Testing the limits of micro-scale analyses of Si stable isotopes by femtosecond laser ablation multicollector inductively coupled plasma mass spectrometry with application to rock weathering

An analytical protocol for accurate in-situ Si stable isotope analysis has been established on a new second-generation custom-built femtosecond laser ablation system. The laser was coupled to a multicollector inductively coupled plasma mass spectrometer (fsLA-MC-ICP-MS). We investigated the influence of laser parameters such as spot size, laser focussing, energy density and repetition rate, and ICP-MS operating conditions such as ICP mass load, spectral and non-spectral matrix effects, signal intensities, and data processing on precision and accuracy of Si isotope ratios. We found that stable and reproducible ICP conditions were obtained by using He as aerosol carrier gas mixed with Ar/H2O before entering the plasma. Precise delta Si-29 and delta Si-30 values (better than +/- 0.23 parts per thousand, 2SD) can be obtained if the area ablated is at least 50 x 50 mu m, or, alternatively, for the analysis of geometric features down to the width of the laser spot (about 20 mu m) if an equivalent area is covered. Larger areas can be analysed by rastering the laser beam, whereas small single spot analyses reduce the attainable precision of delta Si-30 to ca. +/- 0.6 parts per thousand, 2SD, for <30 mu m diameter spots. It was found that focussing the laser beam beneath the sample surface with energy densities between 1 and 3.8 J/cm(2) yields optimal analytical conditions for all materials investigated here. Using pure quartz (NIST 8546 aka. NBS-28) as measurement standard for calibration (standard-sample-bracketing) did result in accurate and precise data of international reference materials and samples covering a wide range in chemical compositions (Si single crystal IRMM-017, basaltic glasses KL2-G, BHVO-2G and BHVO-2, andesitic glass ML3B-G, rhyolitic glass ATHO-G, diopside glass JER, soda-lime glasses NIST SRM 612 and 610, San Carlos olivine). No composition-dependent matrix effect was discernible within uncertainties of the method. The method was applied to investigate the Si isotope signature of rock weathering at the micro-scale in a corestone sampled from a highly weathered roadcut profile in the tropical Highlands of Sri Lanka. The results show that secondary weathering products accumulated in cracks and grain boundaries are isotopically lighter than their unweathered plagioclase host, consistent with isotopically heavy dissolved Si found in rivers. (C) 2014 Elsevier B.V. All rights reserved.