The redox-sensitive fission product technetium-99 has been investigated in systems containing different reducing solid phases (pyrite, magnetite, ironsulphide and Gorleben sand) on the one hand and Gorleben groundwater, which contains a high amount of humic substances, on the other hand. Initially, technetium-99 was added to these systems as pertechnetate (Tc(VII)), which was reduced in presence and absence of humic substances with the aid of the different reducing surfaces (neutral to alkaline pH). Both in absence and presence of humic substances, Tc concentrations were observed which exceeded the TcO2 solubility limit, whereby the presence of humic substances had a 100 fold higher Tc concentration compared to its absence. Using the La-precipitation method, it was shown that Tc(IV) inorganic colloids and organic colloids were quantitatively precipitated. It was demonstrated for the first time by a combination of chemical speciation methods (La-precipitation method an gel permeation chromatography) and XANES spectroscopy of the humic substance containing supernatant solutions, that Tc(IV) species were formed in these systems, indicating an association between Tc(IV) and humic substances.