Structural defects in microcrystalline silica

The structure of the microcrystalline silica varieties chalcedony, flint, moganite, opal-C and -CT is characterized by X-ray powder diffractometry and transmission electron microscopy (TEM). The role of impurities is investigated by infrared spectroscopy and chemical analysis. Microcrystalline opal, chalcedony and flint have a disordered intergrowth structure composed of cristobalite and tridymite domains in opal, and quartz and moganite domains in chalcedony and flint. Each constituent phase has different cell dimensions and symmetry. The main impurity is water which is enriched at the intergrowth interfaces. Density and refractive indices of microcrystalline silica depend on the water content.     

Solution behavior of C-O-H volatiles in FeO-Na2O-Al2O3-SiO2 melts in equilibrium with liquid iron alloy and graphite at 4 GPa and 1550°C

In order to elucidate the solution behavior of carbon and hydrogen in iron-bearing magmatic melts in equilibrium with a metallic iron phase and graphite at oxygen fugacity (fO₂) values 2–5 orders of magnitude below the iron-wustite buffer equilibrium, fO₂ (IW), experiments were carried out at 4 GPa and 1550°C with melts of FeO-Na₂O-SiO₂-Al₂O₃ compositions. Melt reduction in response to an fO₂ decrease was accompanied by a decrease in FeO content. The values of fO₂ in the experiments were determined on the basis of equilibrium between Fe-C-Si alloy and silicate liquid. Infrared and Raman spectroscopy showed that carbon compounds are formed in FeO-Na₂O-SiO₂-Al₂O₃ melts: CH₄ molecules, CH₃ complexes (Si-O-CH₃), and complexes with double C=O bonds. The content of CO₂ molecules and carbonate ions (CO ₃ ^2? ) is very low. In addition to carbon-bearing compounds, dissolved hydrogen occurs in melt as H₂ and H₂O molecules and OH^? groups. The spectral characteristics of FeO-Na₂O-SiO₂-Al₂O₃ glasses indicate the occurrence of redox reactions in the melt, which are accompanied at decreasing fO₂ by a significant decrease in H₂O and OH^?, a slight decrease in H₂, and a significant concomitant increase in CH₄ content. The content of species with the double C=O bond increases considerably at decreasing fO₂ and reaches a maximum at ΔlogfO₂(IW) = ?3. According to the obtained IR spectra, the total water content (OH^? + H₂O) in the glasses is 1.2–5.8 wt % and decreases with decreasing fO₂. The high H₂O contents are due largely to oxygen release related to FeO reduction in the melt. The total carbon content at high H₂O (4.9–5.8 wt %) is approximately 0.4 wt %. The carbon content in liquid iron alloys depends on silicon content and, probably, oxygen solubility and ranges from 0.3 to 3.65 wt %. Low carbon contents were observed at a significant increase in Si content in liquid iron alloy, which may be as high as ～13 wt % at fO₂ values 4–5 orders of magnitude below fO₂(IW).     

Stability and composition relations of calcic amphiboles in ultramafic rocks

Calcic amphiboles are observed in ultramafic rocks that have equilibrated under a broad span of geological conditions and might prove to be good indicators of metamorphic grade if their stabilities could be determined as a function of their compositions. Experiments were performed on the stability of tremolite plus forsterite in the system H₂O-CaO-MgO-SiO₂ from 5 to 20 kbar. A univariant curve was fitted to the experimental brackets using volume, water fugacity, and heat capacity data. The results indicate that the maximum stability of tremolite in the presence of forsterite is about 825° C at 5 kbar. Addition of Al₂O₃ to this system increases the stability of tremolitic amphibole by only 20°–40° C and induces solubility of 5–7 wt.% Al₂O₃ in the amphibole, as determined from quantitative SEM analyses of individual amphibole crystals. Thus substitution of the tschermakite component (Ca₂(Mg₃Al₂) (Si₆Al₂) O₂₂(OH)₂) alone cannot lead to the greatly enhanced Al₂O₃ contents or thermal stability of natural calcic amphiboles. Comparison of the results from this study with experimental results from other studies on synthetic calcic amphiboles indicates that the high thermal stability of natural amphiboles is strongly linked with the substitution of alkalies (Na in particular) in the form of the component Na-Ca₂(Mg₄Al) (Si₆Al₂)O₂₂(OH)₂ (pargasite). Accordingly, experimental data from studies on pargasite have been combined with the appropriate univariant curves to obtain a phase diagram for amphibole-bearing ultramafic rocks modelled by the system H₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂.     

