AN EXPERIMENTAL INVESTIGATION OF THE PARTITIONING OF REE BETWEEN GARNET AND LIQUID WITH REFERENCE TO THE ROLE OF DEFECT EQUILIBRIA

The partitioning of samarium and thulium between garnets and melts in the systems Mg 3Al 2-Si 3O 12-H 2O and Ca 3Al 2Si 3O 12-H 2O has been studied as a function of REE concentration in the garnets at 30 kbar pressure. Synthesis experiments of variable time under constant P, T conditions indicate that garnet initially crystallizes rapidly to produce apparent values of D Sm (D Sm=concentration of Sm in garnet/concentration of Sm in liquid) which are too large in the case of pyrope and too small in the case of grossular. As the experiment proceeds, Sm diffuses out of or into the garnet and the equilibrium value of D Sm is approached. Approximate values of diffusion coefficients for Sm in pyrope garnet obtained by this method are 6 × 10 -13 cm 2 s -1 at 1,300 ° C and 2 × 10 -12 cm 2 s -1 at 1,500 ° C, and for grossular, 8.3 × 10 -12 cm 2 s -1 at 1,200 ° C and 4.6 × 10 -11 cm 2 s -1 at 1,300 ° C. The equilibrium values of D Sm have been reversed by experiments with Sm-free pyrope and Sm-bearing glass, and with Sm-bearing grossular and Sm-free glass. Between 12 ppm and 1,000 ppm Sm in pyrope at 1,300 ° C and between 80 ppm and >2 wt.% Tm in pyrope at 1,500 ° C, partition coefficients are constant and independent of REE concentration. Above 100 ppm of Sm in garnet at 1,500 ° C, partition coefficients are independent of Sm concentration. At lower concentrations, however, D Sm is dependent upon the Sm content of the garnet. The two regions may be interpreted in terms of charge-balanced substitution of Sm 3Al 5O 12 in the garnet at high Sm concentrations and defect equilibria involving cation vacancies at low concentrations. At very low REE concentrations (< 1 ppm Tm in grossular at 1,300 ° C) D REE garnet/liquid again becomes constant with an apparent Henry's Law value greater than that at high concentrations. This may be interpreted in terms of a large abundance of cation vacancies relative to the number of REE ions. The importance of defects in the low concentration region has been confirmed by adding other REE (at 80 ppm level) to the system Mg 3Al 2Si 3O 12-H 2O at low Sm concentrations. These change D Sm in the defect region, demonstrating their role in the production of vacancies. Experiments on a natural pyropic garnet indicate that defect equilibria are of importance to REE partitioning within the concentration ranges found in nature. © 1980 Springer-Verlag