Uranium Speciation As a Function of Depth in Contaminated Hanford Sediments - A Micro-XRF, Micro-XRD, and Micro- And Bulk-XAFS Study

Journal Article · Mon Jan 05 04:00:00 EST 2009 · Environmental Science and Technology

DOI:https://doi.org/10.1021/es8021045· OSTI ID:950166

Singer, David M. ^[1]; Zachara, John M. ^[2]; Brown, Gordon E. ^[3]

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1. Stanford Univ., CA (United States)
2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
3. SLAC National Accelerator Lab., Menlo Park, CA (United States)

Processing ponds at the Hanford, Washington Area 300 site were used for storing basic sodium aluminate and acidic U(VI)-Cu(II)-containing waste from 1943 to 1975. One result of this use is a groundwater plume containing elevated levels of U and Cu beneath the dry ponds and adjacent to the Columbia River. We have used synchrotron-based micro-X-ray fluorescence (μXRF) imaging, micro-X-ray absorption fine structure (μXANES) spectroscopy, and micro-X-ray diffraction (μXRD) techniques combined with bulk U LIII-edge X-ray absorption fine structure (XAFS) spectroscopy to determine the distribution and speciation of U and Cu through the vadose and groundwater zones beneath North Processing Pond #2 (NPP2). Sediment samples were collected from the vadose zone (8’ and 12’ depths), and a sample from the groundwater zone was collected just below the water table (12’-14’ depth). μXRF imaging revealed two major U occurrences within the vadose and groundwater zones: (1) low to moderate concentrations of U(VI) associated with mineral surfaces (particularly chlorite), and (2) high concentration U(VI)-containing micron-sized particles associated with surface coatings on grains of muscovite and chlorite. These U(VI) hot spots are frequently spatially correlated with Cu(II) hot spots. In the groundwater zone, these particles were identified as the copper-uranyl-silicate cuprosklodowskite and the cupper-uranyl-phosphate metatorbernite. In contrast, the U-Cu-containing particles are X-ray amorphous in the vadose zone. Fits of U LIII-edge XAFS spectra by linear-combination fitting indicate that U speciation consists of ~ 75% uranyl sorbed to clays and ~25% metatorbernite-like X-ray amorphous U-Cu-phosphates (8’ depth); nearly 100% sorbed uranyl (12’ depth); and ~70% sorbed uranyl and ~30% cuprosklodowskite/metatorbernite (ground water zone). These findings suggest that the dissolution of U(VI)-Cu(II)-bearing solids as well as the desorption of U(VI), mainly from phyllosilicates, are important sources of U(VI) in the Area 300 groundwater plume.

• Research Organization: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 950166
• Report Number(s): PNNL-SA--61175; KP1504010
• Journal Information: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 3 Vol. 43; ISSN 0013-936X
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

Related Subjects

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS
ABSORPTION
ALUMINATES
COLUMBIA RIVER
FINE STRUCTURE
FLUORESCENCE
HOT SPOTS
MUSCOVITE
PLUMES
PONDS
SEDIMENTS
SILICATE MINERALS
SODIUM
SPECTRA
SPECTROSCOPY
SURFACE COATING
URANIUM
URANIUM MINERALS
WASTES
WATER TABLES