The solubility of Gd<Subscript>2</Subscript>Ti<Subscript>2</Subscript>O<Subscript>7</Subscript> and the hydrolysis of Gd<Superscript>3+</Superscript> in acidic solutions at 250°C and saturation vapor pressure

The solubility of Gd₂Ti₂O₇ ceramic in acidic solutions (HCl and HClO₄) was studied at 250°C and saturation vapor pressure within pH 2.5–5.2. The dissolution process occurs mainly via two reactions: 0.5 Gd₂Ti₂O_7(cr) + 3H⁺ = Gd³⁺ + TiO_2(cr) + 1.5 H₂O at pH < 3 and 0.5Gd₂Ti₂O₇(cr) + H⁺ + 0.5H₂O = Gd(OH) ₂ ⁺ TiO₂(cr) at pH 3–5. The thermodynamic equilibrium constants were calculated at the 0.95 confidence level as log K ₍₁₎ ^o = 4.12 ± 0.47; = ?0.97 ± 0.16 at 250°C. It was shown that Gd³⁺ undergoes hydrolysis in solutions with pH > 3, and the species Gd(OH) ₂ ⁺ dominates up to at least pH 5. At pH < 3, Gd occurs in solutions as Gd³⁺. The second constant of Gd³⁺ hydrolysis was determined at 250°C as K ^o = ?5.09 ± 0.5, and the thermodynamic characteristics of the initial Gd₂Ti₂O₇ solid phase were determined: S _298.15 ^o = 251.4 J/(mol K) and ΔfG _298.15 ^o = ?3630 ± 10 kJ/mol.     

Remineralization Ratios in the Subtropical North Pacific Gyre

Based on a new mixing model of two end-members, the water column remineralization ratios of P/N/C_org - O₂ = 1/13 ± 1/135 ± 18/170 ± 9 are obtained for the Hawaii Ocean Time-series (HOT) data set at station ALOHA. The traditional Redfield ratios of P/N/C_org/–O₂ = 1/16/106/138 have standard deviations of more than 50%, when they are based on the average composition of phytoplankton. Apparently, the remineralization processes in the water column have smoothed out the observed large variability of plankton compositions. A new molar formula for the remineralized plankton may be written as ₁₃₅H₂₈₀O₁₀₅N₁₃P or C₂₅(CH₂O)₁₀₁(CH₄)₉(NH₃)₁₃(H₃PO₄). Oxidation of this formula results inC₂₅(CH₂O)₁₀₁(CH₄)₉(NH₃)₁₃(H₃PO₄) + 170O₂ 135CO₂ + 132H₂O + 13NO₃ ^- + H₂PO₄ ^- + 14H⁺.For comparison, remineralization using Redfield's formula gives:(CH₂O)₁₀₆(NH₃)₁₆(H₃PO₄) + 138O₂ 106CO₂ + 122H₂O + 16NO₃ ^-+ H₂PO₄ ^- + 17H⁺     

Crystal chemistry of a natural schorlomite and Ti-andradites synthesized at different oxygen fugacities

Ti-andradites were synthesized at a pressure of P(H₂O)=3 kbar and temperatures of 700–800° C. Oxygen fugacities were controlled by solid state buffers (Ni/NiO; SiO₂ + Fe/Fe₂SiO₄). The Fe²⁺-and Fe³⁺-distribution was determined by low temperature Mössbauer spectroscopy. The water content was measured by a solid's moisture analyzer. The chemical composition of the synthetic and the natural sample has been determined by electron microprobe. Ti-andradites from runs at high oxygen fugacities have Fe³⁺ on octahedral and tetrahedral sites; Ti-andradites from runs at low oxygen fugacities have tetrahedrally and octahedrally coordinated Fe²⁺ as well. These “reduced” garnets must also contain Ti³⁺ on octahedral sites. Charge balance is maintained due to substitution of O^2? by (OH)^? by two mechanisms: (SiO₄)^4? ? (O₄H₄)^4? and (Fe³⁺O₆)^9? ? (Fe²⁺O₅OH)^9?. FTIR spectra of the synthetic samples do show the presence of structurally bound (OH)^?. In a natural sample tetrahedrally and octahedrally coordinated Fe³⁺ are observed together with Fe²⁺ on all three cation sites of the garnet structure.     

