ABSTRACT
The effect of the anthropogenic complexing agent EDTA on thorium transport in groundwater has been studied using sand-packed columns and flow rates in the range of 20-100 m y⻹. The concentrations injected into the columns were in the range of 0.4-4 mM for Th and 4-40 mM for EDTA, and with EDTA:Th ratios in the range 1:1 to 10:1. The results show that EDTA can significantly increase Th transport, but two very different behaviours are observed at Th concentrations of 0.4 and 4 mM. At the lower concentration, Th breakthrough is retarded with respect to a conservative tracer, with a peak width that is consistent with a single K(d) value, followed by a longer tail, and the behaviour is very sensitive to the flow rate. However at 4 mM Th, the breakthrough peak appears near to that of the tracer, and the width of the peak is consistent with a distribution of K(d) values and/or a larger dispersivity than the tracer. Speciation and transport modelling have been used to interpret the data, and a model was developed that could explain the 0.4 mM behaviour. This suggests that ternary surface complexes are important in these systems, with at least two different species involved, although the complexity of Th speciation in these systems leads to significant uncertainty in the values of the equilibrium and kinetic parameters. For the 4 mM systems, the rapid transport observed could not be explained by a simple chemical model; instead it is likely that EDTA plays an important role in stabilising and transporting thorium colloids and clusters.
Subject(s)
Edetic Acid/chemistry , Groundwater/chemistry , Silicon Dioxide , Thorium/chemistry , Models, TheoreticalABSTRACT
Electrospray ionisation-mass spectrometry (ESI-MS) has been used to investigate the speciation of Th in the presence of two common organic complexing agents found in radioactive wastes, EDTA and NTA. These ligands may enhance radionuclide migration from nuclear wastes and contaminated land, and characterisation of the complexes formed will improve our understanding of their environmental mobility. When acetic acid and ammonia were used to adjust the pH, the dominant Th-EDTA species changed from the mixed ligand [ThEDTAac](-) complex to [ThEDTAOH](-) and [ThEDTA(OH)(2)ac](3-) as the pH increased, with all species co-existing, to some extent, over the pH range (2.5-10.8). A previously suggested Th-NTA species, [ThNTA(2)](2-), dominates from pH 6.0-8.5 but at high pH (10.0-10.8) NTA was not able to solubilise Th to a measurable extent. In the presence of both EDTA and NTA, Th formed a mixed ligand complex, [ThEDTANTA](3-) which has also been characterised in independent experiments. The identification of the importance of [ThNTA(2)](2-), [ThEDTANTA](3-) and [ThEDTA(OH)(2)](2-) (with an additional acetate ligand) highlights that these species are not included in current speciation databases and thus may impact on predictions of the environmental mobility of Th. ESI-MS has therefore been used to identify and confirm fundamentally important Th complexes. It has proved to be a useful tool for elucidating radionuclide speciation, adding to our knowledge of Th geochemistry and providing a means of critically examining existing stability constant data.
