Discerning crystal growth from diffusion profiles in zoned olivine by in situ Mg-Fe isotopic analyses

Mineral zoning is used in diffusion-based geospeedometry to determine magmatic timescales. Progress in this field has been hampered by the challenge to discern mineral zoning produced by diffusion from concentration gradients inherited from crystal growth. A zoned olivine phenocryst from Kilauea Iki lava lake (Hawaii) was selected for this study to evaluate the potential of Mg and Fe isotopes for distinguishing these two processes. Microdrilling of the phenocryst (similar to 300 mu m drill holes) followed by MC-ICPMS analysis of the powders revealed negatively coupled Mg and Fe isotopic fractionations (delta Mg-26 from + 0.1 parts per thousand to - 0.2 parts per thousand and delta Fe-56 from -1.2 parts per thousand to -0.2 parts per thousand from core to rim), which can only be explained by Mg-Fe exchange between melt and olivine. The data can be explained with ratios of diffusivities of Mg and Fe isotopes in olivine scaling as D-2/D-1 = (m(1)/m(2))(beta) with beta(Mg) similar to 0.16 and beta(Fe) similar to 0.27. LA-MC-ICPMS and MC-SIMS Fe isotopic measurements are developed and are demonstrated to yield accurate delta Fe-56 measurements within precisions of similar to 0.2 parts per thousand (1 SD) at spatial resolutions of similar to 50 mu m. delta Fe-56 and delta Mg-26 stay constant with Fo# in the rim (late-stage overgrowth), whereas in the core (original phenocryst) delta Fe-56 steeply trends toward lighter compositions and delta Mg-26 trends toward heavier compositions with higher Fo#. A plot of delta Fe-56 vs. Fo# immediately distinguishes growth-controlled from diffusion-controlled zoning in these two regions. The results are consistent with the idea that large isotopic fractionation accompanies chemical diffusion in crystals, whereas fractional crystallization induces little or no isotopic fractionation. The cooling timescale inferred from the chemical-isotope zoning profiles is consistent with the documented cooling history of the lava lake. In the absence of geologic context, in situ stable isotopic measurements may now be used to interpret the nature of mineral zoning. Stable isotope measurements by LA-MCICPMS and MC-SIMS can be used as standard petrologic tools to identify samples for diffusion-based geospeedometry. (C) 2013 Elsevier Ltd. All rights reserved.