Allanite age-dating: Non-matrix-matched standardization in quadrupole LA-ICP-MS

Abstract:

Allanite Th-U-Pb age-dating has recently been found to be powerful in unraveling the timing of geological processes such as the metamorphic dynamics in subduction zones and crystallization velocity of magmas. However, inconsistencies among analytical techniques have raised doubts about the accuracy of allanite age data. Spot analysis techniques such as LA-ICP-MS are claimed to be crucially dependent on matrix-matched standards, the quality of which is variable.

We present a new approach in LA-ICP-MS data reduction that allows non-matrix-matched standardization via well constrained zircon reference materials as primary standards. Our data were obtained using a GeoLas Pro 193 nm ArF excimer laser ablation system coupled to an ELAN DRC-e quadrupole ICP-MS. We use 32 µm and 24 µm spot sizes; laser operating conditions of 9 Hz repetition rate and 2.5 J/cm² fluence have proven advantageous. Matrix dependent downhole fractionation evolution is empirically determined by analyzing ²⁰⁸Pb/²³²Th and ²⁰⁶Pb/²³⁸U and applied prior to standardization. The new data reduction technique was tested on three magmatic allanite reference materials (SISSb, CAPb, TARA); within error these show the same downhole fractionation evolution for all allanite types and in different analytical sessions, provided measurement conditions remain the same. Although the downhole evolution of allanite and zircon differs significantly, a link between zircon and allanite matrix is established by assuming CAPb and TARA to be fixed at the corresponding reference ages. Our weighted mean ²⁰⁸Pb/²³²Th ages are 30.06 ± 0.22 (2σ) for SISSb, 275.4 ± 1.3 (2σ) for CAPb, and 409.9 ± 1.8 (2σ) for TARA. Precision of single spot age data varies between 1.5 and 8 % (2σ), dependent on spot size and common lead concentrations. Quadrupole LA-ICP-MS allanite age-dating has thus similar uncertainties as do other spot analysis techniques. The new data reduction technique is much less dependent on quality and homogeneity of allanite standard reference materials. This method of correcting for matrix-dependent downhole fractionation evolution opens new possibilities in the field of LA-ICP-MS data acquisition, e.g. the use of a NIST standard glass to date all material types given a set of well constrained reference materials.