Infrared spectroscopic signatures of (NH4)(2)SO4 aerosols

Ammonium sulfate particles in air with average diameters ranging from 0.1 to 0.5-mu m have been generated by atomizing aqueous solutions of (NH4)(2)SO4 of various concentrations at ambient temperatures and pressures. The infrared spectra from 4000 to 600 cm(-1) of the resulting aerosols have been investigated. This spectral region has allowed us to study the four infrared-active vibrational modes of this salt: nu(3)(NH4+), nu(4)(NH4+), nu(3)(SO42-), and nu(4)(SO42-. The frequencies of these modes are similar to published results obtained from infrared studies of the single crystal but are displaced to higher wavenumbers. Depending on relative humidity, the aerosol particles are crystalline or supersaturated aqueous droplets. These phase identifications are possible because liquid water absorption features are found in the droplets but not in the crystals. Extensive Mie theory calculations have been performed for spheres of diameters ranging from 0.1-mu m to 2.0-mu m to explore frequency shifts and the relative contributions to extinction of scattering and absorption with particle size. We show that, for the smaller particles, the molecular cross section in the nu(3)(SO42-) region can be used to determine the number of (NH4)(2)SO4 molecules in an aerosol sample. The (small) frequency shifts in this region provide information on the aerosol particle size. A Mie theory calculation of extinction for a model polydisperse aerosol, believed to approximate that of an experimental aerosol, gives reasonable agreement with the observed spectrum. While calculated band centers of the four modes are within 1% of those observed, values of extinction can differ by as much as 50%. We discuss possible reasons for the discrepancies. Spectroscopic changes observed for an aerosol as the particles settle are discussed in terms of kinetic models and Mie theory. We discuss the potential of spectroscopic signatures of tropospheric (NH4)(2)SO4 aerosols for the characterization of their size, morphology, phase, and composition. Finally, we propose a field experiment to measure sulfate aerosol in the arctic troposphere.