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1.
This study used batch reactors to quantify the mechanisms and rates of calcite dissolution in the presence and absence of a single heterotrophic bacterial species (Burkholderia fungorum). Experiments were conducted at T = 28°C and ambient pCO2 over time periods spanning either 21 or 35 days. Bacteria were supplied with minimal growth media containing either glucose or lactate as a C source, NH4+ as an N source, and H2PO4− as a P source. Combining stoichiometric equations for microbial growth with an equilibrium mass-balance model of the H2O-CO2-CaCO3 system demonstrates that B. fungorum affected calcite dissolution by modifying pH and alkalinity during utilization of ionic N and C species. Uptake of NH4+ decreased pH and alkalinity, whereas utilization of lactate, a negatively charged organic anion, increased pH and alkalinity. Calcite in biotic glucose-bearing reactors dissolved by simultaneous reaction with H2CO3 generated by dissolution of atmospheric CO2 (H2CO3 + CaCO3 → Ca2+ + 2HCO3−) and H+ released during NH4+ uptake (H+ + CaCO3 → Ca2+ + HCO3−). Reaction with H2CO3 and H+ supplied ∼45% and 55% of the total Ca2+ and ∼60% and 40% of the total HCO3−, respectively. The net rate of microbial calcite dissolution in the presence of glucose and NH4+ was ∼2-fold higher than that observed for abiotic control experiments where calcite dissolved only by reaction with H2CO3. In lactate bearing reactors, most H+ generated by NH4+ uptake reacted with HCO3− produced by lactate oxidation to yield CO2 and H2O. Hence, calcite in biotic lactate-bearing reactors dissolved by reaction with H2CO3 at a net rate equivalent to that calculated for abiotic control experiments. This study suggests that conventional carbonate equilibria models can satisfactorily predict the bulk fluid chemistry resulting from microbe-calcite interactions, provided that the ionic forms and extent of utilization of N and C sources can be constrained. Because the solubility and dissolution rate of calcite inversely correlate with pH, heterotrophic microbial growth in the presence of nonionic organic matter and NH4+ appears to have the greatest potential for enhancing calcite weathering relative to abiotic conditions.  相似文献   

2.
The interaction of Pu3+ bearing solutions with the muscovite (0 0 1) basal plane is explored using a combination of ex-situ approaches including alpha-counting, to determine the Pu3+ adsorption isotherm, and X-ray reflectivity (XR) and resonant anomalous X-ray reflectivity (RAXR), to probe the interfacial structure and Pu-specific distribution, respectively. Pu uptake to the muscovite (0 0 1) surface from Pu3+ solutions in a 0.1 M NaClO4 background electrolyte at pH 3 follows an approximate Langmuir isotherm with an apparent adsorption constant, Kapp = 5 × 104 M−1, and with a maximum coverage that is consistent with the amount needed to fully compensate the surface charge by trivalent Pu. The XR results show that the muscovite surface reacted with a 10−3 M Pu3+ solution (at pH 3 with 0.1 M NaClO4) and dried in the ambient environment, maintains a 30-40 Å thick layer, indicating the presence of a residual hydration layer (possibly including adventitious carbon). The RAXR results indicate that Pu sorbs on the muscovite surface with an intrinsically broad distribution with an average height of 18 Å, substantially larger than heights expected for any specifically adsorbed inner- or outer-sphere complexes. These results are discussed in the context of recent studies of cation adsorption trends on muscovite and the possible roles of Pu hydrolysis species in controlling the Pu-muscovite interactions.  相似文献   

