A LA-ICP-MS Comparison of Reference Materials Used in Cassiterite U-Pb Geochronology

Abstract

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) is used to compare the suitability of four cassiterite (SnO₂) materials (SPG, Yankee, AY-4 and Jian-1), and three matrix-mismatched reference materials (NIST SRM 612, NIST SRM 614 and 91500 zircon) for normalisation of U-Pb and Pb-Pb isotope ratios in cassiterite. The excess variance of ages determined by LA-ICP-MS is estimated to be ±0.33% for ²⁰⁷Pb/²⁰⁶Pb vs. ²⁰⁸Pb/²⁰⁶Pb isochron ages and ± 1.8% and for U-Pb ages. Incorporation of this excess variance in cassiterite ages is necessary for realistic uncertainties. ²⁰⁷Pb-²⁰⁶Pb ages are advantageous for dating Precambrian cassiterite such as SPG compared with U-Pb ages as matrix effect on instrumental mass fractionation of Pb isotopes are generally considered to be minor. We note minor bias in ²⁰⁷Pb/²⁰⁶Pb vs. ²⁰⁸Pb/²⁰⁶Pb isochron ages (~ 0.6%) when using either the NIST SRM 614 or 91500 zircon reference materials and emphasise the requirement for uncertainty propagation of all sources of error and reference materials with comparable U and Pb mass fraction to the cassiterite. The ²³⁸U/²⁰⁶Pb isotopic ratios from normalisation to matrix-mismatched reference materials show varied results, which emphasises the need to use matrix-matched reference materials for calculating U-Pb ages. When cross-calibrated against each other, LA-ICP-MS U-Pb ages of the ca. 1535 Ma SPG, ca. 245 Ma Yankee and ca. 155 Ma Jian-1 cassiterites are all consistent with their ID-TIMS values.