A novel, gas-tight API interface for gas chromatography-mass spectrometry was used to study the ionization mechanism in direct and dopant-assisted atmospheric pressure photoionization (APPI) and atmospheric pressure laser ionization (APLI). Eight analytes (ethylbenzene, bromobenzene, naphthalene, anthracene, benzaldehyde, pyridine, quinolone, and acridine) with varying ionization energies (IEs) and proton affinities (PAs), and four common APPI dopants (toluene, acetone, anisole, and chlorobenzene) were chosen. All the studied compounds were ionized by direct APPI, forming mainly molecular ions. Addition of dopants suppressed the signal of the analytes with IEs above the IE of the dopant. For compounds with suitable IEs or Pas, the dopants increased the ionization efficiency as the analytes could be ionized through dopant-mediated gas-phase reactions, such as charge exchange, proton transfer, and other rather unexpected reactions, such as formation of [M + 77](+) in the presence of chlorobenzene. Experiments with deuterated toluene as the dopant verified that in case of proton transfer, the proton originated from the dopant instead of proton-bound solvent clusters, as in conventional open or non-tight APPI sources. In direct APLI using a 266 nm laser, a narrower range of compounds was ionized than in direct APPI, because of exceedingly high IEs or unfavorable two-photon absorption cross-sections. Introduction of dopants in the APLI system changed the ionization mechanism to similar dopant-mediated gas-phase reactions with the dopant as in APPI, which produced mainly ions of the same form as in APPI, and ionized a wider range of analytes than direct APLI.

We provide experimental and theoretical evidence that the primary ionization process in the dopant-assisted varieties of the atmospheric pressure ionization methods atmospheric pressure photoionization and atmospheric pressure laser ionization in typical liquid chromatography-mass spectrometry settings is--as suggested in the literature--dopant radical cation formation. However, instead of direct dopant radical cation-analyte interaction--the broadly accepted subsequent step in the reaction cascade leading to protonated analyte molecules--rapid thermal equilibration with ion source background water or liquid chromatography solvents through dopant ion-molecule cluster formation occurs. Fast intracluster chemistry then leads to almost instantaneous proton-bound water/solvent cluster generation. These clusters interact either directly with analytes by ligand switching or association reactions, respectively, or further downstream in the intermediate-pressure regions in the ion transfer stages of the mass spectrometer via electrical-field-driven collisional decomposition reactions finally leading to the predominantly observed bare protonated analyte molecules [M + H](+).

It is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region.

Abstract. In this work, the characteristics of gas flow in inlet capillaries are examined. Such inlet capillaries are widely used as a first flow restriction stage in commercial atmospheric pressure ionization mass spectrometers. Contrary to the common assumption, we consider the gas flow in typical glass inlet capillaries with 0.5 to 0.6 mm inner diameters and lengths about 20 cm as transitional or turbulent. The measured volume flow of the choked turbulent gas stream in such capillaries is 0.8 L·min −1 to 1.6 L·min −1 under typical operation conditions, which is in good agreement to theoretically calculated values. Likewise, the change of the volume flow in dependence of the pressure difference along the capillary agrees well with a theoretical model for turbulent conditions as well as with exemplary measurements of the static pressure inside the capillary channel. However, the results for the volume flow of heated glass and metal inlet capillaries are neither in agreement with turbulent nor with laminar models. The velocity profile of the neutral gas in a quartz capillary with an inner diameter similar to commercial inlet capillaries was experimentally determined with spatially resolved ion transfer time measurements. The determined gas velocity profiles do not contradict the turbulent character of the flow. Finally, inducing disturbances of the gas flow by placing obstacles in the capillary channel is found to not change the flow characteristics significantly. In combination the findings suggest that laminar conditions inside inlet capillaries are not a valid primary explanation for the observed high ion transparency of inlet capillaries under common operation conditions.

We report on the development of a novel atmospheric pressure photoionization setup and its applicability for in situ degradation product studies of atmospherically relevant compounds. A custom miniature spark discharge lamp was embedded into an ion transfer capillary, which separates the atmospheric pressure from the low pressure region in the first differential pumping stage of a conventional atmospheric pressure ionization mass spectrometer. The lamp operates with a continuous argon flow and produces intense light emissions in the VUV. The custom lamp is operated windowless and efficiently illuminates the sample flow through the transfer capillary on an area smaller than 1 mm 2 . Limits of detection in the lower ppbV range, a temporal resolution of milliseconds in the positive as well as the quasi simultaneously operating negative ion mode, and a significant reduction of ion transformation processes render this system applicable to real time studies of rapidly changing chemical systems. The method termed capillary atmospheric pressure photo ionization (cAPPI) is characterized with respect to the lamp emission properties as a function of the operating conditions, temporal response, and its applicability for in situ degradation product studies of atmospherically relevant compounds, respectively.