3.
Adsorption of Rb+ and Sr2+ at the orthoclase (0 0 1)-solution interface is probed with high-resolution X-ray reflectivity and resonant anomalous X-ray reflectivity. Specular X-ray reflectivity data for orthoclase in contact with 0.01 m RbCl solution at pH 5.5 reveal a systematic increase in electron density adjacent to the mineral surface with respect to that observed in contact with de-ionized water (DIW). Quantitative analysis indicates that Rb+ adsorbs at a height of 0.83 ± 0.03 Å with respect to the bulk K+ site with a nominal coverage of 0.72 ± 0.10 ions per surface unit mesh (55.7 Å2). These results are consistent with an ion-exchange reaction in which Rb+ occupies an inner-sphere adsorption (IS) site. In contrast, X-ray reflectivity data for orthoclase in contact with 0.01 m Sr(NO3)2 solution at pH 5.3 reveal few significant changes with respect to DIW. Resonant anomalous X-ray reflectivity was used to probe Sr2+ adsorption and to image its vertical distribution. This element-specific measurement reveals that Sr2+ adsorbs with a total coverage of 0.37 ± 0.02 ions per surface unit mesh, at a substantially larger height (3.28 ± 0.05 Å) than found for Rb+, and with a relatively broad density distribution (having a root-mean-square width of 1.88 ± 0.08 Å for a single-peak model), implying that Sr2+ adsorbs primarily as a fully-hydrated outer-sphere (OS), species. Comparison to a two-height model suggests that 13 ± 5% of the adsorbed Sr2+ may be present as an IS species. This partitioning implies a ∼5 kJ/mol difference in free energy between the IS and OS Sr2+ on orthoclase. Differences in the partitioning of Sr2+ between IS and OS species for orthoclase (0 0 1) and muscovite (0 0 1) suggest control by the geometry of the IS adsorption site. Results for the OS distribution are compared to predictions of the Poisson-Boltzmann equation in the strong coupling regime, which predicts an intrinsically narrow vertical diffuse ion distribution; the OS distribution might thus be thought of as the diffuse ion profile in the limit of high surface charge.  相似文献   

4.
This study used batch reactors to characterize the mechanisms and rates of elemental release (Al, Ca, K, Mg, Na, F, Fe, P, Sr, and Si) during interaction of a single bacterial species (Burkholderia fungorum) with granite at T = 28 °C for 35 days. The objective was to evaluate how actively metabolizing heterotrophic bacteria might influence granite weathering on the continents. We supplied glucose as a C source, either NH4 or NO3 as N sources, and either dissolved PO4 or trace apatite in granite as P sources. Cell growth occurred under all experimental conditions. However, solution pH decreased from ∼7 to 4 in NH4-bearing reactors, whereas pH remained near-neutral in NO3-bearing reactors. Measurements of dissolved CO2 and gluconate together with mass-balances for cell growth suggest that pH lowering in NH4-bearing reactors resulted from gluconic acid release and H+ extrusion during NH4 uptake. In NO3-bearing reactors, B. fungormum likely produced gluconic acid and consumed H+ simultaneously during NO3 utilization.Over the entire 35-day period, NH4-bearing biotic reactors yielded the highest release rates for all elements considered. However, chemical analyses of biomass show that bacteria scavenged Na, P, and Sr during growth. Abiotic control reactors followed different reaction paths and experienced much lower elemental release rates compared to biotic reactors. Because release rates inversely correlate with pH, we conclude that proton-promoted dissolution was the dominant reaction mechanism. Solute speciation modeling indicates that formation of Al-F and Fe-F complexes in biotic reactors may have enhanced mineral solubilities and release rates by lowering Al and Fe activities. Mass-balances further reveal that Ca-bearing trace phases (calcite, fluorite, and fluorapatite) provided most of the dissolved Ca, whereas more abundant phases (plagioclase) contributed negligible amounts. Our findings imply that during the incipient stages of granite weathering, heterotrophic bacteria utilizing glucose and NH4 only moderately elevate silicate weathering reactions that consume atmospheric CO2. However, by enhancing the dissolution of non-silicate, Ca-bearing trace minerals, they could contribute to high Ca/Na ratios commonly observed in granitic watersheds.  相似文献   