Crystal structure and refined formula of garyansellite Mg<Subscript>2</Subscript>Fe<Superscript>3+</Superscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH) · 2H<Subscript>2</Subscript>O

Single-crystal study of the structure (R = 0.0268) was performed for garyansellite from Rapid Creek, Yukon, Canada. The mineral is orthorhombic, Pbna, a = 9.44738(18), b = 9.85976(19), c = 8.14154(18) Å, V = 758.38(3) ų, Z = 4. An idealized formula of garyansellite is Mg₂Fe³⁺(PO₄)₂(OH) · 2H₂O. Structurally the mineral is close to other members of the phosphoferrite–reddingite group. The structure contains layers of chains of M(2)O₄(OH)(H₂O) octahedra which share edges to form dimers and connected by common edges with isolated from each other M(1)O₄(H₂O)₂ octahedra. The neighboring chains are connected to the layer through the common vertices of M(2) octahedra and octaahedral layers are linked through PO₄ tetrahedra.     

The solution behavior of H2O in peralkaline aluminosilicate melts at high pressure with implications for properties of hydrous melts

Solubility and solution mechanisms of H₂O in depolymerized melts in the system Na₂O-Al₂O₃-SiO₂ were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na₂Si₄O₉-Na₂(NaAl)₄O₉] with Al/(Al+Si) = 0.00-0.25. The H₂O solubility was fitted to the expression, X_H2O=0.20+0.0020f_H2O-0.7X_Al+0.9(X_Al)², where X_H2O is the mole fraction of H₂O (calculated with O = 1), f_H2O the fugacity of H₂O, and X_Al = Al/(Al+Si). Partial molar volume of H₂O in the melts, , calculated from the H₂O-solulbility data assuming ideal mixing of melt-H₂O solutions, is 12.5 cm³/mol for Al-free melts and decreases linearly to 8.9 cm³/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H₂O, , increases with Al/(Al+Si).Solution mechanisms of H₂O were obtained by combining Raman and ²⁹Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H₂O content. The rate of NBO/T-change with H₂O is negatively correlated with H₂O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q⁴-species to form Q² species. Steric hindrance appears to restrict bonding of H⁺ with nonbridging oxygen in Q³ species. The presence of Al³⁺ does not affect the water solution mechanisms significantly.     

Calorimetric Study of Natural Anapaite

The thermochemical study of natural hydrous calcium and iron phosphate, anapaite Ca₂Fe(PO₄)₂ · 4H₂O (Kerch iron ore deposit, Crimea, Russia), was carried out using high-temperature melt solution calorimetry with a Tian-Kalvet microcalorimeter. The enthalpy of formation of the mineral from elements was obtained to be Δ _f H_el°(298.15 K) =–4812 ± 16 kJ/mol. The values of the standard entropy and the Gibbs energy of anapaite formation are S°(298.15 K) = 404.2 J/K mol and Δ _f G_el°(298.15 K) =–4352 ± 16 kJ/mol, respectively.     

The role of water in the 1944 Vesuvius eruption

The P-T path of magma associated with the 1944 Vesuvius eruption has been outlined on the basis of probe mineralogy and the relationships between the crystallising phases. Equilibrium P-T values, obtained from the reactions:

1. CaMgSi₂O_6(liq) = CaMgSi₂O_6(cpx)
2. NaAlSi₃O_{8 (liq)} = NaAlSi₃O_{8 (plag)}
3. CaAl₂Si₂O_{8 (plag)}=CaAl₂SiO_6(cpx)+SiO_2(liq) have been established for three intracrustal crystallisation stages: I) 8.0 kbar and 1255 °C; II) 4.0 kbar and 1178 °C; III) 0.5 kbar and 1105 °C.

