Lithium in garnet as a tracer of subduction zone metamorphic reactions: The record in ultrahigh-pressure metapelites at Lago di Cignana, Italy
Authors: Bebout Gray E. , Ota Tsutomu , Kunihiro Takuya , Carlson William D. , Nakamura Eizo 
Published: April 2022

Abstract
Lithium is of great interest as a tracer of metamorphic reactions and related fluid-mineral interactions because of its potential to isotopically fractionate during inter- and intracrystalline diffusional processes. Study of its transfer through subduction zones, based on study of arc volcanic and metamorphic rocks, can yield insight regarding ocean-to-mantle chemical cycling.
We investigated major- and trace-element concentrations and δ7Li in garnet in ultrahigh-pressure (UHP) Lago di Cignana metasedimentary rocks, relating these observations to reconstructed prograde devolatilization history. In all garnet crystals we studied, heavy rare earth elements (HREEs), Y, and Li showed strong zoning, with elevated concentrations in cores (15–50 ppm Li) and marked high-concentration anomalies (up to 117 ppm Li, 5500 ppm Y; little or no major-element shift) as growth annuli, in which some crystals showed subtle elevation in δ7Li greater than analytical error of ~3% (2σ). Rutile inclusions appeared abruptly at annuli and outward toward rims, accompanied by inclusions of a highly zoned, Ca- and rare earth element–rich phase and decreased Nb concentrations in garnet. These relationships are interpreted to reflect prograde garnet-forming reaction(s), in part involving titanite breakdown to stabilize rutile, which resulted in delivery of more abundant Y and HREEs at surfaces of growing garnet crystals to produce annuli. Co-enrichments in Li and Y + REEs are attributed to mutual incorporation via charge-coupled substitutions; thus, increased Li uptake was a passive consequence of elevated concentrations of Y + REEs. The small-scale fluctuations in δ7Li (overall range of ~9%) observed in some crystals may correlate with abrupt shifts in major- and trace-element concentrations, suggesting that changes in reactant phases exerted some control on the evolution of δ7Li. For one garnet crystal, late-stage growth following partial resorption produced deviation in major- and trace-element compositions, including Li concentration, accompanied by a 10%–15% negative shift in δ7Li, perhaps reflecting a change in the mechanism of incorporation or source of Li.
These results highlight the value of measuring the major- and trace-element and isotope compositions of garnets in high-pressure and UHP metamorphic rocks in which matrix mineral assemblages are extensively overprinted by recrystallization during exhumation histories. Lithium concentrations and isotope compositions of the garnets can add valuable information regarding prograde (and retrograde) reaction history, kinetics of porphyroblast growth, intracrystalline diffusion, and fluid-rock interactions. This work, integrated with previous study of devolatilization in the Schistes Lustrés/Cignana metasedimentary suite, indicates retention of a large fraction of the initially subducted sedimentary Li budget to depths approaching those beneath volcanic fronts, despite the redistribution of this Li among mineral phases during complex mineral reaction histories.