The solubility of gold and silver in the system AuAgSO2H2O at 25°C and 1 atm.

During supergene alteration of auriferous carbonate ore, the weathering fluids formed are likely to be alkaline and therefore unsuitable as a medium for gold transport as a chloride complex. Secondary gold remobilization in such deposits can often be attributed instead to gold complexing by sulphur-bearing ligands. Gold and silver solubility in the systems AuSO₂H₂O and AgSO₂H₂O respectively, from the thermodynamic data available, is due to complex formation with thiosulphate and bisulphide ligands. The most stable gold complexes, Au(S₂O₃)₂³⁻ (at φO₂ > 10⁻⁶⁰) and Au(HS)⁻₂ (atφO₂ < 10⁻⁶⁰), exist in neutral or alkaline solutions. Like gold, silver forms a stable thiosulphate complex, Ag(S₂O₃)³⁻₂ in moderately oxidizing, and bisulphide complexes, AgHS⁰ and Ag(HS)⁻₂ in reducing, alkaline media. Silver solubility in highly oxidized, neutral or acid solutions is increased by formation of AgS₂O₃⁻, Ag⁺ and AgSO₄⁻ complexes.Colloidal, crystalline and alloyed gold and silver reacted with 0.1 M Na₂S₂O₃ do not, however, demonstrate independent solubility. The rate of gold solubility in 0.1 M Na₂S₂O₃, for example, is increased both by the presence of silver-thiosulphate complexes and alloyed silver. It is possible that such behaviour is due to the formation a mixed metal complex of the type (Au, Ag)(S₂O₃)₂³⁻.The nature and mineral association of secondary gold in the oxidized zone of carbonate ore at Wau. in Papua New Guinea, is consistent with prior remobilization as a thiosulphate complex. Here the secondary gold is coarsely crystalline, alloyed with 50–75 at% Ag and enriched at the watertable and with manganese dioxide in the oxidized zone.     

FeMgMn relations of ureilite olivines and pyroxenes and the genesis of ureilites

The Fe/Mn-Fe/Mg relations of published microprobe analyses of ureilite olivine cores suggest that FeO reduction in the magmatic stage was important in the genesis of some of these meteorites. Consideration of Mg/Mn and Fe/Mn partitioning between olivine and pigeonite cores shows that these two phases are not in equilibrium. The data are consistent with combined fractional crystallization and FeO reduction being the major processes of ureilite genesis. Few, if any, of the analyzed ureilites are consistent with a partial melting residue model.     

Calcite solubility in supercritical CO2H2O fluids

An extraction-quench apparatus was used to measure calcite solubilities in supercritical CO₂H₂O mixtures. Experiments were conducted at 1 kbar and 2 kbar, between 240°C and 620°C and from X_CO2 = .02 toX_CO2 = .15 in order to determine the solubility behavior as a function of pressure, temperature and CO₂ content. The results indicate that calcite solubilities under these conditions behave similarly to previously investigated calcite solubilities at lower pressures and temperatures (SHARP and Kennedy, 1965). At constant X_CO2, the solubility increases with increasing pressure, but it decreases with increasing temperature. When the temperature and pressure are constant, the calcite solubility rises with increasing X_CO2 to a maximum value at X_CO2 between 0.02 and 0.05. For higher CO₂ contents, up to X_CO2 = .15, the calcite solubility decreases, probably due to the decrease of H₂O activities to values significantly below unity.The solubility behavior can be successfully modeled by making the assumption that Ca⁺⁺ is the dominant calcium species and that the carbon-bearing species are CO_2(aq) and HCO⁻₃. Since for these dilute H₂OCO₂ fluids, all activity coefficients can be assumed to not differ significantly from unity, ionization constants for the reaction H₂O + CO_2(aq) H⁺ + HCO⁻₃ can be calculated at 1 and 2 kbar between 250°C and 550°C. These calculated values are in good agreement with the low temperature determinations of the ionization constants for this reaction determined by Read (1975). Values of the molal Gibbs free energy of CO_2(aq) obtained in our study exhibit a much greater positive departure from ideality than those calculated with the modified Redlich-Kwong equations of either Flowers (1979) or Kerrick and Jacobs (1981) for dilute CO₂ aqueous solutions.     

