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Bjorn O. Mysen 《Geochimica et cosmochimica acta》2007,71(7):1820-1834
Solubility and solution mechanisms of H2O in depolymerized melts in the system Na2O-Al2O3-SiO2 were deduced from spectroscopic data of glasses quenched from melts at 1100 °C at 0.8-2.0 GPa. Data were obtained along a join with fixed nominal NBO/T = 0.5 of the anhydrous materials [Na2Si4O9-Na2(NaAl)4O9] with Al/(Al+Si) = 0.00-0.25. The H2O solubility was fitted to the expression, XH2O=0.20+0.0020fH2O-0.7XAl+0.9(XAl)2, where XH2O is the mole fraction of H2O (calculated with O = 1), fH2O the fugacity of H2O, and XAl = Al/(Al+Si). Partial molar volume of H2O in the melts, , calculated from the H2O-solulbility data assuming ideal mixing of melt-H2O solutions, is 12.5 cm3/mol for Al-free melts and decreases linearly to 8.9 cm3/mol for melts with Al/(Al+Si) ∼ 0.25. However, if recent suggestion that is composition-independent is applied to constrain activity-composition relations of the hydrous melts, the activity coefficient of H2O, , increases with Al/(Al+Si).Solution mechanisms of H2O were obtained by combining Raman and 29Si NMR spectroscopic data. Degree of melt depolymerization, NBO/T, increases with H2O content. The rate of NBO/T-change with H2O is negatively correlated with H2O and positively correlated with Al/(Al+Si). The main depolymerization reaction involves breakage of oxygen bridges in Q4-species to form Q2 species. Steric hindrance appears to restrict bonding of H+ with nonbridging oxygen in Q3 species. The presence of Al3+ does not affect the water solution mechanisms significantly. 相似文献
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Bjorn O. Mysen Kathryn Kumamoto Marilyn L. Fogel 《Geochimica et cosmochimica acta》2011,75(20):6183-6199
Solubility and solution mechanisms in silicate melts of oxidized and reduced C-bearing species in the C-O-H system have been determined experimentally at 1.5 GPa and 1400 °C with mass spectrometric, NMR, and Raman spectroscopic methods. The hydrogen fugacity, fH2, was controlled in the range between that of the iron-wüstite-H2O (IW) and the magnetite-hematite-H2O (MH) buffers. The melt polymerization varied between those typical of tholeiitic and andesitic melts.The solubility of oxidized (on the order of 1-2 wt% as C) and reduced carbon (on the order of 0.15-0.35 wt% as C) is positively correlated with the NBO/Si (nonbridging oxygen per silicon) of the melt. At given NBO/Si-value, the solubility of oxidized carbon is 2-4 times greater than under reducing conditions. Oxidized carbon dioxide is dissolved as complexes, whereas the dominant reduced species in melts are CH3-groups forming bonds with Si4+ together with molecular CH4. Formation of complexes results in silicate melt polymerization (decreasing NBO/Si), whereas solution of reduced carbon results in depolymerization of melts (increasing NBO/Si).Redox melting in the Earth’s interior has been explained with the aid of the different solution mechanisms of oxidized and reduced carbon in silicate melts. Further, effects of oxidized and reduced carbon on melt viscosity and on element partitioning between melts and minerals have been evaluated from relationships between melt polymerization and dissolved carbon combined with existing experimental data that link melt properties and melt polymerization. With total carbon contents in the melts on the order of several mol%, mineral/melt element partition coefficients and melt viscosity can change by several tens to several hundred percent with variable redox conditions in the range of the Earth’s deep crust and upper mantle. 相似文献
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Bjorn O. Mysen 《Geochimica et cosmochimica acta》2007,71(22):5500-5513
