Date of Award

1-2011

Degree Name

Doctor of Philosophy

Department

Geosciences

First Advisor

Dr. Carla M. Koretsky

Abstract

Within anoxic near surface aqueous settings where U02(S) may be released an opportunity to encounter and complex with organic acids may occur. Reactions between U02(S) and ligands may promote the solubility and mobility of uranium. Organic ligands investigated in the dissolution work include citric acid, NTA and EDTA. Exposure to the ligands had little effect on U02(S) solubility. The log activity of U02(S) hydrolysis under reduced conditions was -6.56. Under all measured conditions of ligand concentration, the data consistently show an increase in uranium concentration to a median log U activity of -4.89. The observed solubility of U02(S) in the presence of chelating organic ligands is inconsistent with expected values based on literature data, possibly due to inefficient controls on oxidation. Although the solubilities values are higher than expected, these experiments suggest that strong chelating agents will have little effect on U02(S) solubility.

The second part of this study concerned U(VI) sorption onto Georgia kaolinite (KGal-b). Sorption was investigated as a function of ionic strength and pC02 concentration in the presence or absence of EDTA, citrate and fulvic acid. U(VI) sorption on kaolinite does not depend strongly on ionic strength, but a strong dependence on pC02 is observed, with less sorption of U(VI) occurring with increasing pC02. U(VI) sorption is enhanced by the addition of EDTA, citric acid or fulvic acid at low pH, likely due to formation of ternary surface complexes. At high pH, U(VI) sorption decreases, presumably due to formation of competitive aqueous organic ligand-U(VI) complexes. Surface complexation of U(VI) as a function of ionic strength and pC02 is well described using a nonelectrostatic or a double diffuse layer model. However, neither model correctly simulates all of the U(VI) sorption edges in the presence of ligands, possibly due to incorrect estimates of C02-3(aq) concentrations, inaccuracies in the predicted aqueous U(VI)-ligand speciation, partial dissolution of the clay by the organic ligands, or due to poor representation of the electrical double layer in the presence of the organic ligands.

Access Setting

Dissertation-Open Access

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