Zirconium isotopic composition of zircon reference materials by laser ablation multi-collector inductively coupled plasma mass spectrometry

Abstract

Zirconium isotopes have been suggested as a new geochemical fingerprint for tracing magmatic evolution and continental crust differentiation. In this study, we optimized the Zr isotope measurement by laser-ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) and reported stable Zr isotope compositions for different zircon reference materials (ZRMs). The RESOLution laser, coupled with MC-ICP-MS, yielded better results than the New Wave laser when comparing crater shape and depth indices, signal intensity, and isotopic ratio variations. The best working conditions for Zr isotope measurements were found to be with a laser spot size of 23 μm, a repetition rate of 2 Hz, and energy density of 3 J cm−2 which resulted in a crater depth of ∼8 μm. The 90Zr intensities increased by a factor of 3.2, and the raw 94Zr/90Zr ratio remained constant within a broader range of sample gas flow rate with the addition of 8 mL min−1 N2 compared to the normal mode. Negligible interferences were identified from the gas blank and also from the different integrated cycles between the bracketing standard and samples. Using the above-mentioned parameters, we obtained a long-term δ94/90ZrGJ-1 stability of 0.08‰, comparable with femtosecond laser-ablation (fsLA)-MC-ICP-MS methods. ZRMs (e.g., 91,500, Plešovice, Penglai, SA01, Tanz, and Ban-1) yielded homogeneous Zr isotope compositions, consistent with double spiked solution methods within error. Furthermore, zircon megacrysts of LKZ-1 and Cam-1, synthetical MUN-zircon with high Yb content, and MTUR1 zircon standard from carbonatite also had homogeneous Zr isotope compositions that indicate they could be used as tuning and monitoring standards. On the contrary, GHR1, Temora-2, Qinghu, and Jilin zircons were not ideal ZRMs for Zr isotope measurement. Zr isotope variations among homogeneous ZRMs (except Plešovice) further prove that Zr isotopes are a potentially powerful geochemical tracer.