Nature and Reactivity of Sediment-Associated Spiked Fe(II) Toward Abiotic Uranium Reduction

Uranium (U) is a priority contaminant at U.S. Department of Energy Uranium Mill Tailings Remedial Action (UMTRA) sites. Mobility of U in contaminated aquifers is governed by a complex assortment of site-specific biogeochemical and hydrological properties, sediment Fe-mineralogy, and redox status. There is a particular interest in understanding factors governing U attenuation to Fe-mineralogy under natural conditions. Thus, the goal of this work is to investigate geochemical effects of Fe redox state on U mobility under conditions relevant to the Rifle aquifer, an UMTRA site. Particularly, the focus is to gain insights into the degree and mechanism of Fe(II) uptake by Rifle sediments that exhibit complex Fe-mineralogy composed of various Fe-oxides and Fe-containing clays and on the possibility of abiotic U(VI) reduction by adsorbed Fe(II) and secondary Fe(II) minerals. Earlier field studies where Fe(II)-amended groundwater was injected into the Rifle aquifer indicated: a) Fe(II) uptake by Rifle sediments is extensive and b) abiotic U(VI) reduction by Fe(II) may be important at pH 8.3. Batch reactions between Rifle sediment and 57Fe(II) (57Fe isotope is a Mossbauer sensitive nuclide with a natural abundance of 2%) under conditions relevant to the Rifle aquifer indicated that, depending on the solution conditions: a) a large fraction of the spiked 57Fe(II) (55-100%) is oxidized to 57Fe(III) on sediment surfaces and, at pH 7.2, the degree of oxidation decreased as Fe(II) loading increased; b) the 57Fe(II)-oxidation is coupled to the transformation of an intrinsic ferrihydrite-like mineral to a nanoparticulate, Fe(II)/57Fe(III)-like mineral phase, and c) increasing pH from 7.2 to 8.3 and including carbonate in the medium has little or no effect on percent oxidation or mineral transformation. Preliminary X-ray absorption near edge structure (XANES) spectroscopy studies suggested that 20-30% of abiotic U(VI) reduction occurred, both at pH 7.2 and 8.3, in the sediments containing 39 umol/g of spiked 57Fe(II). Thus, the combined field and laboratory studies suggest that both the amount of sorbed Fe(II) and the system's pH appear to play a significant role in reduction of U(VI) to U(IV). Additional experiments are in progress to: a) determine the type of secondary Fe(II) mineral formation [e.g., siderite, Fe(OH)2] as a function of both the amount of spiked Fe(II) content and assortment of geochemical parameters, such as pH, carbonate content/alkalinity, and redox status, as well as their reactivity toward U(VI), and b) U speciation by extended X-ray adsorption spectroscopy (EXAFS).