Capability of fs-LA-ICP-MS for sulfide analysis in comparison to ns-LA-ICP-MS: reduction of laser induced matrix effects?

Abstract

We applied three different LA systems (213 nm nanosecond solid state, 193 nm nanosecond excimer, and 200 nm femtosecond laser) coupled to a quadrupole ICP-MS or a sector field ICP-MS, respectively, for the analysis of different sulfide minerals (pyrrhotite, chalcopyrite, and sphalerite). Ablation craters were investigated via back-scattered electron (BSE) images to compare the amounts of melt produced, and fractionation factors were calculated to determine the degree of down-hole fractionation. Our results show significant differences in melting between the three LA systems. While samples show massive melting when using the ns systems, no melting has been observed utilizing the fs laser. Fractionation factors for a variety of elemental pairs indicate the absence of down-hole fractionation even at the highest melt production. The extent of melting of different sulfide specimens is independent of melting temperatures of these materials. Although no down-hole fractionation has been observed, Fe/S fractionation as calculated from sensitivities deviate among pyrrhotite and chalcopyrite when applying the 193 nm ns and 200 nm fs systems. Analyses of synthetic pyrrhotite with known PGE concentrations using the 200 nm fs LA system yielded moderately precise and accurate concentration data (3–4%; 4–14% 2SD) utilizing sulfide as the external reference material. Application of NIST610 as the reference material improved the precision to 1.4–2.4% 2SD and the deviation from reference values to 5–7%.