Carbonatites are the most important primary sources for the rare earth elements (REEs). While fractional crystallization of carbonate minerals results in the enrichment of volatiles, alkalis, and REEs in the remaining melts, the transition from carbonatitic magmas to hydrothermal brines remains unclear. Here, we investigated the pressure-temperature-composition (P-T-X) properties of the Na₂CO₃-H₂O system up to 700°C and 11.0 kbar using a hydrothermal diamond anvil cell and a Raman spectrometer. Our results show that Na₂CO₃becomes increasingly soluble under highP-Tconditions, leading to the disappearance of melt-fluid immiscibility and the continuous transition from Na₂CO₃melts to hydrothermal brines under deep crustal conditions. Given the abundance of Na₂CO₃in highly evolved carbonatitic systems, we suggest that the continuous melt-fluid transition in deep-seated carbonatites results in REEs being sufficiently concentrated in the brine-melts to form economic ore bodies, whereas in shallow systems, REEs preferentially partition into carbonatitic magmas over synmagmatic brines and disperse in carbonatite rocks that underwent limited fractionation.

Earth carbon cycle shapes the evolution of our planet and our habitats. As a key region of carbon cycle, subduction zone acts as a sole channel transporting supracrustal carbonate rocks down to the mantle, balancing carbon budget between the Earth’s surface and the interior, and regulating CO₂ concentration of the atmosphere. How carbonates evolve at depth is thus, a most fundamental issue in understanding carbon flux and carbon sequestration mechanism in the Earth. This study reviews prominent progresses made in the field of crystal chemistry of carbonates along subduction geotherms. It clearly finds that, in addition to common carbonates in the Earth’s crust, several new polymorphs of carbonates have been discovered to be stable under high-pressure and high-temperature conditions. This opens possibilities for oxidized carbon species in the deep Earth. However, metamorphic decarbonatation and reduction reactions restrict subducting carbonates to the top-mid region of the lower mantle. Specifically, subsolidus decarbonatation in the form of carbonates reacting with silicates has been proposed as an efficient process releasing CO₂ from slabs to the mantle. Besides, carbonate reduction in the metal-saturated mantle likely results in generation of super-deep diamonds and a considerable degree of carbon isotope fractionation. Review of these novel findings leads us to consider three issues in the further studies, including 1) searching for new chemical forms of carbon in the mantle, 2) determining the reduction efficiency of carbonates to diamonds and the accompanying carbon isotope fractionation and 3) concerning carbon cycle in subduction of continental crust.

Malachite Cu₂(CO₃)(OH)₂ is a common hydroxycarbonate that contains about 15.3 wt % H₂O. Its structural chemistry sheds light on other hydroxyl minerals that play a role in the water recycling of our planet. Here using Raman and infrared spectroscopy measurements, we studied the vibrational characteristics and structural evolution of malachite in a diamond anvil cell at room temperature (25 °C) up to ~29 GPa. Three types of vibrations were analyzed including Cu–O vibrations (300–600 cm⁻¹), [CO₃]²⁻ vibrations (700–1600 cm⁻¹), and O–H stretches (3200–3500 cm⁻¹). We present novel observations of mode discontinuities at pressures of ~7, ~15, and ~23 GPa, suggesting three phase transitions, respectively. First, pressure has a great effect on the degree of deformation of the [CuO₆] octahedron, as is manifested by the various shifting slopes of the Cu–O modes. [CuO₆] deformation results in a rotation of the structural unit and accordingly a phase transition at ~7 GPa. Upon compression to ~15 GPa, the O–H bands redshift progressively with significant broadness, indicative of an enhancement of the hydrogen bonding, a shortening of the O···O distance, and possibly somewhat of a desymmetrization of the O–H···O bond. O–H mode hardening is identified above ~15 GPa coupled with a growth in the amplitude of the lower-energy bands. These observations can be interpreted as some reorientation or reordering of the hydrogen bonding. A further increment of pressure leads to a change in the overall compression mechanism of the structure at ~23 GPa, which is characterized by the blueshift of the O–H stretches and the softening of the O–C–O in-plane bending bands. The hydrogen bonding weakens due to a substantial enhancement of the Cu–H repulsion effect, and the O···O bond length shows no further shortening. In addition, the change in the local geometry of hydrogen is also induced by the softening of the [CO₃]²⁻ units. In this regard we may expect malachite and other analogous hydroxyl minerals as capable of transporting water downward towards the Earth’s transition zone (~23 GPa). Our results furnish our knowledge on the chemistry of hydrogen bonding at mantle conditions and open a new window in understanding the synergistic relations of water and carbon recycling in the deep Earth.

The structural chemistry of carbonates under mantle conditions facilitates our understanding of carbon recycling pathways in the earth’s interior. It also has impacts on the dynamics of mantle–slab interactions. Aragonite is a common calcium carbonate mineral in pelagic marine sediments. The structural chemistry of single-crystal aragonite during successive compression and the behavior of a structural H⁺ have been investigated by micro-vibrational spectroscopy and synchrotron X-ray diffraction techniques in diamond anvil cells. We describe a reduction of the b-axial compressibility beginning at ~15 GPa, and the related discontinuities in the first-order derivatives of the vibrational modes. The structural modifications of aragonite are manifested by mutations occurring in the pressure relations of the wavenumbers of the O-C-O bending modes, and of the bandwidth and band intensities of the measured internal and external modes. These anomalies are indicative of changes occurring in the force constant of the C-O bonds, and possibly a second-order phase transition. Besides, the [CaO₉] polyhedra begin to deform, possibly with some Ca-O bonds becoming elongated and the others shortening. An increase in the co-ordination number for the Ca²⁺ sites could be expected under higher pressures. Additionally, the weakening of the OH modes may imply H⁺-loss from the aragonite lattice above 11.5 GPa.