An experimental study of Cobalt (II) complexation in Cl and H2S-bearing hydrothermal solutions

The speciation of cobalt (II) in Cl⁻ and H₂S-bearing solutions was investigated spectrophotometrically at temperatures of 200, 250, and 300 °C and a pressure of 100 bars, and by measuring the solubility of cobaltpentlandite at temperatures of 120-300 °C and variable pressures of H₂S. From the results of these experiments, it is evident that CoHS⁺ and predominate in the solutions except at 150 °C, for which the dominant chloride complex is CoCl₃⁻. The logarithms of the stability constant for CoHS⁺ show moderate variation with temperature, decreasing from 6.24 at 120 °C to 5.84 at 200 °C, and increasing to 6.52 at 300 °C. Formation constants for chloride species increase smoothly with temperature and at 300°C their logarithms reach 8.33 for , 6.44 for CoCl₃⁻, 4.94 to 5.36 for , and 2.42 for CoCl⁺. Calculations based on the composition of a model hydrothermal fluid (Ksp-Mu-Qz, KCl = 0.25 m, NaCl = 0.75 m, ΣS = 0.3 m) suggest that at temperatures ?200 °C, cobalt occurs dominantly as CoHS⁺, whereas at higher temperatures the dominant species is .     

The effect of sulfur on the partitioning of Ni and other first-row transition elements between olivine and silicate melt

The effect of sulfur dissolved as sulfide (S²⁻) in silicate melts on the activity coefficients of NiO and some other oxides of divalent cations (Ca, Cr, Mn, Fe and Co) has been determined from olivine/melt partitioning experiments at 1400 °C in six melt compositions in the system CaO-MgO-Al₂O₃-SiO₂ (CMAS), and in derivatives of these compositions at 1370 °C, obtained from the six CMAS compositions by substituting Fe for Mg (FeCMAS). Amounts of S²⁻ were varied from zero to sulfide saturation, reaching 4100 μg g⁻¹ S in the most sulfur-rich silicate melt. The sulfide solubilities compare reasonably well with those predicted from the parameterization of the sulfide capacity of silicate melts at 1400 °C of O’Neill and Mavrogenes (2002), although in detail systematic deviations indicate that a more sophisticated model may improve the prediction of sulfide capacities.The results show a barely discernible effect of S²⁻ in the silicate melt on Fe, Co and Ni partition coefficients, and also surprisingly, a tiny but resolvable effect on Ca partitioning, but no detectable effect on Cr, Mn or some other lithophile incompatible elements (Sc, Ti, V, Y, Zr and Hf). Decreasing Mg# of olivine (reflecting increasing FeO in the system) has a significant influence on the partitioning of several of the divalent cations, particularly Ca and Ni. We find a remarkably systematic correlation between and the ionic radius of M²⁺, where M = Ca, Cr, Mn, Fe, Co or Ni, which is attributable to a simple relationship between size mismatch and excess free energies of mixing in Mg-rich olivine solid solutions.Neither the effect of S²⁻ nor of Mg#^ol is large enough by an order of magnitude to account for the reported variations of obtained from electron microprobe analyses of olivine/glass pairs from mid-ocean ridge basalts (MORBs). Comparing these MORB glass analyses with the Ni-MgO systematics of MORB from other studies in the literature, which were obtained using a variety of analytical techniques, shows that these electron microprobe analyses are anomalous. We suggest that the reported variation of with S content in MORB is an analytical artifact.Mass balance of melt and olivine compositions with the starting compositions shows that dissolved S²⁻ depresses the olivine liquidus of haplobasaltic silicate melts by 5.8 × 10⁻³ (±1.3 × 10⁻³) K per μg g⁻¹ of S²⁻, which is negligible in most contexts. We also present data for the partitioning of some incompatible trace elements (Sc, Ti, Y, Zr and Hf) between olivine and melt. The data for Sc and Y confirm previous results showing that and decrease with increasing SiO₂ content of the melt. Values of average 0.01 with most falling in the range 0.005-0.015. Zr and Hf are considerably more incompatible than Ti in olivine, with and about 10⁻³. The ratio / is well constrained at 0.611 ± 0.016.     

