The significance of Mn‐rich ilmenite and the determination of P–T paths from zoned garnet in metasedimentary rocks from the western Cape Breton Highlands, Nova Scotia

Abstract The Jumping Brook Metamorphic Suite in the western Cape Breton Highlands of Nova Scotia is part of an inverted Barrovian sequence that formed during a Late Silurian–Early Devonian promontory–promontory collision in the Canadian Appalachians. In this study, systematic discrepancies between geochemical observations and thermodynamic model predictions led to the discovery of a systematic relationship linking the style of garnet core isopleth intersection (GCII) to the pyrophanite (MnTiO 3 ) component of co‐existing ilmenite. Samples that yielded tight GCIIs at or near the garnet‐in curve were found to contain ilmenite with negligible pyrophanite components, whereas samples yielding GCIIs far removed (up to 105°C) from the garnet‐in curve were found to contain ilmenite with significant pyrophanite and/or ecandrewsite (ZnTiO 3 ) components. Based on petrographic and geochemical observations, Mn(±Zn)‐rich ilmenite are interpreted to have sequestered Mn throughout prograde metamorphism due to sluggish intracrystalline diffusion. The amount of reactive Mn input into the thermodynamic models from whole‐rock analyses were, in some cases, overestimated, resulting in garnet‐in curve topologies that extend to erroneously low P–T conditions. Modifications to the whole‐rock chemistry that account for Mn sequestration into ilmenite, however, yielded robust model results. Our results show that, in addition to uncertainties in thermodynamic data sets and phenomenon related to reaction kinetics, Mn‐rich ilmenite may superimpose additional complexities related to the interpretation of predicted equilibria involving garnet. Numerical simulations of garnet crystallization were used to infer P–T paths of metamorphism for one sample from the garnet zone (Mn corrected) and two samples from the staurolite zone (Mn uncorrected) of the inverted sequence. Model results are remarkably similar among the three samples and indicate that garnet crystallization occurred along relatively steep (31–37°C/km) clockwise P–T paths. The peak conditions of garnet crystallization and metamorphism (560–590°C, 7.4–8.0 kbar) are interpreted to have been attained approximately simultaneously, such that the paths are characterized by tight prograde‐to‐retrograde transitions. The hairpin nature of the P–T paths is interpreted to represent the onset of thrust‐related exhumation and isograd inversion along ductile shear zones, consistent with available field and geochronological constraints.