5.
The structure of silicate melts in the system Na2O·4SiO2 saturated with reduced C-O-H volatile components and of coexisting silicate-saturated C-O-H solutions has been determined in a hydrothermal diamond anvil cell (HDAC) by using confocal microRaman and FTIR spectroscopy as structural probes. The experiments were conducted in-situ with the melt and fluid at high temperature (up to 800 °C) and pressure (up to 1435 MPa). Redox conditions in the HDAC were controlled with the reaction, Mo + H2O = MoO2 + H2, which is slightly more reducing than the Fe + H2O = FeO + H2 buffer at 800 °C and less.The dominant species in the fluid are CH4 + H2O together with minor amounts of molecular H2 and an undersaturated hydrocarbon species. In coexisting melt, CH3 - groups linked to the silicate melt structure via Si-O-CH3 bonding may dominate and possibly coexists with molecular CH4. The abundance ratio of CH3 - groups in melts relative to CH4 in fluids increases from 0.01 to 0.07 between 500 and 800 °C. Carbon-bearing species in melts were not detected at temperatures and pressures below 400 °C and 730 MPa, respectively. A schematic solution mechanism is, Si-O-Si + CH4?Si-O-CH3+H-O-Si. This mechanism causes depolymerization of silicate melts. Solution of reduced (C-O-H) components will, therefore, affect melt properties in a manner resembling dissolved H2O.  相似文献   

6.
Fluid inclusions were synthesized in a piston-cylinder apparatus under mineral-buffered conditions over a range of Cl concentration (0.29 to 11.3 mol kg−1), temperature (525 to 725 °C), and pressure (0.3 to 1.7 GPa). All fluids were buffered by the mineral assemblage native copper + cuprite + talc + quartz. In situ fluid composition was determined by analysing individual fluid inclusions by LA-ICPMS and independently analysing the quench solution. The solubility data provide basic information necessary to model the high temperature behaviour of Cu in magmatic-hydrothermal systems. Copper concentrations up to ∼15 wt% were measured at 630 °C and 0.34 GPa. These results give an upper limit for Cu in natural fluids and support field-based observations of similar high Cu concentrations in fluids at near-magmatic conditions. Experimental evidence indicates that Cu+ may form neutral chloride complexes with the general stoichiometry with n up to 4, though n ? 2 is typical for the majority of the experimental conditions. At high pressure (>∼0.5 GPa) there is evidence that hydroxide species, e.g., CuOH0, become increasingly important and may predominate over copper(I)-chloride complexes. The roles of fluid mixing, cooling and decompression in ore-forming environments are also discussed.  相似文献   

