Co-adsorption of water and methane onto polymeric adsorbent LiChrolut EN, activated carbon adsorbent, fumed alumina and Silochrome modified by 3-aminopropylmethyldimethoxy silane was studied using H-1 NMR spectroscopy with layer-by-layer freezing out of bulk and bound adsorbates. At a certain amount of adsorbed water the adsorption of methane can increase. Bound water can be in strongly (changes in Gibbs free energy Delta G < -1 kJ/mol) and weakly (Delta G > -1 kJ/mol) bound and strongly (chemical shift of the proton resonance delta(H) = 3-6 ppm) and weakly (delta(H) = 1-2 ppm) associated states. With the presence of adsorbed methane contribution of weakly associated water increases. (C) 2008 Elsevier B.V. All rights reserved.