Well-characterized Au nanoparticles were deposited on commercial TiO2 (P25, Degussa) and analyzed by means of STEM and thermogravimetry coupled with mass spectrometry (TG-MS). The adsorption was studied on Au/TiO2 samples with Au loadings in the range of 1.1-9.9 wt.% by injecting pulses of CH3SH (methyl mercaptane, MM) until no further mass increase could be observed. A prerequisite for determination of the surface area of the deposited gold nanoparticles is the proper discrimination of species adsorbing on the Au nanoparticles and the titania support. The adsorption of methyl mercaptane on the titania support strongly depended on the pretreatment temperature (30-400 degrees C), whereas the adsorption on Au nanoparticles was virtually unaffected by this parameter. A very mild thermal pretreatment was identified as a requirement for avoiding the adsorption of the MM on the titania support. CH3SH adsorbed on the support desorbed at lower temperatures (maximal rate of desorption was centered at ca. 150 degrees C) compared to species desorbing from Au nanoparticles (maximum at ca. 200-220 degrees C). Moreover, CH3SH adsorbed on Au nanoparticles desorbed in the form of dimethyl sulfide (CH3)(2)S. Part of MM adsorbed on the gold surface was not desorbed even at high temperatures (above 500 degrees C) and stayed on the surface in the form of relatively stable CxHySz fragments. This residue could be removed by oxygen pulses resulting in the formation of CO2, SO2, and H2O. The good discrimination of MM chemisorption on Au nanoparticles and on titania renders the determination of the Au surface area viable. Potential and limitations of the CH3SH chemisorption for the surface area determination of Au nanoparticles are discussed. (C) 2009 Elsevier Inc. All rights reserved.