7.
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.  相似文献   

8.
Stepped heating and crushing experiments have been used to investigate the noble gas and halogen degassing behaviour of quartz in detail. Samples with diverse character were selected from the Eloise and Osborne, Iron Oxide Copper Gold (IOCG) ore deposits, and the Railway Fault, 13 km south of the Mt Isa Mine, in the Proterozoic Mt Isa Inlier of northeast Australia. Quartz has been shown to have a bimodal degassing profile. The first degassing mode at temperatures of <700 °C is caused by thermally induced mechanical decrepitation of fluid inclusions. Changes in the Br/Cl, I/Cl, Ar/Cl and 40Ar/36Ar composition of gas released at different temperatures up to 700 °C can be related to the decrepitation of different types of fluid inclusion observed by microthermometry. These variations with temperature permit deconvolution of the complex fluid inclusion assemblages associated with the IOCG samples; the ultra high salinity, multi solid (MS) and liquid-vapour-daughter (LVD) fluid inclusions, with a predominantly primary origin, decrepitate at higher temperatures than lower salinity liquid-vapour (LV) and monophase (M) fluid inclusions that have a predominantly secondary origin. Three of the IOCG samples have primary MS and LVD fluid inclusions characterized by molar Br/Cl values of between 0.25 × 10−3 and 0.66 × 10−3, I/Cl between 0.37 × 10−6 and 5.0 × 10−6, 40Ar/36Ar values of <1000 and low 36Ar concentrations of 0.7-1.0 × 10−6 cm3 cm−3H2O. These low values are most easily explained by the involvement of halite dissolution water in IOCG genesis. One of the IOCG samples has Br/Cl of 1.3-2.0 × 10−3 and I/Cl of 10 × 10−6, similar to juvenile magmatic fluids in Phanerozoic Porphyry Copper Deposits. This sample also has a higher 36Ar concentration of 3.5 × 10−6 cm3 cm−3H2O and a slightly elevated 40Ar/36Ar of 2236. Step heating reveals limited and non-systematic variation within the more homogenous population of LV fluid inclusions from the Railway Fault. The samples have mean values of 8.1 × 10−3 for Br/Cl; 9.4-12 × 10−6 for I/Cl; <2000 for 40Ar/36Ar; and 4.7-4.8 × 10−6 cm3 cm−3H2O for 36Ar concentration. The Br/Cl values are similar to those previously reported for basinal brines present in silicic alteration at the Mt Isa Mine and the additional data can be explained by interaction of such a bittern brine with fine grained sedimentary rocks in the sub-surface. The second mode of quartz degassing occurs between 1200 and 1450 °C and releases a greater volume of gas than the first degassing mode. Several lines of evidence, including microscope observations, indicate that the gas released at high temperature is also from the fluid inclusion reservoir. However, its release may be triggered by a metastable phase transition of quartz (∼1200 °C) and caution is required in interpretation of the fluid compositions obtained at these temperatures. The data provide an improved understanding of fluid inclusion decrepitation behaviour that is different to that obtained in lower temperatures experiments designed by other workers to investigate H-isotope fractionation.  相似文献   

9.
The structure of H2O-saturated silicate melts and of silicate-saturated aqueous solutions, as well as that of supercritical silicate-rich aqueous liquids, has been characterized in-situ while the sample was at high temperature (to 800 °C) and pressure (up to 796 MPa). Structural information was obtained with confocal microRaman and with FTIR spectroscopy. Two Al-bearing glasses compositionally along the join Na2O•4SiO2-Na2O•4(NaAl)O2-H2O (5 and 10 mol% Al2O3, denoted NA5 and NA10) were used as starting materials. Fluids and melts were examined along pressure-temperature trajectories of isochores of H2O at nominal densities (from PVT properties of pure H2O) of 0.85 g/cm3 (NA10 experiments) and 0.86 g/cm3 (NA5 experiments) with the aluminosilicate + H2O sample contained in an externally-heated, Ir-gasketed hydrothermal diamond anvil cell.Molecular H2O (H2O°) and OH groups that form bonds with cations exist in all three phases. The OH/H2O° ratio is positively correlated with temperature and pressure (and, therefore, fugacity of H2O, fH2O) with (OH/H2O°)melt > (OH/H2O°)fluid at all pressures and temperatures. Structural units of Q3, Q2, Q1, and Q0 type occur together in fluids, in melts, and, when outside the two-phase melt + fluid boundary, in single-phase liquids. The abundance of Q0 and Q1 increases and Q2 and Q3 decrease with fH2O. Therefore, the NBO/T (nonbridging oxygen per tetrahedrally coordination cations), of melt is a positive function of fH2O. The NBO/T of silicate in coexisting aqueous fluid, although greater than in melt, is less sensitive to fH2O.The melt structural data are used to describe relationships between activity of H2O and melting phase relations of silicate systems at high pressure and temperature. The data were also combined with available partial molar configurational heat capacity of Qn-species in melts to illustrate how these quantities can be employed to estimate relationships between heat capacity of melts and their H2O content.  相似文献   

10.
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 NaSi3O6.5 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.  相似文献   

