The technique of proton transfer reaction mass spectrometry (PTR-MS) couples a proton transfer reagent, usually H3O+, with a drift tube and mass spectrometer to determine concentrations of volatile organic compounds. Here we describe a first attempt to use chemical ionization (CI) reagents other than proton transfer species inside a PTR-MS instrument. The ability to switch to other types of CI reagents provides an extra dimension to the technique. This capability is demonstrated by focusing on the ability to distinguish several isobaric aldehydes and ketones, including the atmospherically important molecules methacrolein and methyl vinyl ketone. Two CI reagents were selected, H3O+ and NO+, both being cleanly generated in a low intensity radioactive source prior to injection into the drift tube. By recording spectra with both of these reagents, the contributions from different isobaric molecules can be separated by virtue of their unique spectrometric 'fingerprints'. The work demonstrates that this form of instrumentation is not restricted to proton transfer reagents and is the basis of a more general technique, chemical ionization reaction mass spectrometry (CIRMS).

Chemical ionization reaction time-of-flight mass spectrometry (CIR-TOF-MS) has been used for the analysis of prepared mixtures of chemical weapon agents (CWAs) sarin and sulfur mustard. Detection of the CWA simulants 2-chloroethyl ethyl sulfide, triethyl phosphate, and dimethyl methyl phosphonate has also been investigated. Chemical ionization of all the agents and simulants was shown to be possible using the CIR-TOF-MS technique with a variety of reagent ions, and the sensitivity was optimized by variation of instrument parameters. The ionization process was found to be largely unaffected by sample humidity levels, demonstrating the potential suitability of the method to a range of environmental conditions, including the analysis of CWAs in air and in the breath of exposed individuals.

Abstract. The prospects for exploiting Proton Transfer Reaction-Time of Flight-Mass Spectrometry(PTR-ToF-MS) in medical diagnostics are illustrated through a series of case studies. Measurements of acetone levels in the breath of 68 healthy people are presented along with a longitudinal study of a single person over a period of one month. The median acetone concentration across the population was 484 ppbV with a geometric standard deviation (GSD) of 1.6, whilst the average GSD during the single subject longtitudinal study was 1.5. An additional case study is presented which highlights the potential of PTR-ToF-MS in pharmacokinetic studies, based upon the analysis of online breath samples of a person following the consumption of ethanol. PTR-ToF-MS comes into its own when information across a wide mass range is required, particularly when such information must be gathered in a short time during a breathing cycle. To illustrate this property, multicomponent breath analysis in a small study of cystic fibrosis patients is detailed, which provides tentative evidence that online PTR-ToF-MS analysis of tidal breath can distinguish between active infection and non-infected patients.2

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