High-pressure compressibility and thermal expansion of aragonite

Abstract:

An important component of Earth’s deep carbon cycle is the return of surficial carbon to the planet’s interior. Most recycled carbon is bound in CaCO3 minerals, of which aragonite is the most significant at upper mantle pressures. It is therefore essential to understand the phase stability and compressibility of aragonite at high pressures and temperatures. Aragonite has an orthorhombic 2/m 2/m 2/m structure and a Z of 4. The high-pressure behavior of aragonite has been studied under dynamic and static compression using both X-ray diffraction and spectroscopic techniques, but these results have been contradictory and inconclusive. To address these issues, a single-crystal synchrotron X-ray diffraction study of aragonite under hydrostatic compression was performed to 40 GPa in a diamond anvil cell at ambient temperature. To supplement the compressional experiment, thermal expansion was also measured via powder X-ray diffraction at ambient pressure between 298-673 K. Ambient-pressure single-crystal measurements confirm the orthorhombic 2/m 2/m 2/m structure and yield a unit cell volume of 226.932(5) ų. At room temperature, aragonite is stable in the orthorhombic structure to 40 GPa, with an isothermal bulk modulus of 66.5(7) GPa and K’ = 5.0(1). The a-axis is most compressible and the c-axis is the least compressible. The b-axis is intermediate, but starts to decrease in compressibility at ~15 GPa. Between 25-30 GPa the aragonite unit cell distorts due to the stiffening of the b-axis, which is controlled by the orientation and distortion of the carbonate groups, layered in the aragonite structure parallel to the a-axis. The carbonate groups elongate and deform from equilateral to isosceles between 15 and 30 GPa, thus influencing the compressibility of the b-axis. The thermal expansion measurements yield expansion coefficients a₀ = 4.9(2) x 10^‑5 and a₁ =3.7(5) x 10^-8, in agreement with previous data. The combination of the isothermal and isobaric studies allows the derivation of a thermal equation of state. The new data provide constraints on the behavior of carbonates and carbon cycling in the Earth’s crust and mantle.