The influence on olivine/melt transition metal (Mn, Co, Ni) partitioning of substitution in the tetrahedral network of silicate melt structure has been examined at ambient pressure in the 1450-1550 °C temperature range. Experiments were conducted in the systems NaAlSiO4-Mg2SiO4- SiO2 and CaAl2Si2O8-Mg2SiO4-SiO2 with about 1 wt% each of MnO, CoO, and NiO added. These compositions were used to evaluate how, in silicate melts, substitution and ionization potential of charge-balancing cations affect activity-composition relations in silicate melts and mineral/melt partitioning.The exchange equilibrium coefficient, , is a positive and linear function of melt Al/(Al + Si) at constant degree of melt polymerization, NBO/T. The is negatively correlated with the ionic radius, r, of the M-cation and also with the ionization potential (Z/r2, Z = electrical charge) of the cation that serves to charge-balance Al3+ in tetrahedral coordination in the melts. The activity coefficient ratio, (γM/γMg)melt, is therefore similarly correlated.These melt composition relationships are governed by the distribution of Al3+ among coexisting Q-species in the peralkaline (depolymerized) melts coexisting with olivine. This distribution controls Q-speciation abundance, which, in turn, controls (γM/γMg)melt and . The relations between melt structure and olivine/melt partitioning behavior lead to the suggestion that in natural magmatic systems mineral/melt partition coefficients are more dependent on melt composition and, therefore, melt structure the more alkali-rich and the more felsic the melt. Moreover, mineral/melt partition coefficients are more sensitive to melt composition the more highly charged or the smaller the ionic radius of the cation of interest. 相似文献
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We have measured apatite solubility in calcic carbonatitic liquids and determined apatite/melt partition coefficients for a series of trace elements, including the rare earth elements (REE), high field strength elements (HFSE), Rb, Sr, U-Th-Pb. Experiments were performed between 4 and 6 GPa, from 1200 to 1380 °C, using the multianvil apparatus. Trace element concentrations were determined by laser ablation ICP-MS and electron microprobe. In addition, a specific protocol was designed to measure carbon concentration in the apatites, using the electron microprobe. Two starting apatite samples were used in order to test for the effect of apatite chemistry on partitioning behavior.Apatite solubility is lower in calcitic melts by a factor 3-5 compared to dolomitic melts (3-5.5 vs. 10-18 wt.% P2O5 in melt). We interpret this difference in terms of solubility product in the liquid and propose an empirical model for apatite saturation that takes into account melt calcium content. We conclude that calcitic melts that may form by melting of carbonated eclogites could be saturated with residual apatite, contrary to dolomitic melts formed in carbonated peridotites.Compatibility behavior of the REE depends on apatite silica content: REE are compatible in apatites containing 3.5-5 wt.% SiO2, with values between 1.5 and 4, whereas REE are incompatible in apatites containing 0.2 wt.% SiO2. HFSE, U, Th, and Y are compatible in silica-rich apatite, with while . Strontium is always retained in the melt, with of the order of 0.5. Lead appears to be incompatible in apatite, although this finding is weakened by almost complete Pb loss to sample container. High silica concentration favors REE incorporation in apatite by allowing for charged balanced coupled substitution. Sulfur and carbonate may also favor REE incorporation in apatite. Our results allow to reconcile previously published experimental determinations of REE partitioning. We use our experimentally determined partition coefficients to investigate the impact of residual apatite during partial melting of recycled carbonated material (eclogite + sediments) and discuss how the chemical characteristics of the produced liquids can be affected by residual apatite. 相似文献
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John W. Washington Robert C. Thomas Katherine L. Schroer 《Geochimica et cosmochimica acta》2006,70(14):3533-3548
Excess N from agriculture induces eutrophication in major river systems and hypoxia in coastal waters throughout the world. Much of this N is from headwaters far up the watersheds. In turn, much of the N in these headwaters is from ground-water discharge. Consequently, the concentrations and forms of N in groundwater are important factors affecting major aquatic ecosystems; despite this, few data exist for several species of N in groundwater and controls on speciation are ill-defined. Herein, we report N speciation for a spring and well that were selected to reflect agricultural impacts, and a spring and well that show little to no agricultural-N impact. Samples were characterized for NO3−, NO2−, N2O, NH4+, urea, particulate organic N(), and dissolved organic N(). These analytes were monitored