Europium retention onto clay minerals from 25 to 150 °C: Experimental measurements, spectroscopic features and sorption modelling

The sorption of Eu(III) onto kaolinite and montmorillonite was investigated up to 150 °C. The clays were purified samples, saturated with Na in the case of montmorillonite. Batch experiments were conducted at 25, 40, 80 and 150 °C in 0.5 M NaClO₄ solutions to measure the distribution coefficients (Kd) of Eu as a trace element (<10⁻⁶ mol/L) between the solution and kaolinite. For the Na-montmorillonite, we used Kd results from a previous study [Tertre, E., Berger, G., Castet, S., Loubet, M., Giffaut, E., 2005. Experimental study of adsorption of Ni²⁺, Cs⁺ and Ln³⁺ onto Na-montmorillonite up to 150 °C. Geochim. Cosmochim. Acta69, 4937-4948] obtained under exactly the same conditions. The number and nature of the Eu species sorbed onto both clay minerals were investigated by time resolved laser fluorescence spectroscopy (TRLFS) in specific experiments in the same temperature range. We identified a unique inner-sphere complex linked to the aluminol sites in both clays, assumed to be AlOEu²⁺ at the edge of the particles, and a second exchangeable outer-sphere complex for montmorillonite, probably in an interlayer position. The Kd values were used to adjust the parameters of a surface complexation model (DLM: diffuse layer model) from 25 to 150 °C. The number of Eu complexes and the stoichiometry of reactions were constrained by TRLFS. The acidity constants of the amphoteric aluminol sites were taken from another study [Tertre, E., Castet, S., Berger, G., Loubet, M., Giffaut, E. Acid/base surface chemistry of kaolinite and Na-montmorillonite at 25 and 60 °C: experimental study and modelling. Geochim. Cosmochim. Acta, in press], which integrates the influence of the negative structural charge of clays on the acid/base properties of edge sites as a function of temperature and ionic strength. The results of the modelling show that the observed shift of the sorption edge towards low pH with increasing temperature results solely from the contribution of the AlOEu²⁺ edge complexes. Finally, we successfully tested the performance of our model by confronting the predictions with experimental Kd data. We used our own data obtained at lower ionic strength (previous study) or higher suspension density and higher starting concentration (TRLFS runs, this study), as well as published data from other experimental studies [Bradbury, M.H., Baeyens, B., 2002. Sorption of Eu on Na and Ca-montmorillonite: experimental investigations and modeling with cation exchange and surface complexation. Geochim. Cosmochim. Acta66, 2325-2334; Kowal-Fouchard, A., 2002. Etude des mécanismes de rétention des ions U(IV) et Eu(III) sur les argiles: influence des silicates. Ph.D. Thesis, Université Paris Sud, France, 330p].     

An experimental study of the solubility and speciation of neodymium (III) fluoride in F-bearing aqueous solutions

The solubility of neodymium (III) fluoride was investigated at temperatures of 150, 200 and 250 °C, saturated water vapor pressure, and a total fluoride concentration (HF°_aq + F⁻) ranging from 2.0 × 10⁻³ to 0.23 mol/l. The results of the experiments show that Nd³⁺ and NdF²⁺ are the dominant species in solution at the temperatures investigated and were used to derive formation constants for NdF²⁺ and a solubility product for NdF₃. The solubility product of NdF₃(logK_sp=loga_Nd³⁺+3loga_F^-) is −24.4 ± 0.2, −22.8 ± 0.1, and −21.5 ± 0.2 at 250, 200 and 150 °C, respectively, and the formation constant of NdF²⁺(logβ=loga_NdF²⁺-loga_Nd³⁺-loga_F^-) is 6.8 ± 0.1, 6.2 ± 0.1, and 5.5 ± 0.2 at 250, 200 and 150 °C, respectively. The results of this study show that published theoretical predictions significantly overestimate the stability of NdF²⁺ and the solubility of NdF₃.The potential impact of the results on natural systems was evaluated for a hypothetical fluid with a composition similar to that responsible for REE mineralization in the Capitan pluton, New Mexico. In contrast to results obtained using the theoretical predictions of Haas [Haas J. R., Shock E. L., and Sassani D. C. (1995) Rare earth elements in hydrothermal systems: estimates of standard partial molal thermodynamic properties of aqueous complexes of the rare earth elements at high pressures and temperatures. Geochim. Cosmochim. Acta59, 4329-4350.], which indicate that NdF²⁺ is the dominant species in solution, calculations employing the data presented in this paper and previously published experimental data for chloride and sulfate species [Migdisov A. A., and Williams-Jones A. E. (2002) A spectrophotometric study of neodymium(III) complexation in chloride solutions. Geochim. Cosmochim. Acta66, 4311-4323; Migdisov A. A., Reukov V. V., and Williams-Jones A. E. (2006) A spectrophotometric study of neodymium(III) complexation in sulfate solutions at elevated temperatures. Geochim. Cosmochim. Acta70, 983-992.] show that neodymium chloride species predominate and that neodymium fluoride species are relatively unimportant. This suggests that accepted models for REE deposits that invoke fluoride complexation as the method of hydrothermal REE transport may need to be re-evaluated.     

