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Ca-Mg inter-diffusion in synthetic polycrystalline dolomite-calcite aggregate at elevated temperatures and pressure
Authors:Wuu-Liang Huang  Teh-Ching Liu  Pouyan Shen  Allen Hsu
Institution:1. Department of Geosciences, National Taiwan University, Taipei, Taiwan
2. Department of Earth Sciences, National Taiwan Normal University, Taipei, Taiwan
3. Institute of Materials Science and Engineering, National Sun Yat-sen University, Kaohsiung, Taiwan
4. Department of Geosciences, National Taiwan University, Taipei, Taiwan
Abstract:This study measures the reaction rate of dolomite and aragonite (calcite) into Mg-calcite at 800, 850, and 900°C and 1.6 GPa. The dry synthetic dolomite-aragonite aggregate transformed very rapidly into dolomite-calcite polycrystalline aggregate while Mg-calcites formed at a relatively slow rate, becoming progressively richer in Mg with run time. We modeled the reaction progress semi-empirically by the first-order rate law. The temperature dependence of the overall transport rate of MgCO3 into calcite can be described by the kinetic parameters (E?=?231.7 kJ/mol and A o ?=?22.69 h?1). Extrapolation using the Arrhenius equation to the conditions during exhumation of UHPM rocks indicates that the reaction of dolomite with aragonite into Mg-saturated calcite can be completed as the P-T path enters the Mg-calcite stability field in a geologically short time period (<1 Ky). On the other hand, the extrapolation of the rate to prograde metamorphic conditions reveals that the Mg-calcite formed from dolomitic marble in the absence of metamorphic fluid may not reach Mg-saturation until temperatures corresponding to high-grade metamorphism (e.g., >340°C and >10 My). SEM-EDS analysis of individual calcite grains shows compositional gradients of Mg in the calcite grains. The Mg-Ca inter-diffusion coefficient at 850°C is around 1.68?×?10?14 m2/sec if diffusion is the major control of the reaction. The calculated closure temperatures for Ca-Mg inter-diffusion as a function of cooling rate and grain size reveal that Ca/Mg resetting in calcite in a dry polycrystalline carbonate aggregate (with grain size around 1 mm) may not occur at temperatures below 480°C at a geological cooling rate around 10°C/My, unless other processes, such as short-circuit interdiffusion along grain boundaries and dislocations, are involved.
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