ALBERT

Notes: Abstract Diffusion rates for the three tetravalent cations U, Th and Hf have been measured in synthetic zircon. Diffusant sources included oxide powders and ground pre-synthesized silicates. Rutherford backscattering spectrometry (RBS) was used to measure depth profiles. Over the temperature range 1400–1650 °C, the following Arrhenius relations were obtained (diffusion coefficients in m2sec−1): log D Th = (1.936 ± 0.9820) + (− 792 ± 34 kJ mol−1 /2.303 RT) log D U = (0.212 ± 2.440) + (− 726 ± 83 kJ mol−1 /2.303 RT) log D Hf = (3.206 ± 1.592) + (− 812 ± 54 kJ mol−1 /2.303 RT) The data show a systematic increase in diffusivity with decreasing ionic radius (i.e., faster diffusion rates for Hf than for U or Th), a trend also observed in our earlier study of rare earth diffusion in zircon. Diffusive fractionation may be a factor in the Lu-Hf system given the much slower diffusion rates of tetravalent cations when compared with the trivalent rare earths. The very slow diffusion rates measured for these tetravalent cations suggest that they are essentially immobile under most geologic conditions, permitting the preservation of fine-scale chemical zoning and isotopic signatures of inherited cores.

Notes: Abstract The diffusivity (D) of dissolved SiO2 in quartz-saturated H2O was determined at 1 GPa and ∼530–870 °C using a custom-designed Ag diffusion cell consisting of two chambers – both containing quartz + H2O – connected by a narrow capillary. During a diffusion experiment, quartz saturation was maintained at different levels in the two chambers by placing the diffusion cell in the thermal gradient of a standard piston-cylinder assembly. The diffusivity was computed from the total mass of SiO2 transported from the “hot” to the “cold” chamber during the course of an experiment. Over the temperature range investigated, the results conform to an Arrhenius-type dependence of D SiO2 (m2/s) upon T(K)−1: The significance of the constants in this equation (in particular, the ∼52 kJ/mole apparent activation energy) is uncertain, because the SiO2 content of the fluid varies markedly with temperature, due to the strong temperature dependence of quartz solubility. Nevertheless, the above expression is probably a good representation of the temperature dependence of D SiO2 in the crust, where aqueous fluids are likely to approach quartz saturation at all depths. One experimental result at 0.6 GPa suggests little dependence of D SiO2 upon pressure at crustal conditions. At the low end of the temperature range investigated, the measured diffusivities are identical to values calculated from the Stokes-Einstein equation using high P-T viscosity estimates for H2O. Disagreement between measured and calculated diffusivities at higher temperatures (a factor of ∼4 at 850 °C) may be due to one or more of the following factors: (1) inadequacy of the Stokes-Einstein relationship as a description of transport in supercritical H2O; (2) inaccuracy of viscosity estimates of H2O; or (3) concentration effects on diffusion over the temperature range investigated. Given the presence of interconnected porosity in deep-seated rocks, the diffusive transport distances for aqueous silica implied by the above equation are impressive even on a geologic scale, exceeding 0.5 km in 106 years at temperatures of 500 °C or higher. The combined effect of the high D SiO2 with the high and strongly temperature-dependent solubility of quartz at crustal conditions raises the possibility of significant diffusive fluxes through a stationary fluid in a normal geothermal gradient.