Using bromide tracer to measure uranium diffusivity in ground water sediments

More than 129 million liters of groundwater are contaminated with uranium at Old Rifle, Colorado – a former uranium-processing site that operated until 1958. The original Department of Energy (DOE) strategy for remediation, involving natural flushing of U from the groundwater through mixing with surface water, has not proven successful. Thin pockets of silt-, clay-, and organic-rich sediments referred to as naturally reduced zones (NRZs) act both as sinks and sources of U to the aquifer, contribute to plume persistence, and appear to be diffusion limited controlled. To better understand how the NRZs are diffusion limited controlled, a bromide tracer was used to measure uranium diffusivity at two depths from the JB-02 well at Old Rifle: one depth in the middle of the NRZ and one depth at the bottom edge of the NRZ. A NaBr reservoir was allowed to diffuse into the sediments for several days with reservoir samples collected twice a day and analyzed using inductively coupled plasma mass spectrometry (ICP-MS) for bromide concentrations. This data was then used to calculate net flux, effective diffusivity, and the tortuosity effect within the sediments, which will inform uranium management strategies not only at the Old Rifle site but potentially other DOE legacy sites including Riverton, Wyoming and Shiprock, New Mexico

Urban Airborne Lead: X-Ray Absorption Spectroscopy Establishes Soil as Dominant Source

BACKGROUND: Despite the dramatic decrease in airborne lead over the past three decades, there are calls for regulatory limits on this potent pediatric neurotoxin lower even than the new (2008) US Environmental Protection Agency standard. To achieve further decreases in airborne lead, what sources would need to be decreased and what costs would ensue? Our aim was to identify and, if possible, quantify the major species (compounds) of lead in recent ambient airborne particulate matter collected in El Paso, TX, USA. METHODOLOGY/PRINCIPAL FINDINGS: We used synchrotron-based XAFS (x-ray absorption fine structure) to identify and quantify the major Pb species. XAFS provides molecular-level structural information about a specific element in a bulk sample. Pb-humate is the dominant form of lead in contemporary El Paso air. Pb-humate is a stable, sorbed complex produced exclusively in the humus fraction of Pb-contaminated soils; it also is the major lead species in El Paso soils. Thus such soil must be the dominant source, and its resuspension into the air, the transfer process, providing lead particles to the local air. CONCLUSIONS/SIGNIFICANCE: Current industrial and commercial activity apparently is not a major source of airborne lead in El Paso, and presumably other locales that have eliminated such traditional sources as leaded gasoline. Instead, local contaminated soil, legacy of earlier anthropogenic Pb releases, serves as a long-term reservoir that gradually leaks particulate lead to the atmosphere. Given the difficulty and expense of large-scale soil remediation or removal, fugitive soil likely constrains a lower limit for airborne lead levels in many urban settings

Element release and reaction-induced porosity alteration during shale-hydraulic fracturing fluid interactions

The use of hydraulic fracturing techniques to extract oil and gas from low permeability shale reservoirs has increased significantly in recent years. During hydraulic fracturing, large volumes of water, often acidic and oxic, are injected into shale formations. This drives fluid-rock interaction that can release metal contaminants (e.g., U, Pb) and alter the permeability of the rock, impacting the transport and recovery of water, hydrocarbons, and contaminants. To identify the key geochemical processes that occur upon exposure of shales to hydraulic fracturing fluid, we investigated the chemical interaction of hydraulic fracturing fluids with a variety of shales of different mineralogical texture and composition. Batch reactor experiments revealed that the dissolution of both pyrite and carbonate minerals occurred rapidly, releasing metal contaminants and generating porosity. Oxidation of pyrite and aqueous Fe drove precipitation of Fe(III)-(oxy)hydroxides that attenuated the release of these contaminants via co-precipitation and/or adsorption. The precipitation of these (oxy)hydroxides appeared to limit the extent of pyrite reaction. Enhanced removal of metals and contaminants in reactors with higher fluid pH was inferred to reflect increased Fe-(oxy)hydroxide precipitation associated with more rapid aqueous Fe(II) oxidation. The precipitation of both Al- and Fe-bearing phases revealed the potential for the occlusion of pores and fracture apertures, whereas the selective dissolution of calcite generated porosity. These pore-scale alterations of shale texture and the cycling of contaminants indicate that chemical interactions between shales and hydraulic fracturing fluids may exert an important control on the efficiency of hydraulic fracturing operations and the quality of water recovered at the surface

