中酸性硅酸盐熔体-水体系氢同位素分馏的压力效应

对0．2－2000MPa条件下钠长石熔体，钾长石熔体以及0．2－150MPa条件下流纹岩熔体－－水体系的氢同位素分馏实验数据进行了筹压拟合，发现硅酸盐熔体与水之间的氢同位素分馏存在显著的压力效应，在800，1000和1200度条件下对钠长石熔体，水体系和流夺熔体－－水体系氢同位素分馏压力方程进行的等温拟合表明，只有在特定的压力条件下才可以用钠长石熔体－水体系来近似流纹岩熔体－－水体系的氢同位素分馏行为，当压力超过临界值时，硅酸盐熔体－水体系氢同位素分馏会发生变化，本文拟合的硅酸盐熔体－水体系氢同位素分馏等值线在P－T空间的形态变化特征与矿物－水体系存在较大差异，依据流纹岩熔体与水之间氢同位素分馏的压力效应，成功地模拟了美国西部Glass Creek流纹岩δD值和水含量变化规律与岩浆去气之间的关系。     

Li isotope fractionation in peridotites and mafic melts

We have measured the Li isotope ratios of a range of co-existing phases from peridotites and mafic magmas to investigate high-temperature fractionations of ⁷Li/⁶Li. The Li isotopic compositions of seven mantle peridotites, reconstructed from analyses of mineral separates, show little variation (δ⁷Li 3.2-4.9‰) despite a wide range in fertility and radiogenic isotopic compositions. The most fertile samples yield a best estimate of δ⁷Li ∼ 3.5‰ for the upper mantle. Bulk analyses of olivine separates from the xenoliths are typically ∼1.5‰ isotopically lighter than co-existing orthopyroxenes, suggestive of a small, high-temperature equilibrium isotope fractionation. On the other hand, bulk analyses of olivine phenocrysts and their host melts are isotopically indistinguishable. Given these observations, equilibrium mantle melting should generate melts with δ⁷Li little different from their sources (<0.5‰ lighter). In contrast to olivine and orthopyroxene, that dominate peridotite Li budgets, bulk clinopyroxene analyses are highly variable (δ⁷Li = 6.6‰ to −8.1‰). Phlogopite separated from a modally metasomatised xenolith yielded an extreme δ⁷Li of −18.9‰. Such large Li isotope variability is indicative of isotopic disequilibrium. This inference is strongly reinforced by in situ, secondary ion mass-spectrometry analyses which show Li isotope zonation in peridotite minerals. The simplest zoning patterns show isotopically light rims. This style of zoning is also observed in the phenocrysts of holocrystalline Hawaiian lavas. More dramatically, a single orthopyroxene crystal from a San Carlos xenolith shows a W-shaped Li isotope profile with a 40‰ range in δ⁷Li, close to the isotope variability seen in all terrestrial whole rock analyses. We attribute Li isotope zonation in mineral phases to diffusive fractionation of Li isotopes, within mineral phases and along melt pathways that pervade xenoliths. Given the high diffusivity of Li, the Li isotope profiles we observe can persist, at most, only a few years at magmatic temperatures. Our results thus highlight the potential of Li isotopes as a high-resolution geospeedometer of the final phases of magmatic activity and cooling.     

Isotopic fractionation of the major elements of molten basalt by chemical and thermal diffusion

Samples produced in piston cylinder experiments were used to document the thermal isotopic fractionation of all the major elements of basalt except for aluminum and the fractionation of iron isotopes by chemical diffusion between a natural basalt and rhyolite. The thermal isotopic fractionations are summarized in terms of a parameter Ω_i defined as the fractionation in per mil per 100 °C per atomic mass units difference between the isotopes. For molten basalt we report Ω_Ca = 1.6, Ω_Fe = 1.1, Ω_Si = 0.6, Ω_O = 1.5. In an earlier paper we reported Ω_Mg = 3.6. These fractionations represent a steady state balance between thermal diffusion and chemical diffusion with the mass dependence of the thermal diffusion coefficient being significantly larger than the mass dependence of the chemical diffusion coefficients for isotopes of the same element. The iron isotopic measurements of the basalt-rhyolite diffusion couple showed significant fractionation that are parameterized in terms of a parameter β_Fe = 0.03 when the ratio of the diffusion coefficients D₅₄ and D₅₆ of ⁵⁴Fe and ⁵⁶Fe is expressed in terms of the atomic mass as D₅₄/D₅₆ = (56/54)^β_Fe. This value of β_Fe is smaller than what we had measured earlier for lithium, magnesium and calcium (i.e., β_Li = 0.215, β_Ca = 0.05, β_Mg = 0.05) but still significant when one takes into account the high precision with which iron isotopic compositions can be measured (i.e., ±0.03‰) and that iron isotope fractionations at magmatic temperatures from other causes are extremely small. In a closing section we discuss technological and geological applications of isotopic fractionations driven by either or both chemical and thermal gradients.     

