Boron, arsenic and antimony recycling in subduction zones: New insights from interactions between forearc serpentinites and CO2-rich fluids at the slab-mantle interface

Abstract

Hydrous minerals in the hybridized zone at the slab-mantle interface play a critical role in retaining and transporting fluid mobile elements in subduction zones. The observed high B and As concentrations and high δ11B values in arc magmas were previously thought to have been resulted from the mechanical transport of forearc serpentinites down to subarc depths by mantle corner flows or through subduction channels because B, As, and Sb are mostly released during early stages of subduction. This study provides new insights into the recycling of B, As, and Sb in subduction zones via an in-situ study on a set of carbonate-bearing serpentinite samples from the Mianlue mélange complex in the Qinling Orogen. Petrological observations and bulk-rock Sr-Pb isotopes reveal that the Jianchaling serpentinites were formed by interactions between forearc peridotites and sediment-derived fluids at a shallow depth in the subduction channel. Some Jianchaling serpentinites experienced the lizardite to antigorite transition at 300–400 °C with infiltrations of CO2-rich fluids. In contrast, the Liangyazi antigorite serpentinites were produced at a greater depth. Antigorite grains in the Jianchaling serpentinites have lower Feapfu than those in the Liangyazi serpentinites and most antigorite with geochemical data in the literature. Meanwhile, B, As, and Sb concentrations of Fe-poor antigorite from the Jianchaling serpentines (385–653 ppm B, 198–334 ppm As, and 6.24–8.01 ppm Sb) are not only higher than those of the Fe-rich antigorite from the Liangyazi serpentinites but also 2–3.5 times higher than those of the surrounding lizardite. The lower modal percentage of spinel and ferritchromite in antigorite veinlets, together with the lower bulk-rock FeO content of antigorite-lizardite serpentinites than that of lizardite serpentinites from the Jianchaling region, indicates that some FeO might be lost during the lizardite to antigorite transition. The presence of carbonate minerals in the antigorite veinlets and the remarkably high B, As, and Sb concentrations in the Jianchaling antigorite indicate that the penetrating fluids during the lizardite to antigorite transition are most likely derived from sediment and metabasite decarbonations at <350 °C. Infiltrations of CO2-rich fluids at the slab-mantle interface could buffer a relatively low pH to significantly enhance the mobility of Fe2+, which is produced by reduction of the cronstedtite component in lizardite or Fe3+ in magnetite during the lizardite to antigorite transition, and facilitate the formation of Fe-poor antigorite at the slab-mantle interface. The oxygen fugacity in such a CO2-rich water–rock system is also high enough for the occurrence of As5+ in the surrounding fluids. Therefore, once IVFe3+ is lost from the serpentine lattice structure during the lizardite to antigorite transition, B3+, As5+, and Sb5+ in the surrounding fluids can occupy the tetrahedral sites in the newly formed Fe-poor antigorite. The formation of Fe-poor antigorite at the slab-mantle interface is therefore made available to transport shallow slab-derived B, As, and Sb to a greater depth, where destabilization of antigorite at 600–700 °C liberates these elements into the arc magma source.