in the agricultural spring for up to two years along with other analytes that we reported upon previously. For all samples, when oxidized N was present, the dominant species was NO3− (88-98% of total fixed N pool) followed by (<4-12%) and only trace fractions of the other N analytes. In the non-agriculturally impacted well sample, which had no quantifiable NO3− or dissolved O2, comprised the dominant fraction (68%) followed by NH4+ (32%), with only a trace balance comprised of other N analytes. Water drawn from the well, spring and a wetland situated in the agricultural watershed also were analyzed for dissolved N2 and found to have a fugacity in excess of that of the atmosphere. H2O2 was analyzed in the agricultural spring to evaluate the O2/H2O2 redox potential and compare it to other calculated potentials. The potential of the O2/H2O2 couple was close in value to the NO3−/NO2− couple suggesting the important role of H2O2 as an O2-reduction intermediate product and that O2 and NO3− are reduced concomitantly. The O2/H2O2 and NO3−/NO2− couples also were close in value to a cluster of other inorganic N and Fe couples indicating near partial equilibrium among these species. Urea mineralization to NO2− was found to approach equilibrium with the reduction of O2 to H2O2. By modeling as amide functional groups, as justified by recent analytical work, similar thermodynamic calculations support that mineralization to NO2− proceeds nearly to equilibrium with the reduction of O2 to H2O2 as well. This near equilibration of redox couples for urea- and -oxidation with O2-reduction places these two couples within the oxidized redox cluster that is shared among several other couples we have reported previously. In the monitored agricultural spring, [NO3−] was lower in the summer than at other times, whereas [N2O] was higher in the summer than at other times, perhaps reflecting a seasonal variation in the degree of denitrification reaction progress. No other N analytes were observed to vary seasonally in our study. In the well having no agricultural-N impact, Corg/Norg = 5.5, close to the typical value for natural aqueous systems of about 6.6. In the agricultural watershed Corg/Norg varied widely, from ∼1.2 to ?9. 相似文献
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Boris R. Tagirov Stefano Salvi Nina N. Baranova 《Geochimica et cosmochimica acta》2005,69(8):2119-2132
The solubility of gold was measured in KCl solutions (0.001-0.1 m) at near-neutral to weakly acidic pH in the presence of the K-feldspar-muscovite-quartz, andalusite-muscovite-quartz, and pyrite-pyrrhotite-magnetite buffers at temperatures 350 to 500°C and pressures 0.5 and 1 kbar. These mineral buffers were used to simultaneously constrain pH, f(S2), and f(H2). The experiments were performed using a CORETEST flexible Ti-cell rocking hydrothermal reactor enabling solution sampling at experimental conditions. Measured log m(Au) (mol/kg H2O) ranges from −7.5 at weakly acid pH to −5.9 in near-neutral solutions, and increases slightly with temperature. Gold solubility in weakly basic and near-neutral solutions decreases with decreasing pH at all temperatures, which implies that Au(HS)2 is the dominant Au species in solution. In more acidic solutions, solubility is independent of pH. Comparison of the experimentally measured solubilities with literature values for Au hydrolysis constants demonstrates that at 350°C dominates Au aqueous speciation at the weakly acidic pH and f(S2)/f(H2) conditions imposed by the pyrite-pyrrhotite-magnetite buffer. In contrast, at temperatures >400°C becomes less important and predominates in weakly acid solutions. Solubility data collected in this study were used to calculate the following equilibrium reaction constants:
