Abstract

The performance of the ion sources used in selected ion flow tube mass spectrometry, SIFT-MS, instruments is paramount in determining their sensitivities and detection limits for trace gas analysis. The microwave discharge plasma ion source that is currently used for the production of currents of the precursor H 3O +, NO + and O 2 + ions for SIFT-MS is described, and the ion chemistry occurring within the plasma and the dissociation of the precursor ions on the helium carrier gas are considered. Thus, it is shown that the most suitable ion source gas composition is a mixture comprising maximal water vapour and minimal air at the lowest total pressure at which the discharge is sustained and stable. It is also shown that the injection energies of the precursor ions into the helium carrier gas must be kept low to minimize collisional dissociation of the ions and thus to minimize the fraction of reactive impurity ions in the carrier gas. Under these conditions, count rates greater than 10 6 s −1 of all three precursor ion species with less than 1% of impurity ions have been achieved, which has moved the detection limit of SIFT-MS analyses of the volatile metabolites present in exhaled breath and ambient air into the 0.1–1 parts-per-billion concentration regime.

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