Surface ions generated by electron stimulated desorption from mass spectrometer ion source grids are frequently observed, but often misidentified. For example, in the case of mass 19, the source is often assumed to be surface fluorine, but since the metal oxide on grid surfaces has been shown to form water and hydroxides, a more compelling case can be made for the formation of hydronium. Further, fluorine is strongly electronegative, so it is rarely generated as a positive ion. A commonly used metal for ion source grids is 316L stainless steel. Thermal vacuum processing by bakeout or radiation heating from the filament typically alters the surface composition to predominantly Cr2O3. X-ray photoelectron spectral shoulders on the O 1s and Cr 2P(3/2) peaks can be attributed to adsorbed water and hydroxides, the intensity of which can be substantially increased by hydrogen dosing. On the other hand, the sub-peak intensities are substantially reduced by heating and/or by electron bombardment. Electron bombardment diode measurements show an initial work function increase corresponding to predominant hydrogen desorption (H,) and a subsequent work function decrease corresponding to predominant oxygen desorption (CO). The fraction of hydroxide concentration on the surface was determined from X-ray photoelectron spectroscopy and from the deconvolution of temperature desorption spectra. Electron stimulated desorption yields from the surface show unambiguous H3O+ peaks that can be significantly increased by hydrogen dosing. Time. of flight secondary ion mass spectrometry sputter yields show small signals of H3O+, as well as its constituents (H+, O+ and OH+) and a small amount of fluorine as F-, but no F+ or F+ comp exes (HF+, etc.). An electron stimulated desorption cross-section of sigma(+) similar to 1.4 x 10(-20) cm(2) was determined for H3O+ from 316L stainless steel for hydrogen residing in surface chromium hydroxide. (c) 2006 Elsevier B.V. All rights reserved.