Advanced Quadrupole Ion Trap Instrumentation for Low Level Vehicle Emissions Measurements

Abstract

Quadrupole ion trap mass spectrometry has been evaluated for its potential use in vehicle emissions measurements in vehicle test facilities as an analyzer for the top 15 compounds contributing to smog generation. A variety of ionization methods were explored including ion trap in situ chemical ionization, atmospheric sampling glow discharge ionization, and nitric oxide chemical ionization in a glow discharge ionization source coupled with anion trap mass spectrometer. Emphasis was placed on the determination of hydrocarbons and oxygenated hydrocarbons at parts per million to parts per billion levels. Ion trap in situ water chemical ionization and atmospheric sampling glow discharge ionization were both shown to be amendable to the analysis of arenes, alcohols, aldehydes and, to some degree, alkenes. Atmospheric sampling glow discharge also generated molecular ions of methy-t-butyl ether (MTBE). Neither of these ionization methods, however, were found to generate diagnostic ions for the alkanes. Nitric oxide chemical ionization, on the other hand, was found to yield diagnostic ions for alkanes, alkenes, arenes, alcohols, aldehydes, and MTBE. The ability to measure a variety of hydrocarbons present at roughly 15 parts per billion at measurement rates of 3 Hz was demonstrated. All of the ions with potential to serve as parent ions in a tandem mass spectrometry experiment were found to yield parent-to-product conversion efficiencies greater than 75%. The flexibility afforded to the ion trap by use of tailored wave-forms applied to the end-caps allows parallel monitoring schemes to be devised that provide many of the advantages of tandem mass spectrometry without major loss in measurement rate. A large loss in measurement rate would ordinarily result from the use of conventional tandem mass spectrometry experiments carried out in series for a large number of targeted components. These results have demonstrated that the ion trap has an excellent combination of sensitivity, specificity, speed, and flexibility with respect to the technical requirements of the top 15 analyzer.