Origin of the suppressed matrix effect for improved analytical performance in determination of major and trace elements in anhydrous silicate samples using 200 nm femtosecond laser ablation sector-field inductively coupled plasma mass spectrometry

Abstract

We have tested an ultraviolet (200 nm) femtosecond laser ablation (200FsLA) sector-field inductively coupled plasma mass spectrometry (SF-ICPMS) system for major and trace element analyses in anhydrous silicate glasses and minerals. Use of the 200FsLA minimized the matrix effect by 50% compared to that of a 193 nm nanosecond excimer LA. The origin of this improvement was identified as the suppression of ‘melting point (MP)-induced’ element fractionation at the LA site due to a decreased thermal effect of the 200FsLA. Sensitivity enhancement in elements with high first ionization energy remained for the basalt aerosols relative to silica-rich aerosols. This is interpreted as being due to the higher thermal conductivity of the basalt aerosols in the inductively coupled plasma enhanced ionization, which is essentially controlled by the first ionization energy of an element. This was confirmed by simulation using Saha's equation and by the analytical data after reduction of the MP-induced fractionation at the LA site. Accurate determination of trace elements (within 5% of accepted values) was achieved for MPI-DING glasses ranging from komatiite to rhyolite, using a single basalt glass BHVO-2G as the calibration standard. This method is also applicable to anhydrous silicate minerals such as plagioclase, pyroxenes, and garnet. However, SRM610 glass, which has a very different matrix compared to BHVO-2G, is preferred for zircon. Apart from this exception, the proposed method requires no external analytical techniques when the amounts of unmeasured elements in the materials, such as halogens or water, are negligibly low, which is the case for many geological materials.