Equilibrium dihedral angles in the system H2O−CO2−NaCl-calcite,and implications for fluid flow during metamorphism

Fluid-calcite-calcite dihedral angles have been measured for fluids in the system H₂O−CO₂−NaCl, between 1 and 2 kbar, and 550–750° C. It is found that the calcite-calcite-H₂O dihedral angle decreases steadily with addition of NaCl from a value of about 80° (pure water) to 44° (60 wt% NaCl). The CO₂−H₂O system displays a well-defined minimum at , with a dihedral angle of 50°, in contrast to those of pure CO₂ and H₂O which are 90° and 80° respectively. Experiments containing fluids which are immiscible at run conditions showed a bimodal distribution of dihedral angles in the CO₂−H₂O−NaCl system, which can be approximately correlated with the compositions of the two fluid phases. Such bimodality was only observed for immiscible fluids in the H₂O−NaCl system if the quench rate exceeded about 200°C per min. This is probably due to the extremely rapid establishment of the single phase dihedral angle on quenching. The fluid phase topology in devolatilising marbles will only be a connected network for very saline brines and fluids with close to 0.5. Fluids trapped in fluid inclusions in calcite grains in marbles may be predominantly H₂O-rich or CO₂-rich, and of low salinity. All other fluid compositions in the H₂O−CO₂−NaCl-calcite system will occupy isolated pores, the largest of which will grow at the expense of the smallest. Escape of fluid produced during devolatilisation reactions under such conditions will occur by fluid overpressuring and hydrofracture. In contrast, previous experimental studies of quartz-fluid dihedral angles between 950° and 1100° C (Watson and Brenan 1987) predict that quartz-dominated lithologies will permit pervasive flow of H₂O−NaCl fluids, but not of H₂O−CO₂ fluids. Documented geological examples of differences in permeability and fluid flow mechanism between metamorphic argillites, psammites and limestones which support the results of the experimental studies are discussed.     

Kar and RbSr whole-rock ages reset during pan african event in the sinai peninsula (Ataqa Area)

A low pressure metamorphic Pan African terrain, composed mainly of schists and hornfels, ranging from high greenschist to low amphibolite facies, is exposed west of Dahab, southeastern Sinai, located between the metamorphic Kid Complex and the Feirani Volcanics.The studied metamorphic unit was dated using RbSr and KAr methods. A RbSr whole-rock isochron (based on seven samples) yields an age of 602 ± 11 Ma with an initial (⁸⁷Sr/⁸⁶Sr) ratio of 0.7041 ± 4. The RbSr age is assumed to be the age of a metamorphic phase (600 ± 10 Ma) well known in the area. On the other hand, KAr whole-rock ages (based on nine samples) show different values ranging from 590 to 526 Ma. These low KAr ages are due to the resetting of the KAr system by a thermal event, before 530 Ma affecting the Ar behaviour without disturbing the RbSr system. The Ar escape took place mainly from K-bearing feldspars, which were not affected by later textural, crystallographic or mineralogic variations.     

CuFeNiS mineral assemblages in upper-mantle peridotites from the Table Mountain and Blow-Me-Down Mountain ophiolite massifs (Bay of Islands area,Newfoundland): Their relationships with fluids and silicate melts

Plastically deformed ultramafic rocks in the Table Mountain and Blow-Me-Down Mountain ophiolites comprise a basal unit of slightly depleted Iherzolites, an intermediate sequence of strongly depleted harzburgites and an upper zone of dunites, also referred to as a transition zone intensively percolated by basaltic melts or magmatic fluids. Thirty-five samples including all of the above rock types have been investigated on 100 polished thin sections for CuFeNiS mineral assemblages. Most of them contain traces of CuFeNi sulfides, native metals and locally Ni arsenide. Compositional features of opaque assemblages as well as their textural sites in the rocks indicate that the present CuFeNiS minerals derive from an upper-mantle sulfide component through extensive subsolidus re-equilibration down to 100°C. The primitive component (predominant pentlandite, minor pyrrhotite and chalcopyrite) is preserved as sulfide inclusions in chromites of the transition zone, due to a subsolidus re-equilibration in a closed system. On the contrary, sulfide assemblages interstitial to silicates and spinel have extensively reacted with reducing serpentinizing fluids to produce sulfur-deficient sulfides such as heazlewoodite and mackinawite and native metals (native copper and awaruite). Microscale variations of redox conditions and the removal of Fe from the silicate during serpentinization may account for the peculiar “grain-by-grain” equilibrium state of intergranular assemblages. In spite of low-temperature alteration, a gradual depletion in sulfide component has been recognized from the basal lherzolites to the intermediate harzburgites while the sulfide content gradually increases in the transition zone (up to 0.2% by volume). The first pattern is consistent with the low-melting nature of the sulfide component in mantle melting processes. Microstructural criteria such as the absence of sulfide inclusions in olivine neoblasts demonstrate that the sulfide component postdates plastic deformation of the transition zone. The sulfide-enrichment pattern is thus ascribed to the percolation of a sulfur-saturated basaltic magma into residual dunites.     

