Trace element analysis of high-Mg olivine by LA-ICP-MS – Characterization of natural olivine standards for matrix-matched calibration and application to mantle peridotites

The trace element composition of olivine is becoming increasingly important in petrological studies due to the ubiquity of olivine in the Earth's upper mantle and in primitive magmatic rocks. The LA-ICP-MS method allows for the routine analysis of trace elements in olivine to sub-ppm levels, but a major drawback of this method is the lack of knowledge about possible downhole fractionation effects when non matrix-matched calibration is used. In this contribution, we show that matrix-matched (i.e., olivine-based) calibration is preferable for small laser spot sizes (<100 μm) due to significant laser-induced inter-element fractionation between olivine and commonly used silicate glass calibration materials, e.g., NIST SRM 612, GSD-1G and BHVO-2G. As a result, we present two Mg-rich natural olivine standards (355OL and SC-GB) that have been characterized by independent methods (EPMA, solution ICP-MS), and by LA-ICP-MS in four different laboratories. These natural olivines have been used 1) as primary standards for the matrix-matched calibration of olivine samples for most elements of interest (e.g., Li, Na, Al, P, Ca, Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Zn), and 2) as secondary standards to assess the accuracy of results. Comparison of olivine- and silicate glass-calibrated results for natural peridotitic olivine reveals that matrix-matched calibration is essential when using small laser spot sizes (<100 μm) in order to mitigate downhole fractionation effects for certain elements, especially Na, P, Mn, Co, Ni and Zn. If matrix-matched calibration is not feasible, we recommend that spot sizes of ≥100 μm, laser fluence of ≤4.0 J/cm², and total laser shot counts of ≤250 (e.g., 5 Hz repetition rate for 50 s) are used in order to minimize fractionation effects between olivine and silicate glass calibration materials. We demonstrate the applicability of matrix-matched calibration on olivine from a suite of different mantle peridotite xenoliths sampled by kimberlites and alkali basalts from on-craton and off-craton localities.