The effect of supercritical fluids on Nb-Ta fractionation in subduction zones: Geochemical insights from a coesite-bearing eclogite-vein system

Abstract

Supercritical fluids are ideal media for mass transfer from the subducting slab into the mantle wedge. However, little is known about the role of natural supercritical fluids in subduction zones. A combined study of petrology, geochemistry and zirconology was carried out for a coesite-bearing eclogitic vein and its surrounding eclogites from the Dabie orogen, one of the typical continental subduction zones on Earth. The results are used to reveal the composition and source of supercritical fluids, the P-T conditions and timing of their formation and their geochemical effects in subduction zones. The eclogitic vein is composed of garnet, omphacite, quartz, amphibole, rutile and apatite, with minor amounts of epidote, plagioclase and zircon. Coesite was identified in omphacite in the vein, demonstrating its formation under ultrahigh-pressure (UHP) metamorphic conditions that correspond to subarc depths in oceanic subduction zones. Zircons from the vein give concordant U-Pb ages of 225 ± 5 Ma and flat HREE patterns for newly grown rims, consistent with their crystallization at the UHP eclogite facies. The vein shows similar Hf-O isotope compositions to the host UHP eclogites, indicating that the UHP vein-forming fluid is internally buffered within the UHP eclogites. Minerals in the vein contain not only higher contents of Cr, Ni, Sr, REE and HFSE, but also multiphase crystal inclusions (such as omphacite, quartz, epidote, apatite, amphibole, plagioclase, mica, rutile, calcite, and anhydrite) as well as liquid and gas phases of H2O. The calculated fluid composition of major elements is 31 wt% SiO2, 20 wt% CaO, 10 wt% (SO4)2−, 8 wt% (CO3)2−, 8 wt% FeO, 7 wt% Al2O3, and 9 wt% H2O, with traces of Na2O, K2O and TiO2. This composition is responsible for the UHP veining from supercritical silicate-rich fluids in equilibrium with peak UHP minerals. The P-T-t path of the UHP eclogite-vein system indicates that the second critical endpoint of the basalt-H2O system is located close to 3.4 GPa and 770°C. The high contents of sulfate and carbonate in the vein suggest that supercritical fluids were oxidized and likely a predominant agent to transfer sulfur and carbon at subarc depths. High Nb/Ta ratios of rutile crystals in the vein and quantitative modelling indicate that dehydration of subducting eclogites at subarc depths can produce supercritical fluids with suprachondritic Nb/Ta ratios. The UHP eclogites and mantle wedge peridotites metasomatized by supercritical fluids can acquire suprachondritic Nb/Ta ratios and thus provide a complementary reservoir to balance the subchondritic reservoirs on Earth. Based on a statistics of Nb-Ta data, two indices are proposed to identify the existence of supercritical fluids in fossil subduction zones: (1) rutile crystallized from supercritical fluids shows lower Nb contents than that from aqueous solutions and hydrous melts; (2) UHP eclogites associated with supercritical fluids exhibit a distance >0.1 in their Nb-Ta compositions to the line defined by basalts in the plot of log[Nb] vs log[Ta]. Therefore, the existence of supercritical fluids during UHP metamorphism at subarc depths can be recognized from their effect on the mobility of fluid-immobile trace elements in UHP metamorphic rocks.