Solubility of the buffer assemblage pyrite + pyrrhotite + magnetite in NaCl solutions from 200 to 350°C

In the design of hydrothermal solubility studies it is important that the system be completely defined chemically. If the solubilities of minerals containing m metallic elements are to be determined in hydrothermal NaCl solutions, the phase rule requires that a total of m + 6 independent intensive parameters be controlled or measured in order to determine completely the system.In this study the solubility of the univariant assemblage pyrite + pyrrhotite + magnetite has been determined in vapor saturated hydrothermal solutions from 200 to 350°C for NaCl concentrations ranging from 0.0 to 5.0 molal. At any temperature, oxygen and sulfur fugacities were buffered by the chosen assemblage. System pH was determined from excess CO₂ partial pressures and computed ionic equilibria. Equilibrium constants were calculated by regression analysis of solubility data. The results show that more than 10 ppm of each mineral can dissolve in typical hydrothermal solutions under geologically realistic conditions. Solubilities were best represented by the species Fe²⁺ and FeCl⁺ at 200 and 250°C; Fe²⁺, FeCl⁺ and FeCl₂⁰ at 300°C; and Fe²⁺ and FeCl₂⁰ at 350°C. Ore deposition would occur by lowering temperature, diluting chloride concentration, or by raising pH through wall rock alteration reactions.     

Amorphous silica solubilities—I. Behavior in aqueous sodium nitrate solutions; 25–300°C, 0–6 molal

The solubility of amorphous silica was obtained in aqueous sodium nitrate solutions up to six molal and at temperatures from 25 to 300°C. It was expected that solubilities in aqueous sodium chloride solutions would be similar. At 25°C, the solubility of amorphous silica is lowered from that in water to 0.00086 m in 6.12 m sodium nitrate, or a decrease of 60%. At 300°C, the corresponding decrease is only 27% from a solubility of 0.0269 m in H₂O. From the change in solubility with temperature at a given constant molality of sodium nitrate, the molal heat of solution over the range, 100 to 300°C, increases from + 2.93 kcal mol^?1 in water to + 3.64 kcal mol^?1 in 6m sodium nitrate. The value approaches a constant of +3.8 kcal mol^?1 as sodium nitrate approaches saturation at 10.8 molal.     

Experimental investigation of the solubility of albite and jadeite in H2O, with paragonite + quartz at 500 and 600 °C, and 1-2.25 GPa

The solubilities of the assemblages albite + paragonite + quartz and jadeite + paragonite + quartz in H₂O were determined at 500 and 600 °C, 1.0-2.25 GPa, using hydrothermal piston-cylinder methods. The three minerals are isobarically and isothermally invariant in the presence of H₂O, so fluid composition is uniquely determined at each pressure and temperature. A phase-bracketing approach was used to achieve accurate solubility determinations. Albite + quartz and jadeite + quartz dissolve incongruently in H₂O, yielding residual paragonite which could not be retrieved and weighed. Solution composition fixed by the three-mineral assemblage at a given pressure and temperature was therefore bracketed by adding NaSi₃O_6.5 glass in successive experiments, until no paragonite was observed in run products. Solubilities derived from experiments bounding the appearance of paragonite thus constrain the equilibrium fluid composition. Results indicate that, at a given pressure, Na, Al, and Si concentrations are higher at 600 °C than at 500 °C. At both 500 and 600 °C, solubilities of all three elements increase with pressure in the albite stability field, to a maximum at the jadeite-albite-quartz equilibrium. In the jadeite stability field, element concentrations decline with continued pressure increase. At the solubility maximum, Na, Al, and Si concentrations are, respectively, 0.16, 0.05, and 0.48 molal at 500 °C, and 0.45, 0.27, and 1.56 molal at 600 °C. Bulk solubilities are 3.3 and 10.3 wt% oxides, respectively. Observed element concentrations are everywhere greater than those predicted from extrapolated thermodynamic data for simple ions, monomers, ion pairs, and the silica dimer. The measurements therefore require the presence of additional, polymerized Na-Al-Si-bearing species in the solutions. The excess solubility is >50% at all conditions, indicating that polymeric structures are the predominant solutes in the P-T region studied. The solubility patterns likely arise from combination of the large solid volume change associated with the albite-jadeite-quartz equilibrium and the rise in Na-Al-Si polymerization with approach to the hydrothermal melting curves of albite + quartz and jadeite + quartz. Our results indicate that polymerization of Na-Al-Si solutes is a fundamental aspect of fluid-rock interaction at high pressure. In addition, the data suggest that high-pressure metamorphic isograds can impose unexpected controls on metasomatic mass transfer, that significant metasomatic mass transfer prior to melting should be considered in migmatitic terranes, and that polymeric complexes may be an important transport agent in subduction zones.     

