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Generally, the intensity and magnitude of explosive volcanic activity increase in parallel with SiO content. Pyroclastic-flow-forming eruptions in the Colli Albani ultrapotassic volcanic district (Italy) represent the most striking exception on a global scale, with volumes on the order of tens of cubic kilometres and K-foiditic compositions (SiO even <42 wt.%). Here, we reconstruct the pre-eruptive scenario and event dynamics of the ~456 ka Pozzolane Rosse (PR) eruption, the largest mafic explosive event of the Colli Albani district. In particular, we focus on the driving mechanisms for the unusually explosive eruption of a low-viscosity, mafic magma. Geologic, petrographic and geochemical data with mass balance calculations, supported by experimental data for Colli Albani magma compositions, provide evidence for significant ingestion of carbonate wall rocks by the Pozzolane Rosse K-foiditic magma. Moreover, the scattered occurrence of cored bombs in Pozzolane Rosse pyroclastic-flow deposits records carbonate entrainment even at the eruptive time scale, as also tested quantitatively by thermal modelling of magma-carbonate interaction and carbonate assimilation experiments. We suggest that the addition of free CO from decarbonation of country rocks was the major factor controlling magma explosivity. High CO activity in the volatile component, coupled with magma depressurisation, produced extensive leucite crystallisation at short time scales, resulting in a dramatic increase in magma viscosity and volatile pressurisation, which was manifested a change of eruptive dynamics from early effusion to the Pozzolane Rosse's highly explosive eruption climax. [ABSTRACT FROM AUTHOR]