Experimental partitioning of halogens and other trace elements between olivine, pyroxenes, amphibole and aqueous fluid at 2 GPa and 900–1,300 °C

We present new partition coefficients for various trace elements including Cl between olivine, pyroxenes, amphibole and coexisting chlorine-bearing aqueous fluid in a series of high-pressure experiments at 2 GPa between 900 and 1,300 °C in natural and synthetic systems. Diamond aggregates were added to the experimental capsule set-up in order to separate the fluid from the solid residue and enable in situ analysis of the quenched solute by LA–ICP–MS. The chlorine and fluorine contents in mantle minerals were measured by electron microprobe, and the nature of OH defects was investigated by infrared spectroscopy. Furthermore, a fluorine-rich olivine from one selected sample was investigated by TEM. Results reveal average Cl concentrations in olivine and pyroxenes around 20 ppm and up to 900 ppm F in olivine, making olivine an important repository of halogens in the mantle. Chlorine is always incompatible with Cl partition coefficients D _Cl ^{olivine/fluid} varying between 10^?5 and 10^?3, whereas D _Cl ^{orthopyroxene/fluid} and D _Cl ^{clinopyroxene/fluid} are ~10^?4 and D _Cl ^{amphibole/fluid} is ~5 × 10^?3. Furthermore, partitioning results for incompatible trace element show that compatibilities of trace elements are generally ordered as D ^amph/fluid ≈ D ^cpx/fluid > D ^opx/fluid > D ^ol/fluid but that D ^{mineral/fluid} for Li and P is very similar for all observed silicate phases. Infrared spectra of olivine synthesized in a F-free Ti-bearing system show absorption bands at 3,525 and ~3,570 cm^?1. In F ± TiO₂-bearing systems, additional absorption bands appear at ~3,535, ~3,595, 3,640 and 3,670 cm^?1. Absorption bands at ~3,530 and ~3,570 cm^?1, previously assigned to humite-like point defects, profit from low synthesis temperatures and the presence of F. The presence of planar defects could not be proved by TEM investigations, but dislocations in the olivine lattice were observed and are suggested to be an important site for halogen incorporation in olivine.     

Microtextural constraints on the interplay between fluid–rock reactions and deformation

Schists from two mylonitic localities in the footwall of a low-angle normal fault in the eastern Alps record different degrees of embrittlement during exhumation, depending on the extent to which fluid–rock reactions proceeded. At one site, graphitic schists preserve textural evidence for two metamorphic reactions that modified and/or fluid volume: (1) reaction between graphite and aqueous fluid that increased without changing the molar amount of fluid, and (2) replacement of titanite by rutile, calcite, and quartz. The latter reaction involved net consumption of increasingly CO₂-rich fluid. Areas where the first reaction proceeded are associated with abundant Mode I microcracks. Fluid inclusion arrays within the microcracks show that increased from ∼0.1 to 0.6 during decompression from 4.75 to 2 kbar at a reference temperature of 500°C. Titanite consumption is most pronounced within transgranular Mode I microcracks, but microcracks do not crosscut products of this reaction; fluid consumption during reaction was coeval with the end of microcracking, at least on a local scale. At the other site, graphitic schists lack small-scale Mode I cracks as well as evidence for graphite consumption during decompression. SEM imaging shows that graphite is anhedral and pitted at the first site, but occurs in clusters of euhedral grains at the second site. Mass balance calculations demonstrate that rocks with partially consumed graphite were infiltrated by an externally derived, H₂O-rich fluid that drove subsequent graphite-fluid reaction. Evidence for similar fluid infiltration is absent at the second site. Variations in the degree of reaction progress indicate that fluid pathways and deformation style were heterogeneous on the scale of millimeters to kilometers during exhumation from mid-crustal depths.     

