Relationship among titanium, rare earth elements, U–Pb ages and deformation microstructures in zircon: Implications for Ti-in-zircon thermometry

A zircon grain in an orthopyroxene–garnet–phlogopite–zircon–rutile-bearing xenolith from Udachnaya, Siberia, preserves a pattern of crystallographic misorientation and subgrain microstructure associated with crystal–plastic deformation. The zircon grain records significant variations in titanium (Ti) from 2.6 to 30 ppm that corresponds to a difference in calculated Ti-in-zircon temperatures of over several hundred degrees Celsius. The highest Ti concentration is measured at subgrain centres (30 ppm), and Ti is variably depleted at low-angle boundaries (down to 2.6 ppm). Variations in cathodoluminescence coincide with the deformation microstructure and indicate localised, differential enrichment of rare earth elements (REE) at low-angle boundaries. Variable enrichment of U and Th and systematic increase of Th/U from 1.61 to 3.52 occurs at low-angle boundaries. Individual SHRIMP-derived U–Pb ages from more deformed zones (mean age of 1799 ± 40, n = 22) are systematically younger than subgrain cores (mean age of 1851 ± 65 Ma, n = 7), and indicate that open system behaviour of Ti–Th–U occurred shortly after zircon growth, prior to the accumulation of significant radiogenic Pb. Modelling of trace-element diffusion distances for geologically reasonable thermal histories indicates that the observed variations are ~ 5 orders of magnitude greater than can be accounted for by volume diffusion. The data are best explained by enhanced diffusion of U, Th and Ti along deformation-related fast-diffusion pathways, such as dislocations and low-angle (< 5°) boundaries. These results indicate chemical exchange between zircon and the surrounding matrix and show that Ti-in-zircon thermometry and U–Pb geochronology from deformed zircon may not yield information relating to the conditions and timing of primary crystallisation.

Research Highlights
► Zircon in a Siberain xenolith preserves crystal plastic deformation microstructures.
► Variable Ti depletion, and Th, U and REE enrichment is associated with deformation.
► ‘Apparent’ Ti-in-zircon temperatures range over a few hundred degrees Celsius across the grain.
► Geochemical modification occurred via deformation-related fast-pathway diffusion.
► U-Pb data show that Ti-Th-U diffusion occurred soon after zircon growth at ~1850 Ma.