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Abstract: Laboratory experiments are used to document isotopic fractionation of magnesium by chemical diffusion in a silicate melt and the results compared to the magnesium isotopic composition across contacts between igneous rocks of different composition in natural settings. The natural samples are from transects from felsic to mafic rocks at Vinal Cove in the Vinalhaven Intrusive Complex, Maine and from the Aztec Wash pluton in Nevada. Two laboratory diffusion couples made by juxtaposing melts made from powders of the felsic and mafic compositions sampled at Vinal Cove were annealed at about 1500°C for 22.5 and 10h, respectively. The transport of magnesium in the diffusion couples resulted in easily measured magnesium isotopic fractionations at the interface (δ 26Mg∼1.5‰). These isotopic fractionations provide a distinctive isotopic “fingerprint” that we use to determine whether chemical gradients in natural settings where melts of different composition were juxtaposed were due to chemical diffusion. The magnesium isotopic fractionation along one profile at Vinal Cove is exactly what one would expect based on the fractionations found in the laboratory experiments. This is an important result in that it shows that the isotope fractionation by chemical diffusion found in highly controlled laboratory experiments can be found in a natural setting. This correspondence implies that chemical diffusion was the dominant process responsible for the transport of magnesium across this particular contact at Vinal Cove. A second Vinal Cove profile has a very similar gradient in magnesium concentration but with significantly less magnesium isotopic fractionation than expected. This suggests that mass transport at this location was only partly by diffusion and that some other mass transport mechanism such as mechanical mixing must have also played a role. The magnesium isotopic composition of samples from Aztec Wash shows no resolvable isotopic fractionation across the contact between the mafic and felsic rocks. The different degrees of magnesium isotopic fractionation associated with otherwise similar composition gradients in natural settings show that kinetic isotope fractionations provide a key discriminator for establishing whether or not molecular diffusion was the process responsible for an observed elemental gradient. In the one case of a contact at Vinal Cove where we are confident that the magnesium elemental and isotopic gradients were produced by diffusion, we deduced a cooling rate of about 1.5°C per day. [Copyright &y& Elsevier]

Abstract: Isotope distributions in natural systems can be highly sensitive to the mass (m) dependence of solute diffusion coefficients (D) in liquid water. Isotope geochemistry studies routinely have assumed that this mass dependence either is negligible (as predicted by hydrodynamic theories) or follows a kinetic-theory-like inverse square-root relationship (D ∝ m −0.5). However, our recent experimental results and molecular dynamics (MD) simulations showed that the mass dependence of D is intermediate between hydrodynamic and kinetic theory predictions (D ∝ m − β with 0⩽ β <0.2 for Li+, Cl−, Mg2+, and the noble gases). In this paper, we present new MD simulations and experimental results for Na+, K+, Cs+, and Ca2+ that confirm the generality of the inverse power-law relation D ∝ m − β . Our new findings allow us to develop a general description of the influence of solute valence and radius on the mass dependence of D for monatomic solutes in liquid water. This mass dependence decreases with solute radius and with the magnitude of solute valence. Molecular-scale analysis of our MD simulation results reveals that these trends derive from the exponent β being smallest for those solutes whose motions are most strongly coupled to solvent hydrodynamic modes. [Copyright &y& Elsevier]

Abstract: Two types of laboratory experiments were used to quantify magnesium isotopic fractionations associated with chemical and thermal (Soret) diffusion in silicate liquids. Chemical diffusion couples juxtaposing a molten natural basalt (SUNY MORB) and a molten natural rhyolite (Lake County Obsidian) were run in a piston cylinder apparatus and used to determine the isotopic fractionation of magnesium as it diffused from molten basalt to molten rhyolite. The thermal diffusion experiments were also run in a piston cylinder apparatus but with a sample made entirely of molten SUNY MORB displaced from the hotspot of the assembly furnace so that the sample would have a temperature difference of about 100–200°C from one end to the other. The chemical diffusion experiments showed fractionations of 26Mg/24Mg by as much as 7‰, which resulted in an estimate for the mass dependence of the self-diffusion coefficients of the magnesium isotopes corresponding to with β =0.05. The thermal diffusion experiments showed that a temperature difference of about 100°C resulted in the MgO, CaO, and FeO components of the basalt becoming slightly enriched by about 1wt% in the colder end while SiO2 was enriched by several wt% in the hotter end. The temperature gradient also fractionated the magnesium isotopes. A temperature difference of about 150°C produced an 8‰ enrichment of 26Mg/24Mg at the colder end relative to the hotter end. The magnesium isotopic fractionation as a function of temperature in molten basalt corresponds to 3.6×10−2‰/°C/amu. [Copyright &y& Elsevier]

Abstract: Experiments specifically designed to measure the ratio of the diffusivities of ions dissolved in water were used to determine . The measured ratio of the diffusion coefficients for Li and K in water (DLi/DK =0.6) is in good agreement with published data, providing evidence that the experimental design being used resolves the relative mobility of ions with adequate precision to also be used for determining the fractionation of isotopes by diffusion in water. In the case of Li, we found measurable isotopic fractionation associated with the diffusion of dissolved LiCl . This difference in the diffusion coefficient of 7Li compared to 6Li is significantly less than that reported in an earlier study, a difference we attribute to the fact that in the earlier study Li diffused through a membrane separating the water reservoirs. Our experiments involving Mg diffusing in water found no measurable isotopic fractionation . Cl isotopes were fractionated during diffusion in water whether or not the co-diffuser (Li or Mg) was isotopically fractionated. The isotopic fractionation associated with the diffusion of ions in water is much smaller than values we found previously for the isotopic fractionation of Li and Ca isotopes by diffusion in molten silicate liquids. A major distinction between water and silicate liquids is that water surrounds dissolved ions with hydration shells, which very likely play an important but still poorly understood role in limiting the isotopic fractionation associated with diffusion. [Copyright &y& Elsevier]

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. [Copyright &y& Elsevier]