Application of ion chemistry and the SIFT technique to the quantitative analysis of trace gases in air and on breath

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Abstract
Our major objective in this paper is to describe a new method we have developed for the analysis of trace gases at partial pressures down to the ppb level in atmospheric air, with special emphasis on the detection and quantification of trace gases on human breath. It involves the use of our selected ion flow tube (Sift) technique which we previously developed and used extensively for the study of gas phase ionic reactions occurring in ionized media such as the terrestrial atmosphere and interstellar gas clouds. Before discussing this analytical technique we describe the results of our very recent Sift and flowing afterglow (FA) studies of the reactions of the H3O+ and OH− ions, of their hydrates H3O+(H2O)1,2,3 and OH− (H2O)1,2, and of NO+ and O2 +, with several hydrocarbons and oxygen-bearing organic molecules, studies that are very relevant to our trace gas analytical studies. Then follows a detailed discussion of the application of our Sift technique to trace gas analysis, after which we present some results obtained for the analyses of laboratory air, the breath of a healthy non-smoking person, the breath of a person who regularly smokes cigarettes, the complex vapours emitted by banana and onion, and the molecules present in a butane/air flame. We show how the quantitative analysis of breath can be achieved from only a single exhalation and in real time (the time response of the instrument is only about 20 ms). We also show how the time variation of breath gases over long time periods can be followed, using the decay of ethanol on the breath after the ingestion of distilled liquor as an example, yet simultaneously following several other trace gases including acetone and isoprene which are very easily detected on the breath of all individuals because of their relatively high partial pressures (typically 100 to 1000 ppb). The breath of a smoker is richer in complex molecules, some nitrogen containing organics apparently being very evident at the 5 to 50 ppb level. These results and those for banana and onion vapours and butane/air flame forcibly demonstrate the value and the scope of our Sift ion chemistry approach to the analysis of very complex gas mixtures, and that this method is accurately quantitative if the appropriate ion chemistry is properly understood.

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