Ablation behavior and constraints on the U–Pb and Th–Pb geochronometers in titanite analyzed by quadrupole inductively coupled plasma mass spectrometry coupled to a 193 nm excimer laser

• This study presents ablation experiments on Khan titanite compared Plešovice zircon.
• Matrix effects related to laser induced elemental fractionation are monitored.
• Low frequency and fluence conditions are required for precise U–Th–Pb titanite data.
• The Khan titanite can hardly be substituted by a zircon as external reference standard.

U–Th–Pb geochronology of titanite by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a promising technique to constrain the history of igneous and metamorphic rocks. However, the quality of the resulting ages depends strongly on protocol adopted for the analyses and data reduction. There is no general agreement on the laser ablation settings and methodology that should be applied for titanite LA-ICP-MS geochronology. In particular it is essential to define an analytical procedure that could minimize the elemental fractionation for titanite U–Th–Pb geochronology, and to evaluate if non matrix-matched standards and samples (e.g. zircon and titanite) are suitable to obtain precise and accurate ages. In this study, ablation experiments were carried out in spot mode using an ArF 193 nm excimer laser coupled to a quadrupole ICP-MS, with varying fluence, spot size and repetition rate conditions. The ablation behavior of the Khan titanite reference material was described in details and compared to the Plešovice zircon standard. The ratio-of-the-mean intensity method was used for data reduction. Three sources of fractionation and systematic errors between zircon and titanite are considered together: mass bias coefficients, shape of the time-dependent fractionation, and differences of ablated volumes. Even if the laser-induced elemental fractionation and matrix effects can be minimized between the Plešovice zircon standard and the Khan titanite, a matrix-matched standardization with a titanite standard is required for precise U–Th–Pb titanite ages, as well as at low frequency and fluence conditions.