Amorphous silica solubilities—II. Effect of aqueous salt solutions at 25°C

The solubility of amorphous silica was measured at 25°C in ten separate sets of aqueous salt solutions—potassium chloride, potassium nitrate, sodium chloride, lithium chloride, lithium nitrate, magnesium chloride, calcium chloride, magnesium sulfate, sodium bicarbonate and sodium sulfate. The concentrations of the salts were varied from zero to saturation with both salt and amorphous silica. With increasing concentration of salt, the solubility of amorphous silica always decreased as expected from an average value of 0.00218 m in water. Nevertheless, the extent of decrease differed greatly from a 6% decrease in a solution saturated with NaHCO₃ to a 95.7% decrease in a solution saturated with CaCl₂. A striking correlation was observed: In the 1-1 and 2-1 electrolyte salt solutions at a given molality the effect on the solubility of silica depended upon the cation in the order Mg²⁺, Ca²⁺ > Li⁺ > Na⁺ > K ⁺.     

Experimental study and modeling of fluid reaction paths in the quartz-kyanite ± muscovite-water system at 0.7 GPa in the 350-550 °C range: Implications for Al selective transfer during metamorphism

In order to quantify Al transfer in response to fluid-mineral equilibration under evolving metamorphic conditions, isobaric (0.7 GPa) experiments were conducted in the 350-550 °C range. Disequilibrium was induced (1) by holding initially pure water and natural minerals (kyanite + quartz ± muscovite enclosed in a perforated inner capsule) under isothermal conditions and (2) by stepwise temperature variations. In all experiments, secondary Al-bearing phases crystallized in the external tube of a “tube-in-tube” setup (SEM characterization); they are interpreted as witnesses of the evolution of the fluid composition (fluid reaction path). These reaction paths and the subsequent amount of secondary crystallizations were modeled using thermodynamic data from SUPCRT92 and estimates of both starting-mineral dissolution rates and elemental diffusion coefficients from the literature. A major result is that the amount of aluminum transferred to secondary phases is a thousand times larger than the calculated Al concentration in the fluid. Although the crystallization of Al-bearing phases was expected as a response to a temperature decrease, the stepwise temperature increase (20 °C/day) also led to aluminum transfer towards secondary phases. In the course of re-equilibration, the fluid first becomes saturated with respect to aluminosilicates and then reaches silica saturation, due to the low solubility of Al-minerals. Consequently, aluminosilicates partly recrystallize in response to a temperature increase. Crystallization of secondary Al-phases in the external tube implies that aqueous aluminum was efficiently transported from the inner capsule, even in the pure Al₂O₃-SiO₂-H₂O system. Therefore, mass balance calculations considering a constant Al reference frame, i.e., postulating Al immobility, should be regarded with caution.     

Experiments on the Element Distribution between the Granodiorite JG-1a and 2M NaCl Hydrothermal Solution at Temperatures of 300 to 800°C and a Pressure of 1 kb

Abstract. The distribution of Na, K, Ca, Mg, Mn and Fe between the granodiorite JG-la, one of the geochemical standard rocks, and 2M NaCl aqueous solution was experimentally determined at temperatures of 300 to 800C and a pressure of 1 kb using standard cold seal-type pressure vessels. The solid run products melted partially at 800C. Only K shows a significantly different behavior from the experiments using the basalt JB-la (Uchida and Tsutsui, 2000) due to the presence of ortho-clase in the JG-la. The transition elements tend to be preferably partitioned into the aqueous chloride solutions with increasing temperature. At 800C and 1 kb, the Fe concentration of the aqueous chloride solutions reached up to 5,000 ppm, and the Mn concentration up to 350 ppm. The distribution coefficient, K_{D, i} = C_{i, sol}/C_i, rock, is in the order of Na>K>Mn>Ca> Fe>Mg at 300C, but changed in the order of Mn>N>K>Fe>Ca>Mg at 800C. The distribution coefficients of the divalent cations for the JG-la are higher than those for the JB-1a. The distribution coefficient of the transition elements, Fe and Mn, increases significantly with increasing temperature. The thermodynamic analysis for aqueous speciation revealed that this is attributable to the formation of the tri-chloro complexes of the transition elements at higher temperatures.     

