Optimizing LA-ICP-MS analytical procedures for elemental depth profiling of foraminifera shells

Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is becoming a widespread technique for analyzing elemental ratios in foraminiferal calcite. Here we focus on optimizing LA-ICP-MS for high-resolution depth profiling of elemental ratios through shell walls. This application reveals intrashell variability and provides a unique opportunity to quantify trace element incorporation over short time scales of calcification by an individual foraminifer. High-resolution depth profiling requires careful consideration of both ablation and analytical conditions required to resolve differences in shell chemistry across sub-micron shell thickness. We present laser ablation profiles of NIST SRM 610 standard glass data (in cps) and elemental/Ca ratios (in mmol/mol) from foraminiferal calcite obtained over a range of operating conditions using a Photon Machines 193nm UV excimer laser-ablation system, equipped with a dual-volume ANU HelEx chamber, coupled to an Agilent 7700x quadrupole ICP-MS. Different combinations of energy density, repetition rate, and mass spectrometer cycle time can yield varying elemental profiles. This variability can mimic and/or mask real intrashell trace element heterogeneity in foraminifer shells. At low (<3Hz) laser repetition rates, real intrashell element variation can be obscured depending on the laser energy, whereas using moderate (≥3Hz) laser repetition rates and/or a signal-smoothing device improves the accuracy and precision of intrashell trace element profiles. Shell material is ablated rapidly when using a 5Hz or greater repetition rate and an energy density of 3J/cm² or greater, resulting in reduced spatial resolution.