A Field-Based Approach for Determining ATOFMS Instrument Sensitivities to Ammonium and Nitrate

Aerosol time-of-flight mass spectrometry (ATOFMS) instruments measure the size and chemical composition of individual particles in real-time. ATOFMS chemical composition measurements are difficult to quantify, largely because the instrument sensitivities to different chemical species in mixed ambient aerosols are unknown. In this paper, we develop a field-based approach for determining ATOFMS instrument sensitivities to ammonium and nitrate in size-segregated atmospheric aerosols, using tandem ATOFMS-impactor sampling. ATOFMS measurements are compared with collocated impactor measurements taken at Riverside, CA, in September 1996, August 1997, and October 1997. This is the first comparison of ion signal intensities from a single-particle instrument with quantitative measurements of atmospheric aerosol chemical composition. The comparison reveals that ATOFMS instrument sensitivities to both and decline with increasing particle aerodynamic diameter over a 0.32−1.8 μm calibration range. The stability of this particle size dependence is tested over the broad range of fine particle concentrations (PM1.8 = 17.6 ± 2.0−127.8 ± 1.8 μg m-3), ambient temperatures (23−35 °C), and relative humidity conditions (21−69%), encountered during the field experiments. This paper describes a potentially generalizable methodology for increasing the temporal and size resolution of atmospheric aerosol chemical composition measurements, using tandem ATOFMS-impactor sampling

Size and Composition Distribution of Atmospheric Particles in Southern California

Continuous measurements of single particle size and chemical composition in the atmosphere are made using aerosol time-of-flight mass spectrometers (ATOFMS) operated alongside more conventional reference air sampling instruments at a network of three urban air monitoring sites in southern California. Electrical aerosol analyzers and optical particle counters are employed to acquire continuous particle size distribution data, and inertial impactor and bulk filter samples with 4-h resolution are taken for determination of particle size and chemical composition. Filter and impactor samples also are taken upwind of the air basin at Santa Catalina Island in order to characterize background air quality. The airborne particle size and composition distribution as measured by the cascade impactors at inland sites differ from that over the ocean principally due to depletion of sea salt particles accompanied by the addition of fine carbon-containing particles and secondary aerosol nitrate. Data from the ATOFMS systems create a continuous time series of sodium-, ammonium-, nitrate-, and carbon-containing particle counts that provide a high-resolution view of differences in particle composition as a function of location in the air basin. Results show that the characteristic peak in the Los Angeles area aerosol mass distribution in the 0.2−0.3-μm size range observed during the 1987 SCAQS experiments has been reduced, consistent with reductions in diesel soot and elemental carbon emissions since that time