Abstract. We demonstrate the effectiveness of using hydrogen-doped argon as the support gas for the dielectric barrier discharge (DBD) ambient desorption/ionization (ADI) source in mass spectrometry. Also, we explore the chemistry responsible for the signal enhancement observed when using both hydrogen-doped argon and hydrogen-doped helium. The hydrogen-doped argon was tested for five analytes representing different classes of molecules. Addition of hydrogen to the argon plasma gas enhanced signals for gas-phase analytes and for analytes coated onto glass slides in positive and negative ion mode. The enhancements ranged from factors of 4 to 5 for gas-phase analytes and factors of 2 to 40 for coated slides. There was no significant increase in the background. The limit of detection for caffeine was lowered by a factor of 79 using H 2 /Ar and 2 using H 2 /He. Results are shown that help explain the fundamental differences between the pure-gas discharges and those that are hydrogen-doped for both argon and helium. Experiments with different discharge geometries and grounding schemes indicate that observed signal enhancements are strongly dependent on discharge configuration.

a b s t r a c tHigh-resolution images of the spatial distributions of Sc II, Ca II, and Ba II ion densities in the 10 mm upstream from the sampling cone in a laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) were obtained using planar laser induced fluorescence. Images were obtained for each analyte as a function of the carrier gas flow rate with laser ablation (LA) sample introduction and compared to images with solution nebulization (SN) over the same range of flow rates. Additionally, images were obtained using LA at varying fluences and with varying amounts of helium added to a constant flow of argon gas. Ion profiles in SN images followed a pattern consistent with previous work: increasing gas flow caused a downstream shift in the ion profiles. When compared to SN, LA led to ion profiles that were much narrower radially and reached a maximum near the sampling cone at higher flow rates. Increasing the fluence led to ions formed in the ICP over greater axial and radial distances. The addition of He to the carrier gas prior to the ablation cell led to an upstream shift in the position of ionization and lower overall fluorescence intensities.

Petroleomics, which is the characterization, separation, and quantification of the components of petroleum and crude oil, is an emerging area of study. However, the repertoire of analytical methods available to understand commercial automotive lubricant oils (ALOs) is very limited. Ambient mass spectrometry is one of the most sensitive analytical methods for real-time and in situ chemical analysis. With this technique, the chemical fingerprinting of ALOs can be performed quickly and simply using dielectric barrier discharge ionization time-of-flight mass spectrometry. In this study, the mass spectra of 35 samples were obtained without any sample preparation in positive-ion mode, and no carryover was observed. To elucidate the similarities and differences between the ALO samples, the data generated from these spectra were analyzed using four chemometric techniques: principal component analysis, multivariate curve resolution, hierarchical cluster analysis, and pattern recognition entropy. The ALO samples were readily differentiated according to their American Petroleum Institute classification and base oil types: mineral, semisynthetic, and synthetic. The development of this new methodology will aid in the semiquantitative control analysis of ALOs and offers an improved ability to identify the components therein.

A new model of a plasma ionization source anchored by experimental data giving a comprehensive view of the discharge mechanism.