A lithium isotopic study of sub-greenschist to greenschist facies metamorphism in an accretionary prism, New Zealand

To investigate the behavior of Li during low-grade metamorphism and fluid flux in an accretionary prism we measured the Li concentrations ([Li]) and isotopic compositions (δ7Li) of sub-greenschist and greenschist-facies Otago Schist composites, as well as cross-cutting quartz veins, which are interpreted to have precipitated from slab-derived fluids. The average [Li] of sub-greenschist facies composites (41 ± 13 μg/g, 2σ) is statistically distinct (97% confidence level, student t test) to that of greenschist facies composites (34 ± 9 μg/g, 2σ), which have experienced mass addition of silica in the form of quartz veins having [Li] between 0.4-2.3 μg/g. A linear regression of the correlation between [Li] and calculated mass additions suggests that the depletion of [Li] in greenschist facies composites is due to both dilution from the addition of the quartz veins, as well as metamorphic dehydration. The [Li] of both groups of composites correlates with their CIA (Chemical Index of Alteration) values (50-58), which are low, consistent with the inferred graywacke protolith of the Otago Schist. The δ7Li of sub-greenschist and greenschist facies composites are remarkably constant, with an average δ7Li of 0.2 ± 1.7 (2σ) and −0.5 ± 1.9 (2σ), respectively, and comparable to that of the average upper continental crust. Thus, metamorphism has had no discernable effect on δ7Li in these samples. The Li isotopic signature of the schists is similar to that seen in pelitic sedimentary rocks and likely reflects the δ7Li of the protoliths. The surprisingly light δ7Li of the quartz veins (−2.8 to −1.4) likely records kinetic fractionation associated with Li ingress into the veins from surrounding wallrock.An isotopic equilibrium fluid flow model indicates that: 1) if the [Li] of slab-derived fluids is less than a few μg/g, the δ7Li of the overlying lithologies (i.e., the schists) is not significantly influenced by the fluid flux, regardless of the δ7Li of the fluids, 2) the slab-derived fluids will have heavy δ7Li of > + 10 after reacting with the prism sediments during their ascent, and 3) the [Li] of the slab-derived fluids is likely in the range of 0 < [Li] ≤ 41(μg/g). Thus, isotopically heavy slab-derived fluids that traverse sediments in accretionary prisms may leave little trace in the rocks and their surface compositional characteristics will reflect the net result of their interaction with the sediments of the prism.

Research Highlights► Greenschist facies metamorphism may have depleted the Li concentrations; it had no discernible effect on the rocks' Li isotopic compositions. ► Further depletion of [Li] in greenschist facies composites is caused by mass addition of Li-poor quartz veins. ► The δ7Li of the precursor sediments can be preserved after fluid fluxing if the [Li] in the fluid is relatively low. ► The fluids have δ7Li > + 10 when they approach the surface after reacting with the sediments. ► The [Li] of the slab-derived fluids is in the range of 0 < [Li] ≤ 41(μg/g).