Stable U(IV) Complexes Form at High-Affinity Mineral Surface Sites

Uranium (U) poses a significant contamination hazard to soils, sediments, and groundwater due to its extensive use for energy production. Despite advances in modeling the risks of this toxic and radioactive element, lack of information about the mechanisms controlling U transport hinders further improvements, particularly in reducing environments where UIV predominates. Here we establish that mineral surfaces can stabilize the majority of U as adsorbed UIV species following reduction of UVI. Using X-ray absorption spectroscopy and electron imaging analysis, we find that at low surface loading, UIV forms inner-sphere complexes with two metal oxides, TiO2 (rutile) and Fe3O4 (magnetite) (at <1.3 U nm–2 and <0.037 U nm–2, respectively). The uraninite (UO2) form of UIV predominates only at higher surface loading. UIV–TiO2 complexes remain stable for at least 12 months, and UIV–Fe3O4 complexes remain stable for at least 4 months, under anoxic conditions. Adsorbed UIV results from UVI reduction by FeII or by the reduced electron shuttle AH2QDS, suggesting that both abiotic and biotic reduction pathways can produce stable UIV–mineral complexes in the subsurface. The observed control of high-affinity mineral surface sites on UIV speciation helps explain the presence of nonuraninite UIV in sediments and has important implications for U transport modeling

Remediation of Uranium in the Hanford Vadose Zone Using Ammonia Gas: FY 2010 Laboratory-Scale Experiments

This investigation is focused on refining an in situ technology for vadose zone remediation of uranium by the addition of ammonia (NH3) gas. Objectives are to: a) refine the technique of ammonia gas treatment of low water content sediments to minimize uranium mobility by changing uranium surface phases (or coat surface phases), b) identify the geochemical changes in uranium surface phases during ammonia gas treatment, c) identify broader geochemical changes that occur in sediment during ammonia gas treatment, and d) predict and test injection of ammonia gas for intermediate-scale systems to identify process interactions that occur at a larger scale and could impact field scale implementation.Overall, NH3 gas treatment of low-water content sediments appears quite effective at decreasing aqueous, adsorbed uranium concentrations. The NH3 gas treatment is also fairly effective for decreasing the mobility of U-carbonate coprecipitates, but shows mixed success for U present in Na-boltwoodite. There are some changes in U-carbonate surface phases that were identified by surface phase analysis, but no changes observed for Na-boltwoodite. It is likely that dissolution of sediment minerals (predominantly montmorillonite, muscovite, kaolinite) under the alkaline conditions created and subsequent precipitation as the pH returns to natural conditions coat some of the uranium surface phases, although a greater understanding of these processes is needed to predict the long term impact on uranium mobility. Injection of NH3 gas into sediments at low water content (1% to 16% water content) can effectively treat a large area without water addition, so there is little uranium mobilization (i.e., transport over cm or larger scale) during the injection phase

Uranium redox transition pathways in acetate-amended sediments

Redox transitions of uranium [from U(VI) to U(IV)] in low-temperature sediments govern the mobility of uranium in the environment and the accumulation of uranium in ore bodies, and inform our understanding of Earth's geochemical history. The molecular-scale mechanistic pathways of these transitions determine the U(IV) products formed, thus influencing uranium isotope fractionation, reoxidation, and transport in sediments. Studies that improve our understanding of these pathways have the potential to substantially advance process understanding across a number of earth sciences disciplines. Detailed mechanistic information regarding uranium redox transitions in field sediments is largely nonexistent, owing to the difficulty of directly observing molecular-scale processes in the subsurface and the compositional/physical complexity of subsurface systems. Here, we present results from an in situ study of uranium redox transitions occurring in aquifer sediments under sulfate-reducing conditions. Based on molecular-scale spectroscopic, pore-scale geochemical, and macroscale aqueous evidence, we propose a biotic-abiotic transition pathway in which biomass-hosted mackinawite (FeS) is an electron source to reduce U(VI) to U(IV), which subsequently reacts with biomass to produce monomeric U(IV) species. A species resembling nanoscale uraninite is also present, implying the operation of at least two redox transition pathways. The presence of multiple pathways in low-temperature sediments unifies apparently contrasting prior observations and helps to explain sustained uranium reduction under disparate biogeochemical conditions. These findings have direct implications for our understanding of uranium bioremediation, ore formation, and global geochemical processes