Thermodynamic modeling of binary CH4–CO2 fluid inclusions

An equation of state (EOS) explicit in Helmholtz free energy has been improved to calculate the PVTx and vapor–liquid phase equilibrium properties of CH₄–CO₂ fluid mixture. This EOS, where four mixing parameters are used, is based on highly accurate EOSs recommended by NIST for pure components (CH₄ and CO₂) and contains a simple generalized departure function presented by Lemmon and Jacobsen (1999). Comparison with experimental data available indicates that the EOS can calculate both vapor–liquid phase equilibrium and volumetric properties of this binary fluid system with accuracy close to that of experimental data up to high temperature and pressure within full range of composition. The EOS of CH₄–CO₂ fluid, together with the updated Gibbs free energy model of solid CO₂ (dry ice), is applied to calculate the CH₄ content (x_CH4) and molar volume (V_m) of the CH₄–CO₂ fluid inclusion based on the assumption that the volume of an inclusion keeps constant during heating and cooling. $V_{\text{m}}-x_{{\text{CH}}_4}$ diagrams are presented, which describe phase transitions involving vapor, liquid and CO₂ solid phases of CH₄–CO₂ fluid inclusions. Isochores of CH₄–CO₂ inclusions at given $x_{{\text{CH}}_4}$ and V_m can be easily calculated from the improved EOS.     

Depth of volcanic basalt degassing forecasted from CO2 fluid inclusions

Fluid inclusions have recorded the history of degassing in basalt. Some fluid inclusions in olivine and pyroxene phenocrysts of basalt were analyzed by micro-thermometry and Raman spectroscopy in this paper. The experimental results showed that many inclusions are present almost in a pure CO2 system. The densities of some CO2 inclusions were computed in terms of Raman spectroscopic characteristics of CO2 Fermi resonance at room temperature. Their densities change over a wide range, but mainly between 0.044 g/cm3 and 0.289 g/cm3. Their micro-thermometric measurements showed that the CO2 inclusions examined reached homogenization between 1145.5℃ and 1265℃ . The mean value of homogenization temperatures of CO2 inclusions in basalts is near 1210℃. The trap pressures (depths) of inclusions were computed with the equation of state and computer program. Distribution of the trap depths makes it know that the degassing of magma can happen over a wide pressure (depth) range, but mainly at the depth of 0.48 km to 3.85 km. This implicates that basalt magma experienced intensive degassing and the CO2 gas reservoir from the basalt magma also may be formed in this range of depths. The results of this study showed that the depth of basalt magma degassing can be forecasted from CO2 fluid inclusions, and it is meaningful for understanding the process of magma degassing and constraining the inorganogenic CO2 gas reservoir.     

Copper partitioning between granitic silicate melt and coexisting aqueous fluid at 850 °C and 100 MPa

Experiments on the partitioning of Cu between different granitic silicate melts and the respective coexisting aqueous fluids have been performed under conditions of 850 °C, 100 MPa and oxygen fugacity（f O₂） buffered at approaching Ni–Ni O（NNO）. Partition coefficients of Cu（DCu= cfluid/cmelt） were varied with different alumina/alkali mole ratios [Al₂O₃/（Na₂O·K₂O）, abbreviated as Al/Alk], Na/K mole ratios, and Si O₂ mole contents. The DCu increased from 1.28 ± 0.01 to 22.18 ± 0.22 with the increase of Al/Alk mole ratios（ranging from 0.64 to 1.20）and Na/K mole ratios（ranging from 0.58 to 2.56）. The experimental results also showed that DCuwas positively correlated with the HCl concentration of the starting fluid.The DCuwas independent of the Si O₂ mole content in the range of Si O₂ content considered. No DCuvalue was less than 1 in our experiments at 850 °C and 100 MPa, indicating that Cu preferred to enter the fluid phase rather than the coexisting melt phase under most conditions in the melt-fluid system, and thus a significant amount of Cu could be transported in the fluid phase in the magmatichydrothermal environment. The results indicated that Cu favored partitioning into the aqueous fluid rather than themelt phase if there was a high Na/K ratio, Na-rich, peraluminous granitic melt coexisting with the high Cl-fluid.     

Synthesis of hydrocarbons by CO2 fluid conversion with hydrogen: Experimental modeling at 7.8 GPa and 1350°C

Doklady Earth Sciences - Synthesis of hydrocarbons by the interaction of a CO2 fluid with hydrogen mantle domains has been simulated in an experiment at 7.8 GPa and 1350°C. The synthesized...