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Sphalerite oxidation is a common process under acid-mine drainage (AMD) conditions and results in the release of , Zn and potentially toxic trace metals, which can pollute rivers and oceans. However, there are only a few studies on the mechanisms of aerobic sphalerite oxidation. Oxygen and S isotope investigations of the produced may contribute to the understanding of sphalerite oxidation mechanisms so helping to interpret field data from AMD sites. Therefore, batch oxidation experiments with an Fe-rich sphalerite were performed under aerobic abiotic conditions at different initial pH values (2 and 6) for different lengths of time (2–100 days). The O and S isotope composition of the produced indicated changing oxidation pathways during the experiments. During the first 20 days of the experiments at both initial pH values, molecular O2 was the exclusive O source of . Furthermore, the lack of S isotope enrichment processes between and sphalerite indicated that O2 was the electron acceptor from sphalerite S. As the oxidation proceeded, a sufficient amount of released Fe(II) was oxidized to Fe(III) by O2. Therefore, electrons could be transferred from sphalerite S sites to adsorbed hydrous Fe(III) and O from the hydration sphere of Fe was incorporated into the produced as indicated by decreasing δ18OSO4 values which became more similar to the δ18OH2O values. The enrichment of 32S in relative to the sphalerite may also result from sphalerite oxidation by Fe(III).The incorporation of O2 into during the oxidation of sphalerite was associated with an O isotope enrichment factor εSO4–O2 of ca. −22‰. The O isotope enrichment factor εSO4–H2O was determined to be ?4.1‰. A comparison with O and S studies of other sulfides suggests that there is no general oxidation mechanism for acid-soluble sulfides. 相似文献
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J.A. Tossell 《Geochimica et cosmochimica acta》2006,70(20):5089-5103
Boric acid, B(OH)3, forms complexes in aqueous solution with a number of bidentate O-containing ligands, HL−, where H2L is C2O4H2 (oxalic acid), C3O4H4 (malonic acid), C2H6O2 (ethylene glycol), C6H6O2 (catechol), C10H8O2 (dioxynaphthalene) and C2O3H4 (glycolic acid). McElligott and Byrne [McElligott, S., Byrne, R.H., 1998. Interaction of and in seawater: Formation of . Aquat. Geochem.3, 345-356.] have also found B(OH)3 to form an aqueous complex with . Recently Lemarchand et al. [Lemarchand, E., Schott, J., Gaillardeet, J., 2005. Boron isotopic fractionation related to boron sorption on humic acid and the structure of surface complexes formed. Geochim. Cosmochim. Acta69, 3519-3533] have studied the formation of surface complexes of B(OH)3 on humic acid, determining 11B NMR shifts and fitted values of formation constants, and 11B, 10B isotope fractionations for a number of surface complexation models. Their work helps to clarify both the nature of the interaction of boric acid with the functional groups in humic acid and the nature of some of these coordinating sites on the humic acid. The determination of isotope fractionations may be seen as a form of vibrational spectroscopy, using the fractionating element as a local probe of the vibrational spectrum. We have calculated quantum mechanically the structures, stabilities, vibrational spectra, 11B NMR spectra and 11B,10B isotope fractionations of a number of complexes B(OH)2L− formed by reactions of the type:
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The solubility of KFe(CrO4)2·2H2O, a precipitate recently identified in a Cr(VI)-contaminated soil, was studied in dissolution and precipitation experiments. Ten dissolution experiments were conducted at 4–75°C and initial pH values between 0.8 and 1.2 using synthetic KFe(CrO4)2·2H2O. Four precipitation experiments were conducted at 25°C with final pH values between 0.16 and 1.39. The log KSP for the reaction
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Jun Li 《Geochimica et cosmochimica acta》2011,75(15):4351-4376
A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H2O-CO2-NaCl-CaCO3-CaSO4 system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H+,Na+,Ca2+, , , and CaSO4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results.Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO2 in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model. 相似文献