Element partitioning during precipitation of aragonite from seawater: A framework for understanding paleoproxies

This study presents the results from precipitation experiments carried out to investigate the partitioning of the alkaline earth cations Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ between abiogenic aragonite and seawater as a function of temperature. Experiments were carried out at 5 to 75 °C, using the protocol of Kinsman and Holland [Kinsman, D.J.J., Holland, H.D., 1969. The coprecipitation of cations with CaCO₃ IV. The coprecipitation of Sr²⁺ with aragonite between 16 and 96 °C. Geochim. Cosmochim. Acta33, 1-17.] The concentrations of Mg Sr and Ba were determined in the fluid from each experiment by inductively coupled plasma-mass spectrometry, and in individual aragonite grains by secondary ion mass spectrometry. The experimentally produced aragonite grains are enriched in trace components (“impurities”) relative to the concentrations expected from crystal-fluid equilibrium, indicating that kinetic processes are controlling element distribution. Our data are not consistent with fractionations produced kinetically in a boundary layer adjacent to the growing crystal because Sr²⁺, a compatible element, is enriched rather than depleted in the aragonite. Element compatibilities, and the systematic change in partitioning with temperature, can be explained by the process of surface entrapment proposed by Watson and Liang [Watson, E.B., Liang, Y., 1995. A simple model for sector zoning in slowly grown crystals: implications for growth rate and lattice diffusion, with emphasis on accessory minerals in crustal rocks. Am. Mineral.80, 1179-1187] and Watson [Watson, E.B., 1996. Surface enrichment and trace-element uptake during crystal growth. Geochim. Cosmochim. Acta60, 5013-5020; Watson, E.B., 2004. A conceptual model for near-surface kinetic controls on the trace-element and stable isotope composition of abiogenic calcite crystals. Geochim. Cosmochim. Acta68, 1473-1488]. This process is thought to operate in regimes where the competition between crystal growth rate and diffusivity in the near-surface region limits the extent to which the solid can achieve partitioning equilibrium with the fluid. A comparison of the skeletal composition of Diploria labyrinthiformis (brain coral) collected on Bermuda with results from precipitation calculations carried out using our experimentally determined partition coefficients indicate that the fluid from which coral skeleton precipitates has a Sr/Ca ratio comparable to that of seawater, but is depleted in Mg and Ba, and that there are seasonal fluctuations in the mass fraction of aragonite precipitated from the calcifying fluid (“precipitation efficiency”). The combined effects of surface entrapment during aragonite growth and seasonal fluctuations in “precipitation efficiency” likely forms the basis for the temperature information recorded in the aragonite skeletons of Scleractinian corals.     

An XAS study of the structure and thermodynamics of Cu(I) chloride complexes in brines up to high temperature (400 °C, 600 bar)