High-temperature Si isotope fractionation between iron metal and silicate

The Si stable isotope fractionation between metal and silicate has been investigated experimentally at 1800, 2000, and 2200 °C. We find that there is a significant silicon stable isotope fractionation at high temperature between metal and silicate in agreement with Shahar et al. (2009). Further we find that this fractionation is insensitive to the structure and composition of the silicate as the fractionation between silicate melt and olivine is insignificant within the error of the analyses. The temperature-dependent silicon isotope fractionation is Δ³⁰Si_{silicate-metal} = 7.45 ± 0.41 × 10⁶/T². We also demonstrate the viability of using laser ablation MC-ICPMS as a tool for measuring silicon isotope ratios in high pressure and temperature experiments.     

Structural controls and mechanisms of diffusion in natural silicate melts

The diffusion properties of Na, Cs, Ba, Fe and Eu ions have been determined experimentally for a pantellerite melt and of these ions plus Li, Mn and Co in pitchstone melt, using the radiotracer residual-activity method, and narrow platinum capillaries, over the temperature range 1,200–1,400° C. In addition, Eu diffusion in a basaltic and an andesitic melt was determined. Diffusion of all cations follows an Arrhenius relationship, activation energy values being high for diffusion in the pantellerite melt (e.g. Eu: 100 kcal mol^–1) except in the case of Na (24.3 kcal mol^–1). Activation energies of diffusion in the pitchstone melt are similar to values recorded earlier for andesitic and basaltic melts.The new data are used, along with previously published data for diffusion in other composition melts, to examine the compositional and structural controls on diffusion. The range of diffusivities shows a marked change with melt composition; over two orders of magnitude for a basaltic melt, and nearly four orders for a pantellerite melt (both at 1,300° C). Diffusivity of all cations (except Li and Na) correlates positively with the proportion of network modifying cations. In the case of Li and Na the correlation is negative but the diffusivity of these ions correlates positively with the proportion of Na or of Na + K ions in the bulk melt. Diffusion behaviour in the pantellerite melt departs from the relationships shown by the data for other melt compositions, which could be partly explained by trivalent ions (such as Fe) occupying network forming positions. The diffusivity of alkali metal ions is strongly dependent on ionic radius, but this is not the case with the divalent and trivalent ions; diffusivity of these ions remains relatively constant with change in radius but decreases with increase in ionic charge.A compensation diagram shows four distinct but parallel trends for the majority of the cations in four melt types but the data for Li and Na plot on a separate trend. This and the other relationships are used to elucidate possible mechanisms of diffusion. Exchange mechanisms appear to be common, with the preservation of local charge balance. Li and Na diffuse by a distinct mechanism which involves exchange of similar or identical ions. The diffusion behaviour of the smaller alkali metal ions is sufficiently distinct from all other cations to indicate that diffusion could be an important factor in the geochemical fractionation of the alkali elements.s     