Gold partitioning in melt-vapor-brine systems

We used laser-ablation inductively coupled plasma mass spectrometry to measure the solubility of gold in synthetic sulfur-free vapor and brine fluid inclusions in a vapor + brine + haplogranite + magnetite + gold metal assemblage. Experiments were conducted at 800°C, oxygen fugacity buffered at Ni-NiO (NNO), and pressures ranging from 110 to 145 MPa. The wt% NaCl eq. of vapor increases from 2.3 to 19 and that of brine decreases from 57 to 35 with increasing pressure. The composition of the vapors and brines are dominated by NaCl + KCl + FeCl₂ + H₂O. Gold concentrations in vapor and brine decrease from 36 to 5 and 50 to 28 μg/g, respectively, and the calculated vapor:brine partition coefficients for gold decrease from 0.72 to 0.17 as pressure decreases from 145 to 110 MPa. These data are consistent with the thermodynamic boundary condition that the concentration of gold in the vapor and brine must approach a common value as the critical pressure is approached along the 800°C isotherm in the NaCl-KCl-FeCl₂-HCl-H₂O system.We use the equilibrium constant for gold dissolution as AuOH⁰, extrapolated from lower temperature and overlapping pressure range, to calculate expected concentrations of AuOH⁰ in our experimental vapors. These calculations suggest that a significant quantity of gold in our experimental vapors is present as a non-hydroxide species. Possible chloridogold(I) species are hypothesized based on the positively correlated gold and chloride concentrations in our experimental vapors. The absolute concentration of gold in our synthetic vapor, brine, and melt and calculated mass partition coefficients for gold between these physicochemically distinct magmatic phases suggests that gold solubility in aqueous fluids is a function of aqueous phase salinity, specifically total chloride concentration, at magmatic conditions. However, though we highlight here the effect of salinity, the combination of our data with data sets from lower temperatures evinces a significant decrease in gold solubility as temperature drops from 800°C to 600°C. This decrease in solubility has implications for gold deposition from ascending magmatic fluids.     

焦家金矿床水-岩反应过程及成矿流体组分变化规律

在野外和室内岩相学观察的基础上,详细剖析了蚀变-矿化时序,结合热力学数值模拟方法与定量结果,厘定了水- 岩反应过程中矿物的沉淀次序、流体组分的存在形式、迁移行为、浓度变化和矿物形成机制以及组分之间的化学反应,为 进一步研究水-岩反应与金矿化的关系奠定了基础。研究结果显示反应初期K+由流体带入围岩形成钾长石化,随着反应的 进行,H+浓度持续降低而Fe2+和Al3+含量升高,绢云母和石英大量沉淀,钾长石消失;反应后期各类硫化物开始沉淀,石英 持续沉淀贯穿整个反应过程。成矿流体中SO42-,HS-,Fe2+的含量对蚀变矿物组合影响很大;水-岩反应过程中硫酸盐 （SO42-） 减少生成等量的HS-并伴随着含三价铁矿物的沉淀,可能是焦家金矿床硫化物沉淀的一种重要机制。整个反应过程 中溶液pH值持续升高是原岩中Ca,K,Na,Mg等与溶液中H+发生交换反应的结果;同时pH值的升高也会降低金的溶解度 致使金沉淀。上述研究成果对于理解岩石中的矿物共生组合、生成顺序及蚀变分带的成因机制提供了新的依据。     

Synthesis of tourmaline solid solutions in the system Na2O–MgO–Al2O3–SiO2–B2O3–H2O–HCl and the distribution of Na between tourmaline and fluid at 300 to 700 °C and 200 MPa

