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Title: Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series

Abstract

The chemistry of trivalent transplutonium ions (Am 3+, Cm 3+, Bk 3+, Cf 3+, Es 3+…) is usually perceived as monotonic and paralleling that of the trivalent lanthanide series. We present the first extended X-ray absorption fine structure (EXAFS) study performed on a series of aqueous heavy actinide chelates, extending past Cm. The results obtained on diethylenetriaminepentaacetic acid (DTPA) complexes of trivalent Am, Cm, Bk, and Cf show a break to much shorter metal–oxygen nearest-neighbor bond lengths in the case of Cf 3+. Corroborating those results, density functional theory calculations, extended to Es 3+, suggest that the shorter Cf-O and Es-O bonds could arise from the departure of the coordinated water molecule and contraction of the ligand around the metal relative to the other [M IIIDTPA(H 2O)] 2- (M=Am, Cm, Bk) complexes. Taken together, these experimental and theoretical results demonstrate inhomogeneity within the trivalent transplutonium series that has been insinuated and debated in recent years, and that may also be leveraged for future nuclear waste reprocessing technologies.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [2]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Nuclear Engineering
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1477677
Alternate Identifier(s):
OSTI ID: 1426318; OSTI ID: 1513796
Report Number(s):
LA-UR-17-27807
Journal ID: ISSN 1433-7851
Grant/Contract Number:  
AC52-06NA25396; AC02-05CH11231; AC02-76SF00515
Resource Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 57; Journal Issue: 17; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; actinides; berkelium; californium; chelates; EXAFS spectroscopy

Citation Formats

Deblonde, Gauthier J. -P., Kelley, Morgan P., Su, Jing, Batista, Enrique R., Yang, Ping, Booth, Corwin H., and Abergel, Rebecca J. Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series. United States: N. p., 2018. Web. doi:10.1002/anie.201709183.
Deblonde, Gauthier J. -P., Kelley, Morgan P., Su, Jing, Batista, Enrique R., Yang, Ping, Booth, Corwin H., & Abergel, Rebecca J. Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series. United States. doi:10.1002/anie.201709183.
Deblonde, Gauthier J. -P., Kelley, Morgan P., Su, Jing, Batista, Enrique R., Yang, Ping, Booth, Corwin H., and Abergel, Rebecca J. Thu . "Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series". United States. doi:10.1002/anie.201709183. https://www.osti.gov/servlets/purl/1477677.
@article{osti_1477677,
title = {Spectroscopic and Computational Characterization of Diethylenetriaminepentaacetic Acid/Transplutonium Chelates: Evidencing Heterogeneity in the Heavy Actinide(III) Series},
author = {Deblonde, Gauthier J. -P. and Kelley, Morgan P. and Su, Jing and Batista, Enrique R. and Yang, Ping and Booth, Corwin H. and Abergel, Rebecca J.},
abstractNote = {The chemistry of trivalent transplutonium ions (Am3+, Cm3+, Bk3+, Cf3+, Es3+…) is usually perceived as monotonic and paralleling that of the trivalent lanthanide series. We present the first extended X-ray absorption fine structure (EXAFS) study performed on a series of aqueous heavy actinide chelates, extending past Cm. The results obtained on diethylenetriaminepentaacetic acid (DTPA) complexes of trivalent Am, Cm, Bk, and Cf show a break to much shorter metal–oxygen nearest-neighbor bond lengths in the case of Cf3+. Corroborating those results, density functional theory calculations, extended to Es3+, suggest that the shorter Cf-O and Es-O bonds could arise from the departure of the coordinated water molecule and contraction of the ligand around the metal relative to the other [MIIIDTPA(H2O)]2- (M=Am, Cm, Bk) complexes. Taken together, these experimental and theoretical results demonstrate inhomogeneity within the trivalent transplutonium series that has been insinuated and debated in recent years, and that may also be leveraged for future nuclear waste reprocessing technologies.},
doi = {10.1002/anie.201709183},
journal = {Angewandte Chemie (International Edition)},
number = 17,
volume = 57,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

Scheme 1 Scheme 1: Left: structure of H5DTPA. Right: [AnIIIDTPA]2- complex, with coordinating atoms represented as balls and all others as sticks. Hydrogen atoms are hidden for clarity.

