The present work is part of an ongoing project aiming to a better understanding of the mechanisms of atomization on graphite furnace platforms used for electrothermal atomic absorption spectrometry (ETAAS). It reports the study of unused pyrolytic graphite coated platforms of commercial origin, as well as platforms thermally or thermo-chemically treated under simulated ETAAS analysis conditions. X-ray photoelectron spectroscopy (XPS) was employed to study the elements present at the surfaces of the platforms. New, unused platforms showed the presence of molybdenum, of unknown origin, in concentrations up to 1 at.%. Species in two different oxidations states (Mo6+ and Mo2+) were detected by analyzing the Mo 3d spectral region with high resolution XPS. The analysis of the C Is region demonstrated the presence of several signals, one of these at 283.3 eV related to the presence of Mo carbide. The O 1s region showed also various peaks, including a signal that can be attributed to the presence of MoO3. Some carbon and oxygen signals were consistent with the presence of C=O and C-O- (probably C-OH) groups on the platforms surfaces. Upon thermal treatment up to 2900 'C, the intensity of the Mo signal decreased, but peaks due to Mo oxides (Mo6+ and Mo5+) and carbide (Mo2+) were still apparent. Thermo-chemical treatment with 3 vol.% HCl solutions and heating up to 2900 degrees C resulted in further diminution of the Mo signal, with complete disappearance of Mo carbide species. Depth profiling of unused platforms by Ar+ ion etching at increasing time periods demonstrated that, upon removal of several layers of carbonaceous material, the Mo signal disappears suggesting that this contamination is present only at the surface of the pyrolytic graphite platform. (c) 2005 Elsevier B.V. All rights reserved.