The mechanisms of water diffusion in polymerized silicate melts

Diffusion of water was experimentally investigated for melts of albitic (Ab) and quartz-orthoclasic (Qz₂₉Or₇₁, in wt %) compositions with water contents in the range of 0 to 8.5 wt % at temperatures of 1100 to 1200 °C and at pressures of 1.0 and 5.0 kbar. Apparent chemical diffusion coefficients of water (D _water) were determined from concentration-distance profiles measured by FTIR microspectroscopy. Under the same P-T condition and water content the diffusivity of water in albitic, quartz-orthoclasic and haplogranitic (Qz₂₈Ab₃₈ Or₃₄, Nowak and Behrens, this issue) melts is identical within experimental error. Comparison to data published in literature indicates that anhydrous composition only has little influence on the mobility of water in polymerized melts but that the degree of polymerization has a large effect. For instance, D_water is almost identical for haplogranitic and rhyolitic melts with 0.5–3.5 wt % water at 850 °C but it is two orders of magnitude higher in basaltic than in haplogranitic melts with 0.2–0.5 wt % water at 1300 °C. Based on the new water diffusivity data, recently published in situ near-infrared spectroscopic data (Nowak 1995; Nowak and Behrens 1995), and viscosity data (Schulze et al. 1996) for hydrous haplogranitic melts current models for water diffusion in silicate melts are critically reviewed. The NIR spectroscopy has indicated isolated OH groups, pairs of OH groups and H₂O molecules as hydrous species in polymerized silicate melts. A significant contribution of isolated OH groups to the transport of water is excluded for water contents above 10 ppm by comparison of viscosity and water diffusion data and by inspection of concentration profiles from trace water diffusion. Spectroscopic measurements have indicated that the interconversion of H₂O molecules and OH pairs is relatively fast in silicate glasses and melts even at low temperature and it is inferred that this reaction is an active step for migration of water. However, direct jumps of H₂O molecules from one cavity within the silicate network to another one can not be excluded. Thus, we favour a model in which water migrates by the interconversion reaction and, possibly, small sequences of direct jumps of H₂O molecules. In this model, immobilization of water results from dissociation of the OH pairs. Assuming that the frequency of the interconversion reaction is faster than that of diffusive jumps, OH pairs and water molecules can be treated as a single diffusing species having an effective diffusion coefficient . The shape of curves of D_water versus water content implies that increases with water content. The change from linear to exponential dependence of D_water between 2 and 3 wt % water is attributed to the influence of the dissociation reaction at low water content and to the modification of the melt structure by incorporation of OH groups. Received: 26 March 1996 / Accepted: 23 August 1996     

Magnesium stable isotope fractionation in marine biogenic calcite and aragonite

This survey of magnesium stable isotope compositions in marine biogenic aragonite and calcite includes samples from corals, sclerosponges, benthic porcelaneous and planktonic perforate foraminifera, coccolith oozes, red algae, and an echinoid and brachiopod test. The analyses were carried out using MC-ICP-MS with an external repeatability of ±0.22‰ (2SD for δ²⁶Mg; n = 37), obtained from a coral reference sample (JCp-1).Magnesium isotope fractionation in calcitic corals and sclerosponges agrees with published data for calcitic speleothems with an average Δ²⁶Mg_{calcite-seawater} = −2.6 ± 0.3‰ that appears to be weakly related to temperature. With one exception (Vaceletia spp.), aragonitic corals and sclerosponges also display uniform Mg isotope fractionations relative to seawater with Δ²⁶Mg_{biogenic aragonite-seawater} = −0.9 ± 0.2.Magnesium isotopes in high-Mg calcites from red algae, echinoids and perhaps some porcelaneous foraminifera as well as in all low-Mg calcites (perforate foraminifera, coccoliths and brachiopods) display significant biological influences. For planktonic foraminifera, the Mg isotope data is consistent with the fixation of Mg by organic material under equilibrium conditions, but appears to be inconsistent with Mg removal from vacuoles. Our preferred model, however, suggests that planktonic foraminifera synthesize biomolecules that increase the energetic barrier for Mg incorporation. In this model, the need to remove large quantities of Mg from vacuole solutions is avoided. For the high-Mg calcites from echinoids, the precipitation of amorphous calcium carbonate may be responsible for their weaker Mg isotope fractionation.Disregarding superimposed biological effects, it appears that cation light isotope enrichments in CaCO₃ principally result from a chemical kinetic isotope effect, related to the incorporation of cations at kink sites. In this model, the systematics of cation isotope fractionations in CaCO₃ relate to the activation energy required for cation incorporation, which probably reflects the dehydration of the cation and the crystal surface and bond formation at the incorporation site. This kinetic incorporation model predicts (i) no intrinsic dependence on growth rate, unless significant back reaction upon slow growth reduces the isotope fractionation towards that characteristic for equilibrium isotope partitioning (this may be observed for Ca isotopes in calcites), (ii) a small decrease of isotope fractionation with increasing temperature that may be amplified if higher temperatures promote back reaction and (iii) a sensitivity to changes in the activation barrier caused by additives such as anions or biomolecules or by the initial formation of amorphous CaCO₃.     

