Karlleuite Ca2MnO4 – a first mineral with the Ruddlesden-Popper type structure from Bellerberg volcano, Germany

Karlleuite, ideally Ca₂MnO₄, is a newly approved accessory mineral found in the xenolith sample within the basaltic lava from the Caspar quarry, Bellerberg volcano, Eifel, Germany. It usually occurs as thin tabular/plate crystals, which range from 40 to 80 μm in diameter, and is associated with other members of the perovskite supergroup such as srebrodolskite, brownmillerite, sharyginite, perovskite, and lakargiite distributed within rock-forming minerals represented by reinhardbraunsite, fluorellestadite, fluorapatite, larnite, gehlenite, and several hydrated Ca aluminosilicates. Karlleuite crystals are brown with sub-metallic lustre, a light brown streak, and a good cleavage along (001). It is non-fluorescent, brittle and has an uneven fracture, a Mohs hardness of 3.5 and calculated density D_x = 3.79 g/cm³. The empirical formula of the holotype karlleuite calculated based on O = 4 atoms per formula is (Ca_1.97Ce³⁺_0.06)_2.03(Mn^4 + _0.39Ti_0.36Fe³⁺_0.19Al_0.09)_1.03O₄, which shows that it is a multicomponent phase characterised by various substituents at the octahedral site. Karlleuite is tetragonal I4/mmm (no. 139), with a = 3.7683(2) Å, c = 11.9893(8) Å, V = 170.254(17) ų, and Z = 2. The calculated strongest lines in the X-ray powder diffraction pattern are [d in Å (I) hkl]: 5.995 (43), 2.742 (100), 2.665 (91), 2.023 (25), 1.998 (28), 1.884 (61), 1.553 (38), 1.371 (24). The new mineral is the first natural phase which exhibits a first order of Ruddlesden-Popper type structure, which indicates a modular nature and consists of Ca(Mn, Ti, Fe, Al)O₃ perovskite layers, packed between CaO rock-salt layers arranged along the c-axis. Raman spectroscopy supports the interpretation of the chemical and structural data. Mineral association, structural data, as well as the study of the synthetic Ca-Mn-O system suggest that karlleuite could form under high-temperature conditions, above 1000˚C.