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Title: Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments

Abstract

Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. In this study, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO4-reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K2(UO2)6O4(OH)6·8H2O]- and becquerelite [Ca(UO2)6O4(OH)6·8H2O]-like species. Subsequent further removal of uranium coincided with that of Si and accumulation of boltwoodite, [(K, Na)(UO2)2O4(HSiO4)2•0.5(H2O)]-like species of uranium at 180 and 365 days. When present, PO4 exerted a direct and strong control over U speciation. The detection of meta-ankoleite, [K2(UO2)2O4(PO4)2·6H2O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO4 is absent), after initial precipitation ofmore » more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO4 present, nearly all uranium would have precipitated in the upper soil.« less

Authors:
 [1];  [2];  [3];  [4];  [3];  [5];  [6];  [7];  [8]
  1. Univ. of Vermont, Burlington, VT (United States). Dept. of Geology
  2. Univ. of Arizona, Tucson, AZ (United States). Dept. of Soil Water and Environmental Science; Univ. of Notre Dame, IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Anchor QEA, LLC, Portland, OR (United States)
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Pohang Univ. of Science and Technology (POSTECH) (Korea, Republic of)
  6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  7. Univ. of California, Merced, CA (United States). School of Natural Sciences
  8. Univ. of Arizona, Tucson, AZ (United States). Dept. of Soil Water and Environmental Science
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1413491
Alternate Identifier(s):
OSTI ID: 1476618; OSTI ID: 1548954
Report Number(s):
PNNL-SA-133858
Journal ID: ISSN 0883-2927; PII: S0883292717303657
Grant/Contract Number:  
SBR-DE-SC0006781; AC0576RL01830; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Applied Geochemistry
Additional Journal Information:
Journal Volume: 89; Journal Issue: C; Journal ID: ISSN 0883-2927
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; uranium; Hanford; acid waste; phosphate; uranyl silicates

Citation Formats

Perdrial, Nicolas, Vázquez-Ortega, Angélica, Wang, Guohui, Kanematsu, Masakazu, Mueller, Karl T., Um, Wooyong, Steefel, Carl I., O'Day, Peggy A., and Chorover, Jon. Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments. United States: N. p., 2017. Web. https://doi.org/10.1016/J.APGEOCHEM.2017.12.001.
Perdrial, Nicolas, Vázquez-Ortega, Angélica, Wang, Guohui, Kanematsu, Masakazu, Mueller, Karl T., Um, Wooyong, Steefel, Carl I., O'Day, Peggy A., & Chorover, Jon. Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments. United States. https://doi.org/10.1016/J.APGEOCHEM.2017.12.001
Perdrial, Nicolas, Vázquez-Ortega, Angélica, Wang, Guohui, Kanematsu, Masakazu, Mueller, Karl T., Um, Wooyong, Steefel, Carl I., O'Day, Peggy A., and Chorover, Jon. Tue . "Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments". United States. https://doi.org/10.1016/J.APGEOCHEM.2017.12.001. https://www.osti.gov/servlets/purl/1413491.
@article{osti_1413491,
title = {Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments},
author = {Perdrial, Nicolas and Vázquez-Ortega, Angélica and Wang, Guohui and Kanematsu, Masakazu and Mueller, Karl T. and Um, Wooyong and Steefel, Carl I. and O'Day, Peggy A. and Chorover, Jon},
abstractNote = {Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. In this study, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO4-reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K2(UO2)6O4(OH)6·8H2O]- and becquerelite [Ca(UO2)6O4(OH)6·8H2O]-like species. Subsequent further removal of uranium coincided with that of Si and accumulation of boltwoodite, [(K, Na)(UO2)2O4(HSiO4)2•0.5(H2O)]-like species of uranium at 180 and 365 days. When present, PO4 exerted a direct and strong control over U speciation. The detection of meta-ankoleite, [K2(UO2)2O4(PO4)2·6H2O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO4 is absent), after initial precipitation of more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO4 present, nearly all uranium would have precipitated in the upper soil.},
doi = {10.1016/J.APGEOCHEM.2017.12.001},
journal = {Applied Geochemistry},
number = C,
volume = 89,
place = {United States},
year = {2017},
month = {12}
}

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Figures / Tables:

Figure 1 Figure 1: Evolution of solution chemistry during reaction for pH (a), Total inorganic carbon reported as CO32- (b), U (c), total PO43- (note the break on the y-axis) (d), Si (e) and Mg (f). Note the y-axis break for panel d.

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