Partitioning of rare earth elements between garnet and andesite melt: an autoradiographic study of P-T-X effects

High-pressure equilibrium studies were conducted in piston-cylinder apparatus to determine rare earth element (REE) partitioning between garnet and H₂O-vapor-saturated liquidus, from 20 kbar/980°C to 30 kbar/1060 °C. Ag capsules were employed to eliminate loss of Fe. Partition coefficients (K_D's) were determinined with autoradiographic techniques employing beta-active isotopes of Ce, Sm, and Tm. Major elements in garnet were determined by microprobe analysis. Synthesis and reversal runs of 24 hr or greater duration were used to bracket values of K_D's within analytical uncertainty.The K_D values for all three REE are constant over the radiogenic concentration range of 1 to 350 ppm, suggesting that the high abundance of natural REE in the starting materials may suppress possible deviations from Henry's Law behavior reported in similar autoradiographic studies of synthetic systems with no natural REE. Changes in K_D with increasing pressure and temperature at near-liquidus conditions suggest that the dominant control of K_D is the average size of cations occupying the 8-fold sites in garnet. Specifically, the substitution of 8-fold Ca for Mg and Fe causes an increase in K_D values greater than that attributable to the coincident effects of pressure and temperature. The inverse correlation of increasing K_D with REE ionic radius supports the interpretation that the average size of the 8-fold cation controls the relative variation of K_D among REE.These experimental K_D values produce less relative fractionation in melts between light REE and heavy REE than do previous K_D's derived from data on coexisting natural garnet phenocryst/rockmatrix pairs. Models for the derivation of orogenic andesites from partial melting of subducted basaltic eclogite are qualitatively improved by these new K_D's. Existing calculations of K_D values necessary for the viability of the eclogite fractionation are also in good agreement with these experimental K_D values.