Tourmaline has been synthesized hydrothermally at 200 MPa between 300 and 700 °C from oxide mixtures with Mg-Al ratios for the end members dravite NaMg₃Al₆(Si₆O₁₈)(BO₃)₃(OH)₃(OH) and Mg-foitite &ding6F;(Mg₂Al)Al₆ (Si₆O₁₈)(BO₃)₃(OH)₃(OH). Six different Na concentrations were investigated to determine the distribution of Na between tourmaline and fluid in the SiO₂-saturated system Na₂O-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl. Synthetic tourmaline ranges from X-site vacant (&ding6F;) tourmaline (Mg-foitite) to nearly ideal dravite with Na=0.95 apfu. There are small, but significant, amounts of proton deficiency and negligible tetrahedral Al. Chemical variation is primarily caused by the substitutions Al&ding6F;Mg_-1Na_-1 and minor AlMg_-1H_-1. Varying amounts of Na and &ding6F; determine the Mg/Al ratios. Besides tourmaline and quartz, additional Mg-Al phases are chlorite and, at 700 °C, cordierite. Albite is also present at high Na concentrations in the bulk composition. The c dimension of the tourmaline crystals increases with Na in tourmaline. The amount of Na in the X-site depends strongly on the bulk concentration of Na in the system as well as on the temperature. These factors in turn control the phase assemblage and the composition of the fluid phase. For the assemblage tourmaline + quartz + chlorite/cordierite + fluid, a linear relationship exists between Na concentration in the fluid (quenched after the run) and tourmaline with temperature: T °C [ᆭ °C]=(Na_fluid/Na_tur)앾.878-14.692 (r²=0.96). For the assemblage tourmaline + albite + quartz + fluid, it is: T °C [ᆣ °C]=(Na_fluid/Na_tur)욝.813-6.231 (r²=0.95), where Na_fluid is the concentration of Na⁺ in the final fluid (mol/l) and Na_tur is the number of Na cations in the X-site of tourmaline. The equations are valid in the temperature range of 500-715 °C. Our experiments demonstrate that the occupancy of the X-site in combination with the changing concentrations of Al and Mg can be used to monitor changes in the fluid composition in equilibrium with a growing tourmaline crystal. Currently, this relation can be applied qualitatively to natural tourmaline to explain zoning in Na- and Al/(Al+Mg).     

Compositional variation of muscovite as a function of metamorphic grade and assemblage in metapelites from N.W. Maine

Chemical data are presented for 49 muscovites from high and low Al specimens collected form N.W. Maine at metamorphic grades ranging from the upper staurolite to the upper sillimanite zone. Data also are presented for two muscovite from St. Paul Island, two muscovites+three paragonites from Gassetts, Vermont, and one muscovite from an adamellite in N. W. Maine.These data given further information on the effects of P, T, and bulk composition on muscovite composition. Specifically, temperature clearly influences the Na/Na+K ratio of muscovite in limiting assemblages but may not have much effect on the phengite content. Increase in pressure clearly does cause an increase in phengite content. Bulk composition (assemblage) has a very great effect on both Na/Na+K ratio and phengite content so that attempts to use either of these factors to monitor metamorphic grade should generally be done in the context of a limiting assemblage.     

The stability of annite+quartz: reversed experimental data for the reaction 2 annite+3 quartz=2 sanidine+3 fayalite +2 H2O

Reversals for the reaction 2 annite+3 quartz=2 sanidine+3 fayalite+2 H₂O have been experimentally determined in cold-seal pressure vessels at pressures of 2, 3, 4 and 5?kbar, limiting annite +quartz stability towards higher temperatures. The equilibrium passes through the temperature intervals 500–540°?C (2?kbar), 550–570°?C (3?kbar), 570–590°?C (4?kbar) and 590–610°?C (5?kbar). Starting materials for most experiments were mixtures of synthetic annite +fayalite+sanidine+quartz and in some runs annite+quartz alone. Microprobe analyses of the reacted mixtures showed that the annites deviate slightly from their ideal Si/Al ratio (Si per formula unit ranges between 2.85 and 2.92, Al^VI between 0.06 and 0.15). As determined by Mössbauer spectroscopy, the Fe³⁺ content of annite in the assemblage annite+fayalite +sanidine+quartz is around 5–7%. The experimental data were used to extract the thermodynamic standard state enthalpy and entropy of annite as follows: H ⁰ _f,?Ann =?5125.896±8.319 [kJ/mol] and S ⁰ _Ann=432.62±8.89 [J/mol/K] (consistent with the Holland and Powell 1990 data set), and H ⁰ _f,Ann =?5130.971±7.939 [kJ/mol] and S ⁰ _Ann=424.02±8.39 [J/mol/K] (consistent with the TWEEQ data base, Berman 1991). The preceeding values are close to the standard state properties derived from hydrogen sensor data of the redox reaction annite=sanidine+magnetite+H ₂ (Dachs 1994). The experimental half-reversal of Eugster and Wones (1962) on the annite +quartz breakdown reaction could not be reproduced experimentally (formation of annite from sanidine+fayalite+quartz at 540°?C/1.035?kbar/magnetite-iron buffer) and probable reasons for this discrepancy remain unclear. The extracted thermodynamic standard state properties of annite were used to calculate annite and annite+quartz stabilities for pressures between 2 and 5?kbar.     

