Environmental Remediation Sciences Program at the Stanford Synchrotron Radiation Laboratory

Synchrotron radiation (SR)-based techniques provide unique capabilities to address scientific issues underpinning environmental remediation science and have emerged as major research tools in this field. The high intensity of SR sources and x-ray photon-in/photon-out detection allow noninvasive in-situ analysis of dilute, hydrated, and chemically/structurally complex natural samples. SR x-rays can be focused to beams of micron and sub-micron dimension, which allows the study of microstructures, chemical microgradients, and microenvironments such as in biofilms, pore spaces, and around plant roots, that may control the transformation of contaminants in the environment. The utilization of SR techniques in environmental remediation sciences is often frustrated, however, by an ''activation energy barrier'', which is associated with the need to become familiar with an array of data acquisition and analysis techniques, a new technical vocabulary, beam lines, experimental instrumentation, and user facility administrative procedures. Many investigators find it challenging to become sufficiently expert in all of these areas or to maintain their training as techniques evolve. Another challenge is the dearth of facilities for hard x-ray micro-spectroscopy, particularly in the 15 to 23 KeV range, which includes x-ray absorption edges of the priority DOE contaminants Sr, U, Np, Pu, and Tc. Prior to the current program, there were only two (heavily oversubscribed) microprobe facilities in the U.S. that could fully address this energy range (one at each of APS and NSLS); none existed in the Western U.S., in spite of the relatively large number of DOE laboratories in this region

Coupled Biogeochemical Processes Governing the Stability of Bacteriogenic Uraninite and Release of U(VI) in Heterogeneous Media: Molecular to Meter Scales

In-situ reductive biotransformation of subsurface U(VI) to U(IV) (as ?UO2?) has been proposed as a bioremediation method to immobilize uranium at contaminated DOE sites. The chemical stability of bacteriogenic ?UO2? is the seminal issue governing its success as an in-situ waste form in the subsurface. The structure and properties of chemically synthesized UO2+x have been investigated in great detail. It has been found to exhibit complex structural disorder, with nonstoichiometry being common, hence the designation ?UO2+x?, where 0 < x < 0.25. Little is known about the structures and properties of the important bacteriogenic analogs, which are believed to occur as nanoparticles in the environment. Chemically synthesized UO2+x exhibits an open fluorite structure and is known to accommodate significant doping of divalent cations. The extent to which bacteriogenic UO2+x incorporates common ground water cations (e.g., Ca2+) has not been investigated, and little is known about nonstoichiometry and structure defects in the bacteriogenic material. Particle size, nonstoichiometry, and doping may significantly alter the reactivity, and hence stability, of bacteriogenic UO2+x in the subsurface. The presence of associated sulfide minerals, and solid phase oxidants such as bacteriogenic Mn oxides may also affect the longevity of bacteriogenic UO2 in the subsurface

Submitted to Geochimica et Cosmochimica Acta

FTIR and EXAFS spectroscopic measurements were performed on Pb(II)EDTA adsorbed on goethite as functions of pH (4-6), Pb(II)EDTA concentration (0.11 µM- 72 µM), and ionic strength (16 µM- 0.5M). FTIR measurements show no evidence for carboxylate-Fe(III) bonding or protonation of EDTA at Pb:EDTA = 1:1. Both FTIR and EXAFS measurements suggest that EDTA acts as a hexadentate ligand, with all four of its carboxylate and both amine groups bonded to Pb(II). No evidence was observed for inner-sphere Pb(II)-goethite bonding at Pb:EDTA = 1:1. Hence, the adsorbed complexes should have composition Pb(II)EDTA 2-. Since substantial uptake of PbEDTA(II) 2- occurred in the samples, we infer that Pb(II)EDTA 2- adsorbed as outer-sphere complexes and/or as complexes that lose part of their solvation shells and hydrogen bond directly to goethite surface sites. We propose the term “hydration-sphere ” for the latter type of complexes because they should occupy space in the primary hydration spheres of goethite surface functional groups, and to distinguish this mode of sorption from common structural definitions of inner- and outer-sphere complexes. The similarity of Pb(II) uptake isotherms to those of other divalent metal ions complexed by EDTA suggests that they too adsorb by these mechanisms. The lack of evidence for inner-sphere EDTA-Fe(III) bonding suggests that previously proposed metal-ligand- promoted dissolution mechanisms should be modified, specifically to account for the presence of outer-sphere precursor species

