The heterogeneous replacement of chloride by nitrate in individual sea-salt particles was monitored continuously over time in the troposphere with the use of aerosol time-of-flight mass spectrometry. Modeling calculations show that the observed chloride displacement process is consistent with a heterogeneous chemical reaction between sea-salt particles and gas-phase nitric acid, leading to sodium nitrate production in the particle phase accompanied by liberation of gaseous HCl from the particles. Such single-particle measurements, combined with a single-particle model, make it possible to monitor and explain heterogeneous gas/particle chemistry as it occurs in the atmosphere.

Atmospheric ultrafine particles (diameter < 0.1 µm) are under study by inhalation toxicologists to determine whether they pose a threat to public health, yet, little is known about the chemical composition of ultrafine particles in the atmosphere of cities. In the present work, the number concentration, size distribution, and chemical composition of atmospheric ultrafine particles is determined under wintertime conditions in Pasadena, CA, near Los Angeles. These experiments are conducted using a scanning differential mobility analyzer, laser optical counter, and two micro-orifice impactors. Samples are analyzed to create a material balance on the chemical composition of the ultrafine particles. The number concentration of ultrafine particles in the size range 0.017 < d p < 0.1 µm, analyzed over 24-h periods, is found to be consistently in the range 1.3 × 10 4 ( 8.9 × 10 3 particles cm -3 air. Ultrafine particle mass concentrations are in the range 0.80-1.58 µg m -3 . Organic compounds are the largest contributors to the ultrafine particle mass concentration. A small amount of sulfate is present in these particles, at concentrations too low to tell whether it exists as unneutralized sulfuric acid. Iron is the most prominent transition metal found in the ultrafine particles. These data may assist the health effects research community in constructing realistic animal or human exposure studies involving ultrafine particles.

Aerosol time-of-flight mass spectrometers (ATOFMS) measure the size and chemical composition of single aerosol particles. To date, these instruments have provided qualitative descriptions of aerosols, in part because the fraction of particles actually present in the atmosphere that is detected by these instruments has not been known. In this work, the particle detection efficiencies of three ATOFMS instruments are determined under ambient sampling conditions from the results of colocated sampling with more conventional reference samplers at three locations in southern California. ATOFMS particle detection efficiencies display a power law dependence on particle aerodynamic diameter (D a ) over a calibration range of 0.32 < D a < 1.8 microns. Detection efficiencies are determined by comparison of ATOFMS data with inertial impactor data and are compared to detection efficiencies determined independently by the use of laser optical particle counters. Detection efficiencies are highest for the largest particles and decline by approximately 2 orders of magnitude for the smallest particles, depending on the ATOFMS design. Calibration functions are developed here and applied to scale ATOFMS data to yield continuous aerosol mass concentrations as a function of particle size over an extended period of time.