Sodic pyroxene and sodic amphibole as potential reference materials for in situ lithium isotope determinations by SIMS

Two large pegmatitic crystals of sodic pyroxene (aegirine) and sodic amphibole (arfvedsonite) from the agpaitic igneous Ilímaussaq Complex, south Greenland were found to be suitable as reference materials for in situ Li isotope determinations. Lithium concentrations determined by SIMS and micro-drilled material analysed by MC-ICP-MS generally agreed within analytical uncertainty. The arfvedsonite crystal was homogeneous with [Li] = 639 ± 51 μg g^-1 (2s, n = 69, MC-ICP-MS and SIMS results). The aegirine crystal shows strongly developed sector zoning, which is a common feature of aegirines. Using qualitative element mapping techniques (EPMA), the homogeneous core of the crystal was easily distinguished from the outermost sectors of the crystals. The core had a mean [Li] of 47.6 ± 3.6 μg g^-1 (2s, n = 33) as determined by SIMS. The seven micro-drilled regions measured by solution MC-ICP-MS returned slightly lower concentrations (41-46 μg g^-1), but still overlap with the SIMS data within uncertainty. Based on MC-ICP-MS and SIMS analyses, the variation in δ 7 Li was about 1‰ in each of the two crystals, which is smaller than that in widely used glass reference materials, making these two samples suitable to serve as reference materials. There was, however, a significant offset between the results of MC-ICP-MS and SIMS. The latter deviated from the MC-ICP-MS results by -6.0 ± 1.9‰ (2s) for the amphibole and by -3.9 ± 1.9‰ (2s) for the aegirine. This indicates the presence of a significant matrix effect in SIMS determinations of Li isotopes for amphibole and pyroxene relative to the basalt glasses used for calibration. Based on the MC-ICP-MS results, mean δ 7 Li values of +0.7 ± 1.2‰ (2s, n = 10) for the arfvedsonite crystal and of -3.7 ± 1.2‰ (2s, n = 7) for the core of the aegirine crystal were calculated. Adopting these values, SIMS users can correct for the specific IMF (instrumental mass fractionation) of the ion probe used. We propose that these two crystals serve as reference materials for in situ Li isotope determinations by SIMS and pieces of these two crystals are available from the first author upon request.