11.
Hydrothermal experiments were conducted to determine the partitioning of Cl between rhyolitic to rhyodacitic melts, apatite, and aqueous fluid(s) and the partitioning of F between apatite and these melts at ca. 200 MPa and 900-924 °C. The number of fluid phases in our experiments is unknown; they may have involved a single fluid or vapor plus saline liquid. The partitioning behavior of Cl between apatite and melt is non-Nernstian and is a complex function of melt composition and the Cl concentration of the system. Values of DClapat/melt (wt. fraction of: Cl in apatite/Cl in melt) vary from 1 to 4.5 and are largest when the Cl concentrations of the melt are at or near the Cl-saturation value of the melt. The Cl-saturation concentrations of silicate melts are lowest in evolved, silica-rich melts, so with elevated Cl concentrations in a system and with all else equal, the maximum values of DClapat/melt occur with the most felsic melt. In contrast, values of DFapat/melt range from 11 to 40 for these felsic melts, and many of these are an order of magnitude greater than those applying to basaltic melts at 200 MPa and 1066-1150 °C. The Cl concentration of apatite is a simple and linear function of the concentration of Cl in fluid. Values of DClfluid/apat for these experiments range from 9 to 43, and some values are an order of magnitude greater than those determined in 200-MPa experiments involving basaltic melts at 1066-1150 °C.In order to determine the concentrations and interpret the behavior of volatile components in magmas, the experimental data have been applied to the halogen concentrations of apatite grains from chemically evolved rocks of Augustine volcano, Alaska; Krakatau volcano, Indonesia; Mt. Pinatubo, Philippines; Mt. St. Helens, Washington; Mt. Mazama, Oregon; Lascar volcano, Chile; Santorini volcano, Greece, and the Bishop Tuff, California. The F concentrations of these magmas estimated from apatite-melt equilibria range from 0.06 to 0.12 wt% and are generally equivalent to the concentrations of F determined in the melt inclusions. In contrast, the Cl concentrations of the magmas estimated from apatite-melt equilibria (e.g., ca. 0.3-0.9 wt%) greatly exceed those determined in the melt inclusions from all of these volcanic systems except for the Bishop Tuff where the agreement is good. This discrepancy in estimated Cl concentrations of melt could result from several processes, including the hypothesis that the composition of apatite represents a comparatively Cl-enriched stage of magma evolution that precedes melt inclusion entrapment prior to the sequestration of Cl by coexisting magmatic aqueous and/or saline fluid(s).  相似文献   

12.
Rb and Sr partitioning between haplogranitic melts and aqueous solutions   总被引：2，自引：0，他引：2  
Rubidium and strontium partitioning experiments between haplogranitic melts and aqueous fluids (water or 1.16-3.56 m (NaCl + KCl) ± HCl) were conducted at 750-950 °C and 0.2-1.4 GPa to investigate the effects of melt and fluid composition, pressure, and temperature. In addition, we studied if the applied technique (rapid and slow quench, and in-situ determination of trace element concentration in the fluid) has a bearing on the obtained data. There is good agreement of the data from different techniques for chloridic solutions, whereas back reactions between fluid and melt upon cooling have a significant effect on results from the experiments with water.The Rb fluid-melt partition coefficient shows no recognizable dependence on melt composition and temperature.For chloridic solutions, it is ∼0.4, independent of pressure. In experiments with water, it is one to two orders of magnitude lower and increases with pressure. The strontium fluid-melt partition coefficient does not depend on temperature. It increases slightly with pressure in Cl free experiments. In chloridic fluids, there is a sharp increase in the Sr partition coefficient with the alumina saturation index (ASI) from 0.003 at an ASI of 0.8 to a maximum of 0.3 at an ASI of 1.05. At higher ASI, it decreases slightly to 0.2 at an ASI of 1.6. It is one to two orders of magnitude higher in chloridic fluids compared to those found in H2O experiments. The Rb/Sr ratio in non-chloridic solutions in equilibrium with metaluminous melts increases with pressure, whereas the Rb/Sr ratio in chloridic fluids is independent of pressure and decreases with fluid salinity.The obtained fluid-melt partition coefficients are in good agreement with data from natural cogenetic fluid and melt inclusions. Numerical modeling shows that although the Rb/Sr ratio in the residual melt is particularly sensitive to the degree of fractional crystallization, exsolution of a fluid phase, and associated fluid-melt partitioning is not a significant factor controlling Rb and Sr concentrations in the residual melt during crystallization of most granitoids.  相似文献   