The transport and deposition of copper in saline hydrothermal fluids are controlled by the stability of copper(I) complexes with ligands such as chloride. Despite their role in the formation of most hydrothermal copper deposits, the nature and stability of Cu(I) chloride complexes in highly saline brines remains controversial. We present new X-ray absorption data (P = 600 bar, T = 25-400 °C, salinity up to 17.2 m Cl), which indicate that the linear (x = 1, 2) complexes are stable up to supercritical conditions. Distorted trigonal planar complexes predominate at room temperature and at high salinity (>3 m LiCl): subtle changes in the XANES spectrum with increasing salinity may reflect geometric distortions of this complex. Similar changes were observed in UV-Vis data [Liu, W., Brugger, J., McPhail, D.C., Spiccia, L., 2002. A spectrophotometric study of aqueous copper(I) chloride complexes in LiCl solutions between 100 °C and 250 °C. Geochim. Cosmochim. Acta66, 3615-3633], and were erroneously interpreted as a new species, . Our XAS data and ab-initio XANES calculations show that this tetrahedral species is not present to any significant degree in our solutions. The stability of the complexe decreases with increasing temperature; under supercritical conditions and in brines under magmatic-hydrothermal conditions (e.g., 15.58 m Cl, 400 °C, 600 bar), only the linear Cu(I) chloride complexes were observed. This result and the instability of the complex are also consistent with the recent ab-initio molecular dynamic calculations of Sherman [Sherman D. M.(2007) Complexation of Cu⁺ in hydrothermal NaCl brines: ab-initio molecular dynamics and energetics. Geochim. Cosmochim. Acta71, 714-722]. This study illustrates the power of the quantitative nature of XANES and EXAFS measurements for deciphering the speciation of weak transition metal complexes up to magmatic-hydrothermal conditions.The systematic XANES data are used to retrieve the formation constant for at 150 °C, which is in good agreement with the reinterpretation of the UV-Vis data of Liu et al. (Liu et al., 2002). At high temperatures (?400 °C), the solubility of chalcopyrite in equilibrium with hematite-magnetite-pyrite and K-feldspar-muscovite-quartz calculated with the new properties is lower than that calculated using the previous model, and the calculated solubilities are at the lower end of the range of values measured in brine inclusions from porphyry copper systems.     

An isopiestic study of aqueous NaBr and KBr at 50 °C: Chemical equilibrium model of solution behavior and solubility in the NaBr-H2O, KBr-H2O and Na-K-Br-H2O systems to high concentration and temperature

The isopiestic method has been used to determine the osmotic coefficients of the binary solutions NaBr-H₂O (from 0.745 to 5.953 mol kg⁻¹) and KBr-H₂O (from 0.741 to 5.683 mol kg⁻¹) at the temperature t = 50 °C. Sodium chloride solutions have been used as isopiestic reference standards. The isopiestic results obtained have been combined with all other experimental thermodynamic quantities available in literature (osmotic coefficients, water activities, bromide mineral’s solubilities) to construct a chemical model that calculates solute and solvent activities and solid-liquid equilibria in the NaBr-H₂O, KBr-H₂O and Na-K-Br-H₂O systems from dilute to high solution concentration within the 0-300 °C temperature range. The Harvie and Weare [Harvie C., and Weare J. (1980) The prediction of mineral solubilities in naturalwaters: the Na-K-Mg-Ca-Cl-SO₄-H₂O system from zero to high concentration at 25 °C. Geochim. Cosmochim. Acta44, 981-997] solubility modeling approach, incorporating their implementation of the concentration-dependent specific interaction equations of Pitzer [Pitzer K. (1973) Thermodynamics of electrolytes. I. Theoretical basis and general equations. J. Phys. Chem.77, 268-277] is employed. The model for binary systems is validated by comparing activity coefficient predictions with those given in literature, and not used in the parameterization process. Limitations of the mixed solutions model due to data insufficiencies are discussed. This model expands the variable temperature sodium-potassium model of Greenberg and Moller [Greenberg J., and Moller N. (1989) The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-K-Ca-Cl-SO₄-H₂O system to high concentration from 0 to 250 °C. Geochim. Cosmochim. Acta53, 2503-2518] by evaluating Br⁻ pure electrolyte and mixing solution parameters and the chemical potentials of three bromide solid phases: NaBr-2H₂O (cr), NaBr (cr) and KBr (cr).     

Water and magmas: clarification of a controversy on applications of the Gibbs-Duhem equation

It is shown mathematically that if the activity coefficient of water in ternary water-magma (aluminosilicate) systems is constant or varies only with the mole fraction of water, it is not necessary that the binary magmas form ideal solutions contrary to the claims by Burnham et al. (1978, Geochim. Cosmochim. Acta42, 275–276). A molecular viewpoint is presented to support this argument. The properties of analytical equations capable of representing the activity coefficients of usual and unusual systems are discussed. The correct form of the Gibbs-Dunhem equation for dissociative dissolution processes is presented to disprove the claims by Burnham (1975, Fortschr. Mineral.52, 101–118; 1975, Geochim. Cosmochim. Acta39, 1077–1084), and by Burnhamet al. (1978, Geochim. Cosmochim. Acta42, 275–276).     