The univariant curve liquid = forsterite + anorthite + diopside in the system CMAS at 1 bar: solid solutions and melt structure

One atmosphere liquid-present experiments were carried out in the CMAS system using an ordinary quench furnace apparatus. The runs, including reversal and duplicate experiments, describe the univariant curve l=fo+an+ di between the invariant points Q: l+fo+an=di+sp and F: l+fo=an+di+oen, located respectively at 1245±1° C and 1244±1° C. The thermal divide on this curve M₃: l= fo+an+di is located at 1275±1° C and plots well within the silica-saturated field, in agreement with Longhi's (1987) experiments. Along the univariant curve l=fo+an+di, liquid composition evolves away from the thermal divide either toward invariant points Q or F and pierces the silica saturation plane, i.e., the join Di-An-En, in the silica saturated field. In this compositional range, the Al solubility in clinopyroxene changes drastically from one side of the thermal divide to the other, with great increase of Al solubility in the silica-undersaturated field. Four endmembers must be used to describe the complex solid solution of anorthite: CaAl₂Si₂O₈, CaMgSi₃O₈, MgAl₂Si₂O₈ and [] Si₄O₈. The last two of these are present only within the silica-saturated field. Unlike clinopyroxene, the Mg content of anorthite is insensitive to the thermal barrier but is only sensitive to silica-saturation plane. Olivine composition can be described by a binary solid solution of forsterite and monticellite with no Ca in the M₂ site. As with anorthite, olivine compositions exhibit a marked change with crossing of the silica-saturation plane. The above features imply that the solubility of minor elements in crystalline phases (Al in clinopyroxene, Ca in olivine and Mg in anorthite) selectively respond to only one or another of these particular plane. Results have many important consequences. One is the likelihood of changes in melt speciation depending on position with respect to the thermal divide and the silica-saturation plane.     

Advances in understanding the Kombolgie Subgroup and unconformity-related uranium deposits in the Alligator Rivers Uranium Field and how to explore for them using lithogeochemical principles