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Four or five sets of ab initio models, including Unrestricted Hartree Fock (UHF) and hybrid Density Functional Theory (DFT) are calculated for each species in a series of aqueous ferric aquo-chloro complexes: , , , FeCl3(H2O)3, FeCl3(H2O)2, , FeCl5H2O2−, , ) in order to determine the relative isotopic fractionation among the complexes, to compare the results of different models for the same complexes, to examine factors that influence the magnitude of the isotopic fractionation, and to compare bond-partner-driven fractionation with redox-driven fractionation.Relative to , all models show a nearly linear decrease in 56Fe/54Fe as the number of Cl− ions per Fe3+ ion increases, with slopes of −0.8‰ to −1.0‰ per Cl− at 20 °C. At 20 °C, 1000 ln β (β = 56Fe/54Fe reduced partition function ratio relative to a dissociated Fe atom) values range from 8.93‰ to 9.73‰ for , 8.04-9.12‰ for , 7.61-8.73‰ for , 7.14-8.25‰ for , and 3.09-4.41‰ for . The fractionation between and ranges from 1.5‰ to 2.6‰, depending on the model; this is comparable in magnitude to fractionation effects due to Fe3+/Fe2+ redox reactions. β values from the UHF models are consistently higher than those from the hybrid DFT models.Isotopic fractionation is shown to be sensitive to differences in ligand bond stiffness (above), coordination number, bond length, and the frequency of the asymmetric Fe-X stretching vibrational mode, as predicted by previous theoretical studies. Complexes with smaller coordination numbers have higher 1000 ln β (7.46‰, 5.25‰, and 3.48‰ for , ,, respectively, from the B3LYP/6-31G(d) model). Species with the same number of chlorides but fewer waters also show the effect of coordination number on 1000 ln β: (7.46‰ vs. 7.05‰ for FeCl3(H2O)2 vs. FeCl3(H2O)3 and 5.25‰ vs. 4.94‰ for vs. FeCl5H2O2− with the B3LYP/6-31G(d) model). As more Fe-Cl bonds substitute for Fe-OH2 bonds (with a resulting decrease in β), the lengths of the Fe-Cl bonds and the Fe-O bonds increase.Preliminary modeling of shows an Fe3+/Fe2+ fractionation of 3.2‰ for the B3LYP/6-31G(d) model, in agreement with previous studies. The addition of an explicit outer hydration sphere of 12 H2O molecules to models of improves agreement with measured vibrational frequencies and bond lengths; 1000 ln β increases by 0.8-1.0‰. An additional hydration sphere around increases 1000 ln β by only 0.1‰.Isotopic fractionations predicted for this simple system imply that ligands present in an aqueous iron environment are potentially important drivers of fractionation, and suggest that significant fractionation effects are likely in other aqueous systems containing sulfides or organic ligands. Fractionation effects due to both speciation and redox must be considered when interpreting iron isotope fractionations in the geological record. 相似文献
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Synthetic fluid inclusions in quartz were grown from cassiterite-saturated fluids in cold-seal pressure vessels at and subsequently analyzed by laser ablation-ICP-MS. Most inclusions were synthesized using a new technique that allows entrapment of fluid that had no immediate contact to the capsule walls, such that potential disequilibrium effects due to alloying could be avoided. Measured Sn solubilities increase with increasing ligand concentration in the fluid, ranging from 100 to 800 ppm in NaCl-bearing fluids (5-35 wt% NaCl), from 70 to 2000 ppm in HF-bearing fluids (0.5-3.2 m HF), and from 0.8 to 11 wt% in HCl-bearing fluids (0.5-4.4 m HCl). Two runs performed with the in-situ cracking method after 1 week of pre-equilibration demonstrate that the speed of hydrogen diffusion through the capsule wall relative to that of fluid inclusion formation is a critical factor in fO2-dependent solubility studies. Graphical evaluation of the solubility data suggests that Sn may have been dissolved as Sn(OH)Cl in the NaCl-bearing fluids, as Sn(OH)Cl and SnCl2 in the HCl-bearing fluids, and as SnF2 in the HF-bearing fluids. Experiments with NaF-bearing fluids produced an additional melt phase with an approximate composition of 53 wt% SiO2, 25 wt% H2O, 14 wt% NaF and 8 wt% SnO, which caused the composition of the coexisting fluid to be buffered at 0.5 wt% NaF and 150 ppm Sn. Fluorine-rich, peralkaline melts may therefore serve as important transport media for Sn in the final crystallization stages of tin granites. Based on the available cassiterite-solubility data in fluids and melts, in natural granite systems is estimated to be in the order of 0.1-4 (depending on their aluminosity), suggesting that Sn is not easily mobilized by magmatic-hydrothermal fluids. This interpretation is in accordance with the high degrees of Sn-enrichment commonly observed in highly fractionated melt inclusions. is primarily controlled by the HCl concentration in the fluid, which in turn is a function of the aluminum saturation index of the magma. Compared to HCl, the effect of fluorine on is subordinate. 相似文献