Comment on “A critical evaluation of the boron isotope-pH proxy: The accuracy of ancient ocean pH estimates” by M. Pagani, D. Lemarchand, A. Spivack and J. Gaillardet

Pagani et al. [Pagani M., Lemarchand D., Spivack A., and Gaillardet J. (2005). A critical evaluation of the boron isotope-pH proxy: the accuracy of ancient ocean pH estimates. Geochim. Cosmochim. Acta69(4), 953-961] use data from previous boron isotope studies to suggest that the fractionation between boric acid and borate in seawater as well as the history of δ¹¹B in seawater are poorly understood, thus limiting our ability to capture realistic ocean pH with this proxy. Although we agree with the authors that the long recognized uncertainty in the secular variation of δ¹¹B_seawater imposes a temporal limit on paleo-pH reconstructions, their evaluation of the δ¹¹B/pH relationship in carbonates is flawed. Potential complications from vital, temperature and dissolution effects reported in that paper are based on studies that are experimentally and/or analytically poorly constrained. Using published validation studies we will demonstrate that many of the problems outlined by Pagani et al. have already been addressed, or are based on misinterpretations of previous work. Most importantly, statistical evaluation suggests empirical data are best described by a fractionation of ∼20‰. Recent paleoreconstructions confirm that the boron isotope proxy can be used with confidence, if sample selection and analyses are done carefully.     

Response to the Comment by J. Horita and R.N. Clayton on “The studies of oxygen isotope fractionation between calcium carbonates and water at low temperatures”

The apparent inconsistency in calcite-water fractionation does occur between the arithmetic combination of Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2003) An experimental study of oxygen isotope fractionation between inorganically precipitated aragonite and water at low temperatures. Geochim. Cosmochim. Acta67, 387-399] and the experimental determination of Zhou and Zheng [Zhou G.-T., and Zheng Y.-F. (2005) Effect of polymorphic transition on oxygen isotope fractionation between aragonite, calcite and water: a low-temperature experimental study. Am. Mineral90, 1121-1130]. To resolve this issue is to acknowledge whether or not the isotope salt effect of dissolved minerals would occur on oxygen isotope exchange between water and the minerals of interest. The question is whether or not a term of mineral-water interaction should be taken into account when calculating mineral-water 10³ln α factors by an arithmetic combination between theoretical 10³ln β factors for mineral and water, respectively. The hydrothermal experiments of Hu and Clayton [Hu G.-X., and Clayton R.N. (2003) Oxygen isotope salt effects at high pressure and high temperature, and the calibration of oxygen isotope geothermometers. Geochim. Cosmochim. Acta67, 3227-3246] demonstrate the absence of isotope salt effect on the oxygen isotope fractionation between calcite and water, and this abnormal behavior reasonably explains the so-called inconsistency in the calcite-water fractionations of Zhou and Zheng (2003, 2005). We argue that the mineral-water correction is still necessary for calculation of fractionations in mineral-water systems. New experimental data for oxygen isotope fractionations involving dolomite and cerussite are consistent with the calculations of Zheng [Zheng Y.-F. (1999a) Oxygen isotope fractionation in carbonate and sulfate minerals. Geochem. J.33, 109-126], but also shed light on the assumptions used in modifying the increment method. We argue that the modified increment method has developed into a theoretical mean of predictive power for calculation of oxygen isotope fractionation factors for crystalline minerals of geochemical interest.     

