Volume and grain boundary diffusion of calcium in natural and hot-pressed calcite aggregates

Calcium self-diffusion rates in natural calcite single crystals were experimentally determined at 700 to 900 degrees C and 0.1 MPa in a stream of CO2. Diffusion coefficients (D) were determined from Ca-42 concentration profiles measured with an ion microprobe. The Arrhenius parameters yield an activation energy (Q) = 382 +/- 37 kJ/mol and pre-exponential factor (D-0) = 0.13 m(2)/s, and there is no measurable anisotropy. Calcium grain boundary diffusion rates were experimentally determined in natural (Solnhofen) limestone and hot-pressed calcite aggregates at 650 degrees to 850 degrees C and 0.1 to 100 MPa pressure. The Solnhofen limestone was first pre-annealed for 24 h at 700 degrees C and 100 MPa confining pressure under anhydrous conditions to produce an equilibrium microstructure for the diffusion experiments. Values for the product of the grain boundary diffusion coefficient (D') and the effective grain boundary diffusion width (delta) were determined from Ca-42 concentration profiles measured with an ion microprobe. The results show that there is no measurable difference between D'delta values obtained for pre-annealed Solnhofen samples at 0.1 and 100 MPa or between hot-pressed calcite aggregates and pre-annealed Solnhofen samples. The temperature dependence for calcium grain boundary diffusion in Solnhofen samples annealed at 0.1 MPa is described by the Arrhenius parameters D'(0) delta = 1.5 x 10(-9) m(3)/s and Q = 267 +/- 47 kJ/mol. Comparison of the results of this study with previously published data show that calcium is the slowest volume diffusing species in calcite. The calcium diffusivities measured in this study place constraints on several geological processes that involve diffusive mass transfer including diffusion-accommodated mechanisms in the deformation of calcite rocks.