Timescale for hygroscopic conversion of calcite mineral particles through heterogeneous reaction with nitric acid

Atmospheric heterogeneous reactions can potentially change the hygroscopicity of atmospheric aerosols as they undergo chemical aging processes in the atmosphere. A particle’s hygroscopicity influences its cloud condensation nuclei (CCN) properties with potential impacts on cloud formation and climate. In this study, size-selected calcite mineral particles were reacted with controlled amounts of nitric acid vapour over a wide range of relative humidities in an aerosol flow tube to study the conversion of insoluble and thus apparently non-hygroscopic calcium carbonate into soluble and hygroscopic calcium nitrate. The rate of hygroscopic change particles undergo during a heterogeneous reaction is derived from experimental measurements for the first time. The chemistry of the reacted particles was determined using an ultrafine aerosol time-of-flight mass spectrometer (UF-ATOFMS) while the particles’ hygroscopicity was determined through measuring CCN activation curves fit to a single parameter of hygroscopicity, κ. The reaction is rapid, corresponding to atmospheric timescales of hours. At low to moderate HNO₃ exposures, the increase in the hygroscopicity of the particles is a linear function of the HNO₃(g) exposure. The experimentally observed conversion rate was used to constrain a simple but accurate kinetic model. This model predicts that calcite particles will be rapidly converted into hygroscopic particles (κ > 0.1) within 4 h for low HNO₃ mixing ratios (10 pptv) and in less than 3 min for 1000 pptv HNO₃. This suggests that the hygroscopic conversion of the calcite component of atmospheric mineral dust aerosol will be controlled by the availability of nitric acid and similar reactants, and not by the atmospheric residence time.