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Works referenced in this record:

Complexation of Cm( iii ) with the recombinant N-lobe of human serum transferrin studied by time-resolved laser fluorescence spectroscopy (TRLFS)
journal, January 2015

  • Bauer, N.; Smith, V. C.; MacGillivray, R. T. A.
  • Dalton Transactions, Vol. 44, Issue 4
  • DOI: 10.1039/C4DT03403A

Structural optimization of molecular clusters with density functional theory combined with basin hopping
journal, October 2012

  • Do, Hainam; Besley, Nicholas A.
  • The Journal of Chemical Physics, Vol. 137, Issue 13
  • DOI: 10.1063/1.4755994

Speciation of americium in seawater and accumulation in the marine sponge Aplysina cavernicola
journal, January 2015

  • Maloubier, Melody; Michel, Hervé; Solari, Pier Lorenzo
  • Dalton Transactions, Vol. 44, Issue 47
  • DOI: 10.1039/C5DT02805A

The Curium Aqua Ion
journal, April 2007

  • Skanthakumar, S.; Antonio, Mark R.; Wilson, Richard E.
  • Inorganic Chemistry, Vol. 46, Issue 9
  • DOI: 10.1021/ic061798b

A spectrophotometric study of Am( iii ) complexation with nitrate in aqueous solution at elevated temperatures
journal, January 2014


The Chemistry of TALSPEAK: A Review of the Science
journal, December 2014


Approaching actinide(+III) hydration from first principles
journal, January 2007

  • Wiebke, J.; Moritz, A.; Cao, X.
  • Phys. Chem. Chem. Phys., Vol. 9, Issue 4
  • DOI: 10.1039/B614092K

Determination of the Hydration Number of Cm(III) in Various Aqueous Solutions
journal, January 1996


Confirmation of standard error analysis techniques applied to EXAFS using simulations
journal, November 2009


Intramolecular sensitization of americium luminescence in solution: shining light on short-lived forbidden 5f transitions
journal, January 2016

  • Sturzbecher-Hoehne, M.; Yang, P.; D'Aléo, A.
  • Dalton Transactions, Vol. 45, Issue 24
  • DOI: 10.1039/C6DT00328A

New Insights into Formation of Trivalent Actinides Complexes with DTPA
journal, November 2012

  • Leguay, Sébastien; Vercouter, Thomas; Topin, Sylvain
  • Inorganic Chemistry, Vol. 51, Issue 23
  • DOI: 10.1021/ic3011019

Parameter-free calculations of X-ray spectra with FEFF9
journal, January 2010

  • Rehr, John J.; Kas, Joshua J.; Vila, Fernando D.
  • Physical Chemistry Chemical Physics, Vol. 12, Issue 21
  • DOI: 10.1039/b926434e

TRLFS study on the complexation of Cm( iii ) and Eu( iii ) with SO 3 -Ph-BTBP
journal, January 2015

  • Wagner, Christoph; Müllich, Udo; Geist, Andreas
  • Dalton Transactions, Vol. 44, Issue 39
  • DOI: 10.1039/C5DT02923F

Characterization of berkelium(III) dipicolinate and borate compounds in solution and the solid state
journal, August 2016


Complexation thermodynamics and structural studies of trivalent actinide and lanthanide complexes with DTPA, MS-325 and HMDTPA
journal, April 2013

  • Thakur, Punam; Conca, James L.; Dodge, Cleveland J.
  • Radiochimica Acta, Vol. 101, Issue 4
  • DOI: 10.1524/ract.2013.2018

Theoretical insights into covalency driven f element separations
journal, January 2013

  • Roy, Lindsay E.; Bridges, Nicholas J.; Martin, Leigh R.
  • Dalton Trans., Vol. 42, Issue 7
  • DOI: 10.1039/C2DT31485A

Berkelium redox speciation
journal, January 2002


X-ray-absorption fine-structure standards: A comparison of experiment and theory
journal, September 1995


Alternatives to HDEHP and DTPA for Simplified TALSPEAK Separations
journal, June 2011

  • Braley, Jenifer C.; Grimes, Travis S.; Nash, Kenneth L.
  • Industrial & Engineering Chemistry Research, Vol. 51, Issue 2
  • DOI: 10.1021/ie200285r

Emergence of californium as the second transitional element in the actinide series
journal, April 2015

  • Cary, Samantha K.; Vasiliu, Monica; Baumbach, Ryan E.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7827

First Investigation on the L Edges of the 249 Cf Aquo Ion by X-ray Absorption Spectroscopy
journal, September 1999

  • Revel, R.; Den Auwer, C.; Madic, C.
  • Inorganic Chemistry, Vol. 38, Issue 18
  • DOI: 10.1021/ic990214l

The syntheses of lanthanide metal complexes with diethylenetriamine-N,N,N′,N″,N″-pentaacetic acid and the comparison of their crystal structures
journal, March 2003


On the Origin of Covalent Bonding in Heavy Actinides
journal, July 2017

  • Kelley, Morgan P.; Su, Jing; Urban, Matthew
  • Journal of the American Chemical Society, Vol. 139, Issue 29
  • DOI: 10.1021/jacs.7b03251

