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

Abstract

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 (~300μm drill holes) followed by MC-ICPMS analysis of the powders revealed negatively coupled Mg and Fe isotopic fractionations (δ²⁶Mg from +0.1% to -0.2% and δ⁵⁶Fe from -1.2% to -0.2% 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<inf>2</inf>/D<inf>1</inf>=(m<inf>1</inf>/m<inf>2</inf>)^β with β<inf>Mg</inf> ~0.16 and β<inf>Fe</inf> ~0.27. LA-MC-ICPMS and MC-SIMS Fe isotopic measurements are developed and are demonstrated to yield accurate δ⁵⁶Fe measurements within precisions of ~0.2% (1 SD) at spatial resolutions of ~50μm. δ⁵⁶Fe and δ²⁶Mg stay constant with Fo# in the rim (late-stage overgrowth), whereas in the core (original phenocryst) δ⁵⁶Fe steeply trends toward lighter compositions and δ²⁶Mg trends toward heavier compositions with higher Fo#. A plot of δ⁵⁶Fe 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-MC-ICPMS and MC-SIMS can be used as standard petrologic tools to identify samples for diffusion-based geospeedometry. © 2013 Elsevier Ltd.