Ophicarbonates transport carbon to the deep mantle: a case study from the Zermatt-Saas ophiolite

A large body of work has challenged the paradigm of carbonate stability at the forearc and subarc (> 80 km) conditions in subducted slabs and revealed a variety of complex processes that play an important role in the so-called slow C cycle. Serpentinite-hosted carbonate rocks (i.e., ophicarbonates) are an important rock type for the deep C cycle because they can occur either in the slab or in the mantle wedge. The question revolves around phase stability and metamorphic reactions upon subduction that can lead to a change in carbonate phase assemblage and fluid composition. Moreover, the phase relation between carbonates, silicates, oxide and sulfide minerals in ophicarbonates can be informative about the redox conditions during prograde metamorphism.

We present a case study of ophicarbonate rocks from the Zermatt-Saas unit, Western Alps, that were subducted up to eclogite facies conditions at 2.5 GPa, 560° C. In the study area, ophicarbonates overlie a large body of partially dehydrated serpentinites. This allows us to understand whether fluids released from the serpentinites infiltrated the ophicarbonates or not, and to what extent decarbonation reactions occurred in an open or closed system. We investigated three carbonate-bearing rock types: ophicarbonates, olivine-carbonate veins, and a talc-magnesite reaction rind at the contact between ultramafic and mafic/felsic lithologies. Our petrological and geochemical investigation, as well as thermodynamic modelling, reveal that the metamorphic evolution of the ophicarbonate was in a closed system, where calcite/aragonite was replaced by metamorphic dolomite and diopside, and that this reaction is nearly CO₂ conservative, with the released fluid composition close to pure water. In situ LA-ICP-MS trace element analyses also show that carbonate in olivine-carbonate veins was most likely sourced from the ophicarbonates. Our thermodynamic modelling indicates that the talc-magnesite reaction zone was most likely formed during early exhumation between 9-13 kbar and 530-460° C, at X_CO2 between 0.007 and 0.009. Lastly, we will discuss how the silicate-oxide-sulfide redox buffering assemblage indicates that all three rock types were equilibrated at redox conditions < FMQ.

In conclusion, our study demonstrates that in the absence of external fluid infiltration, carbonates in ultramafic lithologies are stable at subduction conditions. This suggests that ophicarbonate have a potential important role in the deep, long term, carbon cycle.