Carbonate-silicate reactions at conditions of the Earth’s mantle and the role of carbonates as possible trace-element carriers

Abstract

Carbonates play a key role in the chemistry and dynamics of our planet. They are directly connected to the CO2 budget of our atmosphere and have a great impact on the deep carbon cycle. Moreover, recent studies have shown that carbonates are stable along the geothermal gradient down to Earth's lower mantle conditions, changing their crystal structure and related properties. Subducted carbonates may also react with silicates to form new phases. These reactions will redistribute elements, such as calcium (Ca), magnesium (Mg), iron (Fe) and carbon in the form of carbon dioxide (CO2), but also trace elements, that are carried by the carbonates. The trace elements of most interest are strontium (Sr) and rare earth elements (REE) which have been found to be important constituents in the composition of the primitive lower mantle and in mineral inclusions found in super-deep diamonds. However, the stability of carbonates in presence of mantle silicates at relevant temperatures is far from being well understood. Related to this, very little is known about distribution processes of trace elements between carbonates and mantle silicates. To shed light on these processes, we studied reactions between Sr- and REE-containing CaCO3 and Mg/Fe-bearing silicates of the system (Mg,Fe)2SiO4 - (Mg,Fe)SiO3 at high pressure and high temperature using synchrotron radiation based μ-X-ray diffraction (μ-XRD) and μ-X-ray fluorescence (μ-XRF) with μm-resolution in a laser-heated diamond anvil cell. X-ray diffraction is used to derive the structural changes of the phase reactions whereas X-ray fluorescence gives information on the chemical changes in the sample. In-situ experiments at high pressure and high temperature were performed at beamline P02.2 at PETRA III (Hamburg, Germany) and at beamline ID27 at ESRF (Grenoble, France). In addition to μ-XRD and μ-XRF, ex-situ measurements were made on the recovered sample material using transmission electron microscopy (TEM) and provided further insights into the reaction kinetics of carbonate-silicate reactions. Our investigations show that CaCO3 is unstable in presence of mantle silicates above 1700 K and a reaction takes place in which magnesite plus CaSiO3-perovskite are formed. In addition, we observed that a high content of iron in the carbonate-silicate system favours dolomite formation during the reaction. The subduction of natural carbonates with significant amounts of Sr leads to a comprehensive investigation of the stability not only of CaCO3 phases in contact with mantle silicates but also of SrCO3 (and of Sr-bearing CaCO3). We found that SrCO3 reacts with (Mg,Fe)SiO3-perovskite to form magnesite and gained evidence for the formation of SrSiO3-perovskite. To complement our study on the stability of SrCO3 at conditions of the Earth's lower mantle, we performed powder X-ray diffraction and single crystal X-ray diffraction experiments at ambient temperature and up to 49 GPa. We observed a transformation from SrCO3-I into a new high-pressure phase SrCO3-II at around 26 GPa with Pmmn crystal structure and a bulk modulus of 103(10) GPa. This information is essential to fully understand the phase behaviour and stability of carbonates in the Earth's lower mantle and to elucidate the possibility of introducing Sr into mantle silicates by carbonate-silicate reactions. Simultaneous recording of μ-XRD and μ-XRF in the μm-range over the heated areas provides spatial information not only about phase reactions but also on the elemental redistribution during the reactions. A comparison of the spatial intensity distribution of the XRF signal before and after heating indicates a change in the elemental distribution of Sr and an increase in Sr-concentration was found around the newly formed SrSiO3-perovskite. With the help of additional TEM analyses on the quenched sample material the elemental redistribution was studied at a sub-micrometer scale. Contrary to expectations from combined μ-XRD and μ-XRF measurements, we found that La and Eu were not incorporated into the silicate phases, instead they tend to form either isolated oxide phases (e.g. Eu2O3, La2O3) or hydroxyl-bastnasite (La(CO3)(OH)). In addition, we observed the transformation from (Mg,Fe)SiO3-perovskite to low-pressure clinoenstatite during pressure release. The monoclinic structure (P21/c) of this phase allows the incorporation of Ca as shown by additional EDX analyses and, to a minor extent, Sr too. Based on our experiments, we can conclude that a detection of the trace elements in-situ at high pressure and high temperature remains challenging. However, our first findings imply that silicates may incorporate the trace elements provided by the carbonates and indicate that carbonates may have a major effect on the trace element contents of mantle phases.