Aerosol mass spectrometry has become an essential tool in monitoring tropospheric aerosols. Various approaches have been developed for analyzing particles that range in size from 10 nm to 10 m in diameter, and which consist of salts, soot, crustal matter, metals, and organic molecules, often mixed together. This wide variety of particle types has generated an equally wide variety of ionization sources, which include electron impact, laser ionization, laser desorption, chemical ionization, and electron capture ionization. Some instruments are capable of single particle analysis, while others require the collection of an ensemble of particles to obtain sufficient sample for analysis. Most instruments have been designed to ionize and analyze particular classes of compounds (e.g. salts, soot, or organics). This review provides a very broad overview of the aerosol mass spectrometry field and serves as an introduction to the many papers in this issue that deal with details about specific instruments.
The oleic acid ozonolysis in mixed oleic and myristic acid particles was studied in a flow tube reactor using single particle mass spectrometry. The change in reactivity was investigated as a function of the myristic acid concentration in these 2 micron particles. For pure oleic acid aerosol, the reactive ozone uptake coefficient, gamma, was found to be 3.4 (+/-0.3) x 10(-4) after taking secondary reactions into account. At the myristic acid crystallization point, where only 2.5% of the particle is in the solid phase, the uptake coefficient was reduced to 9.7 (+/-1.0) x 10(-5). This dramatic drop in the uptake coefficient is explained by the presence of a crystalline monolayer of myristic acid, through which ozone diffusion is reduced by several orders of magnitude, relative to liquid oleic acid. Scanning electron microscope images of the mixed particles confirm that the particle surface is crystalline when the myristic acid mole fraction exceeds 0.125. The findings of these experiments illustrate that particle morphology is important to understanding the reactivity of species in a mixed particle. The decay of myristic acid during the course of ozonolysis is explained in terms of a reaction with stabilized Criegee intermediates, which attack the acidic groups of the oleic and myristic acids with equal rate constants.
Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe results in greater adverse pulmonary effects compared with DE. Male Sprague Dawley rats were exposed to filtered air, DE, or DECe for 5 h/day for 2 days. N-acetyl glucosaminidase activity was increased in bronchial alveolar lavage fluid (BALF) of rats exposed to DECe but not DE. There were also marginal but insignificant increases in several other lung injury biomarkers in both exposure groups (DECe > DE for all). To further characterize DECe toxicity, rats in a second study were exposed to filtered air or DECe for 5 h/day for 2 days or 4 weeks. Tissue analysis indicated a concentration- and time-dependent accumulation of lung and liver cerium followed by a delayed clearance. The gas-phase and high concentration of DECe increased lung inflammation at the 2-day time point, indicating that gas-phase components, in addition to particles, contribute to pulmonary toxicity. This effect was reduced at 4 weeks except for a sustained increase in BALF γ-glutamyl transferase activity. Histopathology and transmission electron microscopy revealed increased alveolar septa thickness due to edema and increased numbers of pigmented macrophages after DECe exposure. Collectively, these findings indicate that DECe induces more adverse pulmonary effects on a mass basis than DE. In addition, lung accumulation of cerium, systemic translocation to the liver, and delayed clearance are added concerns to existing health effects of DECe.
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