Silicon isotopic fractionation of CAI-like vacuum evaporation residues

Calcium-, aluminum-rich inclusions (CAIs) are often enriched in the heavy isotopes of magnesium and silicon relative to bulk solar system materials. It is likely that these isotopic enrichments resulted from evaporative mass loss of magnesium and silicon from early solar system condensates while they were molten during one or more high-temperature reheating events. Quantitative interpretation of these enrichments requires laboratory determinations of the evaporation kinetics and associated isotopic fractionation effects for these elements. The experimental data for the kinetics of evaporation of magnesium and silicon and the evaporative isotopic fractionation of magnesium is reasonably complete for Type B CAI liquids (Richter F. M., Davis A. M., Ebel D. S., and Hashimoto A. (2002) Elemental and isotopic fractionation of Type B CAIs: experiments, theoretical considerations, and constraints on their thermal evolution. Geochim. Cosmochim. Acta66, 521-540; Richter F. M., Janney P. E., Mendybaev R. A., Davis A. M., and Wadhwa M. (2007a) Elemental and isotopic fractionation of Type B CAI-like liquids by evaporation. Geochim. Cosmochim. Acta71, 5544-5564.). However, the isotopic fractionation factor for silicon evaporating from such liquids has not been as extensively studied. Here we report new ion microprobe silicon isotopic measurements of residual glass from partial evaporation of Type B CAI liquids into vacuum. The silicon isotopic fractionation is reported as a kinetic fractionation factor, α_Si, corresponding to the ratio of the silicon isotopic composition of the evaporation flux to that of the residual silicate liquid. For CAI-like melts, we find that α_Si = 0.98985 ± 0.00044 (2σ) for ²⁹Si/²⁸Si with no resolvable variation with temperature over the temperature range of the experiments, 1600-1900 °C. This value is different from what has been reported for evaporation of liquid Mg₂SiO₄ (Davis A. M., Hashimoto A., Clayton R. N., and Mayeda T. K. (1990) Isotope mass fractionation during evaporation of Mg₂SiO₄. Nature347, 655-658.) and of a melt with CI chondritic proportions of the major elements (Wang J., Davis A. M., Clayton R. N., Mayeda T. K., and Hashimoto A. (2001) Chemical and isotopic fractionation during the evaporation of the FeO-MgO-SiO₂-CaO-Al₂O₃-TiO₂-REE melt system. Geochim. Cosmochim. Acta65, 479-494.). There appears to be some compositional control on α_Si, whereas no compositional effects have been reported for α_Mg. We use the values of α_Si and α_Mg, to calculate the chemical compositions of the unevaporated precursors of a number of isotopically fractionated CAIs from CV chondrites whose chemical compositions and magnesium and silicon isotopic compositions have been previously measured.     

Molecular dynamics simulations of the orthoclase (0 0 1)- and (0 1 0)-water interfaces

Molecular dynamics simulations of water in contact with the (0 0 1) and (0 1 0) surfaces of orthoclase (KAlSi₃O₈) were carried out to investigate the structure and dynamics of the feldspar-water interface, contrast the intrinsic structural properties of the two surfaces, and provide a basis for future work on the diffusion of ions and molecules in microscopic mineral fractures. Electron density profiles were computed from the molecular dynamics trajectories and compared with those derived experimentally from high-resolution X-ray reflectivity measurements by Fenter and co-workers [Fenter P., Cheng L., Park C., Zhang H. and Sturchio N. C. (2003a) Structure of the orthoclase (0 0 1)- and (0 1 0)-water interfaces by high-resolution X-ray reflectivity. Geochim. Cosmochim. Acta67, 4267-4275]. For each surface, three scenarios were considered whereby the interfacial species is potassium, water, or a hydronium ion. Excellent agreement was obtained for the (0 0 1) surface when potassium is the predominant interfacial species; however, some discrepancies in the position of the interfacial peaks were obtained for the (0 1 0) surface. The two surfaces showed similarities in the extent of water ordering at the interface, the activation energies for water and potassium desorption, and the adsorption localization of interfacial species. However, there are also important differences between the two surfaces in the coordination of a given adsorbed species, adsorption site densities, and the propensity for water molecules in surface cavities and those in the first hydration layer to coordinate to surface bridging oxygen atoms. These differences may have implications for the extent of dissolution in the low-pH regime since hydrolysis of Si(Al)OSi(Al) bonds is a major dissolution mechanism.     

Temperature independent thermal expansivities of calcium aluminosilicate melts between 1150 and 1973 K in the system anorthite-wollastonite-gehlenite (An-Wo-Geh): A density model

