Tracing serpentinite dehydration in a subduction channel: Chromium element and isotope evidence from subducted oceanic crust

Abstract

Serpentinite is one of the most important sources of volatiles and fluid-mobile elements in subduction zones. Attempts have been made to discriminate serpentinite-derived fluid from other sources (e.g., sediments, altered oceanic crusts) using a variety of geochemical tools, but such differentiation has proven to be changeling because fluids from different lithologies are dynamically mixed in the subduction channel. Serpentinites are essentially distinguished by high Cr contents and variable degrees of 53Cr excess. Given high Cr mobility in Cl-rich metamorphic fluids based on experimental determination, Cr elemental and isotope compositions could be potential markers for fluid-mediated mass transfer from serpentinites. Here, we test this hypothesis by analyzing Cr concentrations and isotope compositions of meta-basalts, as well as country mica schists, marbles and serpentinites from the southwestern Tianshan Orogen. The meta-basalts have highly variable Cr concentrations (30.0–625 ppm) and resolvable δ53Cr variations (−0.25‰ to −0.05‰), while mica schists and marbles have similar isotope compositions and low Cr contents (δ53Cr of −0.15‰ to −0.14‰ with Cr contents of 89.5–110 ppm for mica schists, δ53Cr of −0.21‰ to −0.17‰ with Cr contents of 4.1–8.73 ppm for marbles, respectively). Most of the investigated meta-basalts were carbonated. The positive correlations of loss on ignition (LOI), CO2, Sb and Sb/Ce with Cr contents, as well as with δ53Cr for these carbonated meta-basalts indicate that the metamorphic fluids are at least partially sourced from serpentinites and sedimentary carbonates. High pressure serpentinites display similar δ53Cr variations from −0.19‰ to −0.02‰, but high Cr contents ranging from 934 to 4920 ppm. Chromium isotope variations of these serpentinites could not be generated by serpentinization, due to opposite trends of Cr isotopes and serpentinization indexes compared with previous observations. Instead, dehydration of serpentinites during subduction/exhumation accounts for Cr isotope variations, generating fluids with high Cr concentrations and relatively lighter isotope compositions. According to a Rayleigh dehydration model, the estimated Cr isotope fractionation factor (αfluid-residue) between fluids and residual serpentinites is approximately 0.99995 –0.99975, implying that Cr species in the subducted serpentine derived fluid is probably as complexes of Cr3+-Cl−H2O(OH–). The mixing model reveals that investigated carbonated meta-basalts were sourced from initial evolved oceanic basalts metamorphosed by fluids from serpentinite dehydrations, with contributions from sedimentary carbonates. This work emphasizes that coupled Cr element and isotope systems present the potential ability to discriminate the complex fluid sources in subduction zones, particularly serpentinites.