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Title: The coordination chemistry of Cm III , Am III , and Ac III in nitrate solutions: an actinide L 3 -edge EXAFS study

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C8SC02270D· OSTI ID:1462444
 [1];  [1];  [1];  [1];  [2]; ORCiD logo [1];  [3];  [1];  [4]
  1. Los Alamos National Laboratory,, USA
  2. Los Alamos National Laboratory,, USA, Department of Physics, University of Washington, Seattle
  3. Stanford University, USA
  4. Department of Physics, University of Washington, Seattle, USA
+ Show Author Affiliations

Understanding actinide(III) (AnIII = CmIII, AmIII, AcIII) solution-phase speciation is critical for controlling many actinide processing schemes, ranging from medical applications to reprocessing of spent nuclear fuel. Unfortunately, in comparison to most elements in the periodic table, AnIII speciation is often poorly defined in complexing aqueous solutions and in organic media. This neglect – in large part – is a direct result of the radioactive properties of these elements, which make them difficult to handle and acquire. Here in this paper, we surmounted some of the handling challenges associated with these exotic 5f-elements and characterized CmIII, AmIII, and AcIII using AnIII L3-edge X-ray absorption spectroscopy (XAS) as a function of increasing nitric acid (HNO3) concentration. Our results revealed that actinide aquo ions, An(H2O)x3+ (x = 9.6 ± 0.7, 8.9 ± 0.8, and 10.0 ± 0.9 for CmIII, AmIII, and AcIII), were the dominant species in dilute HNO3 (0.05 M). In concentrated HNO3 (16 M), shell-by-shell fitting of the extended X-ray fine structure (EXAFS) data showed the nitrate complexation increased, such that the average stoichiometries of Cm(NO3)4.1±0.7(H2O)5.7±1.3(1.1±0.2)-, Am(NO3)3.4±0.7(H2O)5.4±0.5(0.4±0.1)-, and Ac(NO3)2.3±1.7(H2O)8.3±5.2(0.7±0.5)+ were observed. Data obtained at the intermediate HNO3 concentration (4 M) were modeled as a linear combination of the 0.05 and 16 M spectra. Here, for all three metals, the intermediate models showed larger contributions from the 0.05 M HNO3 spectra than from the 16 M HNO3 spectra. Additionally, these efforts enabled the Cm–NO3 and Ac–NO3 distances to be measured for the first time. Moreover, the AnIII L3-edge EXAFS results, contribute to the growing body of knowledge associated with CmIII, AmIII, and AcIII coordination chemistry, in particular toward advancing understanding of AnIII solution phase speciation.

Research Organization:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
20180005DR; AC52-06NA25396; AC02-76SF00515
OSTI ID:
1462444
Alternate ID(s):
OSTI ID: 1463561
Report Number(s):
LA-UR-18-22688; CSHCBM
Journal Information:
Chemical Science, Journal Name: Chemical Science Vol. 9 Journal Issue: 35; ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)Copyright Statement
Country of Publication:
United Kingdom
Language:
English
Citation Metrics:
Cited by: 37 works
Citation information provided by
Web of Science

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Cited By (3)

Coordination chemistry of lanthanides in a AOT–CMPO solvent extraction system: UV-Vis and XAFS studies journal January 2018
Response to “Comment on ‘On the development of polarizable and Lennard-Jones force fields to study hydration structure and dynamics of actinide(III) ions based on effective ionic radii’” [J. Chem. Phys. 150 , 097101 (2019)] journal March 2019
Selective Extraction of Americium from Curium and the Lanthanides by the Lipophilic Ligand CyMe 4 BTPhen Dissolved in Aliquat-336 Nitrate Ionic Liquid journal January 2020

Figures / Tables (9)

Fig. 1(p. 3)figure Fig. 1
Fig. 2(p. 4)figure Fig. 2
Table 1(p. 4)table Table 1
Table 2(p. 6)table Table 2
Fig. 3(p. 7)figure Fig. 3
Scheme 1(p. 7)figure Scheme 1
Scheme 2(p. 8)figure Scheme 2
Fig. 4(p. 9)figure Fig. 4
Fig. 5(p. 9)figure Fig. 5

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