The thermal expansivities of 10 compositions from within the anorthite-wollastonite-gehlenite (An-Wo-Geh) compatibility triangle have been investigated using a combination of calorimetry and dilatometry on the glassy and liquid samples. The volumes at room temperature were derived from densities measured using the Archimedean buoyancy method. For each sample, density was measured at 298 K using glass that had a cooling-heating history of 10-10 K min⁻¹. The thermal expansion coefficient of the glass from 298 K to the glass transition interval was measured by a dilatometer and the heat capacity was measured using a differential scanning calorimeter from 298 to 1135 K. The thermal expansion coefficient and the heat flow were determined at a heating rate of 10 K min⁻¹ on glasses which were previously cooled at 10 K min⁻¹. Supercooled liquid density, molar volume and molar thermal expansivities were indirectly determined by combining differential scanning calorimetric and dilatometric measurements assuming that the kinetics of enthalpy and shear relaxation are equivalent. The data obtained on supercooled liquids were compared to high-temperature predictions from the models of (Lange, R.A., Carmichael, I.S.E., 1987. Densities of Na₂O-K₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-TiO₂-SiO₂ liquids: New measurements and derived partial molar properties. Geochim. Cosmochim. Acta51, 2931-2946; Courtial, P., Dingwell, D.B., 1995. Nonlinear composition dependence of molar volume of melts in the CaO-Al₂O₃-SiO₂ system. Geochim. Cosmochim. Acta59 (18), 3685-3695; Lange, R.A., 1997. A revised model for the density and thermal expansivity of K₂O-Na₂O-CaO-MgO-Al₂O₃-SiO₂ liquids from 700 to 1900 K: extension to crustal magmatic temperatures. Contrib. Mineral. Petrol.130, 1-11). The best linear fit combines the supercooled liquid data presented in this study and the high temperature data calculated using the Courtial and Dingwell (1995) model. This dilatometric/calorimetric method of determining supercooled liquid molar thermal expansivity greatly increases the temperature range accessible for thermal expansion. It represents a substantial increase in precision and understanding of the thermodynamics of calcium aluminosilicate melts. This enhanced precision demonstrates clearly the temperature independence of the melt expansions in the An-Wo-Geh system. This contrasts strongly with observations for neighboring system such as anorthite-diopside and raises the question of the compositional/structural origins of temperature dependence of thermal expansivity in multicomponent silicate melts.     

The role of reaction affinity and secondary minerals in regulating chemical weathering rates at the Santa Cruz Soil Chronosequence, California

In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation, and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka Marine Terrace Chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized [White A. F., Schulz M. S., Vivit D. V., Blum A., Stonestrom D. A. and Anderson S. P. (2008) Chemical weathering of a Marine Terrace Chronosequence, Santa Cruz, California. I: interpreting the long-term controls on chemical weathering based on spatial and temporal element and mineral distributions. Geochim. Cosmochim. Acta72 (1), 36-68] and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisserand [Hellmann R. and Tisserand D. (2006) Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar. Geochim. Cosmochim. Acta70 (2), 364-383] or the aluminum inhibition model proposed by Oelkers et al. [Oelkers E. H., Schott J. and Devidal J. L. (1994) The effect of aluminum, pH, and chemical affinity on the rates of aluminosilicate dissolution reactions. Geochim. Cosmochim. Acta58 (9), 2011-2024], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site.Additionally, observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO₂(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total mass removed from the weathering profile. Our analysis suggests that secondary clay precipitation is as important as aqueous transport in governing the amount of dissolution that occurs within a profile because clay minerals exert a strong control over the reaction affinity of the dissolving primary minerals. The modeling also indicates that the weathering advance rate and the total mass of mineral dissolved is controlled by the thermodynamic saturation of the primary dissolving phases plagioclase and K-feldspar, as is evident from the difference in propagation rates of the reaction fronts for the two minerals despite their very similar kinetic rate laws.     

A numerical model of trace-element coprecipitation in a physicochemical calcification system: Application to coral biomineralization and trace-element ‘vital effects’

A mixed equilibrium/kinetic steady-state numerical model of coral calcification has been developed to test whether a physicochemical calcification mechanism is able to account for recent geochemical observations, in particular correlated trace-element variations presented in a companion paper [Sinclair, D.J., 2005. Correlated trace-element ‘vital effects’ in tropical corals: a new tool for probing biomineralization chemistry. Geochim. Cosmochim. Acta69 (13), 3265-3284]. The model simulates trace-element partitioning from a CaCO₃ supersaturated extracellular calcifying fluid (ECF) which has been modified by enzymatic input of Ca²⁺ and removal of 2H⁺ by CaATPase. CO₂ input is modelled as a diffusion process, while the ECF is continuously replenished by fresh seawater, which is the sole source of minor and trace-elements (TEs). Trace-element species fully equilibrate in the ECF, and selected trace-element species kinetically compete with Ca²⁺ or at the surface of the growing crystal. Each simulation is run to steady-state, and results are presented for a grid of CaATPase ion pumping rates and seawater replenishment rates. The dominant feature of the model output occurs when CaATPase ion pumping is high while seawater replenishment rates are low. At this point, CO₂ diffusion reaches its maximum, C input becomes limiting, buffering capacity is reduced and the pH of the system rises dramatically; significantly affecting the TE composition of the skeleton. At more modest pumping rates, the model reproduces the relative amplitudes of trace-element variations and slopes of the mutually positive correlations between B, Sr and U observed by Sinclair [Sinclair, D.J., 2005. Correlated trace-element ‘vital effects’ in tropical corals: a new tool for probing biomineralization chemistry. Geochim. Cosmochim. Acta69 (13), 3265-3284], but does not reproduce the negative correlations with Mg. The best fit between model and observation occurs when the coral simultaneously increases ion pumping and seawater replenishment rates: a strategy which allows rapid calcification while avoiding dangerously high pH variations. The model predicts that calcification occurs at only moderate pH elevations (8.3-8.4) with seasonal TE variations being explained by a shift of only 0.3 pH units. The model does not reproduce the full amplitude of diurnal pH variations observed recently. Sensitivity tests show that the model output is relatively insensitive to changes in the composition of the fluid from which the ECF is drawn (such as might occur if photosynthesis or active C transport mechanisms significantly modify the penultimate fluid source). Further research, however, is needed to establish the consequences of active transport of TEs and anions to the calcifying site.     

