Accurate quantification of melt inclusion chemistry by LA-ICPMS: a comparison with EMP and SIMS and advantages and possible limitations of these methods

Abstract

Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) has recently emerged as a powerful in situ microanalytical technique for major to trace elements in heterogeneous samples such as fluid and melt inclusions. Here, a rigorous comparison of melt inclusion (MI) data acquired by electron microprobe (EMP), ion microprobe (the secondary ion mass spectrometry, SIMS) and LA-ICPMS is used to evaluate the applicability and advantages/drawbacks of these approaches. We are specifically interested in determining if LA-ICPMS data on entire, unexposed, crystallized MI that cannot be homogenized in the lab are accurate and of a useful precision. Quantification of LA-ICPMS MI signals requires the use of an internal standard, i.e., the concentration of one element, or an element ratio, at the time of MI entrapment must be known independently, in order to derive the pure MI composition from the MI plus host mixed signal. Analysis of plagioclase-hosted glassy MI of a mid-ocean ridge basalt (MORB) sample from the East Pacific Rise illustrates that melt inclusion chemistry can be accurately quantified by LA-ICPMS, including the correction for postentrapment sidewall crystallisation of the host mineral without prior reheating in the lab. The LA-ICPMS data obtained on crystallized MI demonstrate agreement with the EMP and SIMS data on exposed glassy MI at the 1 standard deviation uncertainty level except for a few elements close to their limits of detection. LA-ICPMS data reduction schemes include the quantification of analytical uncertainty on each element of single MI. Therefore, weighted average element concentrations can be obtained for MI assemblages, at precisions that compare well with those of average element concentrations obtained by EMP and SIMS. Simple sample preparation minimizing inclusion loss through polishing combined with the analytical efficiency of 50 inclusions plus neighbouring host mineral at up to 40 elements per day enable the collection of statistically relevant datasets by LA-ICPMS. These allow to recognize nonrepresentative MI (e.g., heterogeneous entrapment). Application to individual clinopyroxene crystals from the AD79 pumice horizon of Mt. Somma-Vesuvius reveals chemical variability that exceeds the analytical precision on single melt inclusions. This variability was not obvious from the limited data set obtained by SIMS and EMP. The largest source of nonquantifiable error for EMP and SIMS data stems from the requirement of reheating the melt inclusions in the lab in order to reverse postentrapment crystallisation onto inclusion walls or growth of crystallites. For LA-ICPMS analysis of unexposed MI, the reliability with which the internal standard (IS) element concentration is known determines the quality of the data. LA-ICPMS, however, cannot analyse H 2O, F, S and Cl reliably, has higher limits of detection (LODs) than SIMS for some elements for MI below ∼25 μm, has lower spatial resolution than both EMP and SIMS and consumes much more sample per analysis. Therefore, EMP, SIMS and LA-ICPMS are complementary in MI research, and the type of application will determine the analytical method or methods of choice.