Oxygen diffusion in three silicate melts along the join diopside-anorthite

The self-diffusion of oxygen has been measured for three silicate melts along the join diopsideanorthite. The experiments were done by isotope exchange between an “infinite” reservoir of oxygen gas and spheres of melt. The oxygen self-diffusion coefficients for the three melts are given as: C-1(diopside): D = 1.64 × 10¹ exp(?(63.2 ± 20)(kcal/mole)/RT) cm²/sec C-2(Di₅₈An₄₂): D = 1.35 × 10^?1 exp(?(46.8 ± 9)(kcal/mole)/RT) cm²/sec C-3(Di₄₀An₆₀): D = 1.29 × 10^?2 exp(?(44.2 ± 6)(kcal/mole)/RT) cm²/secThe self-diffusion coefficients do not agree with the Eyring equation unless mean ionic jump distances (λ) considerably larger than the diameter of oxygen anion are assumed. However, the sense of variation of the actual diffusivities is as the Eyring equation predicts.Consideration of the results of this study and the bulk of previous work shows that oxygen appears to conform to the compensation law for cationic diffusion in silicate melts and glasses. The range of oxygen diffusivities was also found to encompass the field of divalent cation diffusivities in silicate melts.Those results imply that the diffusion of oxygen in silicate melts may involve a contribution from a cation-like diffusion mechanism (discrete O^2? anions) as well as contributions from the diffusion of larger structural units.     

Empirical models relating viscosity and tracer diffusion in magmatic silicate melts

The Adam-Gibbs equations describing relaxation in silicate melts are applied to diffusion of trace components of multicomponent liquids. The Adam-Gibbs theory is used as a starting point to derive an explicit relation between viscosity and diffusion including non-Arrhenian temperature dependence. The general form of the equation is D_iη = A_iexp{Δ(s_cE_i)/TS_c}, where D is diffusivity, η is melt viscosity, T is absolute temperature, Δ(s_cE_i) is the difference between the products of activation energies and local configurational entropies for viscous and diffusive relaxation, A_i is a constant that depends on the characteristics of the diffusing solute particles, and S_c is configurational entropy of the melt. The general equation will be impractical for most predictive purposes due to the paucity of configurational entropy data for silicate melts. Under most magmatic conditions the proposed non-Arrhenian behaviour can be neglected, allowing the general equation to be simplified to a generalized form of the Eyring equation to describe diffusion of solutes that interact weakly with the melt structure: D_iη/T = Q_iexp{ΔE_i/RT}, where Q_i and ΔE_i depend on the characteristics of the solute and the melt structure. If the diffusing solute interacts strongly with the melt structure or is a network-forming cation itself, then ΔE_i = 0, and the relation between viscosity and diffusion has the functional form of the classic Eyring and Stokes-Einstein equations; D_iη/T = Q_i. If the diffusing solute can make diffusive jumps without requiring cooperative rearrangement of the melt structure, the diffusivity is entirely decoupled from melt viscosity and should be Arrhenian, i.e., D_i = Q_iexp{B_i/T}. A dataset of 594 published diffusivities in melts ranging from the system CAS through diopside, basalt, andesite, anhydrous rhyolite, hydrous rhyolite, and peralkaline rhyolite to albite, orthoclase, and jadeite is compared with the model equations. Alkali diffusion is completely decoupled from melt viscosity but is related to melt structure. Network-modifying cations with field strength Z_i²/r between 1 and 10 interact weakly with the melt network and can be modelled with the extended form of the Eyring equation. Diffusivities of cations with high field strength have activation energies essentially equal to that of viscous flow and can be modelled with a simple reciprocal Eyring-type dependence on viscosity. The values of Q_i, ΔE_i and B_i for each cation are different and can be related to the cation charge and radius as well as the composition of the melt through the parameters Z_i²/r, M/O, and Al/(Na + K + H). I present empirical fit parameters to the model equations that permit prediction of cation diffusivities given only charge and radius of the cation and temperature, composition and viscosity of the melt, for the entire range of temperatures accessible to magmas near to or above their liquidus, for magmas ranging in composition from basalt through andesite to hydrous or anhydrous rhyolite. Pressure effects are implicitly accounted for by corrections to melt viscosity. Ninety percent of diffusivities predicted by the models are within 0.6 log units of the measured values.     