Ammonium loss and nitrogen isotopic fractionation in biotite as a function of metamorphic grade in metapelites from western Maine, USA

Ammonium fixed in micas of metamorphic rocks is a sensitive indicator both of organic-inorganic interactions during diagenesis as well as of the devolatilization history and fluid/rock interaction during metamorphism. In this study, a collection of geochemically well-characterized biotite separates from a series of graphite-bearing Paleozoic greenschist- to upper amphibolite-facies metapelites, western Maine, USA, were analyzed for ammonium nitrogen () contents and isotopic composition (δ¹⁵N_NH4) using the HF-digestion distillation technique followed by the EA-IRMS technique. Biotite separates, sampled from 9 individual metamorphic zones, contain 3000 to 100 ppm with a wide range in δ¹⁵N from +1.6‰ to +9.1‰. Average contents in biotite show a distinct decrease from about 2750 ppm for the lowest metamorphic grade (∼500 °C) down to 218 ppm for the highest metamorphic grade (∼685 °C). Decreasing abundances in are inversely correlated in a linear fashion with increasing K⁺ in biotite as a function of metamorphic grade and are interpreted as a devolatilization effect. Despite expected increasing δ¹⁵N_NH4 values in biotite with nitrogen loss, a significant decrease from the Garnet Zones to the Staurolite Zones was found, followed by an increase to the Sillimanite Zones. This pattern for δ¹⁵N_NH4 values in biotite inversely correlates with Mg/(Mg + Fe) ratios in biotite and is discussed in the framework of isotopic fractionation due to different exchange processes between or , reflecting devolatilization history and redox conditions during metamorphism.     

Apatite solubility in carbonatitic liquids and trace element partitioning between apatite and carbonatite at high pressure

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.     

Comparative carbonate and hydroxide complexation of cations in seawater

Comparative concentrations of carbonate and hydroxide complexes in natural solutions can be expressed in terms of reactions with bicarbonate that have no explicit pH dependence (). Stability constants for this reaction with n = 1 were determined using conventional formation constant data expressed in terms of hydroxide and carbonate. Available data indicate that stability constants appropriate to seawater at 25 °C expressed in the form are on the order of 10^4.2 for a wide range of cations (M^z+) with z = +1, +2 and +3. Φ₁ is sufficiently large that species appear to substantially dominate MOH^z−1 species in seawater. Evaluations of comparative stepwise carbonate and hydroxide stability constant behavior leading to the formation of n = 2 and n = 3 complexes suggest that carbonate complexes generally dominate hydroxide complexes in seawater, even for cations whose inorganic speciation schemes in seawater are currently presumed to be strongly dominated by hydrolyzed forms (). Calculated stability constants, and , indicate that the importance of carbonate complexation is sufficiently large that carbonate and hydroxide complexes would be generally comparable even if calculated Φ₂ and Φ₃ values are overestimated by two or more orders of magnitude. Inclusion of mixed ligand species in carbonate-hydroxide speciation models allows cation complexation intensities (M_T/[M^z+]) to be expressed in the following form:

     

Sorption of phosphate onto calcite; results from batch experiments and surface complexation modeling

