Depth of formation of super-deep diamonds: Raman barometry of CaSiO3-walstromite inclusions

"Super-deep" diamonds are thought to have a sub-lithospheric origin (i.e., below ~300 km depth) because some of the mineral phases entrapped within them as inclusions are considered to be the products of retrograde transformation from lower-mantle or transition-zone precursors. CaSiO3-walstromite, the most abundant Ca-bearing mineral inclusion found in super-deep diamonds, is believed to derive from CaSiO3-perovskite, which is stable only below ~600 km depth, although its real depth of origin is controversial. The remnant pressure (Pinc) retained by an inclusion, combined with the thermoelastic parameters of the mineral inclusion and the diamond host, allows calculation of the entrapment pressure of the diamond-inclusion pair. Raman spectroscopy, together with X ray diffraction, is the most commonly used method for measuring the Pinc without damaging the diamond host. In the present study we provide, for the first time, a calibration curve to determine the Pinc of a CaSiO3-walstromite inclusion by means of Raman spectroscopy without breaking the diamond. To do so, we performed high-pressure micro-Raman investigations on a CaSiO3-walstromite crystal under hydrostatic stress conditions within a diamond-Anvil cell. We additionally calculated the Raman spectrum of CaSiO3-walstromite by ab initio methods both under hydrostatic and non-hydrostatic stress conditions to avoid misinterpretation of the results caused by the possible presence of deviatoric stresses causing anomalous shift of CaSiO3-walstromite Raman peaks. Last, we applied single-inclusion elastic barometry to estimate the minimum entrapment pressure of a CaSiO3-walstromite inclusion trapped in a natural diamond, which is ~9 GPa (~260 km) at 1800 K. These results suggest that the diamond investigated is certainly sub-lithospheric and endorse the hypothesis that the presence of CaSiO3-walstromite is a strong indication of super-deep origin.