The addition of Ca-containing compounds can reduce mass loss from agricultural biomass during storage. The resulting alkaline environment is detrimental to microorganisms present in the material. Theoretical analysis of Ca-containing biomass suggests that combustion properties are improved with respect to slagging. To validate the theoretical calculations, barley straw was utilized as a typical model agricultural biomass and combustion characteristics of straw pre-treated with 2 and 4 w/w% CaCO₃ for combined improvement of storage and combustion properties were determined through combustion at 700 °C in a bench-scale bubbling fluidized-bed reactor (5 kW) using quartz and olivine sand as bed materials. The combustion characteristics were determined in terms of elemental composition and compound identification in bed ash and bed material including agglomerates, fly ash, particulate matter as well as flue gas measurements. The addition of CaCO₃ to straw had both positive and negative effects on its combustion characteristics. Both additive levels raised the total defluidization temperature for both quartz and olivine, and olivine proved to be less susceptible than quartz to reactions with alkali. With Ca-additives, the composition of deposits and fine particulate matter changed to include higher amounts of KCl potentially leading to higher risk for alkali chloride-induced corrosion. Flue gas composition was heavily influenced by CaCO₃ additives by significantly elevated CO concentrations likely related to increased levels of gaseous alkali compounds. The results suggest that it is necessary to reduce gaseous alkali compounds, e.g. through kaolin or sulphur addition, if alkali-rich straw is to be co-combusted with Ca-rich biomass or large amounts of Ca-additives