Diffusive fractionation of trace elements in basaltic melt

Abstract

The chemical diffusivities of 25 trace elements (Sc, V, Rb, Sr, Y, Zr, Nb, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb, Lu, Hf, Ta, Th, and U) in basaltic melt were measured in diffusion couple experiments performed at 1 GPa pressure and temperatures from 1250 to 1500 °C. Trace element concentration gradients developed in the glasses were simultaneously characterized using laser ablation ICP/MS to create an internally consistent data set. A ratio-fitting technique was employed to accurately determine the relative diffusivities of the rare earth elements (REE). All diffusion coefficients conform to the expected Arrhenius relation D = D0exp(−Ea/RT), where the constant log(D0, m2/s) ranges from −3.81 to −5.11 and Ea ranges from 161.73 to 223.81 kJ/mol. The slowest diffusivities are obtained for the high-field-strength elements; the fastest diffusivities are obtained for the low-field-strength elements. Trace element diffusion in MORB follows the compensation law, where log D0 is linearly correlated with Ea. Arrhenius parameters for diffusion of trivalent REE monotonically increase from La to Lu and are near-linear functions of bond strength (the variation in Arrhenius parameters means that the diffusivities decrease monotonically from La to Lu at a given T). The new data for trace element diffusion in basaltic melt can be used to explore the potential for diffusive fractionation of trace elements using kinetic models. Concentrations of the slower-diffusing heavy REE may be altered relative to those of the faster-diffusing light REE as a diffusive boundary layer develops in melt–melt and crystal–melt systems. The results indicate that diffusion in basalt can be an effective mechanism to fractionate trace elements from one another.