The H₂O content in the magma has been estimated from an experimental calibration of \(a_{^{CaMgSi_2 O_6 } }^{liq}\) as a function of \(X_{H_2 O}^{liq}\) at P _tot = 2 kbar. The estimated water contents of the magma for the three stages, I) 0.7%; II) 0.9%; III) 1.1%, are consistent with the pattern of activity of the 1944 Vesuvius eruption and with the relationship between the lavas. The shallow depth of H₂O-saturation of the magma, 0.24 kbar at 1100 °C, is consistent with the eruption sequence of lava flows followed by lava fountain activity.     

Calorimetric Study of Natural Basic Copper Phosphate—Pseudomalachite

The thermochemical study of a natural basic copper phosphate, pseudomalachite Cu₅(PO₄)₂(OH)₄ (Virneberg deposit, Germany), was carried out using high-temperature melt solution calorimetry method with a Tian–Calvet microcalorimeter. The enthalpy of formation of the mineral from elements was obtained to be Δ _f H_el(298.15 K) =–3214 ± 13 kJ/mol. The value of the Gibbs energy of pseudomalachite formation calculated using literature data on its standard entropy is Δ _f H_el^°(298.15 K) =–2812 ± 13 kJ/mol.     

Crystal structure and growth fabric of length-fast chalcedony

Chalcedony from Brazilian agates, has been investigated by using transmission-electron microscopy, X-ray-diffraction, thermogravimetry and optical techniques. The quartz fibers of length-fast chalcedony are composed of submicroscopical polysynthetic, lamellar-twinned right- and lefthanded crystals, according to the Brazil law. This very narrow twinning causes 3 systems of diffuse diffraction streaks (corresponding to the three-fold symmetry) parallel to 〈10.1〉, very frequently possessing an intensity maximum at h±1/2, k, l±1/2. These extra reflections were detected both in electron- and X-ray-diffraction patterns. Wall-lining chalcedony is parallel fibrous consisting of smaller crystallites with a higher total water content (0.06±0.01 μm and 1.2±0.1 wt %) than spherulitic chalcedony in horizontal agate bands (ca. 0.1 μm and 0.7±0.1 wt%).     

The Al2O3 contents of enstatite in equilibrium with garnet in the system MgO-Al2O3-SiO2 at 15–40 kbar and 900°–1,600° C

Forty-six reversed determinations of the Al₂O₃content of enstatite in equilibrium with garnet were made in the P/T range 15–40 kbar/900–1,600° C in the MgO-Al₂O₃-SiO₂ system. Starting materials were mixtures of synthetic pyrope+Al-free enstatite and pyrope+enstatite (5–12% Al₂O₃). Al₂O₃ contents in reversal run pairs closely approached common values from both the high- and low-Al sides. Most experiments were done in a piston-cylinder device using a NaCl medium; some runs at very high temperatures were made in pyrex/NaCl or pyrex/talc assemblies. The measured enstatite compositions, expressed as mole fractions of Mg₂(MgAl)(AlSi₃)O₁₂(X _Opy ^En ) were fitted by a Monte-Carlo method to the equilibrium condition: $$\begin{gathered} \Delta H_{970}^0 - 970\Delta S_{970}^0 \hfill \\ + \mathop \smallint \limits_1^P \Delta V_{970}^0 dP - \mathop \smallint \limits_{970}^T \Delta S_T^0 dT + RT\ln X_{Opy}^{En} = 0 \hfill \\ \end{gathered}$$ where the best fit parameters of ΔH, ΔS and ΔV (1 bar, 970 K) for the reaction pyrope=opy are 2,040 cal/mol, 2.12 eu and 9.55 cc/mol. In addition to the determination of Al₂O₃ contents of enstatite, the univariant reaction pyrope+forsterite=enstatite+spinel was reversibly located in the range 1,100–1,400°C. A “best-fit” line passes through 22, 22.5 and 25 kbar at 1,040, 1,255 and 1,415°C, respectively. Our results for the univariant reaction are in agreement with previous studies of MacGregor (1974) and Haselton (1979). However, comparison of the experimentally determined curve with thermochemical calculations suggests that there may be a small error in the tabulated ΔH _f(970,1) ⁰ value for enstatite. A value of?8.32 rather than?8.81 kcal/mole (Charlu et al. 1975) is consistent with the present data. Application of garnet-enstatite-spinel-forsterite equilibria to natural materials is fraught with difficulties. The effects of nonternary components are poorly understood, and the low solubilities of Al₂O₃ in enstatite under most geologically reasonable conditions make barometric or thermometric calculations highly sensitive. More detailed studies, including reversed determinations in low-friction assemblies, are sorely needed before the effects of important diluents such as Fe, Ca and Cr can be fully understood.     

