Browse > Article
http://dx.doi.org/10.7733/jnfcwt.2018.16.4.397

Radioanalytical and Spectroscopic Characterizations of Hydroxo- and Oxalato-Am(III) Complexes  

Kim, Hee-Kyung (Korea Atomic Energy Research Institute)
Cho, Hye-Ryun (Korea Atomic Energy Research Institute)
Jung, Euo Chang (Korea Atomic Energy Research Institute)
Cha, Wansik (Korea Atomic Energy Research Institute)
Publication Information
Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT) / v.16, no.4, 2018 , pp. 397-410 More about this Journal
Abstract
When considering the long-term safety assessment of spent-nuclear fuel management, americium is one of the most radio-toxic actinides. Although spectroscopic methods are widely used for the study of actinide chemistry, application of those methods to americium chemistry has been limited. Herein, we purified $^{241}Am$ to obtain a highly pure stock solution required for spectroscopic studies. Quantitative and qualitative analyses of purified $^{241}Am$ were carried out using liquid scintillation counting, and gamma and alpha radiation spectrometry. Highly sensitive absorption spectrometry coupled with a liquid waveguide capillary cell and time-resolved laser fluorescence spectroscopy were employed for the study of Am(III) hydrolysis and oxalate (Ox) complexation. $Am^{3+}$ ions under acidic conditions exhibit maximum absorbance at 503 nm, with a molar absorption coefficient of $424{\pm}8cm^{-1}{\cdot}M^{-1}$. $Am(OH)_3(s)$ colloidal particles formed under near neutral pH conditions were identified by monitoring the absorbance at around 506-507 nm. The formation of ${Am(Ox)_3}^{3-}$ was detected by red-shifts of the absorption and luminescence spectra of 4 and 5 nm, respectively. In addition, considerable enhancements of the luminescence intensities were observed. The luminescence lifetime of ${Am(Ox)_3}^{3-}$ increased from 23 to 56 ns, which indicates that approximately six water molecules are replaced by carboxylate ligands in the inner-sphere of the Am(III). These results suggest that ${Am(Ox)_3}^{3-}$ is formed through the bidentate coordination of the oxalate ligands.
Keywords
Americium; Radio-analysis; UV-Vis spectroscopy; TRLFS; Chemical speciation;
Citations & Related Records
Times Cited By KSCI : 1  (Citation Analysis)
연도 인용수 순위
1 G. Meinrath and J.I. Kim, "The Carbonate Complexation of the Am(III) Ion", Radiochim. Acta, 52-53(1), 29-34 (1991).
2 H.-R. Cho, E.C. Jung, K.K. Park, K. Song, and J.-I. Yun, "Effect of reduction on the stability of Pu(VI) hydrolysis species", Radiochim. Acta, 98(9-11), 555-561 (2010).   DOI
3 H.-R. Cho, E.C. Jung, W. Cha, K. Song, and K.K. Park, Purification of Americium Reagent, Korea Atomic Energy Research Institute, KAERI/TR-4800/2012 (2012).
4 T.-H. Park, E.-H. Jeon, Y.S. Choi, J.-H. Park, H.J. Ahn, and Y.J. Park, "Rapid quantification of alpha emitters in low- and intermediate-level dry radioactive waste", J. Radioanal. Nucl. Chem., 307(1), 645-651 (2016).   DOI
5 H.-R. Cho, K.K. Park, E.C. Jung, K. Song, "A Sensitive Detection of Actinides Species in Solutions using a Capillary Cell", J. Nucl. Fuel Cycle Waste Technol., 7(2), 109-114 (2009).
