Crystal chemistry of Eu-bearing tuite synthesized at high-pressure and high-temperature conditions

Abstract

Tuite, γ-Ca3(PO4)2, is a potential host for rare-earth elements in the deep mantle. Eu-bearing tuite single crystals with chemical formulas of Ca2.93Eu0.04(PO4)2 and Ca2.88Eu0.07Na0.06(PO4)2 were synthesized at 16 GPa and 1600 °C, and their structures were investigated at room temperature with single-crystal X-ray diffraction. The structure refinements of Eu-bearing tuite indicate the preference of Eu3+ for the smaller 6-coordinated Ca1 site with a coupled vacancy due to the substitution of 2Eu3+ + □ → 3 Ca2+. In NaEu-bearing tuite, both Eu3+ and Na+ occupy the smaller 6-coordinated Ca1 site according to the coupled substitution of Eu3+ + Na+ → 2 Ca2+. The presence of Na results in more Eu2O3 in NaEu-bearing tuite, because the coupled substitution is energetically more favorable. REE-bearing tuite could be found on the Moon and the deep Earth’s mantle as a consequence of REE-bearing apatite or/and merrillite transformation under high-pressure and high-temperature conditions.