Phase and Composition Changes of Titanite during Laser Ablation Inductively Coupled Plasma Mass Spectrometry Analysis

Abstract

Changes in phase and chemical composition of the mineral titanite (monoclinic CaTiSiO(5)) during laser ablation and plasma-aerosol interaction were investigated using electron diffraction and electron microbeam X-ray analysis with transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Laser ablation of titanite with a solid state 213 nm nanosecond laser generates a bimodal aerosol consisting of condensed nanoparticles and spherical micrometer-sized particles. The two types of particles produced by laser ablation are amorphous on the scale resolvable by the electron diffraction. The ratio of Ca-Si-Ti does not change significantly during laser ablation. Aerosol of titanite particles introduced into the ICP and collected after interaction with the plasma contains nanometer-sized particles of a condensate and spherical micrometer-sized particles with a molten surface. The condensed particles are enriched in silicon whereas the spherical micrometer-sized particles show a deficiency in Si relative to the titanite composition. During laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) analysis of titanite, Si and Ti showed positive and negative fractionation trends relative to Ca, respectively. This is consistent with the observed chemical composition changes of the titanite aerosol within the ICP. This study links for the first time the chemical and phase changes of a sample within the ICP to the elemental fractionation during LA-ICPMS.