13.
The structure and mechanism of cation sorption at the (0 0 1) muscovite-water interface were investigated in 0.01 and 0.5 m KCl, CsCl, and CaCl2 and 0.01 m BaCl2 solutions at slightly acidic pH by high-resolution X-ray reflectivity. Structural relaxations of atom positions in the 2M1 muscovite were small (?0.07 Å) and occurred over a distance of 30 to 40 Å perpendicular to the interface. Cations in all solutions were sorbed dominantly in the first and second solution layers adjacent to the mineral surface. The derived heights of the first solution layer in KCl and CsCl solutions, 1.67(6)-1.77(7) and 2.15(9)-2.16(2) Å, respectively, differ in magnitude by the approximate difference in crystallographic radii between K and Cs, and correspond closely to the interlayer cation positions in bulk K- and Cs-mica structures. The first solution layer heights in CaCl2 and BaCl2 solutions, 2.46(5)-2.56(11) and 2.02(5) Å, respectively, differ in a sense opposite to that expected based on crystallographic or hydrated radii of the divalent cations. The derived ion heights in all solutions imply that there is no intercalated water layer between the first solution layer and the muscovite surface. Molecular compositions were assigned to the first two solution layers in the electron density profiles using models that constrain the number density of sorbed cations, water molecules, and anions by considering the permanent negative charge of the muscovite and average solution density. The models result in partial charge balance (at least 50%) by cations sorbed in the first two layers in the 0.01 m solutions and approximately full charge balance in the 0.5 m solutions. Damped oscillations of model water density away from the first two solution layers agree with previous X-ray reflectivity results on the muscovite (0 0 1) surface in pure water.  相似文献   

14.
The solubility of molybdenum (Mo) was determined at temperatures from 500 °C to 800 °C and 150 to 300 MPa in KCl-H2O and pure H2O solutions in cold-seal experiments. The solutions were trapped as synthetic fluid inclusions in quartz at experimental conditions, and analyzed by laser ablation inductively coupled plasma mass spectrometry (LA ICPMS).Mo solubilities of 1.6 wt% in the case of KCl-bearing aqueous solutions and up to 0.8 wt% in pure H2O were found. Mo solubility is temperature dependent, but not pressure dependent over the investigated range, and correlates positively with salinity (KCl concentration). Molar ratios of ∼1 for Mo/Cl and Mo/K are derived based on our data. In combination with results of synchrotron X-ray absorption spectroscopy of individual fluid inclusions, it is suggested that Mo-oxo-chloride complexes are present at high salinity (>20 wt% KCl) and ion pairs at moderate to low salinity (<11 wt% KCl) in KCl-H2O aqueous solutions. Similarly, in the pure H2O experiments molybdic acid is the dominant species in aqueous solution. The results of these hydrothermal Mo experiments fit with earlier studies conducted at lower temperatures and indicate that high Mo concentrations can be transported in aqueous solutions. Therefore, the Mo concentration in aqueous fluids seems not to be the limiting factor for ore formation, whereas precipitation processes and the availability of sulfur appear to be the main controlling factors in the formation of molybdenite (MoS2).  相似文献   

