Electron emission properties of materials are highly dependent to the surface and the first nanometres subsurface. Technical materials, i.e. used within applications are ordinarily exposed to atmosphere, which interacts with the surface. The contamination layer building up at the surface of materials and/or oxidation layer affects dramatically the electron emission proprieties. In this paper, starting from 99.99% pure silver sample, exposed 4 years to ambient atmosphere, we monitored the variations of the electron emission properties and the surface composition during step by step ion etching procedure. (C) 2015 Elsevier B.V. All rights reserved.