The volatile inventory (F, Cl, Br, S, C) of magmatic apatite: An integrated analytical approach

Apatite is ubiquitous in a wide range of magmatic rocks and its F–Cl–Br–S systematics can be used to decipher e.g., mixing processes within a magmatic complex and may give insights into fluid un-mixing and degassing processes during the emplacement and cooling of plutonic rocks. In this study, we analyzed a F-apatite (Durango, Mexico), a Cl-apatite (Ødegården, Norway) and apatites from five plutonic samples from the alkaline Mt. Saint Hilaire Complex (Canada) by means of Electron Microprobe Analysis (EPMA), Laser Ablation ICP-MS (LA-ICP-MS), Secondary Ion Mass Spectrometry (SIMS), pyrohydrolysis combined with ion chromatography, Fourier Transformed Infrared Spectroscopy (FTIR), Instrumental Neutron Activation Analysis (INAA) and Total Reflection X-ray Fluorescence Analysis (TXRF). The special focus of our study is Br, since the analytical possibilities for this element are especially in the low- to sub-μg/g range restricted and thus, reliable concentration data for Br in rock-forming minerals are scarce. We demonstrate here that TXRF, which is barely used in geosciences so far, is suitable for analyzing the bulk content of Br and Cl as well as of a range of important trace metals (e.g., Sr, Ce, Fe, Mn, As) in apatite simultaneously. The TXRF method combines the advantages of low to very low detection limits (μg/g- to sub-μg/g range), small sample amounts needed (mg range) and a relatively fast and inexpensive analytical procedure. Depending on the As content of apatite, reliable concentration data for Br can be produced with detection limits as low as 0.2μg/g. Using the Durango apatite as an internal reference material, SIMS analyses give consistent results with EPMA, INAA and TXRF and allow for detailed insights into the F–Cl–Br–S systematics of apatites. The presented data set reveals significant heterogeneities within and between different apatite grains from a single sample.