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1Surface & Aqueous Geochemistry Group, Department of Geological &
Environmental Sciences, Stanford University, Stanford, CA 94305-2115
Uranium contamination of the subsurface at numerous locations across the DOE's
Hanford site has occurred through the leakage of high-level nuclear waste. At
one site of particular concern, the BX Tank Farm, leakage from the overfilling
of tank BX-102 released approximately 7.5 metric tons of uranium dissolved in
caustic aqueous sludge to the vadose zone. Assessment of the potential hazards
posed by this leakage, as well as the development and application of accurate
contaminant transport models, requires an understanding of the speciation of
uranium in the sediments under tank BX-102. We have applied advanced,
synchrotron-based X-ray spectroscopic and diffraction techniques to
characterize the distribution, phase associations, and chemical form of uranium
in samples from these sediments. X-ray absorption fine structure (XAFS)
spectroscopic studies demonstrate that >95% of the uranium in all samples
occurs as uranium(VI), and that the primary uranium species is likely a
uranium(VI) silicate from the uranophane group of minerals. Unfortunately,
XAFS cannot distinguish between the members of this group due to near identical
local coordination environments of uranium in these phases. Combined
micro-scanning x-ray fluorescence (mSXRF) and electron microprobe analyses show
uranium distributed heterogeneously in the sediments, occurring as micron-sized
particles inside cracks in feldspar grains. X-ray microdiffraction
(mXRD)
studies reveal the presence of sodium-boltwoodite, Na
(UO2)(SiO3OH)·1.5H2O; no
other uranophane group mineral was observed.
mXRD studies also confirm the
association of uranium with feldspar. Future release of uranium from these
sediments will occur through dissolution of sodium-boltwoodite, which has the
lowest expected solubility of the uranophane group minerals.
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