Spatially resolved U(VI) partitioning and speciation: Implications for plume scale behavior of contaminant U in the Hanford vadose zone

Journal Article · Sun Feb 01 04:00:00 EST 2009 · Environmental Science and Technology

DOI:https://doi.org/10.1021/es802801b· OSTI ID:950978

Wan, Jiamin; Kim, Yongman; Tokunaga, Tetsu K; Wang, Zheming; Dixit, Suvasis; Steefel, Carl; Saiz, Eduardo; Kunz, Martin; Tamura, Nobumichi

A saline-alkaline brine containing high concentrations of U(VI) was accidentally spilled at the Hanford Site in 1951, introducing 10 tons of U into sediments under storage tank BX-102. U concentrations in the deep vadose zone and groundwater plumes increase with time, yet how the U has been migrating is not fully understood. We simulated the spill event in laboratory soil columns, followed by aging, and obtained spatially resolved U partitioning and speciation along simulated plumes. We found after aging, at apparent steady state, that the pore aqueous phase U concentrations remained surprisingly high (up to 0.022 M), in close agreement with the recently reported high U concentrations (up to 0.027 M) in the vadose zone plume (1). The pH values of aged pore liquids varying from 10 to 7, consistent with the measured pH of the field borehole sediments varying from 9.5 to 7.4 (2), from near the plume source to the plume front. The direct measurements of aged pore liquids together with thermodynamic calculations using a Pitzer approach revealed that UO{sub 2}(CO{sub 3}){sub 3} {sup 4-} is the dominant aqueous U species within the plume body (pH 8-10), while Ca{sub 2}UO{sub 2}(CO{sub 3}){sub 3} and CaUO{sub 2}(CO{sub 3}){sub 3}{sup 2-} are also significant in the plume front vicinity (pH 7-8), consistent with that measured from field borehole porewaters (3). U solid phase speciation varies at different locations along the plume flow path and even within single sediment grains, because of location dependent pore and micropore solution chemistry. Our results suggest that high geochemical stability of UO{sub 2}(CO{sub 3}){sub 3}{sup 4-} in the original carbonate and sodium rich waste solution permits its continues migration and the field observed increases of U concentrations in the vadose zone and groundwater.

• Research Organization: Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, CA (US)
• Sponsoring Organization: Earth Sciences Division
• DOE Contract Number: AC02-05CH11231
• OSTI ID: 950978
• Report Number(s): LBNL-1682E
• Journal Information: Environmental Science and Technology, Journal Name: Environmental Science and Technology; ISSN ESTHAG; ISSN 0013-936X
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
58 GEOSCIENCES
AGING
BOREHOLES
BRINES
CARBONATES
CHEMISTRY
LIQUID WASTES
PH VALUE
PLUMES
SEDIMENTS
SODIUM
SOILS
STABILITY
STORAGE
TANKS
THERMODYNAMICS