Diatomaceous earth was functionalized by grafting organotrialkoxysilane precursors onto the surface of the porous silica cell walls of this biomineral. Vinyl- and mercapto-containing structures were prepared in aqueous media without disruption of the diatomic architecture. Successful grafting of the organic moieties was confirmed using solid state Si-29 MAS NMR spectroscopy, and the presence of the intact diatom framework by scanning electron microscopy. The sorption properties of mercaptopropyl-functionalized diatoms towards heavy metals was studied by measuring the accessibility and diffusion rates of mercury(II) species to the binding sites (-SH) by the means of electrochemical methods. (C) 2007 Elsevier B.V. All rights reserved.