The adsorption of phosphate onto calcite was studied in a series of batch experiments. To avoid the precipitation of phosphate-containing minerals the experiments were conducted using a short reaction time (3 h) and low concentrations of phosphate (?50 μM). Sorption of phosphate on calcite was studied in 11 different calcite-equilibrated solutions that varied in pH, P_CO2, ionic strength and activity of Ca²⁺, and . Our results show strong sorption of phosphate onto calcite. The kinetics of phosphate sorption onto calcite are fast; adsorption is complete within 2-3 h while desorption is complete in less than 0.5 h. The reversibility of the sorption process indicates that phosphate is not incorporated into the calcite crystal lattice under our experimental conditions. Precipitation of phosphate-containing phases does not seem to take place in systems with ?50 μM total phosphate, in spite of a high degree of super-saturation with respect to hydroxyapatite (SI_HAP ? 7.83). The amount of phosphate adsorbed varied with the solution composition, in particular, adsorption increases as the activity decreases (at constant pH) and as pH increases (at constant activity). The primary effect of ionic strength on phosphate sorption onto calcite is its influence on the activity of the different aqueous phosphate species. The experimental results were modeled satisfactorily using the constant capacitance model with >CaPO₄Ca⁰ and either >CaHPO₄Ca⁺ or > as the adsorbed surface species. Generally the model captures the variation in phosphate adsorption onto calcite as a function of solution composition, though it was necessary to include two types of sorption sites (strong and weak) in the model to reproduce the convex shape of the sorption isotherms.     

Experimental study of the incorporation of Li, Sc, Al and other trace elements into olivine

We performed a series of synthesis experiments at 1 atm pressure to investigate the substitution mechanisms of 1+ and 3+ ions into olivine. Forsterite crystals were grown from bulk compositions that contained the element of interest (e.g. Li) and different amounts of additional single trace elements. By working at constant (major element) liquid composition and temperature we eliminated all compositional effects other than those due to the trace elements. Mineral-melt pairs were then analysed to determine the compositional-dependence of the partition coefficient (D), which corresponds to , and where [element] refers to weight concentration of the element in the respective phase.We find that Li forms a stable coupled substitution with Sc and, at above ∼500 ppm Sc in the crystal, Li⁺ and Sc³⁺ ions form an ordered neutral complex ([LiSc]). This complex dissociates at lower trace element concentrations and a second, concentration-independent, mechanism begins to dominate. This second solution mechanism is most likely 2Li⁺ ⇔ Mg²⁺ where one of the Li atoms is in an interstitial position in the crystal lattice. Natural olivines show Li contents slightly greater than Sc (on an atomic basis), indicating that both substitution mechanisms are significant. Unlike Sc, Al does not appear to form a stable complex with Li in the olivine structure.Sodium is highly incompatible in olivine with of ∼0.00015-0.03. Olivine-liquid partitioning of Na⁺ is independent of Sc³⁺ or Al³⁺ concentration. This indicates that the coupled substitution of Na⁺ with any 3+ ions is unlikely. Instead, the relevant substitution mechanism appears to be 2Na⁺ ⇔ Mg²⁺. Although independent of 3+ ion concentration, is inversely correlated with the Li concentration of both melts and crystals, implying that Na competes (unsuccessfully) with Li to replace Mg in the olivine structure.Aluminium is highly incompatible in forsterite . Values of are similar for all phase pairs synthesised from starting materials containing between 10 and 100,000 ppm Al. This suggests that Al is principally incorporated in forsterite by replacing one Mg and one Si atom , where the Al atoms on octahedral (Mg) and tetrahedral (Si) sites are dissociated from one another.The incorporation of gallium into forsterite is influenced by the presence of Li. Where Li concentration in the crystal is much greater than that of Ga (on an atomic basis) we find an excellent correlation between and melt Li content. This relationship indicates that Ga³⁺ and Li⁺ replace 2Mg²⁺ on octahedral sites and that the Ga and Li atoms are, like Sc and Li, strongly associated in the crystal structure.The mechanism by which scandium is incorporated into forsterite is strongly governed by the presence Li. As discussed above, ordered complexes form readily in forsterite in Li-rich experiments. Under Li-absent but Sc-rich conditions (Sc in the crystal >∼500 ppm), is proportional to the concentration of Sc in the melt. This indicates that Sc incorporation is charge-balanced by the formation of magnesium vacancies , and that both species are associated . At lower Sc concentrations (<500 ppm in the crystal), the concentration-dependence of partitioning indicates that the complexes dissociate.Our results demonstrate that partitioning of 1+ and 3+ ions into olivine is complex and involves a range of point defects which yield strongly composition-dependent crystal-melt partition coefficients. Since physical and chemical properties of natural olivine, such as diffusion of ⁶Li and ⁷Li and H₂O solubility, depend on the concentrations of the defects identified in this study, our results provide an important insight into how determining substitution mechanisms can improve our understanding of large-scale mantle processes and properties.     