6 E.C. Jung, M.H. Baik, H.-R. Cho, H.-K. Kim, and W. Cha, "Study on the Interaction of U(VI) Species with Natural Organic Matters in KURT Groundwater", J. Nucl. Fuel Cycle Waste Technol., 15(2), 101-116 (2017).   DOI
7 S.E. Stephanou, J.P. Nigon, and R.A. Penneman, "The solution absorption spectra of americium(III), (V), and (VI)", J. Chem. Phys., 21, 42-45 (1953).   DOI
8 W.D. Horrocks and D.R. Sudnick, "Lanthanide ion probes of structure in biology. Laser-induced luminescence decay constants provide a direct measure of the number of metal-coordinated water molecules", J. Am. Chem. Soc., 101, 334-340 (1979).   DOI
9 T. Kimura and G.R. Choppin, "Luminescence study on determination of the hydration number of Cm(III)", J. Alloy. Comp., 213-214, 313-317 (1994).   DOI
10 T. Kimura and Y. Kato, "Luminescence study on determination of the inner-sphere hydration number of Am(III) and Nd(III)", J. Alloy. Comp., 271-273, 867-871 (1998).   DOI
11 Programme for research, development and demonstration of methods for the management and disposal of nuclear waste, Swedish Nuclear Fuel and Waste Management Co., SKB Technical Report TR-16-15 (2016).
12 J.J. Katz, G.T. Seaborg, and L.R. Morss, The chemistry of the actinide elements, 2nd ed., Chapman and Hall Ltd, New York (1986).
13 W. Runde, Americium and Curium: Radionuclides, John Wiley & Sons, Ltd. (2006).
14 B. Miller, Safety case for the disposal of spent nuclear fuel at Olkiluoto-features, events and processes 2012, Posiva Oy, POSIVA 2012-07 (2012).
15 M. Altmaier, X. Gaona, and T. Fanghanel, "Recent Advances in Aqueous Actinide Chemistry and Thermodynamics", Chem. Rev., 113(2), 901-943 (2013).   DOI
16 X. Tan, M. Fang, and X. Wang, "Sorption Speciation of Lanthanides/Actinides on Minerals by TRLFS, EXAFS and DFT Studies: A Review", Molecules, 15(11), 8431- 8468 (2010).   DOI
17 G. Geipel, "Some aspects of actinide speciation by laser- induced spectroscopy", Coord. Chem. Rev., 250(7- 8), 844-854 (2006).   DOI
18 E.C. Jung, H.R. Cho, M.H. Baik, H. Kim, and W. Cha, "Time-resolved laser fluorescence spectroscopy of $UO_2(CO_3)_3^{4-}$", Dalton Trans., 44, 18831-18838 (2015).   DOI
19 G. Buckau, J.I. Kim, R. Klenze, D.S. Rhee, and H. Wimmer, "A Comparative Spectroscopic Study of the Fulvate Complexation of Trivalent Transuranium Ions", Radiochim. Acta, 57(2-3), 105-111 (1992).
20 W. Hummel, G. Anderegg, L. Rao, I. Puigdomenech, and O. Tochiyama, Chemical thermodynamics Vol. 9: Chemical thermodynamics of compounds and complexes of U, Np, Pu, Am, Tc, Se, Ni and Zr with selected organic ligands, Elsevier Amsterdam, The Netherlands (2005).
21 H. Geckeis, J. Lutzenkirchen, R. Polly, T. Rabung, and M. Schmidt, "Mineral-Water Interface Reactions of Actinides", Chem. Rev., 113(2), 1016-1062 (2013).   DOI
22 T. Fanghanel, J.I. Kim, P. Paviet, R. Klenze, and W. Hauser, "Thermodynamics of Radioactive Trace Elements in Concentrated Electrolyte Solutions: Hydrolysis of $Cm^{3+}$ in NaCl-Solutions", Radiochim. Acta, 66-67(s1), 81-87 (1994).
23 T. Fanghanel, Τ. Weger Η, T. Konnecke, V. Neck, P. Paviet-Hartmann, E. Steinle, and J.I. Kim, "Thermodynamics of Cm(III) in concentrated electrolyte solutions. Carbonate complexation at constant ionic strength (1 M NaCl)", Radiochim. Acta, 82(s1), 47-53 (1998).
24 R. Guillaumont, T. Fanghanel, V. Neck, J. Fuger, D. Palmer, I. Grenthe, and M. H. Rand, Chemical Thermodynamics Vol. 5: Update on the Chemical Thermodynamics of Uranium, Neptunium, Plutonium, Americium, and Technetium, Elsevier, Amsterdam, The Netherlands (2003).
