Dating fluid infiltration and deformation in the subducted ultramafic oceanic lithosphere by perovskite geochronology

Carbonated ultramafic rocks (i.e., ophicarbonates) form by peridotite serpentinization and carbonation at the seafloor. Their metamorphic evolution is linked to that of serpentinites, hence dating deformation and metamorphism in ophicarbonates will add constraints to the P-T-t history of the subducted ultramafic lithosphere. A potential, yet underexplored, suitable mineral for geochronology in ophicarbonates is perovskite (CaTiO3). We present trace element and geochronological data (LA-ICPMS and ID-TIMS) from perovskite in ophicarbonate rocks and calcite veins from two metamorphic terranes, Lanzo Massif and Val Malenco (Alps). Metamorphic perovskite in ophicarbonates is characterized by enrichment in heavy REE, and strong negative anomalies in Zr and Hf, as well as Sr and Pb, which are attributed to coexistence of a Zr-rich phase and mobilization of these elements by fluids, respectively. Other trace elements broadly reflect the composition of the protolith and allow the distinction of perovskite from mafic and ultramafic rocks. In the Lanzo Massif, the 49.6 ± 1.0 Ma age of perovskite in shear bands constrains H2-mediated carbonate reduction and abiotic methane and graphite formation at near peak metamorphic conditions during deformation. Perovskite from Val Malenco is found in calcite veins cutting across serpentinite shear foliation and its age of 48.9 ± 0.5 Ma coincides with a major thrusting and extension event that is distinct in age from the initial nappe stacking. The Val Malenco perovskite age can be reproduced by LA-ICPMS and ID-TIMS and is proposed as a suitable secondary reference material for metamorphic, low U perovskite. These results show that metamorphic perovskite geochronology yields geologically meaningful U-Pb ages and is a viable tool to date deformation and fluid flow in the subducted oceanic lithosphere.