Characterizing Sediment from Riverton, WY

Riverton, Wyoming is home to the seventh-largest Native American Reservation by area and a former uranium processing facility. Milling activities at this site have left the sediments and groundwater with elevated concentrations of uranium that occasionally disrupt water quality to the 12,000 residents of the reservation. The floodplain becomes seasonally wet and sometimes flooded from snowmelt that can be amplified by El Niño events. As a result, the sediments of this area experience periodic droughts and floods. There is concern that a decreased water stage can have major impacts on the geochemical makeup of this ecosystem as 1) a decreased water volume may result in an increase of pollutant concentrations and 2) a decreased water stage can have a significant impact the redox cycling within the subsurface and affect major biogeochemical cycles. This study addresses the need to understand current subsurface elemental distributions in Riverton, Wyoming. Overall, the project explores the sediment characteristics of several Riverton cores in response to drought and flood conditions. Samples for this study were taken over the course of twelve months - at three different time points. This summer, 105 Riverton sediment samples from August 2016 (the final time point) were geochemically characterized and compared to samples from dry conditions (August 2015) prior to the second largest flood on record at this location. We expect the sediments collected prior to the flood to vary greatly from the sediments collected after the flood because the activity of microbial communities is affected by differences in the physical structure of the soil. This data, along with an analysis of the microbial communities present in these sediments, will help the Francis Lab understand what factors shape the distribution and diversity of microbial communities present in order to better understand the subsurface biogeochemistry at Riverton

Characterizing Upper Colorado River Basin Sediments

More than 35 million people in the western United States depend on the Colorado River as a resource for drinking water, irrigation systems, and hydropower. Recent climate change reports predict average water levels within the Colorado River Basin will continue to decrease throughout the next century due to decreased precipitation, warming temperatures, and increased usage. Decreased river flow may have major impacts within the subsurface that are two-fold: 1) decreased water flowing may result in greater issues of water quality-due to accumulation and concentration of some elements within the subsurface, and 2) a decreased water stage may significantly alter the redox cycling within the subsurface and affect major biogeochemical elemental cycles. Therefore, a greater understanding of current subsurface elemental distributions throughout the Upper Colorado River Basin is needed. To examine the elemental distributions throughout the Upper Colorado River Basin, a total of 321 contaminated sediment samples were collected from five Department of Energy-Legacy Management (DOE-LM) sites: Riverton, WY, Shiprock, NM, Naturita, CO, Grand Junction, CO and Rifle, CO to a depth of 5-10m. Sediment samples were characterized for elemental composition by x-ray fluorescence (XRF) and elemental analysis (EA) for their carbon/nitrogen (C:N) content. Sediments were water extracted and measured by pH probe, refractometer, and by spectrophotometry for approximated, in situ values of pH, salinity, and nitrogen species (NO3-, NO2-, NH4+). Overall, this study enhances greater knowledge of elemental distributions throughout the Upper Colorado River Basin, and may help DOE-LM develop regional and site-specific management strategies for future climate scenarios

Impact of microbial Mn oxidation on the remobilization of bioreduced U(IV)

Effects of Mn redox cycling on the stability of bioreduced U(IV) are evaluated here. U(VI) can be biologically reduced to less soluble U(IV) species and the stimulation of biological activity to that end is a salient remediation strategy; however, the stability of these materials in the subsurface environments where they form remains unproven. Manganese oxides are capable of rapidly oxidizing U(IV) to U(VI) in mixed batch systems where the two solid phases are in direct contact. However, it is unknown whether the same oxidation would take place in a porous medium. To probe that question, U(IV) immobilized in agarose gels was exposed to conditions allowing biological Mn(II) oxidation (HEPES buffer, Mn(II), 5% O-2 and Bacillus sp. SG-1 spores). Results show the oxidation of U(IV) to U(VI) is due primarily to O-2 rather than to MnO2. U(VI) produced is retained within the gel to a greater extent when Mn oxides are present, suggesting the formation of strong surface complexes. The implication for the long-term stability of U in a bioremediated site is that, in the absence of competing ligands, biological Mn(II) oxidation may promote the immobilization of U(VI) produced by the oxidation of U(IV)

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