Lithium Behavior during Growth of Metasedimentary Garnets from the Cignana UHP Locality, Italy
Abstract:We investigated major and trace element concentrations and δ7Li in garnets in Lago di Cignana metasedimentary rocks (peak conditions ~550˚C, 2.5-3.0 GPa), following the EPMA-SIMS approach of Tsujimori et al. (2014; IMA conference abstract). Previous work on the devolatilization history of these rocks (Bebout et al., 2013; Cook-Kollars et al., 2014; both in Chemical Geology) provides a petrologic and geochemical context for this study. Lithium is of interest as a tracer of fluid-rock interactions and because of its potential to isotopically fractionate during diffusional processes.
All garnets are almandine-rich with strongly decreasing MnO and increasing MgO toward rims. HREEs, Y, and Li also show strong zoning, with elevated concentrations in cores (15-50 ppm Li) and marked high-concentration anomalies (up to 117 ppm Li, 5500 ppm Y), with little or no major element shift, as growth annuli at which some garnets have elevated δ7Li. In all garnets, rutile inclusions appear abruptly at annuli and outward toward rims, accompanied by inclusions of a Ca- and LREE-rich phase and decreased Nb concentrations in garnet.
These relationships appear to reflect prograde garnet-forming reaction(s) that in part involved titanite breakdown to stabilize rutile, which resulted in delivery of more abundant Y and HREEs at surfaces of growing garnets to produce growth annuli. The co-enrichment of Li and Y+REEs is attributed to their mutual incorporation via a charge-coupled substitution (Carlson et al., 2014; American Mineralogist); thus the increased Li uptake is a passive consequence of the elevated concentrations of Y+REEs. Distributions of δ7Li are complex, with most garnets showing only subtle core-to-rim variation other than at Y+REE annuli. At annuli, some garnets display elevated δ7Li (by up to 8‰), while others in the same rock do not. Small-scale fluctuations in δ7Li may correlate with abrupt shifts in major and trace element concentrations, suggesting that changes in the minerals involved as reactants exert some control on the evolution of δ7Li.