Spectroscopic extended X-ray absorption fine structure (EXAFS) evidence was obtained on the chemical environment of 99Tc(IV) atoms formed upon introduction of TcO4- into four types of laboratory-scale synthetic and natural systems which mimic in situ natural reducing conditions in humic-rich geochemical environments: (a) magnetite/pyrite in synthetic groundwater in the absence of humic substances (HSs), (b) magnetite/pyrite in natural Gorleben groundwater in the presence of HSs, (c) Boom clay sediment mixed with synthetic groundwater, and (d) Gorleben sand mixed with natural Gorleben groundwater. The investigated systems obey to pH 8-9 conditions, and all measured samples show similar EXAFS spectra for Tc, which could be fitted by a hydrated TcO2 x xH2O phase. The results are interpreted as follows: upon introduction of high concentrations (millimolar to micromolar) of TcO4-to chemically reducing environments, small Tc(IV) oxidic polymers are formed, which either may aggregate into larger units (colloids) and finally precipitate or may interact in their polymeric form with (dissolved and immobile) humic substances. This latter type of interaction--Tc(IV) colloid sorption onto HSs--differs significantly from the generally accepted metal--humate complexation and therefore offers new views on the possible reaction pathways of metals and radionuclides in humic-rich environments.

XANES / Technetium-99 / Radionuclides / Humic substances / Metal humate interaction / Valence stateSummary. 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 TcO 2 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 and 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.

Technetium-99 (Tc), a fission product of uranium-238, is an important radionuclide because of its long half-life and its high yield in radioactive waste. To elucidate the Tc geochemical behavior in reducing environments relevant to geological disposal and in the presence of humic substances (HS), experiments were set up that resulted forthe first time in the determination of an interaction constant for Tc with dissolved humic substances. A number of lab-scale Boom Clay (a possible geological underground High-Level Radioactive Waste storage site in Mol, Belgium) batch experiments were set up, combining both different initial Tc(VII) concentrations and different solid/liquid ratios. On these batches several sequential extraction steps with HS-free synthetic Boom Clay water were performed. Equilibration times were fixed at 1 week for each extraction step. Tc(VII) was found to be readily reduced to Tc(IV) by the solid Boom Clay phase. This solid phase was able to sorb Tc(IV) to a very large extent (log Kd approximately 2.5-4.0), and two sorption sinks (one of which is humic substances) were detected. In solution, Tc(IV) was mainly associated with HS. Concentrations in solution were found up to the order of 2 x 10(-6) M. The results were quantitatively described as a competition for Tc(IV) between the solid phase and the dissolved HS (Schubert-like approach). It was concluded that a hydrophobic sorption of uncharged Tc(IV) species in solution would act as the dominating interaction mechanism with HS, with an interaction constant log K(HS) = 5.3 +/- 0.3.

The humic colloid mediated transport of tetravalent actinide and technetium ions is discussed. Numerous published and new results are used from comparable experimental systems and conditions. The results originate from investigations on two humic rich Gorleben groundwater/sediment systems under near-natural conditions. The conditioning time between groundwater and radionuclides vary from few minutes to four years. The migration time (residence time in the column) is varied from four hours to three days. The concentration of radionuclides added is varied between about 10