapid oxidation with either H₂O₂ or dissolved oxygen under neutral and alkaline conditions leads to the formation of ferric oxyhydroxycarbonate GR(CO₃²⁻)∗, Fe^III₆ O₁₂ H₈ CO₃·3H₂O, via a solid-state reaction. By decreasing the flow of oxygen bubbled in the solution, goethite α-FeOOH forms by dissolution-precipitation mechanism whereas a mixture of non-stoichiometric magnetite Fe_(3−x)O₄ and goethite is observed for lower oxidation rates. The intermediate Fe^II-III oxyhydroxycarbonate of formula Fe^II_6(1−x) Fe^III_6x O₁₂ H_2(7−3x) CO₃·3H₂O, i.e. GR(x)∗ for which x ? [1/3, 1], is the synthetic compound that is homologous to the fougerite mineral present in hydromorphic gleysol; in situ oxidation accounts for the variation of ferric molar fraction x = [Fe^III]/{[Fe^II]+[Fe^III]} observed in the field as a function of depth and season but limited to the range [1/3, 2/3]. The domain of stability for partially oxidized green rust is observed in the E_h-pH Pourbaix diagrams if thermodynamic properties of GR(x)∗ is compared with those of lepidocrocite, γ-FeOOH, and goethite, α-FeOOH. Electrochemical equilibrium between GR(x)∗ and Fe^II in solution corresponds to E_h-pH conditions close to those measured in the field. Therefore, the reductive dissolution of GR(x)∗ can explain the relatively large concentration of Fe^II measured in aqueous medium of hydromorphic soils containing fougerite.     

Germanium crystal chemistry in hematite and goethite from the Apex Mine,Utah, and some new data on germanium in aqueous solution and in stottite

At the Apex Mine in southwest Utah, fine-grained hematite contains as much as 1.0 wt. percent Ge, and fine-grained goethite contains as much as 0.7 wt. percent Ge. The mode of Ge incorporation in these minerals was investigated by high-resolution K-edge fluorescence spectroscopy using synchrotron radiation. Analysis of extended fine structure (EXAFS) K-edge data for Ge and Fe shows that Ge substitutes for Fe in the octahedral metal sites of the studied hematite and goethite, with average Ge-ligand bond lengths of 1.88 Å. The solid solution in hematite probably occurs through the coupled substitution 2Fe(III) = Ge(IV) + Fe(II), similar to the coupled substitution 2Fe(III) = Ti(IV) + Fe(II) that occurs in the solid solution series hematite-ilmenite. The solid solution in goethite probably occurs by the loss of an H atom from an OH group, through the coupled substitution Fe(III) + H(I) = Ge(IV). In related experiments, EXAFS data indicate that in a neutral aqueous solution containing 790 ppm Ge, the Ge occurs predominately as Ge(OH)₄, with tetrahedral Ge-OH bond lengths of 1.74 Å. In stottite, FeGe(OH)₆, Fe(II) and Ge(IV) occur in octahedral sites with average Fe-OH and Ge-OH bond lengths of about 2.20 Å and 1.88 Å.     

Fe4O5 and its solid solutions in several simple systems

Experiments at high pressures and temperatures reveal the stability of a Fe₄O₅-type structured phase in several simple chemical systems. On the one hand, the Fe₄O₅ end-member is stable in the presence of SiO₂-rich phases, including stishovite, but contains ≤0.01 Si cations per formula unit. This indicates that Si is essentially excluded from this phase. On the other hand, the Fe₄O₅ phase can form solid solutions with Mg and Cr and can coexist with silicate phases at the high P–T conditions expected in the transition zone of the mantle (i.e. >~9 GPa). It can coexist with both wadsleyite and Mg-rich ringwoodite and can contain at least 25 mol% Mg₂Fe₂O₅ component. The Fe₄O₅ phase always contains the least amount of Mg in any given mineral assemblage. Cr-bearing Fe₄O₅ has been synthesised with up to 46 mol% Fe₂Cr₂O₅ component and can coexist with spinel and/or hematite-eskolatite solid solutions. Substitution of Mg and Cr for Fe²⁺ and Fe³⁺, respectively, leads to variations in Fe³⁺/∑Fe from the ideal value of 0.5 for the Fe₄O₅ end-member composition, which can influence its redox stability. These cations also have contrasting effects on the unit-cell parameters, which indicate that they substitute into different sites. This initial study suggests that Fe₄O₅-type structured phases may be stable over a range of P–T–fO₂ conditions and bulk compositions, and can be important in understanding the post-spinel phase relations in a number of chemical systems relevant to the Earth’s transition zone. Thus, the presence of even small amounts of Fe³⁺ could alter the expected phase relations in peridotitic bulk compositions by stabilising this additional phase.     

Aluminous goethite: A mössbauer study

Mössbauer measurements at 300 K, 77 K and 4.2 K and X-ray data are presented for synthetic aluminous goethites (α Fe_1?x Al _x OOH) in two series containing up to 15 mole percent aluminium (hydrothermal preparation) and 19 mole percent aluminium (low-temperature preparation). The Mössbauer spectra for specimens at 300 K and 77 K display broadened and relaxed line-shapes with the relaxation rate increasing with aluminium substitution, whereas all the 4.2 K spectra can be described by a single magnetically split spectrum. At 4.2 K the magnitude of this splitting is 505 kOe for pure goethite and it decreases by 0.52 kOe per mole percent aluminium substitution. The absolute value of the recoil-free fraction f at 4.2 K has been measured for pure goethite and for aluminous goethites containing 7, 15 and 19 mole percent aluminium; it increases from f=0.69±0.02 to f=0.89±0.02 in this range. The increase is attributed to a stiffening of the goethite lattice as it contracts to accommodate the smaller aluminium ion. At 300 K f is found to decrease from f=0.65±0.05 for pure goethite to f=0.50±0.03 for goethite with 19 mole percent aluminium.