The Alligator Rivers Uranium Field (ARUF) includes the mined and unmined Jabiluka, Ranger, Koongarra and Nabarlek unconformity-related uranium deposits and several small prospects including the newly discovered King River prospect. Uranium mineralisation is hosted by a variety of metamorphosed Nimbuwah Domain lithologies that are unconformably overlain by the Kombolgie Subgroup, a basin package of unmetamorphosed arenites and mafic volcanics. All of the uranium deposits and prospects preserve an identical alteration assemblage that is subdivided into a distal and proximal alteration zone. The distal alteration zone comprises an assemblage of sericite and chlorite that replace albite and amphibole. In some cases, this alteration can be traced >1000 m from the proximal alteration zone that is dominated by uraninite, hematite, chlorite and sericite. Uranium precipitated in the basement as uraninite at 1680 Ma at around 200°C from a fluid having δ¹⁸O_fluid values of 3.0±2.8‰ and δD_fluid values of ?28±13‰ VSMOW reflecting an evolved marine source. These geochemical properties are indistinguishable from those recorded by diagenetic illite and chlorite that were collected from the Kombolgie Subgroup sandstones across the ARUF. The illite and chlorite formed in diagenetic aquifers, and where these aquifers intersected favourable basement rocks, such as those containing graphite or other reductants, U was precipitated as uraninite. Therefore, it is proposed that the Kombolgie Subgroup is the source for fluids that formed the deposits. A post-ore alteration assemblage dominated by chlorite, but also comprising quartz±dolomite±sulfide veins cut the uranium mineralisation at all deposits and has historically been recorded as part of the syn-ore mineralisation event. However, these minerals formed anywhere between 1500 to 630 Ma from fluids that have distinctly lower δ¹⁸O_fluid values around 1.5‰ and lower δD_fluid values around ?45‰ reflecting a meteoric water origin. Despite unconformity-related uranium deposits having a large alteration halo, they remain difficult to find. The subtle alteration of albite to sericite several hundred metres from mineralisation occurs in isolation of any increase in trace elements such as U and radiogenic Pb and can be difficult or impossible to identify in hand specimen. Whole rock geochemical data indicate that Pearce Element Ratio (PER) analysis and General Element Ratio (GER) analysis may vector into this subtle alteration because it does not rely on an increase in trace elements to identify proximity to ore. PER and GER plots, Al/Ti vs (2Ca + Na + K)/Ti, Na/Al vs (Na + K)/Al, K/Al vs (Na + K)/Al and (Fe + Mg)/Al vs (Na + K)/Al provide a visual guide that readily distinguish unaltered from altered samples. A plot of (Na + K)/Al and (Fe + Mg)/Al on the x-axis against the concentration of trace elements on the y-axis reveals that U, Pb, Mo, Cu, B, Br, Ce, Y, Li, Ni, V and Nd are associated with the most intensely altered samples. The lithogeochemical vectors should aid explorers searching for uranium mineralisation in a prospective basin environment, but exploration must first focus on the characteristics of the basin to assess its mineralisation potential. A holistic model that describes the evolution of the Kombolgie Subgroup from deposition through diagenesis to formation of the uranium deposits in the underlying basement rocks is presented and has application to other basins that are considered prospective for unconformity-related uranium deposits. The model outlines that explorers will need to consider the thickness of the sedimentary pile, its lithological composition relative to depositional setting, the depth to which the sediments were buried during diagenesis and the degree of diagenesis achieved, which may be time dependant, before deciding on the prospectivity of the basin.     

Thermodynamic properties of organic iodine compounds

A critical evaluation has been made of the thermodynamic properties reported in the literature for 43 organic iodine compounds in the solid, liquid, or ideal gas state. These compounds include aliphatic, cyclic and aromatic iodides, iodophenols, iodocarboxylic acids, and acetyl and benzoyl iodides. The evaluation has been made on the basis of carbon number systematics and group additivity relations, which also allowed to provide estimates of the thermodynamic properties of those compounds for which no experimental data were available. Standard molal thermodynamic properties at 25 °C and 1 bar and heat capacity coefficients are reported for 13 crystalline, 29 liquid, and 39 ideal gas organic iodine compounds, which can be used to calculate the corresponding properties as a function of temperature and pressure. Values derived for the standard molal Gibbs energy of formation at 25 °C and 1 bar of these crystalline, liquid, and ideal gas organic iodine compounds have subsequently been combined with either solubility measurements or gas/water partition coefficients to obtain values for the standard partial molal Gibbs energies of formation at 25 °C and 1 bar of 32 aqueous organic iodine compounds. The thermodynamic properties of organic iodine compounds calculated in the present study can be used together with those for aqueous inorganic iodine species to predict the organic/inorganic speciation of iodine in marine sediments and petroleum systems, or in the near- and far-field of nuclear waste repositories.     

Uncertainties of geochemical modeling during CO<Subscript>2</Subscript> sequestration applying batch equilibrium calculations

One of the uncertainties in the field of carbon dioxide capture and storage (CCS) is caused by the parameterization of geochemical models. The application of geochemical models contributes significantly to calculate the fate of the CO₂ after its injection. The choice of the thermodynamic database used, the selection of the secondary mineral assemblage as well as the option to calculate pressure dependent equilibrium constants influence the CO₂ trapping potential and trapping mechanism. Scenario analyses were conducted applying a geochemical batch equilibrium model for a virtual CO₂ injection into a saline Keuper aquifer. The amount of CO₂ which could be trapped in the formation water and in the form of carbonates was calculated using the model code PHREEQC. Thereby, four thermodynamic datasets were used to calculate the thermodynamic equilibria. Furthermore, the equilibrium constants were re-calculated with the code SUPCRT92, which also applied a pressure correction to the equilibrium constants. Varying the thermodynamic database caused a range of 61% in the amount of trapped CO₂ calculated. Simultaneously, the assemblage of secondary minerals was varied, and the potential secondary minerals dawsonite and K-mica were included in several scenarios. The selection of the secondary mineral assemblage caused a range of 74% in the calculated amount of trapped CO₂. Correcting the equilibrium constants with respect to a pressure of 125 bars had an influence of 11% on the amount of trapped CO₂. This illustrates the need for incorporating sensitivity analyses into reaction pathway modeling.     