Experimental study of evaporation and isotopic mass fractionation of potassium in silicate melts

The behavior of Na and K during evaporation from chondrule composition melts was studied using a vacuum furnace. Though Na is the less volatile of the two as an element, it is lost more rapidly than K from silicate melts. Mass fractionation of K isotopes was measured by ion microprobe and Rayleigh fractionation is observed for vacuum evaporation (10⁻⁵ atm). With higher pressures of air, the K loss rate decreases but with increasing hydrogen pressure, K is lost more rapidly. δ⁴¹K decreases with higher pressures, because of back reaction between melt and K in the gas. With long heating duration, the release of light K condensed within the furnace leads to interaction with the K-depleted melt and a further reduction of δ⁴¹K. Natural chondrules differ in some ways from our experimental residues. Some (especially type IIA) have superchondritic Na and K, despite their assumed formation in nebular hydrogen, which enhances volatile loss, and chondrules do not show K isotopic fractionation. Type I chondrules in Semarkona (LL3.0) either plot on our evaporation trend, or are depleted in K but slightly enriched in Na, relative to K. In Bishunpur (LL3.1), type I chondrules are mostly K-depleted but moderately to strongly enriched in Na. In petrologic type 3.2 to 3.4 chondrites they are enriched in both K and Na, like type II chondrules. The alkali contents suggest type I chondrules experienced evaporation and subsequent metasomatism. Their normal δ⁴¹K values suggest closed-system evaporation of a chondritic precursor in a gas with relatively high K pressures due to vaporization of dust accompanying chondrule precursor aggregates. Type II chondrules are volatile-rich, as well as unfractionated in K isotopes. They probably formed in a gas with higher pK than in the case of type I chondrules, due to heating of a more dust-rich parcel of gas.     

Isotope fractionation by chemical diffusion between molten basalt and rhyolite

Experimental diffusion couples were used to study chemical diffusion between molten rhyolite and basalt with special emphasis on the associated fractionation of calcium and lithium isotopes. Diffusion couples were made by juxtaposing firmly packed powders of a natural basalt (SUNY MORB) and a natural rhyolite (Lake County Obsidian) and then annealing them in a piston cylinder apparatus for times ranging from 0.1 to 15.7 h, temperatures of 1350-1450°C, and pressures of 1.2-1.3 GPa. Profiles of the major elements and many trace elements were measured on the recovered quenched glasses. The diffusivities of all elements except lithium were found to be remarkably similar, while the diffusivity of lithium was two to three orders of magnitude larger than that of any of the other elements measured. Chemical diffusion of calcium from molten basalt into rhyolite was driven by a concentration ratio of ∼18 and produced a fractionation of ⁴⁴Ca from ⁴⁰Ca of about 6 ‰. Because of the relatively low concentration of lithium in the natural starting materials a small amount of spodumene (LiAlSi₂O₆) was added to the basalt in order to increase the concentration difference between basalt and rhyolite, which was expected to increase the magnitude of diffusive isotopic fractionation of lithium. The concentration ratio between Li-doped basalt and natural rhyolite was ∼15 and the resulting diffusion of lithium into the rhyolite fractionated ⁷Li from ⁶Li by about 40‰. We anticipate that several other major rock-forming elements such as magnesium, iron and potassium will also exhibit similarly larger isotopic fractionation whenever they diffuse between natural melts with sufficiently large differences in the abundance of these elements.     