The ionic strength dependence of lead (II) carbonate complexation in perchlorate media

Lead speciation in many aqueous geochemical systems is dominated by carbonate complexation. However, direct observations of Pb²⁺ complexation by carbonate ions are few in number. This work represents the first investigation of the equilibrium over a range of ionic strength. Through spectrophotometric observations of formation at 25 °C in NaHCO₃-NaClO₄ solutions, formation constants of the form were determined between 0.001 and 5.0 molal ionic strength. Formation constant results were well represented by the equation:

     

Unsteady diagenetic processes and sulfur biogeochemistry in tropical deltaic muds: Implications for oceanic isotope cycles and the sedimentary record

Sedimentary S cycling is usually conceptualized and interpreted within the context of steadily accreting (1-D) transport-reaction regimes. Unsteady processes, however, are common in many sedimentary systems and can result in dramatically different S reaction balances and diagenetic products than steady conditions. Globally important common examples include tropical deltaic topset and inner shelf muds such as those extending from the Amazon River ∼1600 km along the Guianas coast of South America. These deposits are characterized by episodic reworking of the surface seabed over vertical depths of ∼0.1-3 m. Reworked surface sediments act as unsteady, suboxic batch reactors, unconformably overlying relict anoxic, often methanic deposits, and have diagenetic properties largely decoupled from net accumulation of sediment. Despite well-oxygenated water and an abundant reactive organic matter supply, physical disturbance inhibits macrofauna, and benthic communities are dominated by microbial biomass across immense areas. In the surficial suboxic layer, molecular biological analyses, tracer experiments, sediment C/S/Fe compositions, and δ³⁴S, δ¹⁸O of pore water indicate close coupling of anaerobic C, S, and Fe cycles. δ¹⁸O- can increase by 2-3‰ during anaerobic recycling without net change in δ³⁴S-, demonstrating reduction coupled to complete anaerobic reoxidation to and a δ¹⁸O- reduction + reoxidation fractionation factor?12‰ (summed magnitudes). S reoxidation must be coupled to Fe-oxide reduction, contributing to high dissolved Fe²⁺ (∼1 mM) and Fe mobilization-export. The reworking of Amazon-Guianas shelf muds alone may isotopically alter δ¹⁸O- equivalent in mass to?25% of the annual riverine delivery of to the global ocean. Unsteady conditions result in preservation of unusually heavy δ³⁴S isotopic compositions of residual Cr reducible S, ranging from 0‰ to >30‰ in physically reworked deposits. In contrast, bioturbated facies adjacent to physically reworked regions accumulate isotopically light S (δ³⁴S to −20‰) in otherwise similar decomposition regimes. The isotopic patterns of both physically and biologically reworked regions can be simulated with simple diagenetic models. Heavy S isotopic signatures are largely a consequence of unsteady diffusion and progressive anaerobic burndown into underlying deposits, whereas isotopically depleted bioturbated deposits predominantly reflect biogenic diffusive scaling and isotopic distillation/diffusive pumping associated with reoxidation in burrow walls immediately adjacent to reduced zones. The S isotopic transition from unsteady physically controlled regions of the Amazon delta moving laterally into bioturbated facies mimics the transition of S isotopic patterns temporally in the geologic record during the rise of bioturbation. No special role for S disproportionation is required to explain these differences. The potential role of unsteady, suboxic diagenesis and dynamic reworking of sediments has been largely ignored in models of the evolution of surficial elemental cycling and interpretations of the geologic record.     

Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation

Thermal water samples from Yellowstone National Park (YNP) have a wide range of pH (1-10), temperature, and high concentrations of fluoride (up to 50 mg/l). High fluoride concentrations are found in waters with field pH higher than 6 (except those in Crater Hills) and temperatures higher than 50 °C based on data from more than 750 water samples covering most thermal areas in YNP from 1975 to 2008. In this study, more than 140 water samples from YNP collected in 2006-2009 were analyzed for free-fluoride activity by ion-selective electrode (ISE) method as an independent check on the reliability of fluoride speciation calculations. The free to total fluoride concentration ratio ranged from <1% at low pH values to >99% at high pH. The wide range in fluoride activity can be explained by strong complexing with H⁺ and Al³⁺ under acidic conditions and lack of complexing under basic conditions. Differences between the free-fluoride activities calculated with the WATEQ4F code and those measured by ISE were within 0.3-30% for more than 90% of samples at or above 10⁻⁶ molar, providing corroboration for chemical speciation models for a wide range of pH and chemistry of YNP thermal waters. Calculated speciation results show that free fluoride, F⁻, and major complexes (, AlF²⁺, and ) account for more than 95% of total fluoride. Occasionally, some complex species like , FeF²⁺, , MgF⁺ and may comprise 1-10% when the concentrations of the appropriate components are high. According to the simulation results by PHREEQC and calculated results, the ratio of main fluoride species to total fluoride varies as a function of pH and the concentrations and ratios of F and Al.     

Oxygen isotope fractionation between apatite-bound carbonate and water determined from controlled experiments with synthetic apatites precipitated at 10-37 °C

The oxygen isotope fractionation between the structural carbonate of inorganically precipitated hydroxyapatite (HAP) and water was determined in the range 10-37 °C. Values of 1000 ln α() are linearly correlated with inverse temperature (K) according to the following equation: 1000 ln α() = 25.19 (±0.53)·T⁻¹ − 56.47 (±1.81) (R² = 0.998). This fractionation equation has a slightly steeper slope than those already established between calcite and water ( [O’Neil et al., 1969] and [Kim and O’Neil, 1997]) even though measured fractionations are of comparable amplitude in the temperature range of these experimental studies. It is consequently observed that the oxygen isotope fractionation between apatite carbonate and phosphate increases from about 7.5‰ up to 9.1‰ with decreasing temperature from 37 °C to 10 °C. A compilation of δ¹⁸O values of both phosphate and carbonate from modern mammal teeth and bones confirms that both variables are linearly correlated, despite a significant scattering up to 3.5‰, with a slope close to 1 and an intercept corresponding to a 1000 ln α() value of 8.1‰. This apparent fractionation factor is slightly higher or close to the fractionation factor expected to be in the range 7-8‰ at the body temperature of mammals.     

Experimental studies of metal-silicate partitioning of Sb: Implications for the terrestrial and lunar mantles

The terrestrial mantle has a well defined Sb depletion of ∼7 ± 1 (Jochum and Hofmann, 1997), and the lunar mantle is depleted relative to the Earth by a factor of ∼50 ± 5 (Wolf and Anders, 1980). Despite these well defined depletions, there are few data upon which to evaluate their origin—whether due to volatility or core formation. We have carried out a series of experiments to isolate several variables such as oxygen fugacity, temperature, pressure, and silicate and metallic melt compositions, on the magnitude of . The activity of Sb in FeNi metal is strongly composition dependent such that solubility of Sb as a function of fO₂ must be corrected for the metal composition. When the correction is applied, Sb solubility is consistent with 3+ valence. Temperature series (at 1.5 GPa) shows that decreases by a factor of 100 over 400 °C, and a pressure series exhibits an additional decrease between ambient pressure (100 MPa) and 13 GPa. A strong dependence upon silicate melt composition is evident from a factor of 100 decrease in between nbo/t values of 0.3 and 1.7. Consideration of all these variables indicates that the small Sb depletion for the Earth’s mantle can be explained by high PT equilibrium partitioning between metal and silicate melt . The relatively large lunar Sb depletion can also be explained by segregation of a small metallic core, at lower pressure conditions where is much higher (2500).     