Meteoritic component and impact melt composition at the lac à l'Eau Claire (clearwater) impact structures,Quebec

The major and selected trace element composition of the melt at the eastern Lac à l'Eau Claire impact structure can be modelled by 52.3% granodiorite, 15.1% granulite, 25.7% quartz-monzonite plus 6.9% Orgueil (C1-chondrite). A satisfactory fit to melt at the western structure requires 57.4% granulite and 42.6% quartz-monzonite. These models agree with the suggestions of Palmeet al. (1978, Geochim. Cosmochim. Acta42, 313–323) on the type and extent of meteoritic component in the melts.     

Response to the comment by Z.F. Zhao and T.S. Gao (2007) on “Paleozoic ages and excess Ar in garnets from the Bixiling eclogite in dabieshan, China: New insights from Ar/Ar dating by stepwise crushing”

In our paper we supposed that the Paleozoic ages of the Bixiling eclogitic garnets by ⁴⁰Ar/³⁹Ar crushing in vacuo were related to the UHP metamorphism. Zhao and Gao [Zhao Z.-F. and Gao T.-S. (2007) Comment on “Paleozoic ages and excess ⁴⁰Ar in garnets from the Bixiling eclogite in Dabieshan, China:Newinsights from ⁴⁰Ar/³⁹Ar dating by stepwise crushing” by Qiu and Wijbrans (2006). Geochim. Cosmochim. Acta71(24), 6046-6050] dispute our conclusions and re-interpret them as “the age of garnet growth by low-T/HP blueschist/eclogite-facies metamorphism of the UHP eclogite precursor during arc-continent collision in the early Paleozoic” without presenting any new petrological evidence. Based on our present understanding of ⁴⁰Ar/³⁹Ar crushing technique and petrological observations, we do not agree with their re-interpretation and still prefer our original interpretation.     

Calibration of the carbonate ‘clumped isotope’ paleothermometer for otoliths

Paleothermometry is an essential tool for understanding past changes in climate. The ‘carbonate clumped isotope thermometer’ is a temperature proxy related to ordering of ¹³C and ¹⁸O in the carbonate lattice (based on measurements of ¹³C¹⁸O¹⁶O in CO₂ produced by acid digestion of carbonate). This thermometer has been previously calibrated for inorganic calcite and aragonitic corals [Ghosh P., Adkins J., Affek H., Balta B., Guo W. F., Schauble E. A., Schrag D., and Eiler J. M. (2006) C-13-O-18 bonds in carbonate minerals: a new kind of paleothermometer. Geochim. Cosmochim. Acta70 (6), 1439-1456]. Here we determine the relationship between growth temperatures of aragonitic fish otoliths and abundances of ¹³C¹⁸O¹⁶O produced by acid digestion of those otoliths. Our calibration is based on analyses of otoliths from six species from four genera of modern fish sampled from a latitudinal transect of the Atlantic Ocean between 54° S and 65° N, plus one species from the tropical western Pacific. The temperatures at which fish otoliths precipitated were estimated by the mean temperature in the waters in which they lived, averaged over their estimated lifetimes. Estimated growth temperatures of our samples vary between 2 and 25 °C. Our results show that the abundance of ¹³C¹⁸O¹⁶O in CO₂ produced by acid digestion of fish otolith aragonite is a function of growth temperature, following the relationship: , where Δ₄₇ is the enrichment, in per mil, of ¹³C¹⁸O¹⁶O in CO₂ relative to the amount expected for a stochastic (random) distribution of isotopes among all CO₂ isotopologues, and T is the temperature in Kelvin. This relationship closely approaches that previously documented for inorganic calcite and aragonitic coral (Ghosh et al., 2006).     