Theoretical calculation of equilibrium Mg isotope fractionation between silicate melt and its vapor

Isotope fractionation during the evaporation of silicate melt and condensation of vapor has been widely used to explain various isotope signals observed in lunar soils, cosmic spherules, calcium–aluminum-rich inclusions, and bulk compositions of planetary materials. During evaporation and condensation, the equilibrium isotope fractionation factor (α) between high-temperature silicate melt and vapor is a fundamental parameter that can constrain the melt’s isotopic compositions. However, equilibrium α is difficult to calibrate experimentally. Here we used Mg as an example and calculated equilibrium Mg isotope fractionation in MgSiO₃ and Mg₂SiO₄ melt–vapor systems based on first-principles molecular dynamics and the high-temperature approximation of the Bigeleisen–Mayer equation. We found that, at 2500 K, δ²⁵Mg values in the MgSiO₃ and Mg₂SiO₄ melts were 0.141?±?0.004 and 0.143?±?0.003‰ more positive than in their respective vapors. The corresponding δ²⁶Mg values were 0.270?±?0.008 and 0.274?±?0.006‰ more positive than in vapors, respectively. The general \(\alpha - T\) equations describing the equilibrium Mg α in MgSiO₃ and Mg₂SiO₄ melt–vapor systems were: \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.264 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\) and \(\alpha_{{{\text{Mg}}\left( {\text{l}} \right) - {\text{Mg}}\left( {\text{g}} \right)}} = 1 + \frac{{5.340 \times 10^{5} }}{{T^{2} }}\left( {\frac{1}{m} - \frac{1}{{m^{\prime}}}} \right)\), respectively, where m is the mass of light isotope ²⁴Mg and m′ is the mass of the heavier isotope, ²⁵Mg or ²⁶Mg. These results offer a necessary parameter for mechanistic understanding of Mg isotope fractionation during evaporation and condensation that commonly occurs during the early stages of planetary formation and evolution.     

Liquid composition-dependence of calcium isotope fractionation during diffusion in molten silicates

Liquid phase diffusion experiments were carried out to determine whether diffusive isotopic fractionation of a major chemical element (Ca) varies with chemical composition in high-temperature molten silicates. The objective was to determine how differences in silicate liquid structure, such as the ratio of bridging to non-bridging oxygen atoms, as well as bulk transport properties such as viscosity, relate to isotope discrimination during diffusion. This information, in turn, may relate to the lifetimes and sizes of multi-atom structures in the liquid. Diffusion couples consisting of juxtaposed natural mafic and felsic liquids were held at T = 1450 °C and P = 1.0 GPa for durations of 12-24 h in a standard piston-cylinder assembly. Experiments were done using different mafic endmember compositions (two tholeiitic basalts and a ugandite) and a single rhyolite composition. Major-element diffusion profiles and Ca isotope profiles were measured on the recovered quenched glasses. The starting materials were isotopically indistinguishable, but ⁴⁴Ca/⁴⁰Ca variations of ca. 5‰ arose due to a mass dependence of the Ca diffusion coefficients. Results indicate that the mass dependence of Ca diffusion coefficients varies with the magnitude and direction of aluminum gradients and the viscosity of the liquid. Some Ca fractionations result mainly from Al gradients.A simplified multicomponent diffusion model was used to model the experimental results. The model allows for diffusion of Ca in response to gradients in the concentrations of both CaO as well as Al₂O₃, and the model results are consistent with the inferred existence of at least two distinct species of Ca. The magnitude of isotopic discrimination during diffusion also appears to be stronger on the rhyolite versus the basalt/ugandite side of diffusion couples. The results can largely be accounted for by an adaptation of the model of Dingwell (1990), whereby in high silica liquids, Ca diffuses largely by site hopping through a quasi-stationary aluminosilicate matrix, producing strong isotopic effects because the Ca diffusion is not strongly correlated with the movement of the framework atoms. In low-silica liquids, Ca diffusion is correlated with the movement of the other components and there is less mass discrimination. Combining our Ca results with Ca, Mg, and Li data from previous studies, we show that this model can explain most of the cation- and composition-dependence of diffusive isotopic fractionations observed thus far. A key parameter controlling isotopic discrimination is the ratio of the elemental (Ca, Mg, Li) diffusivity to the Eyring (or Si) diffusivity. However, all experiments done so far also exhibit isotopic features that are not yet fully explained; some of these may relate to small temperature gradients in the capsules, or to more complex coupling effects that are not captured in simplified diffusion models.     

