New SIMS reference materials for measuring water in upper mantle minerals

Trace amounts of water in the nominally anhydrous minerals of the upper mantle can dramatically affect their thermodynamic and rheological properties. Secondary ion mass spectrometry (SIMS) has become a mainstream technique for quantifying small amounts of water in these minerals, but depends on standards with known concentrations of water. The current standards in use for mantle minerals are well-characterized (Hauri et al. 2002; Koga et al. 2003; Aubaud et al. 2007; Mosenfelder and Rossman 2013a, 2013b), but a lack of extra material has limited the spread of this technique to other laboratories. We present new SIMS measurements on natural mantle xenolith pyroxenes that are suitable for use as calibration reference materials. They are calibrated off of the pyroxene standards currently in use at the Department of Terrestrial Magnetism of the Carnegie Institution of Washington (Koga et al. 2003; Aubaud et al. 2007). They have homogeneous water contents, defined as a standard deviation of < 10% for analyses across multiple grains. Reference materials for H2O cover ranges from 52 to 328 ppm and from 9 to 559 ppm in orthopyroxene and clinopyroxene, respectively, covering most of the observed range of mantle water contents. The samples are evenly distributed over those ranges. The orthopyroxene reference materials can also be used to measure water in olivine based on previous observations that these two minerals have similar calibration slopes. The new pyroxene reference materials can also be used to calibrate fluorine and phosphorus at low concentrations. We found that fluorine in particular was homogeneous in both orthopyroxene and clinopyroxene, with concentrations of 3 to 50 ppm in orthopyroxene and 0.5 to 118 ppm in clinopyroxene. Phosphorus ranges from below detection up to 19 ppm in orthopyroxene and up to 73 ppm in clinopyroxene, but was more heterogeneous within some samples. Most of the reference materials have concentrations at the lower end of the ranges for fluorine and phosphorus in this study, with only a few samples showing higher concentrations.