Two cation exchange models for direct and inverse modelling of solution major cation composition in equilibrium with illite surfaces

Na/K, Na/Ca and Na/Mg exchange isotherms were performed on the fine fraction (<2 μm) of Imt-2 illite samples at a total normality of about 0.005 mol/L in anionic chloride medium. The derived selectivity coefficients for Na/K, Na/Ca and Na/Mg were found to vary as a function of the exchanger composition and compared well with the data collected in the literature for similar experimental conditions. Two models were built to reproduce the data: the first was a multi(2)-site model with constant Gaines and Thomas selectivity coefficients; the second was a one-site model taking into account surface species activity coefficients. The results of the models were in rather good agreement with both our data and literature data. The multi-site model proved to be efficient in predicting the exchanger composition as a function of the Na/Ca/Mg/K concentrations in solution, whereas the one-site model proved to be a better approach to derive the Na/Ca/Mg/K concentrations in solution based on the knowledge of the exchanger composition and the total normality of the solution. The interest of this approach is illustrated by the need for major cation solute concentration predictions in compacted clay for the characterization of nuclear deep disposal host rock repositories.     

An experimental study of bromine behaviour in water-saturated silicic melts

To assess the effect of the melt composition on bromine concentrations in magmas, we have investigated bromide solubility for water-saturated, iron-free silicic melts with variable Na+K/Al and Si/Al molar ratios (albite, haplogranite, rhyolite, and pantellerite). The experiments were performed in rapid quench cold-seal autoclaves over a range of pressure (1, 1.5, and 2 kbar) and temperature (900, 1000, and 1080 °C) with run durations from 5 to 7 days. A series of natural volcanic glasses and melt inclusions hosted in magmatic minerals were analysed together with the synthetic glasses by PIXE (proton-induced X-ray emission). The Br concentrations range from 5360 to 7850 ppm for albite, from 2800 to 3900 ppm for haplogranite, from 4300 to 5900 ppm for rhyolite, and from 9745 to 11,250 ppm for pantellerite. Br concentrations are negatively correlated with pressure in H₂O-saturated silicic melts and vary with (Na+K)/Al molar ratio with a minimum value at the ratio close to unity. Br behaves similarly to chlorine for all of these melt compositions. The bromide solubility is similar in albitic and rhyolitic melts, which implies that D^f/m is nearly the same for both compositions and is applicable for natural rhyolites as suggested in our previous study (Bureau et al., 2000). This means that the volcanic Br contribution to the atmosphere may be significant. In natural obsidian samples and MI hosted in quartz, olivine, and leucite, the Br concentration varies from < 3 to 28 ppm, with the highest concentrations in pantelleritic melts. We attribute the low Br concentrations of natural melts to a low initial abundance of this halogen in the Earth mantle. However, because Br behaves as an incompatible element before water exsolution, our results imply that magmas could contain much more dissolved Br before eruption and water degassing than the few ppm usually measured in volcanic rocks. Br behaviour during magma crystallisation is controlled by its partitioning into the H₂O-rich fluid phase when this occurs. In addition, its potential high solubility in silicate melts makes it a very sensitive chemical tracer of magma contamination by seawater and Br-rich material. This infers that the investigation of Br behaviour in subduction-zone samples may help for a better understanding of volatiles cycling between the Earth reservoirs.     

The formation of metastable aluminosilicates in the Al-Si-H2O system: Results from solution chemistry and solid-state NMR spectroscopy

We present the results of a series of experiments designed to probe the interactions between Al and the amorphous silica surface as a function of thermodynamic driving forces. The results from ²⁷Al single pulse magic angle spinning (SP/MAS) and ²⁷Al{¹H} rotational echo double resonance (REDOR) allow us to identify the reaction products and constrain their structure. In all cases, despite low Al and Si concentrations we observe the formation of metastable aluminosilicates. Results from low temperature experiments indicate that despite thermodynamic driving forces for the formation of gibbsite we observe the precipitation of separate octahedrally coordinated Al (Al^[6]) and tetrahedrally coordinated Al (Al^[4]) silicate phases. At higher temperatures the Al^[4] silicate phase dominates the speciation. Structural models derived from the NMR data are also proposed, and the results are discussed as they relate to previous work on Al/Si cycling.     

