title: Heterogeneous conversion of calcite aerosol by nitric acid.
abstract: The reaction of nitric acid with calcite aerosol at varying relative humidities has been studied under suspended particle conditions in an atmospheric reaction chamber using infrared absorption spectroscopy. The reactant concentration in the chamber, as well as the appearance of gas phase products and surface adsorbed species, was spectroscopically monitored before and after mixing with CaCO(3) (calcite) particles. The interaction with HNO(3) was found to lead to gas phase CO(2) evolution and increased water uptake due to heterogeneous conversion of the carbonate to particulate nitrate. The reaction was enhanced as the relative humidity of the system was increased, especially at relative humidities above the reported deliquescence point of particulate Ca(NO(3))(2). The measured reaction extent demonstrates that the total calcite particulate mass is available for reaction with HNO(3) and the conversion process is not limited to the particle surface. The spectroscopy of the surface formed nitrate suggests a highly concentrated solution environment with a significant degree of ion pairing. The implications of the HNO(3) loss and the formation of the particulate nitrate product for atmospheric chemistry are discussed.
authors.affiliation: Department of Chemistry, the Optical Science and Technology Center, and the Center for Global and Regional Environmental Research, University of Iowa, Iowa City, IA 52242, USA.
authors.forename: A
authors.initials: A
authors.lastname: Preszler Prince
authors.forename: V H
authors.initials: VH
authors.lastname: Grassian
authors.forename: P
authors.initials: P
authors.lastname: Kleiber
authors.forename: M A
authors.initials: MA
authors.lastname: Young
mesh_terms: D000336:Aerosols / Q000737:chemistry*; D001272:Atmosphere / Q000737:chemistry; D001273:Atmosphere Exposure Chambers; D002119:Calcium Carbonate / Q000737:chemistry*; D002245:Carbon Dioxide / Q000138:chemical synthesis / Q000737:chemistry; D006813:Humidity; D017942:Nitric Acid / Q000737:chemistry*; D010316:Particle Size; D012680:Sensitivity and Specificity; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods; D013499:Surface Properties; D013997:Time Factors
chemical_list: D000336:Aerosols; D002245:Carbon Dioxide; D017942:Nitric Acid; D002119:Calcium Carbonate