The activity coefficients of Fe(III) hydroxide complexes in NaCl and NaClO4 solutions

The osmotic coefficients of FeCl₃ at 25 °C from 0.15 to 1.7 m [Rumyantsev et al., Z. Phys. Chem., 218, 1089-1127, 2004] have been used to determine the Pitzer parameters (β⁽⁰⁾, β⁽¹⁾ and C^?) for FeCl₃. Since the differences in the Pitzer coefficients of rare earths in NaCl and NaClO₄ are small, the values of Fe(ClO₄)₃ have been estimated using the differences between La(ClO₄)₃ and LaCl₃. The Pitzer coefficients for FeCl₃ combined with enthalpy and heat capacity data for the rare earths can be used to estimate the activity coefficients of Fe³⁺ in NaCl over a wide range of temperatures (0 to 50 °C) and ionic strength (0 to 6 m).The activity coefficients of Fe³⁺ in NaCl and NaClO₄ solutions have been used to determine the activity coefficients of Fe(OH)²⁺ in these solutions from the measured first hydrolysis constants of Fe³⁺ [Byrne et al., Mar. Chem., 97, 34-48, 2005]. The activity coefficients of , Fe(OH)₃ and from 0 to 50 °C have also been determined from the solubility measurements of Fe(III) in NaCl solutions [Liu and Millero, Geochim. Cosmochim Acta, 63, 3487-3497, 1999]. These activity coefficients have been fitted to the Pitzer equations. These results can be used to estimate the speciation of Fe(III) with OH⁻ in natural waters with high concentrations of NaCl from 0 to 50 °C.     

Evidence from Ar/Ar ages of lunar impact glasses for an increase in the impact rate ∼800 Ma ago

Geochemical and ⁴⁰Ar/³⁹Ar data on nine impact glasses from the Apollo 14, 16, and 17 landing sites indicate at least seven distinct impact events with ages ∼800 Ma. Rock fragments analyzed by Barra et al. [Barra F., Swindle T. D., Korotev R. L., Jolliff B. L., Zeigler R. A., and Olsen E. (2006) ⁴⁰Ar-³⁹Ar dating of Apollo 12 regolith: implications for the age of Copernicus and the source of nonmare materials, Geochim. Cosmochim. Acta,70, 6016-6031] from the Apollo 12 landing site and some Apollo 12 spherules reported by Levine et al. [Levine J., Becker T. A., Muller R. A., Renne P. R. (2005) ⁴⁰Ar/³⁹Ar dating of Apollo 12 impact spherules, Geophys. Res. Let., 32, L15201, doi: 10.1029/2005GL022874.] show ∼800 Ma ages, close to the accepted age of the Copernicus event, 800 ± 15 Ma [Bogard D. D., Garrison D. H., Shih C. Y., and Nyquist L. E. (1994) ³⁹Ar-⁴⁰Ar dating of two lunar granites: The age of Copernicus, Geochim. Cosmochim. Acta, 58, 3093-3100]. These Apollo 12 samples are thought to have been affected by material from the Copernicus event since there is a Copernicus ray going through the Apollo 12 landing site. When all of these data are viewed collectively, including an Apollo 16 glass bomb [Borchardt R., Stöffler D., Spettel B., Palme H. and Wänke H. (1986) Composition, structure, and age of the Apollo 16 subregolith basement as deduced from the chemistry of post-Imbrium melt bombs. In Proceedings, 17th Lunar and Planetary Science Conference, pp. E43-E54], and in the context of diverse compositional range and sample location, there is a suggestion that there may have been a transient increase in the global lunar impact flux at ∼800 Ma. Therefore, the Copernicus impact event could have been one of many. If correct, there should be evidence for this increased impact flux around 800 Ma ago in the age statistics of terrestrial impact samples.     

A thermodynamic model for calculating methane solubility, density and gas phase composition of methane-bearing aqueous fluids from 273 to 523 K and from 1 to 2000 bar

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.