Primary magmatic calcite reveals origin from crustal carbonate

• Primary calcite crystallized in lava groundmass from a carbonate melt, at high T
• Calcite crystallization linked to interaction between magma and crustal carbonate
• Stability of carbonate melt ensured by the high F activity in the system
• Carbonate melt formed by syn-eruptive melting of crustal carbonate fragments

We have investigated lava flows representative of the whole eruptive history of the Colli Albani ultrapotassic volcanic district (Central Italy). One of the most intriguing features concerning some of these lava flows is the occurrence of primary, magmatic calcite in the groundmass. The primary, magmatic nature of calcite has been inferred by microtextural investigations showing that it typically occurs i) interstitially, associated with clinopyroxene, nepheline and phlogopite, ii) in spherical ocelli, associated with nepheline, fluorite and tangentially arranged clinopyroxene, and iii) in corona-like reaction zones around K-feldspar xenocrysts. These microtextural features distinctly indicate that calcite crystallized from a carbonate melt in a partially molten groundmass, implying that the temperature of the system was above the solidus of the hosted lava flow (> 850 °C). Geochemical features of calcite crystals (i.e., stable isotope values and trace element patterns) corroborate their primary nature and give insights into the origin of the parental carbonate melt. The trace element patterns testify to a high-temperature crystallization process (not hydrothermal) involving a carbonate melt coexisting with a silicate melt. The high δ18O (around 27‰ SMOW) and wide δ13C (− 18 to + 5‰ PDB) values measured in the calcites preclude a mantle origin, but are consistent with an origin in the crust. In this framework, the crystallization of calcite can be linked to the interaction between magmas and carbonate-bearing wall rocks and, in particular, to the entrapment of solid and/or molten carbonate in the silicate magma. The stability of carbonate melt at low pressure and the consequent crystallization of calcite in the lava flow groundmass are ensured by the documented, high activity of fluorine in the studied system and by the limited ability of silicate and carbonate melts to mix at syn-eruptive time scales.