Ambient desorption/ionization (ADI) sources coupled to mass spectrometry (MS) offer outstanding analytical features: direct analysis of real samples without sample pretreatment, combined with the selectivity and sensitivity of MS. Since ADI sources typically work in the open atmosphere, ambient conditions can affect the desorption and ionization processes. Here, the effects of internal source parameters and ambient humidity on the ionization processes of the flowing atmospheric pressure afterglow (FAPA) source are investigated. The interaction of reagent ions with a range of analytes is studied in terms of sensitivity and based upon the processes that occur in the ionization reactions. The results show that internal parameters which lead to higher gas temperatures afforded higher sensitivities, although fragmentation is also affected. In the case of humidity, only extremely dry conditions led to higher sensitivities, while fragmentation remained unaffected.

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Time-of-flight mass spectrometry (TOFMS) is one of the simplest and most powerful approaches for mass spectrometry. Realization of the advantages inherent in TOFMS requires innovation in the theory and practice of the technique. Instrumental developments, in turn, create new capabilities that enable applications in chemical measurement. This review focuses on the recent advances in TOFMS instrumentation. New strategies for ion acceleration, multiplexed detection, miniaturized TOFMS instruments, approaches to extend the length of ion flight, and novel ion detection technologies are reviewed. Techniques that change the basic paradigm of TOFMS by measuring m/z based on ion flight distance are considered, as are applications at the frontiers of instrumental performance.

Atmospheric pressure glow discharges have been widely used in the last decade as ion sources in ambient mass spectrometry analyses. Here, an in-house flowing atmospheric pressure afterglow (FAPA) has been developed as an alternative ion source for differential mobility analysis (DMA). The discharge source parameters (inter-electrode distance, current and helium flow rate) determining the atmospheric plasma characteristics have been optimized in terms of DMA spectral simplicity with the highest achievable sensitivity while keeping an adequate plasma stability and so the FAPA working conditions finally selected were: 35 mA, 1 L min(-1) of He and an inter-electrode distance of 8 mm. Room temperature in the DMA proved to be adequate for the coupling and chemical analysis with the FAPA source. Positive and negative ions for different volatile organic compounds were tested and analysed by FAPA-DMA using a Faraday cup as a detector and proper operation in both modes was possible (without changes in FAPA operational parameters). The FAPA ionization source showed simpler ion mobility spectra with narrower peaks and a better, or similar, sensitivity than conventional UV-photoionization for DMA analysis in positive mode. Particularly, the negative mode proved to be a promising field of further research for the FAPA ion source coupled to ion mobility, clearly competitive with other more conventional plasmas such as corona discharge.