High-pressure phengite decomposition in the Weissenstein eclogite,Münchberger Gneiss Massif,Germany

The petrography, mineral chemistry and petrogenesis of a sample from the Weissenstein eclogite, Bavaria, Germany, has been investigated. The total mineral assemblage comprises garnet, clinopyroxene_I+II, quartz, amphibole_I+II, rutile, phengite, epidote/allanite, plagioclase, biotite, apatite, pumpellyite, titanite (sphene), zircon, alkali feldspar and calcite. Textural observations combined with geothermobarometry (Fe/Mg distribution between clinopyroxene/garnet and phengite/garnet; jadeite-content of omphacite, Si-content of phengite, and An-content of plagioclase) provide indications of two different stages in the metamorphic evolution of the rock. The main phengitequartz-eclogite mineral equilibration occurred at minimum P=13–17kbar, minimum T=620±50° C; the retrograde symplectite stage (clinopyroxene_II, amphibole_II, biotite, plagioclase) occurred at P _total between 12 and 8.5 kbar. Reactions of the symplectite stage are:

1. phengite (core) + Na₂O_aq + CaO_aq=phengite (rim) + biotite + plagioclase + K₂O_aq + H₂O
2. phengite (core) + clinopyroxene_I + Na₂O_aq=phengite (rim + biotite + plagioclase + amphibole_II + SiO₂ + K₂O_aq + CaO_aq + H₂O
3. clinopyroxene_I + SiO₂ + K₂O_aq + H₂O=clinopyroxene_II + plagioclase+amphibole_II + Na₂O_aq + CaO_aq

The phengite decomposition produces H₂O, whereas the clinopyroxene decomposition consumes H₂O. The estimated P-T-conditions for the Weissenstein eclogite are in the same order of magnitude as those for other eclogite bodies from the Alps and Caledonides believed to be related to subduction processes.     

Experimental determination of magnesia and silica solubilities in graphite-saturated and redox-buffered high-pressure COH fluids in equilibrium with forsterite + enstatite and magnesite + enstatite

We experimentally investigated the dissolution of forsterite, enstatite and magnesite in graphite-saturated COH fluids, synthesized using a rocking piston cylinder apparatus at pressures from 1.0 to 2.1 GPa and temperatures from 700 to 1200 °C. Synthetic forsterite, enstatite, and nearly pure natural magnesite were used as starting materials. Redox conditions were buffered by Ni–NiO–H₂O (ΔFMQ = ??0.21 to ??1.01), employing a double-capsule setting. Fluids, binary H₂O–CO₂ mixtures at the P, T, and fO₂ conditions investigated, were generated from graphite, oxalic acid anhydrous (H₂C₂O₄) and water. Their dissolved solute loads were analyzed through an improved version of the cryogenic technique, which takes into account the complexities associated with the presence of CO₂-bearing fluids. The experimental data show that forsterite?+?enstatite solubility in H₂O–CO₂ fluids is higher compared to pure water, both in terms of dissolved silica (mSiO₂?=?1.24 mol/kg_H2O versus mSiO₂?=?0.22 mol/kg_H2O at P?=?1 GPa, T?=?800 °C) and magnesia (mMgO?=?1.08 mol/kg_H2O versus mMgO?=?0.28 mol/kg_H2O) probably due to the formation of organic C–Mg–Si complexes. Our experimental results show that at low temperature conditions, a graphite-saturated H₂O–CO₂ fluid interacting with a simplified model mantle composition, characterized by low MgO/SiO₂ ratios, would lead to the formation of significant amounts of enstatite if solute concentrations are equal, while at higher temperatures these fluid, characterized by MgO/SiO₂ ratios comparable with that of olivine, would be less effective in metasomatizing the surrounding rocks. However, the molality of COH fluids increases with pressure and temperature, and quintuplicates with respect to the carbon-free aqueous fluids. Therefore, the amount of fluid required to metasomatize the mantle decreases in the presence of carbon at high P–T conditions. COH fluids are thus effective carriers of C, Mg and Si in the mantle wedge up to the shallowest level of the upper mantle.     

