The field of ambient desorption/ionization mass spectrometry (ADI-MS) has existed for over a decade. ADI-MS is a technique that offers benefits including fast analysis time, simple ionization sources that are easily constructed, and little to no required sample preparation. The research presented here describes efforts to better understand plasma-based ADI-MS sources and to explore the use of hydrogen-doped plasma gases with these sources. The use of hydrogen-doped argon (H2/Ar) and hydrogen-doped helium (H2/He) as plasma gases for a dielectric barrier discharge (DBD) and an AC glow discharge is presented first. When using the DBD, the intensity of the signal obtained when analyzing organic molecules in positive ion mode was increased by factors up to 37 times. In negative ion mode, only H2/Ar was shown to enhance the signal of an organic analyte. The limits of detection for caffeine when using hydrogen-doped plasma gases were found to decrease by factors of 78 and 1.9 for H2/Ar and H2/He respectively. The same phenomenon was observed when using H2/Ar with the AC discharge, but no signal enhancement was observed when using hydrogen-doped helium with the AC discharge. Similarly, if the DBD was allowed to ground through a wire rather than through the air, no signal enhancement was observed for H2/He. Using H2/Ar with metal samples is presented second. By using the metal sample as the grounded electrode for the AC glow discharge, many different metals could be detected directly with a time-of-flight mass spectrometer (TOF-MS) in the form of atomic ions both on their own and in combination with water and ammonia from the discharge. Any refractory metals tested did not yield signal. In addition to direct analysis with a TOF-MS, the AC discharge was used as a sampling method for an inductively coupled plasma mass spectrometer (ICP-MS). When coupled with an ICP-MS, the AC glow discharge was found capable of sampling even refractory elements, though the power of the ICP was required for ionization and detection. Scanning electron microscope (SEM) images of a copper surface exposed to the plasma discharge showed signs of melting when using the H2/Ar. Finally, a computer simulation of the chemistry and flow dynamics of a DC glow discharge generated in helium is presented. The simulation explores many of the fundamental processes at work and how they depend on the composition of the plasma gas. The generation of important species in the plasma was found to depend more on the amount of N2 and H2O impurities in the plasma gas rather than on the humidity or air pressure.



College and Department

Physical and Mathematical Sciences; Chemistry and Biochemistry



Date Submitted


Document Type





ambient desorption/ionization, mass spectrometry, inductively coupled plasma, glow discharge, dielectric barrier discharge, hydrogen doping, computer simulation, metal sampling

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Chemistry Commons