Silicon isotopic fractionation during adsorption of aqueous monosilicic acid onto iron oxide

The quantification of silicon isotopic fractionation by biotic and abiotic processes contributes to the understanding of the Si continental cycle. In soils, light Si isotopes are selectively taken up by plants, and concentrate in secondary clay-sized minerals. Si can readily be retrieved from soil solution through the specific adsorption of monosilicic acid () by iron oxides. Here, we report on the Si-isotopic fractionation during adsorption on synthesized ferrihydrite and goethite in batch experiment series designed as function of time (0-504 h) and initial concentration (ic) of Si in solution (0.21-1.80 mM), at 20 °C, constant pH (5.5) and ionic strength (1 mM). At various contact times, the δ²⁹Si vs. NBS28 compositions were determined in selected solutions (ic = 0.64 and 1.06 mM Si) by MC-ICP-MS in dry plasma mode with external Mg doping with an average precision of ±0.08‰ (±2σ_SEM). Per oxide mass, ferrihydrite (74-86% of initial Si loading) adsorbed more Si than goethite (37-69%) after 504 h of contact over the range of initial Si concentration 0.42-1.80 mM. Measured against its initial composition (δ²⁹Si = +0.01 ± 0.04‰ (±2σ_SD)), the remaining solution was systematically enriched in ²⁹Si, reaching maximum δ²⁹Si values of +0.70 ± 0.07‰ for ferrihydrite and +0.50 ± 0.08‰ for goethite for ic 1.06 mM. The progressive ²⁹Si enrichment of the solution fitted better a Rayleigh distillation path than a steady state model. The fractionation factor ²⁹ε (±1σ_SD) was estimated at −0.54 ± 0.03‰ for ferrihydrite and −0.81 ± 0.12‰ for goethite. Our data imply that the sorption of onto synthetic iron oxides produced a distinct Si-isotopic fractionation for the two types of oxide but in the same order than that generated by Si uptake by plants and diatoms. They further suggest that the concentration of light Si isotopes in the clay fraction of soils is partly due to sorption onto secondary clay-sized iron oxides.     

Complexation of Cu in Hydrothermal NaCl Brines: Ab initio molecular dynamics and energetics

Chloride complexation of Cu⁺ controls the solubility of copper(I) oxide and sulfide ore minerals in hydrothermal and diagenetic fluids. Solubility measurements and optical spectra of high temperature CuCl solutions have been interpreted as indicating the formation of CuCl, , and complexes. However, no other monovalent cation forms tri- and tetrachloro complexes. EXAFS spectra of high temperature Cu-Cl solutions, moreover, appear to show only CuCl and complexes at T > 100 °C. To reconcile these results, I investigated the nature and stability of Cu-Cl complexes using ab initio cluster calculations and ab initio (Car-Parrinello) molecular dynamics simulations for CuCl-NaCl-H₂O systems at 25 to 450 °C. Ab initio molecular dynamic simulations of 1 m CuCl in a 4 m Cl solution give a stable complex at 25 °C over 4 ps but show that the third Cl⁻ is weakly bound. When the temperature is increased along the liquid-vapour saturation curve to 125 °C, the complex dissociates into and Cl⁻; only forms at 325 °C and 1 kbar. Even in a 15.6 m Cl brine at 450 °C, only the complex forms over a 4 ps simulation run.Cluster calculations with a static dielectric continuum solvation field (COSMO) were used in an attempt directly estimate free energies of complex formation in aqueous solution. Consistent with the MD simulations, the complex is slightly stable at 25 °C but decreases in stability with decreasing dielectric constant (ε). The complex is predicted to be unstable at 25 °C and becomes increasingly unstable with decreasing dielectric constant. In hydrothermal fluids (ε < 30) both the and complexes are unstable to dissociation into and Cl⁻.The results obtained here are at odds with recent equations of state that predict and complexes are the predominant species in hydrothermal brines. In contrast, I predict that only complexes will be significant at T > 125 °C, even in NaCl-saturated brines. The high-temperature (T > 125 °C) optical spectra of CuCl solutions and solubility measurements of Cu minerals in Cl-brines need to be reinterpreted in terms of only the CuCl and complexes.     