15.
A thermodynamic model is presented to calculate methane solubility, liquid phase density and gas phase composition of the H2O-CH4 and H2O-CH4-NaCl systems from 273 to 523 K (possibly up to 573 K), from 1 to 2000 bar and from 0 to 6 mol kg−1 of NaCl with experimental accuracy. By a more strict theoretical approach and using updated experimental data, this model made substantial improvements over previous models: (1) the accuracy of methane solubility in pure water in the temperature range between 273 and 283 K is increased from about 10% to about 5%, but confirms the accuracy of the Duan model [Duan Z., Moller N., Weare J.H., 1992a. Prediction of methane solubilities in natural waters to high ionic strength from 0 to 250 °C and from 0 to 1600 bar. Geochim. Cosmochim. Acta56, 1451-1460] above 283 K up to 2000 bar; (2) the accuracy of methane solubility in the NaCl aqueous solutions is increased from >12% to about 6% on average from 273 K and 1 bar to 523 K and 2000 bar; (3) this model is able to calculate water content in the gas phase and liquid phase density, which cannot be calculated by previous models; and (4) it covers a wider range of temperature and pressure space. With a simple approach, this model is extended to predict CH4 solubility in other aqueous salt solutions containing Na+, K+, Mg2+, Ca2+, Cl− and , such as seawater and geothermal brines, with excellent accuracy. This model is also able to calculate homogenization pressure of fluid inclusions (CH4-H2O-NaCl) and CH4 solubility in water at gas-liquid-hydrate phase equilibrium. A computer code is developed for this model and can be downloaded from the website: www.geochem-model.org/programs.htm.  相似文献   

16.
Realistic simulations of fluid flow in geologic systems have severely been hampered by the lack of a consistent formulation for fluid properties for binary salt-water fluids over the temperature-pressure-composition ranges encountered in the Earth’s crust. As the first of two companion studies, a set of correlations describing the phase stability relations in the system H2O-NaCl is developed. Pure water is described by the IAPS-84 equation of state. New correlations comprise the vapor pressure of halite and molten NaCl, the NaCl melting curve, the composition of halite-saturated liquid and vapor, the pressure of vapor + liquid + halite coexistence, the temperature-pressure and temperature-composition relations for the critical curve, and the compositions of liquid and vapor on the vapor + liquid coexistence surface. The correlations yield accurate values for temperatures from 0 to 1000 °C, pressures from 0 to 5000 bar, and compositions from 0 to 1 XNaCl (mole fraction of NaCl). To facilitate their use in fluid flow simulations, the correlations are entirely formulated as functions of temperature, pressure and composition.  相似文献   

17.
Summary The granites of the Sistema Central Espanol are richer in ammonium than those of most other regions, and have a mean NH4 + content of 84 ppm (range = 1–243 ppm). Among the possible causes for the high level of ammonium, a high proportion of organic-rich pelitic protolith and reducing conditions during anatexis are considered to be the most significant. The behaviour of the ammonium ion during magmatic differentiation is discussed by reference to its distribution in the Pedrobernardo layered intrusion: ammonium is depleted in the final liquid fraction, but there is no relative fractionation of NH4 + and K+. The depletion of the melt in NH4 + during crystallization is attributed to its removal by biotite and to a lesser extent by K-feldspar. The behaviour of the ammonium ion during anatexis is discussed with reference to the Peña Negra migmatite complex. It is shown that large amounts of NH4 + are present in these high grade metamorphic rocks, and that NH4 + is preferentially partitioned into the restite fraction during partial melting. These relationships are attributed to the preferential incorporation of NH4 + into potassic host minerals in the order: biotite > muscovite > K-feldspar.
Ammonium in Zentralspanischen Graniten, und das Verhalten des Ammonium-Ions während Anatexis und fraktionierter Kristallisation
Zusammenfassung Die Granite des Sistema Central Espanol sind reicher an Ammonium als die der meisten anderen Regionen, und haben einen durchschnittlichen NH4 + Gehalt von 84 ppm (von 1-243 ppm). Der hohe Ammoniumgehalt könme auf einen hohen Anteil peiitischer Ausgangsgesteine, die reich an organischen Material sind, and auf reduzierende Bedingungen während der Anatexis zurückgehen. Das Verhalten des Ammonium-Ions während magmatischer Differentiation wind in Hinblick seiner Verteilung in der geschichteten Intrusion von Pedrobernardo diskutiert: Ammonium ist in der finalen Schmelzfraktion angereichert, aber es gibt keine relative Fraktionierung von NH4 + and K+. Die Verarmung der Schmelze an NH4 + wahrend der Kristallisation geht darauf zurück, daß NH4 + von Biotit and in einem geringen Ausmaß von K-Feldspat aufgenommen wird. Das Verhalten des Ammonium-Ions während der Anatexis wird am Peña Negra Migmatit-Komplex diskutiert. Es zeigt rich, daß große Mengen von NH4 + in diesen hochgradig metamorphen Gesteinen vorkommen, and das NH4 + während teilweiser Aufschmelzung vorzugsweise in der Restit-Fraktion angereichert wird. Diese Beziehungen gehen auf die vorzugsweise Aufnahme von NH4 + in Kali-führenden Gastmineralen zurück, and zwar in folgender Ordnung: Biotit > Muskovit > K-Feldspat.

