Interaction of Np( v ) with borate in alkaline, dilute-to-concentrated, NaCl and MgCl 2 solutions
Abstract
The interaction of Np(v) with borate was investigated in 0.1–5.0 M NaCl and 0.25–4.5 M MgCl2 solutions with 7.2 ≤ pHm ≤ 10.0 (pHm = –log[H+]) and 0.004 M ≤ [B]tot ≤ 0.16 M. Experiments were performed under an Ar-atmosphere at T = (22 ± 2) °C using a combination of under- and oversaturation solubility experiments, NIR spectroscopy, and extensive solid phase characterization. A bathochromic shift (≈5 nm) in the Np(v) band at λ = 980 nm indicates the formation of weak Np(v)–borate complexes under mildly alkaline pHm-conditions. The identification of an isosbestic point supports the formation of a single Np(v)–borate species in dilute MgCl2 systems, whereas a more complex aqueous speciation (eventually involving the formation of several Np(v)–borate species) is observed in concentrated MgCl2 solutions. The solubility of freshly prepared NpO2OH(am) remained largely unaltered in NaCl and MgCl2 solutions with [B]tot = 0.04 M within the timeframe of this study (t ≤ 300 days). At [B]tot = 0.16 M, a kinetically hindered but very significant drop in the solubility of Np(v) (3–4 log10-units, compared to borate-free systems) was observed in NaCl and dilute MgCl2 solutions with pHm ≤ 9. The drop in the solubility was accompanied by a clearmore »
- Authors:
-
[1];
[1];
[1];
[2];
- Institute for Nuclear Waste Disposal, Karlsruhe Institute of Technology, Germany
- Department of Chemistry and Biochemistry, Florida State University, USA
- Los Alamos National Laboratory, USA
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST); Florida State Univ., Tallahassee, FL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1582687
- Alternate Identifier(s):
- OSTI ID: 1767699
- Grant/Contract Number:
- SC0016568
- Resource Type:
- Published Article
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Name: Dalton Transactions Journal Volume: 49 Journal Issue: 5; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nuclear; defects; mechanical behavior; corrosion; charge transport; superconductivity; magnetism and spin physics; separations; geophysics/geochemistry; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (predictive); synthesis (scalable processing)
Citation Formats
Hinz, K., Fellhauer, D., Gaona, X., Vespa, M., Dardenne, K., Schild, D., Yokosawa, T., Silver, M. A., Reed, D. T., Albrecht-Schmitt, T. E., Altmaier, M., and Geckeis, H. Interaction of Np( v ) with borate in alkaline, dilute-to-concentrated, NaCl and MgCl 2 solutions. United Kingdom: N. p., 2020.
Web. doi:10.1039/C9DT04430B.
Hinz, K., Fellhauer, D., Gaona, X., Vespa, M., Dardenne, K., Schild, D., Yokosawa, T., Silver, M. A., Reed, D. T., Albrecht-Schmitt, T. E., Altmaier, M., & Geckeis, H. Interaction of Np( v ) with borate in alkaline, dilute-to-concentrated, NaCl and MgCl 2 solutions. United Kingdom. https://doi.org/10.1039/C9DT04430B
Hinz, K., Fellhauer, D., Gaona, X., Vespa, M., Dardenne, K., Schild, D., Yokosawa, T., Silver, M. A., Reed, D. T., Albrecht-Schmitt, T. E., Altmaier, M., and Geckeis, H. Wed .
"Interaction of Np( v ) with borate in alkaline, dilute-to-concentrated, NaCl and MgCl 2 solutions". United Kingdom. https://doi.org/10.1039/C9DT04430B.
@article{osti_1582687,
title = {Interaction of Np( v ) with borate in alkaline, dilute-to-concentrated, NaCl and MgCl 2 solutions},
author = {Hinz, K. and Fellhauer, D. and Gaona, X. and Vespa, M. and Dardenne, K. and Schild, D. and Yokosawa, T. and Silver, M. A. and Reed, D. T. and Albrecht-Schmitt, T. E. and Altmaier, M. and Geckeis, H.},
abstractNote = {The interaction of Np(v) with borate was investigated in 0.1–5.0 M NaCl and 0.25–4.5 M MgCl2 solutions with 7.2 ≤ pHm ≤ 10.0 (pHm = –log[H+]) and 0.004 M ≤ [B]tot ≤ 0.16 M. Experiments were performed under an Ar-atmosphere at T = (22 ± 2) °C using a combination of under- and oversaturation solubility experiments, NIR spectroscopy, and extensive solid phase characterization. A bathochromic shift (≈5 nm) in the Np(v) band at λ = 980 nm indicates the formation of weak Np(v)–borate complexes under mildly alkaline pHm-conditions. The identification of an isosbestic point supports the formation of a single Np(v)–borate species in dilute MgCl2 systems, whereas a more complex aqueous speciation (eventually involving the formation of several Np(v)–borate species) is observed in concentrated MgCl2 solutions. The solubility of freshly prepared NpO2OH(am) remained largely unaltered in NaCl and MgCl2 solutions with [B]tot = 0.04 M within the timeframe of this study (t ≤ 300 days). At [B]tot = 0.16 M, a kinetically hindered but very significant drop in the solubility of Np(v) (3–4 log10-units, compared to borate-free systems) was observed in NaCl and dilute MgCl2 solutions with pHm ≤ 9. The drop in the solubility was accompanied by a clear change in the colour of the solid phase (from green to white-greyish). XRD and TEM analyses showed that the amorphous NpO2OH(am) “starting material” transformed into crystalline solid phases with similar XRD patterns in NaCl and MgCl2 systems. XPS, SEM–EDS and EXAFS further indicated that borate and Na/Mg participate stoichiometrically in the formation of such solid phases. Additional undersaturation solubility experiments using the newly formed Na–Np(v)–borate(cr) and Mg–Np(v)–borate(cr) compounds further confirmed the low solubility ([Np(v)]aq ≈ 10–6–10–7 M) of such solid phases in mildly alkaline pHm-conditions. The formation of these solid phases represents a previously unreported retention mechanism for the highly mobile Np(v) under boundary conditions (pHm, [B]tot, ionic strength) of relevance to certain repository concepts for nuclear waste disposal.},
doi = {10.1039/C9DT04430B},
journal = {Dalton Transactions},
number = 5,
volume = 49,
place = {United Kingdom},
year = {2020},
month = {2}
}
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