High degassing rates for some volcanoes, typically in continental arcs, (e.g., Colli Albani Volcanic District, Etna, Vesuvius, Italy; Merapi, Indonesia; Popocatepetl, Mexico) are thought to be influenced by magma–carbonate interaction in the crust. In order to constrain the nature of reaction and extent of carbonate breakdown, we simulated basalt–limestone wall-rock interactions at 0.5–1.0 GPa, 1100–1200 °C using a piston cylinder and equal mass fractions of calcite (CaCO3) and a hydrous (∼4 wt.% H2O) basalt in a layered geometry contained in AuPd capsules. All experiments produce melt + fluid + calcite ± clinopyroxene ± plagioclase ± calcic-scapolite ± spinel. With increasing T, plagioclase is progressively replaced by scapolite, clinopyroxene becomes CaTs-rich, and fluid proportion, as inferred from vesicle population, increases. At 1.0 GPa, 1200 °C our hydrous basalt is superliquidus, whereas in the presence of calcite, the experiment produces calcite + clinopyroxene + scapolite + melt. With the consumption of calcite with increasing T and decreasing P, melt, on a volatile-free basis, becomes silica-poor (58.1 wt.% at 1.0 GPa, 1100 °C to 34.9 wt.% at 0.5 GPa, 1200 °C) and CaO-rich (6.7 wt.% at 1.0 GPa, 1100 °C to 43.7 wt.% at 0.5 GPa, 1200 °C), whereas Al2O3 drops (e.g., 19.7 at 1100 °C to 12.8 wt.% at 1200 °C at 1.0 GPa) as clinopyroxene becomes more CaTs-rich. High T or low P melt compositions are ‘ultracalcic,’ potentially presenting a new hypothesis for the origin of ultracalcic melt inclusions in arc lava olivines. Wall-rock calcite consumption is observed to increase with increasing T and decreasing P. At 0.5 GPa, our experiments yield carbonate assimilation from 21.6 to 47.6% between 1100 and 1200 °C. Using measured CO2 outflux rates for Mts. Vesuvius, Merapi, Etna and Popocatepetl over a T variation of 1100 to 1200 °C at 0.5 GPa, we calculate 6–92% of magmatic input estimates undergo this extent of assimilation, suggesting that up to ∼3% of the current global arc CO2 flux may be crustally derived. Application of the assimilation extent bracketed in this study to the estimated elevated number of carbonate-assimilating arc magmatic systems active during the late Cretaceous to early Paleogene suggests that magma-induced upper plate decarbonation alone had the potential to contribute up to 2.7×1014–5.6×1015 g/y CO2, assuming no dilution and complete gaseous release of all assimilated carbon. Using an estimated assimilation extent averaged from current systems gives a slightly lower though still significant value of ≤5.5×1014 g/y of excess CO2 being released into the atmosphere.