Effects of nitrate on the stability of uranium in a bioreduced region of the subsurface.
The effects of nitrate on the stability of reduced, immobilized uranium were evaluated in field experiments at a U.S. Department of Energy site in Oak Ridge, TN. Nitrate (2.0 mM) was injected into a reduced region of the subsurface containing high levels of previously immobilized U(IV). The nitrate was reduced to nitrite, ammonium, and nitrogen gas; sulfide levels decreased; and Fe(II) levels increased then deceased. Uranium remobilization occurred concomitant with nitrite formation, suggesting nitrate-dependent, iron-accelerated oxidation of U(IV). Bromide tracer results indicated changes in subsurface flowpaths likely due to gas formation and/or precipitate. Desorption-adsorption of uranium by the iron-rich sediment impacted uranium mobilization and sequestration. After rereduction of the subsurface through ethanol additions, background groundwater containing high levels of nitrate was allowed to enter the reduced test zone. Aqueous uranium concentrations increased then decreased. Clone library analyses of sediment samples revealed the presence of denitrifying bacteria that can oxidize elemental sulfur, H(2)S, Fe(II), and U(IV) (e.g., Thiobacillus spp.), and a decrease in relative abundance of bacteria that can reduce Fe(III) and sulfate. XANES analyses of sediment samples confirmed changes in uranium oxidation state. Addition of ethanol restored reduced conditions and triggered a short-term increase in Fe(II) and aqueous uranium, likely due to reductive dissolution of Fe(III) oxides and release of sorbed U(VI). After two months of intermittent ethanol addition, sulfide levels increased, and aqueous uranium concentrations gradually decreased to <0.1 microM.
Wu
Wei-Min
WM
Department of Civil and Environmental Engineering, Stanford University, Stanford, California 94305, USA.
Carley
Jack
J
Green
Stefan J
SJ
Luo
Jian
J
Kelly
Shelly D
SD
Van Nostrand
Joy
J
Lowe
Kenneth
K
Mehlhorn
Tonia
T
Carroll
Sue
S
Boonchayanant
Benjaporn
B
Löfller
Frank E
FE
Watson
David
D
Kemner
Kenneth M
KM
Zhou
Jizhong
J
Kitanidis
Peter K
PK
Kostka
Joel E
JE
Jardine
Philip M
PM
Criddle
Craig S
CS
D001673:Biodegradation, Environmental; D005740:Gases; D019015:Geologic Sediments / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D009566:Nitrates / Q000737:chemistry*; D009573:Nitrites / Q000737:chemistry; D009584:Nitrogen / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D012336:RNA, Ribosomal, 16S / Q000378:metabolism; D013440:Sulfides / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry; D013499:Surface Properties; D014501:Uranium / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis*
D005740:Gases; D009566:Nitrates; D009573:Nitrites; D012336:RNA, Ribosomal, 16S; D013440:Sulfides; D014874:Water Pollutants, Chemical; D014501:Uranium; D013455:Sulfur; D009584:Nitrogen; D010100:Oxygen