A general method for the calculation of absolute trace gas concentrations in air and breath from selected ion flow tube mass spectrometry data

A complete description is presented of a numerical method that allows the calculation, in real time, of absolute concentrations of trace gases, including volatile organic compounds and water vapour, from selected ion flow tube mass spectrometry, SIFT-MS, data. No assumptions are made concerning the SIFT-MS instrument size or its configuration and thus the calculation can be applied to the currently available, relatively large instruments and the anticipated new generation of smaller SIFT-MS instruments. This numerical method clearly distinguishes those parameters that are obviously specific to a particular instrument, including flow tube geometry, degree of mass discrimination in the analytical mass spectrometer and flow tube reaction time, from general fundamental processes, in particular the differential diffusive loss of ions along the flow tube that is dependent on the properties of those ions involved in the determination of the concentrations of particular trace gases. The essential reaction and transport kinetics are outlined, which describe the formation and loss of the product ions formed in the chemical ionisation of the trace gases by the precursor ions. A generalised calculation of the required ionic diffusion coefficients is introduced with options either for their accurate determination from the molecular geometry of ions or for less accurate but simpler estimates obtained using just the ionic mass. Based on the above ideas, a straightforward calculation sequence is shown to determine trace gas concentrations by SIFT-MS, and its utility demonstrated by an example of the analysis of acetone in exhaled breath.