Effects of magnesium ions on near-equilibrium calcite dissolution: Step kinetics and morphology

Dissolution kinetics at the aqueous solution-calcite interface at 50 °C were investigated using in situ atomic force microscopy (AFM) to reveal the influence of magnesium concentration and solution saturation state on calcite dissolution kinetics and surface morphology. Under near-equilibrium conditions, dissolved Mg²⁺ displayed negligible inhibitory effects on calcite dissolution even at concentrations of . Upon the introduction of , the solution saturation state with respect to calcite, , acted as a “switch” for magnesium inhibition whereby no significant changes in step kinetics were observed at Ω_calcite<0.2, whereas a sudden inhibition from Mg²⁺ was activated at Ω_calcite?0.2. The presence of the Ω-switch in dissolution kinetics indicates the presence of critical undersaturation in accordance with thermodynamic principles. The etch pits formed in solutions with exhibited a unique distorted rhombic profile, different from those formed in Mg-free solutions and in de-ionized water. Such unique etch pit morphology may be associated with the anisotropy in net detachment rates of counter-propagating kink sites upon the addition of Mg²⁺.     

Kinetics of gypsum crystal growth from high ionic strength solutions: A case study of Dead Sea - seawater mixtures

Gypsum precipitation kinetics were examined from a wide range of chemical compositions , ionic strengths (4.75-10 m) and saturation state with respect to gypsum (1.16-1.74) in seeded batch experiments of mixtures of Ca²⁺-rich Dead Sea brine and -rich seawater. Despite the variability in the experimental solutions, a single general rate law was formulated to describe the heterogeneous precipitation rate of gypsum from these mixtures:

     

Molybdenum, tungsten and manganese partitioning in the system pyrrhotite-Fe-S-O melt-rhyolite melt: Impact of sulfide segregation on arc magma evolution

Experiments were performed to determine the partitioning of molybdenum, tungsten and manganese among a rhyolitic melt (melt), pyrrhotite (po), and an immiscible Fe-S-O melt (Fe-S-O). Sulfide phases such as these may be isolated from a silicate melt along with other crystallizing phases during the evolution of arc magma, and partition coefficients are required to model the effect of this process on molybdenum and tungsten budgets.We developed an experimental design to take advantage of properties of the phases under study. Careful control of temperature allowed pyrrhotite and magnetite to be stable along with an Fe-S-O melt, and this phase assemblage allowed the composition of run-product pyrrhotite to be used to calculate both fS₂ and fO₂ for the experiments. At run temperature, (1042 ± 2 °C), a rhyolitic melt can be formed at low pressure, under nominally dry conditions, which removed the need for confining pressure as well as externally imposed fugacities. The silica-saturated melt allowed the charges to be contained in sealed evacuated silica tubes without danger of reaction, and with closed system behavior for molybdenum and tungsten.Experiments were run for durations up to 2000 min. Molybdenite (mb) and wolframite (wo) were added to the experiments as sources for molybdenum and tungsten, respectively. Manganese was added to the system as both a component of the starting rhyolitic pumice, and of Mn-bearing wolframite. Oxygen fugacity in these experiments was fixed at the Ni-NiO oxygen fugacity buffer. Sulfur fugacity was 10⁻¹ bar. Run products were analyzed by EPMA and LA-ICP-MS. Analysis of the run products yielded ( standard deviation of the mean): , , , and . The partition coefficients for manganese in this system are and .Simple Rayleigh fractionation modeling suggests that oxidized felsic melts produced through fractional crystallization may have lost as much as 14% of their initial molybdenum, but only 2% of their initial tungsten, through the removal of an Fe-S-O melt along with crystalline phases. Modeling consistent with conditions of oxygen and sulfur fugacity influenced by assimilation of sulfide (with low concentrations of molybdenum and tungsten) from, for example, sedimentary rock, results in evolved magmas significantly depleted in molybdenum, but only moderately depleted in tungsten. The molybdenum:tungsten ratio can vary by two orders of magnitude. These systematics may help to explain some of the variability in metal ratios of intrusion-related hydrothermal ore deposits.     

