Capillary atmospheric pressure chemical ionization using liquid point electrodes.

Atmospheric pressure chemical ionization (APCI) sources operated with point to plane DC discharges ('Coronas') frequently suffer from point electrode degradation and potentially lead to oxidation and/or fragmentation of the generated analyte ions. It is postulated that these adverse effects are caused by the interaction of these ions with the discharge chemistry as well as en route to the mass analyzer region. The corona discharge metal point electrode is replaced by the conically shaped liquid effluent evolving from a fused-silica capillary, which is analogous but not identical to the Taylor cone formation in electrospray ionization. The liquid consisting of either pure water or water containing 0.1 %V formic acid is fed via a nano-flow delivery stage at typical flow rates between 1-800 μL/h. The liquid flow is continuously replenishing the surface of the point electrode. The source is directly coupled to the inlet capillary of appropriate mass spectrometers, e.g., the Bruker Daltonics and Agilent varieties. The actively pumped liquid flow is supplying a constant amount of the reagent gas (H2O) to the corona region in the 20 ppmV to 30 %V range, leading to controlled, very stable operation of the source. The typical light emission observed for corona discharges is in very close proximity to the aqueous surface. Analyte protonation is the dominating ionization pathway. The degree of primary analyte fragmentation is extremely low. We have developed a novel atmospheric pressure chemical ionization source designed for the hyphenation of nano-flow liquid chromatography and gas chromatography with atmospheric pressure ionization mass spectrometry. The proposed reaction mechanism including the electrochemistry occurring in the source along with formation of protonated analyte molecules via collision-induced dissociation (CID) is in full accord with the experimental results. The system exhibits an extremely stable performance over prolonged operation times, sole generation of protonated molecules, and low degree of analyte ion fragmentation.