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

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 Pb-207/Pb-206, vs. Pb-208/Pb-206 isochron ages and +/- 1.8% and for U-Pb ages. Incorporation of this excess variance in cassiterite ages is necessary for realistic uncertainties. Pb-207-Pb-206 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 Pb-207/Pb-206, vs. Pb-208/Pb-206 isochron ages (similar to 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 U-238/Pb-206 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.

Automated summary

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to compare the suitability of different cassiterite materials for U-Pb and Pb-Pb isotope ratio normalization. The estimated excess variance of ages determined by LA-ICP-MS is necessary for realistic uncertainties. Pb-207/Pb-206 ages are advantageous for dating Precambrian cassiterite. Minor bias in Pb-207/Pb-206 ages was observed when using certain reference materials, emphasizing the requirement for uncertainty propagation and comparable reference materials. The use of matrix-matched reference materials is also emphasized for accurate U-Pb age calculations. The LA-ICP-MS U-Pb ages of different cassiterite samples were consistent with their ID-TIMS values.