ROLE OF GAS-DYNAMICS IN NEGATIVE-ION FORMATION IN AN ATMOSPHERIC SAMPLING GLOW-DISCHARGE IONIZATION SOURCE

A version of the atmospheric sampling glow discharge ionization (ASGDI) source was developed to study the role of gas dynamics on anion formation. This source, which is used in conjunction with mass spectrometry for direct air monitoring, was designed so several key instrumental dimensions as well as operating parameters could be readily changed. Such flexibility permitted the study of ionization processes in ASGDI and the parameters that can be controlled to favor a particular ion product. One aspect of ASGDI that was found to influence ionization yield was the hydrodynamic properties of the sample inlet free-jet expansion. From these investigations, it was found that mean molecular flow of species expanding toward the skimmer could be manipulated to favor kinetically fast reactions over more thermodynamically preferred reactions. In the case of 2,4-dinitrotoluene, observation of the M- ion could be enhanced relative to anions derived from the air-matrix background. The primary ionization mechanism for this compound is believed to be associative electron capture.