Microanalysis of Cl, Br and I in apatite, scapolite and silicate glass by LA-ICP-MS

Constraining the abundance and distribution of halogens in geological materials has the potential to provide novel insights into a broad range of earth system processes (e.g. metasomatism, melting, volatile cycling and ore formation). In this contribution we develop analytical protocols for the in situ measurement of Cl, Br and I in widely distributed standard reference materials (apatite, scapolite, silicate glass) using readily available laser ablation ICP-MS instrumentation. Ablations were performed at a range of square spot sizes (30-80 mu m) using a high repetition rate (25 Hz) and extended analyte dwell times (up to 250 ms) to improve sensitivity and signal stability. A comparison of LA-ICP-MS results with published halogen data was used to calculate the following theoretical limits of quantification; Cl = 360 mu g/g, Br = 8 mu g/g, I = 0.75 mu g/g. A detailed assessment of raw signal intensities for different matrices with known halogen contents, combined with high resolution mass scans, provides new constraints on the origin of apparent halogen signals: on mass Cl-35 signal excesses are likely (OOH)-O-16-O-18 and/or (OO)-O-17-O-18; Br-79 is influenced by peak shoulder overlap from (ArAr)-Ar-40-Ar-40 (a diargon cation, Ar-2(+2)) and a matrix-based interference (Tb-159(2+)) for samples with Br/Tb < 0.6; I-127 signals are similar for all but the highest I materials analysed here, suggesting the presence of ubiquitous gas-based interferences. The observation that false positive halogen signals only occur during sample ablation suggests that they are either matrix derived or related to the process of sample introduction. During ablation, matrix loading may reduce plasma energy, resulting in a greater proportion of polyatomic interferences in the system. For Cl, we provide a new time dependent excess apparent Cl spline correction defined by analysis of halogen-free olivine via a modified version of the Iolite Data Reduction Scheme 'X_Trace_Elements_IS'. The correction improves the limit of linearity to similar to 100 mu g/g for Cl in glasses down to a 38 mu m spot size. We test our methodology on apatite from Permian alkaline lamprophyres in the Pyrenees (Spain) and quartz-hosted melt inclusions from rhyolitic deposits at the Taupo volcanic zone (New Zealand), obtaining results comparable to electron microprobe and SIMS data. We provide recommendations for analytical best practice and highlight the need for well characterised matrix matched SRMs spanning a broad range of concentrations to allow for the identification and removal of nonanalyte related contributions to measured signals.