Transition metal ions in silicate melts—I. Manganese in sodium silicate melts

Optical absorption spectra obtained on glasses quenched from sodium silicate melts show Mn³⁺ to be the dominant species for melts heated in air and Mn²⁺ to be the dominant species for melts heated at Po₂ = 10^?17 bar. The absorption spectrum of Mn³⁺ consists of an intense band at 20,000cm^?1 with a 15,000cm^?1 satellite possibly arising from the Jahn-Teller effect. The independence of the spectrum from melt composition and the high band intensity is offered as evidence for a distinct Mn³⁺ complex in the melt. The spectrum of Mn²⁺ is weak and many expected bands are not observed. A two-band luminescence spectrum from Mn²⁺ has been tentatively interpreted as due to Mn²⁺ in interstitial sites in the network and Mn²⁺ coordinated by non-bridging oxygens.     

Non-traditional fractionation of non-traditional isotopes: Evaporation,chemical diffusion and Soret diffusion

Recent developments documenting high temperature isotope fractionations of a variety of elements (Li, Mg, Si, Ca, Fe, Ni) by a variety of processes (evaporation, chemical diffusion and thermal diffusion) are reviewed along with some recent applications of these fractionations to Earth and meteoritic problems.     

Solution properties of silicate liquids from thermal diffusion experiments

Experimental thermal diffusion (Soret) fractionation of silicate liquids shows SiO₂ to be the principal ingredient of the component fractionating to the hot end of experimental charges. The chemical characteristics of disequilibrium Soret separations resemble those of equilibrium 2-liquid phase separation. This reflects the fact that liquid structural constitution does not depend upon the process leading to chemical separation. The activity-composition relations which lead to silicate liquid immiscibility strongly influence the Soret fractionation behavior of liquids near the solvus. This is especially well illustrated in the system Fa-Lc-Q. The temperature versus composition features of the steady state thermal diffusion profiles may be adequately described by an asymmetric regular solution model for silicate liquids, in contrast to any simpler solution model. This model can be used to quantify Margules parameters and the heat of transport for SiO₂ in these silicate liquids. Observation of the rise time and steady state values of Soret fractionation allows calculation of ordinary and thermal diffusion coefficients for SiO₂.     

Modeling diffusive dissolution in silicate melts

Here empirical models for calculating self-diffusion coefficients and diffusion matrices are combined with MELTS, a thermodynamic model for silicate minerals and melts, to estimate diffusive dissolution rates, interface melt compositions and melt diffusivities. Simulations of olivine dissolution experiments in basalt show that the overall model is capable of accurately reproducing diffusive dissolution rates, and the resulting diffusion profiles, over a range of pressures and temperatures. However, the overall model is less successful at reproducing olivine dissolution in andesite, diopside dissolution in either basalt or andesite, or anorthite dissolution in picrite. Yet, even for these systems the predicted dissolution rates are generally within about a factor of two of the measured ones. Comparisons between simulations and experiments suggest that errors in the self-diffusion and thermodynamic models are responsible for the differences, and show that dissolution experiments could be a powerful way of testing and calibrating these and similar models. The overall model will also be a useful tool for designing future experiments, and for identifying the parameters that control diffusive dissolution (and crystallization) in silicate melts under a wide range of conditions.     

Oxygen diffusion in basalt and andesite melts: experimental results and discussion of chemical versus tracer diffusion

Chemical diffusion coefficients for oxygen in melts of Columbia River basalt (Ice Harbor Dam flow) and Mt. Hood andesite have been determined at 1 atm. The diffusion model is that of sorption or desorption of oxygen into a sphere of uniform initial concentration from a constant and semi-infinite atmosphere. The experimental design utilizes a thermogravimetric balance to monitor the rate of weight change arising from the response of the sample redox state to an imposed fO₂. Oxygen diffusion coefficients are approximately an order-ofmagnitude greater for basaltic melt than for andesitic melt. At 1260° C, the oxygen diffusion coefficients are: D=1.65×10^–6cm²/s and D=1.43×10^–7cm²/s for the basalt and andesite melts, respectively. The high oxygen diffusivity in basaltic melt correlates with a high ratio of nonbridging oxygen/tetrahedrally coordinated cations, low melt viscosity, and high contents of network-modifying cations. The dependence of the oxygen diffusion coefficient on temperature is: D=36.4exp(–51,600±3200/RT)cm²/s for the basalt and D=52.5exp(–60,060±4900/RT)cm²/s for the andesite (R in cal/deg-mol; T in Kelvin). Diffusion coefficients are independent of the direction of oxygen diffusion (equilibrium can be approached from extremely oxidizing or reducing conditions) and thus, melt redox state. Characteristic diffusion distances for oxygen at 1260° C vary from 10^-2 to 10² m over the time interval of 1 to 10⁶ years. A compensation diagram shows two distinct trends for oxygen chemical diffusion and oxygen tracer diffusion. These different linear relationships are interpreted as supporting distinct oxygen transport mechanisms. Because oxygen chemical diffusivities are generally greater than tracer diffusivities and their Arrhenius activation energies are less, transport mechanisms involving either molecular oxygen or vacancy diffusion are favored.     

