Rare earth element diffusion in diopside: influence of temperature, pressure, and ionic radius, and an elastic model for diffusion in silicates

Volume diffusion rates for five rare earth elements (La, Ce, Nd, Dy, and Yb ) have been measured in single crystals of natural diopside at pressures of 0.1 MPa to 2.5 GPa and temperatures of 1,050 to 1,450 degreesC. Polished, pre-annealed crystals were coated with a thin film of rare earth element ox ides, then held at constant temperature and pressure for times ranging from 20 to 882 h. Diffusion profiles in quenched samples were measured by SIMS (secondary ion mass spectrometry) depth profiling. At I atm. pressure, with the oxygen fugacity controlled near the quartz-fayalite-magnetite buffer, the following Arrhenius relations were obtained for diffusion normal to (00 1) (diffusion coefficient D in m(2)/s): log(10)D(Yb) = (-4.64 +/- 0.42)-(41 1 +/- 12 kJ/mol/2.303RT); log(10)D(Dy) = (-3.31 +/- 1.44)-(461 +/- 41 kJ/mo l/2.303RT); log(10)D(Nd) = (-2.95 +/- 2.64)-(496 +/- 77 kJ/ mol/2.303RT); l og(10)D(Ce) = (-4.10 +/- 1.08)-(463 +/- 31 kJ/ mol/2.303RT); log(10)D(Lu) = (-4.22 +/- 2.66)-(466 +/- 78 J/mol /2.303RT). Diffusion rates decrease significantly with increasing ionic radius, with L a a factor of similar to 35 slower than Yb. The relationship between diffus ivity and ionic radius is consistent with a model in which elastic strain p lays a critical role in governing the motion of an ion through the crystal lattice. Activation volumes for Yb and Ce diffusion, at constant temperatur e and oxygen fugacity, are 9.0 +/- 2.0 cm(3)/mol and 8.9 +/- 3.2 cm(3)/mol, respectively, corresponding to an order of magnitude decrease in diffusivi ty as pressure is increased from 0 to 3 GPa at 1,200 degreesC. Diffusion of Nd is such that grain-scale isotopic equilibrium in the mantle can be achi eved in - I My under conditions near the peridotite solidus (similar to1,45 0 degreesC at 2.5 GPa). The equilibration time is much longer under P, T co nditions of the lithospheric mantle or at the eclogite solidus (similar to1 Gy at 1.5 GPa and 1,150 degreesC. Because of the relatively strong decreas e in diffusivity with pressure (two orders of magnitude between 2.5 and 15 GPa along an adiabatic temperature gradient), Nd transport in clinopyroxene will be effectively frozen at pressures approaching the transition zone, o n time scales less than 100 My. Rare earth element diffusion rates are slow enough that significant disequilibrium. uptake of REE by growing clinopyro xene phenocrysts may be preserved under natural conditions of basalt crysta llization. The relative abundances and spatial distributions of REE in such crystals may provide a sensitive record of the cooling and crystallization history of the host lava.