Number of relevant independent points in x-ray-absorption fine-structure spectra
journal, October 1993


Structural and Thermodynamic Properties of the Cm III Ion Solvated by Water and Methanol
journal, April 2016


Binuclear structure in the ammonium salt of gadolinium(III) diethylenetriaminepentaacetate, (NH4)4[Gd2(DTPA)2]·6H2O
journal, April 1995


Coordination Chemistry of Trivalent Lanthanide and Actinide Ions in Dilute and Concentrated Chloride Solutions
journal, February 2000

  • Allen, P. G.; Bucher, J. J.; Shuh, D. K.
  • Inorganic Chemistry, Vol. 39, Issue 3
  • DOI: 10.1021/ic9905953

Actinide oxalates, solid state structures and applications
journal, May 2014

  • Abraham, Francis; Arab-Chapelet, Bénédicte; Rivenet, Murielle
  • Coordination Chemistry Reviews, Vol. 266-267
  • DOI: 10.1016/j.ccr.2013.08.036

Temperature and pH Dependence XAFS Study of Gd(DOTA) - and Gd(DTPA) 2 - Complexes: Solid State and Solution Structures
journal, July 1998

  • Bénazeth, Simone; Purans, Juris; Chalbot, Marie-Cécile
  • Inorganic Chemistry, Vol. 37, Issue 15
  • DOI: 10.1021/ic9707321

Optimized Relaxivity and Stability of [Gd(H(2,2)-1,2-HOPO)(H 2 O)] - for Use as an MRI Contrast Agent 1
journal, June 2007

  • Jocher, Christoph J.; Botta, Mauro; Avedano, Stefano
  • Inorganic Chemistry, Vol. 46, Issue 12
  • DOI: 10.1021/ic700399p

Syntheses and crystal structures of nine-coordinate K2[EuIII(dtpa)(H2O)]·5H2O and Na2[TbIII(Httha)]·6H2O complexes
journal, October 2009


Solving the Hydration Structure of the Heaviest Actinide Aqua Ion Known: The Californium(III) Case
journal, April 2010

  • Galbis, Elsa; Hernández-Cobos, Jorge; den Auwer, Christophe
  • Angewandte Chemie, Vol. 122, Issue 22
  • DOI: 10.1002/ange.200906129

Synthesis and structural determination of binuclear nine-coordinate (NH4)4[Yb2(dtpa)2]·9H2O
journal, August 2002


Solving the Hydration Structure of the Heaviest Actinide Aqua Ion Known: The Californium(III) Case
journal, April 2010

  • Galbis, Elsa; Hernández-Cobos, Jorge; den Auwer, Christophe
  • Angewandte Chemie International Edition, Vol. 49, Issue 22
  • DOI: 10.1002/anie.200906129

Separation of actinides from spent nuclear fuel: A review
journal, November 2016


Covalency in Americium(III) Hexachloride
journal, June 2017

  • Cross, Justin N.; Su, Jing; Batista, Enrique R.
  • Journal of the American Chemical Society, Vol. 139, Issue 25
  • DOI: 10.1021/jacs.7b03755

An EXAFS and TRLFS study of the sorption of trivalent actinides onto smectite and kaolinite
journal, January 2004


X-ray-absorption fine structure in embedded atoms
journal, May 1994


Sensitizing Curium Luminescence through an Antenna Protein To Investigate Biological Actinide Transport Mechanisms
journal, February 2013

  • Sturzbecher-Hoehne, Manuel; Goujon, Christophe; Deblonde, Gauthier J. -P.
  • Journal of the American Chemical Society, Vol. 135, Issue 7
  • DOI: 10.1021/ja310957f

Complexation of Curium(III) with DTPA at 10–70 °C: Comparison with Eu(III)–DTPA in Thermodynamics, Luminescence, and Coordination Modes
journal, January 2015

  • Tian, Guoxin; Zhang, Zhiyong; Martin, Leigh R.
  • Inorganic Chemistry, Vol. 54, Issue 4
  • DOI: 10.1021/ic5016934

The size of actinoid(III) ions – structural analysis vs. common misinterpretations
journal, July 2016


A review of the demonstration of innovative solvent extraction processes for the recovery of trivalent minor actinides from PUREX raffinate
journal, August 2012

  • Modolo, Giuseppe; Wilden, A.; Geist, Andreas
  • Radiochimica Acta, Vol. 100, Issue 8-9
  • DOI: 10.1524/ract.2012.1962

Chelation and stabilization of berkelium in oxidation state +IV
journal, April 2017

  • Deblonde, Gauthier J. -P.; Sturzbecher-Hoehne, Manuel; Rupert, Peter B.
  • Nature Chemistry, Vol. 9, Issue 9
  • DOI: 10.1038/nchem.2759

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.