Chemical composition of pargasite and hornblende in low to High grade metamorphic rocks of the Rhodope zone,Xanthi, Greece

Summary The chemistry of amphiboles from schists, quartzofeldspathic gneisses and migmatites ranging in metamorphic grade from greenschist to amphibolite facies has been determined by electron microprobe. Intercalated amphibolites suggest that some of the rocks retrograded from the eclogite stability field; others were never metamorphosed above greenschist facies. Rocks which contain other mineralogical evidence for an original high pressure assemblage have amphiboles with high Na/K, low Fe and relatively low Ti. Other high-grade rocks contain amphibole of broadly pargasitic composition. The pargasites from more Ca-rich bulk compositions have less substitution of Na for Ca in the M4 site than do those from Ca-poor bulk compositions. A lower grade assemblage of amphiboles ranges from hornblende through actinolitic hornblende to actinolite; this is retrograde in the gneisses and migmatites, but may be prograde in the schists. In contrast, the high-grade assemblage shows almost constant high K with variable Na and quite different trends for edenite-type substitution (^IVAl variation with A site occupancy) and variation of^IVAl with Fe/(Fe + Mg) and with Ti.

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Chemische Zusammensetzung von Pargasit und Hornblende in niedrig- bis hoch-gradig metamorphen Gesteinen der Rhodope-Zone, Xanthi, Griechenland

Zusammenfassung Die Chemische Zusammensetzung von Amphibolen aus Schiefern, Quarz-Feldspat-Gneisen, und Migmatiten, deren metamorpher Grad von Grünschiefer- bis zur Amphibolitfazies reicht, wurde mit der Elektronenstrahl-Mikrosonde bestimmt. Zwischengeschaltete Amphibolite legen die Vermutung nahe, daß einige der Gesteine durch retrograde Metamorphose aus dem Eklogit-Stabilitatsfeld hervorgegangen sind; andere jedoch hatten niemals in ihrer Entwicklung einen höheren Grad als den der Grünschie-ferfazies erreicht. Gesteine, die andere mineralogische Hinweise für eine ursprungliche Hochdruck-Paragenese führen, enthalten Amphibole mit hohem Na/K, niedrigen Eisen und relativ niedrigen Ti. Andere high-grade Gesteine enthalten Amphibol von pargasitischer Zusammensetzung. Die Pargasite aus mehr Kalzium-reichen Gesteinen zeigen geringere Substitution von Natrium für Kalzium an den M4 Plätzen als jene aus Kalzium-armen Gesteinen. Eine niedriger-gradige Paragenese von Amphibolen umfaßt Zusammensetzungen von Hornblende über aktinolitische Hornblende bis zu Aktinolit; diese ist in den Gneisen und Migmatiten retrograd, durfte in den Schiefern jedoch prograd sein. Im Gegensatz dazu zeigt die hochgradige Paragenese fast durchwegs konstant hohe Kalium-Gehalte mit variablem Natrium und einen anderen Trend für Edenit-artige Substitution (^IVAl Variation mit Besetzung der A Plätze) und eine Variation von^IVAl mit Fe/(Fe + Mg) und mit Ti.

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With 4 Figures     

Amorphous silica solubilities IV. Behavior in pure water and aqueous sodium chloride,sodium sulfate,magnesium chloride,and magnesium sulfate solutions up to 350°C

Solubilities of amorphous silica were determined in separate aqueous solutions of sodium chloride, sodium sulfate, magnesium chloride, and magnesium sulfate at temperatures up to 350°C. These salts, of strong interest in hydrothermal oceanography and geothermal energy, generally ranged in concentration from zero to saturation. Solubilities in the sodium chloride solutions followed closely earlier observed decreases in sodium nitrate solutions at high temperatures.Amorphous silica solubilities were depressed most by magnesium chloride, followed by magnesium sulfate, and less by sodium chloride. As the temperature rose the relative decrease in solubility caused by added salt became smaller. Surprisingly, sodium sulfate solutions, showing little effect at 25°C, sharply raised the solubility as the temperature increased to 350°C. Plots of the logarithms of derived activity coefficients against molalities of added salt gave approximately straight lines. These plots allow simple predictions of amorphous silica solubility in single salt solutions.