Thermodynamics of the xanthoconite-proustite and pyrostilpnite-pyrargyrite phase transition as determined by abrasive stripping voltammetry

The electrochemical reduction of xanthoconite, proustite, pyrostilpnite, and pyrargyrite was studied by abrasive stripping voltammetry, a technique which is based upon a preliminary mechanical transfer of trace amounts of the mineral onto the surface of a paraffin impregnated graphite electrode. Because the electrochemical reduction proceeds near to reversibility and is very similar for each pair of minerals, the peak potentials in differential pulse voltammetry can be used to calculate the standard enthalpy of phase transformation of xanthoconite to proustite and of pyrostilpnite to pyrargyrite: _T H _{(xanth proust)} ^O = 35.46 ± 14.15 kJ/mol and _T H _{(pyrostilp pyrarg)} ^O = 38.85 ± 6.60 kJ/mol. These values are not accessible otherwise until now.     

Boninite primary magmas: Evidence from the Cape Vogel Peninsula,PNG

Boninites from Cape Vogel, PNG, are dominantly pyroxene-glass rocks, but many contain olivine, sometimes as refractory as Fo₉₄. We derive a parental magma for this suite (in equilibrium with Fo₉₄) which contains 20 wt.% MgO and is quartz-normative. This liquid is hydrous, and from petrographie evidence and whole rock H₂O⁺ values, we estimate it to contain 2–3 wt.% H₂O. These data suggest olivine fractionation and primary magmatic water are important in boninite genesis, but both are often obscured by later alteration. The derived parental magma has probably formed at 1,250–1,300° C and low pressures (< ?10kB) and is similar to those which gave rise to olivine-clinoenstatite phyric boninites from New Caledonia and from Howqua, Australia, and possibly to a proposed parental magma for the Bushveld Complex.     

Cordierite-garnet-H2O equilibrium: A geological thermometer,barometer and water fugacity indicator

