Plutonium solubility in sediment pore waters.

Using in situ porous cup samplers, dissolved Pu concentrations have been measured over a year in the pore waters from two contrasting sites in the valley of the River Esk, North West England. In saltmarsh sediments, dissolved Pu represents approximately 1 part in 10(6) of the total inventory. The Pu concentration in solution is in the range 1.1-3.5 mBq l-1, varying by a factor of 3 in the course of the year. Most of the changes in dissolved Pu coincide with changes in dissolved Fe and Mn concentrations, with Pu being low in the summer months when Fe and Mn are high. Nevertheless, there are a number of factors which make it unclear as to whether these patterns might be related to seasonal redox changes in the saltmarsh. At the highly organic, reducing reedbed site, the proportion of Pu in solution is typically around 1 part in 10(3), proportionately much higher than in the saltmarsh, giving concentrations ranging between 9.0 and 28.5 mBq l-1, and are apparently maintained by complexation to dissolved organic matter. There is no obvious seasonal pattern at the reedbed site nor is there any relation to any of the dissolved species measured (Fe, Mn, Na, DOC).

Numerical modeling of humic colloid borne americium (III) migration in column experiments using the transport/speciation code K1D and the KICAM model.

The humic colloid borne Am(III) transport was investigated in column experiments for Gorleben groundwater/sand systems. It was found that the interaction of Am with humic colloids is kinetically controlled, which strongly influences the migration behavior of Am(III). These kinetic effects have to be taken into account for transport/speciation modeling. The kinetically controlled availability model (KICAM) was developed to describe actinide sorption and transport in laboratory batch and column experiments. Application of the KICAM requires a chemical transport/speciation code, which simultaneously models both kinetically controlled processes and equilibrium reactions. Therefore, the code K1D was developed as a flexible research code that allows the inclusion of kinetic data in addition to transport features and chemical equilibrium. This paper presents the verification of K1D and its application to model column experiments investigating unimpeded humic colloid borne Am migration. Parmeters for reactive transport simulations were determined for a Gorleben groundwater system of high humic colloid concentration (GoHy 2227). A single set of parameters was used to model a series of column experiments. Model results correspond well to experimental data for the unretarded humic borne Am breakthrough.

Selectivity in the complexation of actinides by humic substances.

The interactions of a range of actinide elements (Th, U, Np, Pu, Am) with humic substances from the Needle's Eye natural analogue site were studied by gel permeation chromatography. Bulk humic substances were isolated by ammonia extraction, followed by dialysis against distilled water and freeze-drying. The gel permeation results suggest that Needle's Eye humic substances can be fractionated into three incompletely resolved fractions with average molecular weights determined by analytical ultracentrifugation around 49 000 for Fraction 1, around 14 700 for Fraction 2 and around 8000 for Fraction 3. Although there are significant differences between the organic matter elution patterns in individual gel permeation experiments, presumably due to differences in column packing, these are much smaller than the differences between metal ions. The uranium that is naturally present in these humic substances is largely bound in the late-eluting fraction. Spikes of the early actinides, including Np and Pu in controlled valency states, have been added to the humic substances, and gel permeation of the spiked humic substances shows that the three humic fractions vary greatly in their effectiveness and selectivity as ligands for early actinides.