Observation of Large, Charged Droplet Signatures within the High-Vacuum Region of a Commercial Electrospray TOF-MS

Electrospray ionization (ESI) is one of the most prominent atmospheric pressure ionization techniques in modern mass spectrometry. It generates charged droplets from an analyte-containing solution as an initial step in the ionization process. Textbooks and the majority of the articles assume the entire droplet evaporation and release of bare analyte ions within the ionization chamber. However, non-mass-spectrometry-related literature and recent reports demonstrate droplet observation in regions of the vacuum systems of a variety of mass spectrometers. In this work, we report on the observation of large droplet fragments within the orthogonal acceleration stage of a Bruker micrOTOF by connecting an oscilloscope to an auxiliary ion current detector downstream of the acceleration stage. Moreover, we detected fragment debris even with the MCP TOF detector by evaluating individual TOF spectra. Droplet fragments appear as pronounced and intensive pulses of the ion current. This observation is clearly connected to ESI, as other atmospheric pressure ionization methods do not show this behavior. The recorded droplet signatures show clear dependencies on the ion source and transfer stage parameters. The existence of large and highly charged droplets may adversely affect or at least impact the analytical performance of the instrument due to space charge or complex heterogeneous chemical reactions. Furthermore, the penetration of large charged aggregates into the vacuum system explains the reported surface contamination after multipole stages. This contamination of critical components leads to substantially higher maintenance efforts.