Bacterial siderophores promote dissolution of UO2 under reducing conditions.

Tetravalent actinides are often considered environmentally immobile due to their strong hydrolysis and formation of sparingly soluble oxide phases. However, biogenic ligands commonly found in the soil environment may increase their solubility and mobility. We studied the adsorption and dissolution kinetics of UO2 in the presence of a microbial siderophore, desferrioxamine-B (DFO-B), under reducing conditions. Using batch and continuous flow stirred tank reactors (CFSTR),we found that DFO-B increases the solubility of UIV and accelerates UO2 dissolution rates through a ligand-promoted dissolution mechanism. DFO-B adsorption to UO2 followed a Langmuir-type isotherm. The maximum adsorbed DFO-B concentrations were 3.3 micromol m(-2) between pH 3 and 8 and declined above pH 8. DFO-B dissolved UO2 at a DFO-B surface-saturated net rate of 64 nmol h(-1) m(-2) (pH 7.5, l = 0.01 M) according to the first-order rate equation R = kL[Lads], with a rate coefficient kL of 0.019 h(-1). Even at very low siderophore concentrations (e.g. 1 microM), net dissolution rates (16 nmol h(-1) m(-2), pH 7.5, l = 0.01 M) were substantially greater than net proton-promoted dissolution rates (3 nmol h(-1) m(-2), pH 7-7.5, l = 0.01 M). Interestingly, adding dissolved FeIII had negligible effects on DFO-B-promoted UO2 dissolution rates, despite its potential as a competitor for DFO-B and as an oxidant of UIV. Our results suggest that strong organic ligands could influence the environmental mobility of tetravalent actinides and should be considered in predictions for nuclear waste storage and remediation strategies.

Molecular characterization of biodegradable dissolved organic matter using bioreactors and [12C/13C] tetramethylammonium hydroxide thermochemolysis GC-MS.

Little is known about the molecular composition of the biodegradable fraction of dissolved organic matter (BDOM) in stream ecosystems. We combined plug-flow biofilm reactors, tetramethylammonium hydroxide (TMAH) thermochemolysis GC-MS, and 13C-labeled TMAH thermochemolysis GC-MS to study the molecular composition of BDOM from two stream ecosystems. TMAH products derived from fatty acids, lignin, and other aromatic molecules were quantified using an internal standard approach. We applied the 13C-TMAH thermochemolysis procedure to differentiate between compounds in dissolved organic matter (DOM) that had natural methoxyl groups from those that acquired methoxyl groups during the TMAH reaction. In Rio Tempisquito, a stream draining a tropical evergreen forest, and White Clay Creek, a stream draining a temperate deciduous woodlands, carbohydrates, fatty acids, and lignin contributed to the DOM and BDOM molecular composition. We observed 97 different peaks in the chromatograms of streamwater, with 57% of the peaks common to both streams. The DOM and BDOM pools from each site also contained a unique suite of compounds. Our combined use of TMAH and 13C-TMAH thermochemolysis revealed that heterotrophic bacteria can selectively degrade and demethylate different types of compounds in the lignin residues of DOM. This demonstration of bacterial demethylation of lignin, an abundant and refractory plant molecule, has potential implications for global carbon cycling.