The high-grade assemblage Cd-Ga-Si-Qz can be thermodynamically modelled from available calorimetric data on the metastable reaction: (I) $$3 MgCd \rightleftarrows 2 Py + 4 Si + 5 Qz$$ naturalK _D ^Fe-Mg between garnet and cordierite and experimental results on cordierite hydration. In the system SiO₂-Al₂O₃-MgO-H₂O, reaction (I) becomes (II) $$3 MgCd \cdot nH_2 O \rightleftarrows 2 Py + 4 Si + 5 Qz + 3 nH_2 O$$ . However, hydrous cordierite is neither a hydrate nor a solid solution between water and anhydrous cordierite and when nH₂O (number of moles of H₂O in Cd) is plotted against \(P_{H_2 O} \) , the resulting isotherms are similar to adsorption isotherms characteristic of zeolitic minerals. Reaction (II) can thus be considered as a combination of reaction (I) with a physical equilibrium of the type nH₂O (in Cd)?nH₂O (in vapor phase). Starting from a point on equilibrium (I), introduction of H₂O into anhydrous Mg-cordierite lowers the chemical potential of MgCd and hence stabilizes this mineral to higher pressure relative to the right-hand assemblage in reaction (I). The pressure increment of stabilization,ΔP, above the pressure limit of anhydrous cordierite stability at constantT, has been calculated using the standard thermodynamics of adsorption isotherms. Cordierite is regarded as a mixture of Mg₂Al₄Si₅O₁₈ and H₂O. The activity of H₂O in the cordierite is evaluated relative to an hypothetical standard state extrapolated from infinite H₂O dilution, by using measured hydration data. The activity of Mg₂Al₄Si₅O₁₈ in the cordierite is then obtained by integration of the Gibbs-Duhem equation, and the pressure stabilization increment,ΔP, computed by means of the relation: $$\Delta V_s \Delta P \cong - RT\ln a_{MgCd}^{MgCd \cdot nH2O} \left( {\Delta V indepentdent of P and T} \right)$$ . Thus, one may contour theP-T plane in isopleths of nH₂O=constant within the area of Mg-cordierite stability allowed by the hydration data for \(P_{H_2 O} = P_{total} \) . The present model indicates greater stabilization of cordierite by H₂O than the model of Newton and Wood (1979) and the calculated curve for metastable breakdown of hydrous MgCd is consistent with experimental data on cordierite breakdown at \(P_{H_2 O} = P_{total} \) . Mg/(Mg+Fe) isopleths have been derived for cordierites of varying nH₂O in the SiO₂-Al₂O₃-MgO-FeO-H₂O system using the additional assumptions that (Fe, Mg) cordierite and (Fe, Mg) garnet behave as ideal solutions, and that typical values of the distribution coefficient of Fe and Mg between coexisting garnet and cordierite observed in natural parageneses can be applied to the calculations. The calculated stable breakdown curve of Fe-cordierite under conditions of \(P_{H_2 O} = P_{total} \) to almandine, sillimanite, quartz and vapor has a positive slope (dP/dT) apparently in contrast to the experimental negative slope. This may be explained by hydration kinetics, which could have allowed systematic breakdown of cordierites of metastable hydration states in the experiments. The bivariant Cd-Ga fields calibrated from the present model are, potentially, good petrogenetic indicators, as, given the iron-magnesium ratio of garnet and cordierite and the hydration number of cordierite, the temperature, pressure and water fugacity are uniquely determined. As this geothermobarometer is in part based on the water content of cordierite, it can be used only if there is some assurance that the actual hydration is inherited from high-grade metamorphic conditions. Such conditions could be realised if the slope of unloading-cooling retrograde metamorphism is more or less parallel to a cordierite isohydron.     

Computer simulation of the transformation of natural living matter into kerogen

Thermodynamic simulation of the system living matter (algae, zooplankton, or green plants) + mineral matter (25% carbonates + 75% clay minerals) + standard seawater at temperatures and pressure corresponding to diagenesis indicates that kerogen can be synthesized, together with hydrocarbons and carbon dioxide, in the reaction mix. The removal of CO₂(g) and N₂(g) from the system is favorable for the reaction Δ₁C₂₉₂H₂₈₈O₁₂ (s; H/C = 0.99, O/C = 0.041) → Δ₂C₁₂₈H₆₈O₇ (s; H/C = 0.53, O/C = 0.055) + xСH₄(aq) + yCO₂(aq) + zH₂O, whose constant and stoichiometric coefficients were calculated based on the simulation results. It is demonstrated that a pressure increase is favorable, while a temperature increase is not, for the procedure of this reaction at P-T parameters of diagenesis: log K =–567 (20°C, 35 bar), 1170 (20°C, 200 bar),–1530 (20°C, 60 bar), and +1030 (20°C, 600 bar).     

The solubility and speciation of molybdenum in water vapour at elevated temperatures and pressures: Implications for ore genesis

The solubility of molybdenum trioxide in liquid-undersaturated water vapour has been investigated experimentally at 300, 320, and 360 °C and 39-154 bars. Results of these experiments show that the solubility of MoO₃ in water vapour is between 1 and 29 ppm, which is 19-20 orders of magnitude higher than the vapour pressure of MoO₃(g). Molybdenum solubility increases exponentially with f_H2O, suggesting the formation of a gaseous hydrated complex of the type MoO₃·nH₂O by the reaction:

(A.1)