Sphalerite oxidation pathways detected by oxygen and sulfur isotope studies

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 δ¹⁸O_SO4 values which became more similar to the δ¹⁸O_H2O 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 ε_SO4–O2 of ca. −22‰. The O isotope enrichment factor ε_SO4–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.     

Oxygen and hydrogen isotope fractionation in serpentine-water and talc-water systems from 250 to 450 °C, 50 MPa

Oxygen and hydrogen isotope fractionation factors in the talc-water and serpentine-water systems have been determined by laboratory experiment from 250 to 450 °C at 50 MPa using the partial exchange technique. Talc was synthesized from brucite + quartz, resulting in nearly 100% exchange during reaction at 350 and 450 °C. For serpentine, D-H exchange was much more rapid than ¹⁸O-¹⁶O exchange when natural chrysotile fibers were employed in the initial charge. In experiments with lizardite as the starting charge, recrystallization to chrysotile enhanced the rate of ¹⁸O-¹⁶O exchange with the coexisting aqueous phase. Oxygen isotope fractionation factors in both the talc-water and serpentine-water systems decrease with increasing temperature and can be described from 250 to 450 °C by the relationships: 1000 ln  = 11.70 × 10⁶/T² − 25.49 × 10³/T + 12.48 and 1000 ln  = 3.49 × 10⁶/T² − 9.48 where T is temperature in Kelvin. Over the same temperature interval at 50 MPa, talc-water D-H fractionation is only weakly dependent on temperature, similar to brucite and chlorite, and can be described by the equation: 1000 ln = 10.88 × 10⁶/T² − 41.52 × 10³/T + 5.61 where T is temperature in Kelvin. Our D-H serpentine-water fractionation factors calibrated by experiment decrease with temperature and form a consistent trend with fractionation factors derived from lower temperature field calibrations. By regression of these data, we have refined and extended the D-H fractionation curve from 25 to 450 °C, 50 MPa as follows: 1000 ln  = 3.436 × 10⁶/T² − 34.736 × 10³/T + 21.67 where T is temperature in Kelvin. These new data should improve the application of D-H and ¹⁸O-¹⁶O isotopes to constrain the temperature and origin of hydrothermal fluids responsible for serpentine formation in a variety of geologic settings.     

The origin of Zn isotope fractionation in sulfides

Isotope fractionation of Zn between aqueous sulfide, chloride, and carbonate species (Zn²⁺, Zn(HS)₂, , , ZnS(HS)⁻, ZnCl⁺, ZnCl₂, , and ZnCO₃) was investigated using ab initio methods. Only little fractionation is found between the sulfide species, whereas carbonates are up to 1‰ heavier than the parent solution. At pH > 3 and under atmospheric-like CO₂ pressures, isotope fractionation of Zn sulfides precipitated from sulfidic solutions is affected by aqueous sulfide species and the δ⁶⁶Zn of sulfides reflect these in the parent solutions. Under high P_CO2 conditions, carbonate species become abundant. In high P_CO2 conditions of hydrothermal solutions, Zn precipitated as sulfides is isotopically nearly unfractionated with respect to a low-pH parent fluid. In contrast, negative δ⁶⁶Zn down to at least −0.6‰ can be expected in sulfides precipitated from solutions with pH > 9. Zinc isotopes in sulfides and rocks therefore represent a potential indicator of mid to high pH in ancient hydrothermal fluids.