Iron speciation and isotope fractionation during silicate weathering and soil formation in an alpine glacier forefield chronosequence

The chemical weathering of primary Fe-bearing minerals, such as biotite and chlorite, is a key step of soil formation and an important nutrient source for the establishment of plant and microbial life. The understanding of the relevant processes and the associated Fe isotope fractionation is therefore of major importance for the further development of stable Fe isotopes as a tracer of the biogeochemical Fe cycle in terrestrial environments. We investigated the Fe mineral transformations and associated Fe isotope fractionation in a soil chronosequence of the Swiss Alps covering 150 years of soil formation on granite. For this purpose, we combined for the first time stable Fe isotope analyses with synchrotron-based Fe-EXAFS spectroscopy, which allowed us to interpret changes in Fe isotopic composition of bulk soils, size fractions, and chemically separated Fe pools over time in terms of weathering processes. Bulk soils and rocks exhibited constant isotopic compositions along the chronosequence, whereas soil Fe pools in grain size fractions spanned a range of 0.4‰ in δ⁵⁶Fe. The clay fractions (<2 μm), in which newly formed Fe(III)-(hydr)oxides contributed up to 50% of the total Fe, were significantly enriched in light Fe isotopes, whereas the isotopic composition of silt and sand fractions, containing most of the soil Fe, remained in the range described by biotite/chlorite samples and bulk soils. Iron pools separated by a sequential extraction procedure covered a range of 0.8‰ in δ⁵⁶Fe. For all soils the lightest isotopic composition was observed in a 1 M NH₂OH-HCl-25% acetic acid extract, targeting poorly-crystalline Fe(III)-(hydr)oxides, compared with easily leachable Fe in primary phyllosilicates (0.5 M HCl extract) and Fe in residual silicates. The combination of the Fe isotope measurements with the speciation data obtained by Fe-EXAFS spectroscopy permitted to quantitatively relate the different isotope pools forming in the soils to the mineral weathering reactions which have taken place at the field site. A kinetic isotope effect during the Fe detachment from the phyllosilicates was identified as the dominant fractionation mechanism in young weathering environments, controlling not only the light isotope signature of secondary Fe(III)-(hydr)oxides but also significantly contributing to the isotope signature of plants. The present study further revealed that this kinetic fractionation effect can persist over considerable reaction advance during chemical weathering in field systems and is not only an initial transient phenomenon.     

Copper isotope fractionation by desert shrubs

Copper has two naturally occurring stable isotopes of masses 63 and 65 which can undergo mass dependent fractionation during various biotic and abiotic chemical reactions. These interactions and their resulting Cu isotope fractionations can be used to determine the mechanisms involved in the cycling of Cu in natural systems. In this study, Cu isotope changes were investigated at the organismal level in the metal-accumulating desert plant, Prosopis pubescens. Initial results suggest that the lighter Cu isotope was preferentially incorporated into the leaves of the plant, which may suggest that Cu was actively transported via intracellular proteins. The roots and stems show a smaller degree of Cu isotope fractionation and the direction and magnitude of the fractionations was dependent upon the levels of Cu exposure. Based on this and previous work with bacteria and yeast, a trend is emerging that suggests the lighter Cu isotope is preferentially incorporated into biological components, while the heavier Cu isotope tends to become enriched in aqueous solutions. In bacteria, plants and animals, intracellular Cu concentrations are strictly regulated via dozens of enzymes that can bind, transport, and store Cu. Many of these enzymes reduce Cu(II) to Cu(I). These initial results seem to fit into a broader picture of Cu isotope cycling in natural systems where oxidation/reduction reactions are fundamental in controlling the distributions of Cu isotopes.