25 X. Tan, X. Ren, C. Chen, and X. Wang, "Analytical approaches to the speciation of lanthanides at solid-water interfaces", Trends Anal. Chem., 61, 107-132 (2014).   DOI
26 P. Thouvenot, S. Hubert, C. Moulin, P. Decambox, and P. Mauchien, "Americium Trace Determination in Aqueous and Solid Matrices by Time-Resolved Laser-Induced Fluorescence", Radiochim. Acta, 61(1), 15-21 (1993).
27 W.T. Carnall, "A systematic analysis of the spectra of trivalent actinide chlorides in $D_{3h}$ site symmetry", J. Chem. Phys., 96(12), 8713-8726 (1992).   DOI
28 J.V. Beitz, "f-State luminescence of trivalent lanthanide and actinide ions in solution", J. Alloy. Comp., 207-208, 41-50 (1994).   DOI
29 A. Barkleit, G. Geipel, M. Acker, S. Taut, and G. Bernhard, "First fluorescence spectroscopic investigation of Am(III) complexation with an organic carboxylic ligand, pyromellitic acid", Spectrochim. Acta Part A: Mol. Biomol. Spec., 78(1), 549-552 (2011).   DOI
30 I. Grenthe, G. Gardhammar, and E. Rundcrantz, "Thermodynamic properties of rare earth complexes", Acta Chemica Scandinavica, 23, 93-108 (1969).   DOI
31 B. Raditzky, S. Sachs, K. Schmeide, A. Barkleit, G. Geipel, and G. Bernhard, "Spectroscopic study of americium(III) complexes with nitrogen containing organic model ligands", Polyhedron, 65, 244-251 (2013).   DOI
32 A. Barkleit, J. Kretzschmar, S. Tsushima, and M. Acker, "Americium(III) and europium(III) complex formation with lactate at elevated temperatures studied by spectroscopy and quantum chemical calculations", Dalton Trans., 43, 11221-11232 (2014).   DOI
33 S. Stadler and J. I. Kim, "Hydrolysis Reactions of Am (III) and Am(V)", Radiochim. Acta, 44-45(1), 39-44 (1988).
34 R. Klenze, J.I. Kim, and H. Wimmer, "Speciation of aquatic actinide ions by pulsed laser spectroscopy", Radiochim. Acta, 52-53(1), 97-103 (1991).
35 G. Tian and D.K. Shuh, "A spectrophotometric study of Am(III) complexation with nitrate in aqueous solution at elevated temperatures", Dalton Trans., 43, 14565-14569 (2014).   DOI
36 T.K. Keenan, "Americium and Curium", J. Chem. Edu., 36(1), 27-31 (1959).   DOI
37 J.I. Kim, D.S. Rhee, and G. Buckau, "Complexation of Am(III) with Humic Acids of Different Origin", Radiochim. Acta, 52-53(1), 49-56 (1991).
38 M. Morgenstern, R. Klenze, and J.I. Kim, "The formation of mixed-hydroxo complexes of Cm(III) and Am(III) with humic acid in the neutral pH range", Radiochim. Acta, 88(1), 7-17 (2000).   DOI
39 J.I. Kim, D.S. Rhee, H. Wimmer, G. Buckau, and R. Klenze, "Complexation of Trivalent Actinide Ions ($Am^{3+}$, $Cm^{3+}$) with Humic Acid: A Comparison of Different Experimental Methods", Radiochim. Acta, 62(1-2), 35-44 (1993).
40 J.I. Kim, D.S. Rhee, G. Buckau, and A. Morgenstern, "Americium(III)-Humate Interaction in Natural Groundwater: Influence of Purification on Complexation Properties", Radiochim. Acta, 79(3), 173-182 (1997).
41 M. Muller, M. Acker, S. Taut, and G. Bernhard, "Complex formation of trivalent americium with salicylic acid at very low concentrations", J. Radioanal. Nucl. Chem., 286(1), 175-180 (2010).   DOI
42 M.A. Brown, A.J. Kropf, A. Paulenova, and A.V. Gelis, "Aqueous complexation of citrate with neodymium(III) and americium(III): a study by potentiometry, absorption spectrophotometry, microcalorimetry, and XAFS", Dalton Trans., 43, 6446-6454 (2014).   DOI