With 5 Figures  相似文献   

18.
The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K1.38Na0.05)(Al2.87Mg0.46Fe3+0.39Fe2+0.28Ti0.07)[Si7.02Al0.98]O20(OH)4 was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H2SO4) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K+ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na+ from the solution and K+ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower RAl (dissolution rate calculated from steady state Al release) than RSi (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.  相似文献   

19.
The position of the Raman methane (CH4) symmetric stretching band (ν1) over the range 1-650 bar and 0.3-22 °C has been determined using a high-pressure optical cell mounted on a Raman microprobe. Two neon emission lines that closely bracket the CH4 band were collected simultaneously with each CH4 spectrum. The peak position was determined after least squares fitting using a summed Gaussian-Lorentzian method, resulting in a precision of ≈±0.02 cm−1 in peak position determination. The CH4ν1 band position shifts to lower wave number with increasing pressure. At a given pressure, the band shifts to lower wave number with decreasing temperature, and the magnitude of the temperature shift increases with increasing pressure. The relationship between the Raman CH4ν1 band position and temperature and pressure determined here may be used to estimate the internal pressure in natural or synthetic CH4-bearing fluid inclusions. This information, in turn, may be used to determine the density of pure CH4 fluid inclusions and the salinity of CH4-bearing aqueous inclusions.  相似文献   

20.
Jarosite is an important mineral on Earth, and possibly on Mars, where it controls the mobility of iron, sulfate and potentially toxic metals. Atomistic simulations have been used to study the incorporation of Al3+, and the M2+ impurities Cd, Cu and Zn, in the (0 1 2) and (0 0 1) surfaces of jarosite. The calculations show that the incorporation of Al on an Fe site is favorable on all surfaces in which terminal Fe ions are exposed, and especially on the (0 0 1) [Fe3(OH)3]6+ surface. Incorporation of Cd, Cu or Zn on a K site balanced by a K vacancy is predicted to stabilize the surfaces, but calculated endothermic solution energies and the high degree of distortion of the surfaces following incorporation suggest that these substitutions will be limited. The calculations also suggest that incorporation of Cd, Cu and Zn on an Fe site balanced by an OH vacancy, or by coupled substitution on both K and Fe sites, is unfavorable, although this might be compensated for by growth of a new layer of jarosite or goethite, as predicted for bulk jarosite. The results of the simulations show that surface structure will exert an influence on uptake of impurities in the order Cu > Cd > Zn, with the most favorable surfaces for incorporation being (0 1 2) [KFe(OH)4]0 and (0 0 1) [Fe3(OH)3]6+.  相似文献   

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