Multicomponent diffusion in aluminosilicate garnet: coupling effects due to charge compensation

摘要

Three kinds of multicomponent diffusion effects, arising from three distinct physical mechanisms, are evident in stranded diffusion profiles at the rims of partially resorbed garnets from the contact aureole of the Makhavinekh Lake Pluton, northern Labrador. Profiles that display a subtle maximum in Ca concentration are explained by the prevailing ideal mean-field theory of multicomponent diffusion, but models implementing that theory cannot replicate inverted profiles for Li and internal maxima for Nd, Sm, and Eu. The anomalous profiles are quantitatively reproduced, however, by numerical simulations employing a model based on coupled movement of charge-compensating groups during diffusional transport of yttrium and the rare-earth elements (Y+REEs). An alkali-type charge-compensation mechanism for the heterovalent substitution of Y+REEs on dodecahedral sites in garnet produces direct charge coupling between Li+ and (Y+REE)(3+) and leads to co-diffusion of Li+-(Y+REE)(3+) pairs, with the result that Li profiles closely mimic those for Y+REEs. A menzerite-type charge-compensation mechanism produces indirect charge coupling among all Y+REE components, with the result that the fluxes of low-abundance REEs become partly dependent on the fluxes of Y+REEs present in higher abundance. These findings have implications for the robustness of Li profiles in garnet as monitors of fluid-rock interaction, for geochronology based on the Sm-Nd and Lu-Hf systems, and for future experimental attempts to quantify rates of diffusion in garnet.