Europium(III) Meets Etidronic Acid (HEDP): A Coordination Study Combining Spectroscopic, Spectrometric, and Quantum Chemical Methods

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Autoren

  • Anne Heller
  • Christian Senwitz
  • Harald Foerstendorf
  • Satoru Tsushima
  • Linus Holtmann
  • Björn Drobot
  • Jerome Kretzschmar

Externe Organisationen

  • Technische Universität Dresden
  • Helmholtz-Zentrum Dresden-Rossendorf (HZDR)
  • Tokyo Institute of Technology
Forschungs-netzwerk anzeigen

Details

OriginalspracheEnglisch
Aufsatznummer4469
FachzeitschriftMOLECULES
Jahrgang28
Ausgabenummer11
PublikationsstatusVeröffentlicht - 31 Mai 2023

Abstract

Etidronic acid (1-Hydroxyethylidene-1,1-diphosphonic acid, HEDP, H4L) is a proposed decorporation agent for U(VI). This paper studied its complex formation with Eu(III), an inactive analog of trivalent actinides, over a wide pH range, at varying metal-to-ligand ratios (M:L) and total concentrations. Combining spectroscopic, spectrometric, and quantum chemical methods, five distinct Eu(III)−HEDP complexes were found, four of which were characterized. The readily soluble EuH2L+ and Eu(H2L)2 species with log β values of 23.7 ± 0.1 and 45.1 ± 0.9 are formed at acidic pH. At near-neutral pH, EuHL0s forms with a log β of ~23.6 and, additionally, a most probably polynuclear complex. The readily dissolved EuL species with a log β of ~11.2 is formed at alkaline pH. A six-membered chelate ring is the key motif in all solution structures. The equilibrium between the Eu(III)–HEDP species is influenced by several parameters, i.e., pH, M:L, total Eu(III) and HEDP concentrations, and time. Overall, the present work sheds light on the very complex speciation in the HEDP–Eu(III) system and indicates that, for risk assessment of potential decorporation scenarios, side reactions of HEDP with trivalent actinides and lanthanides should also be taken into account.

ASJC Scopus Sachgebiete

Zitieren

Europium(III) Meets Etidronic Acid (HEDP): A Coordination Study Combining Spectroscopic, Spectrometric, and Quantum Chemical Methods. / Heller, Anne; Senwitz, Christian; Foerstendorf, Harald et al.
in: MOLECULES, Jahrgang 28, Nr. 11, 4469, 31.05.2023.

Publikation: Beitrag in FachzeitschriftArtikelForschungPeer-Review

Heller, A, Senwitz, C, Foerstendorf, H, Tsushima, S, Holtmann, L, Drobot, B & Kretzschmar, J 2023, 'Europium(III) Meets Etidronic Acid (HEDP): A Coordination Study Combining Spectroscopic, Spectrometric, and Quantum Chemical Methods', MOLECULES, Jg. 28, Nr. 11, 4469. https://doi.org/10.3390/molecules28114469
Heller, A., Senwitz, C., Foerstendorf, H., Tsushima, S., Holtmann, L., Drobot, B., & Kretzschmar, J. (2023). Europium(III) Meets Etidronic Acid (HEDP): A Coordination Study Combining Spectroscopic, Spectrometric, and Quantum Chemical Methods. MOLECULES, 28(11), Artikel 4469. https://doi.org/10.3390/molecules28114469
Heller A, Senwitz C, Foerstendorf H, Tsushima S, Holtmann L, Drobot B et al. Europium(III) Meets Etidronic Acid (HEDP): A Coordination Study Combining Spectroscopic, Spectrometric, and Quantum Chemical Methods. MOLECULES. 2023 Mai 31;28(11):4469. doi: 10.3390/molecules28114469
Heller, Anne ; Senwitz, Christian ; Foerstendorf, Harald et al. / Europium(III) Meets Etidronic Acid (HEDP) : A Coordination Study Combining Spectroscopic, Spectrometric, and Quantum Chemical Methods. in: MOLECULES. 2023 ; Jahrgang 28, Nr. 11.
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title = "Europium(III) Meets Etidronic Acid (HEDP): A Coordination Study Combining Spectroscopic, Spectrometric, and Quantum Chemical Methods",
abstract = "Etidronic acid (1-Hydroxyethylidene-1,1-diphosphonic acid, HEDP, H4L) is a proposed decorporation agent for U(VI). This paper studied its complex formation with Eu(III), an inactive analog of trivalent actinides, over a wide pH range, at varying metal-to-ligand ratios (M:L) and total concentrations. Combining spectroscopic, spectrometric, and quantum chemical methods, five distinct Eu(III)−HEDP complexes were found, four of which were characterized. The readily soluble EuH2L+ and Eu(H2L)2− species with log β values of 23.7 ± 0.1 and 45.1 ± 0.9 are formed at acidic pH. At near-neutral pH, EuHL0s forms with a log β of ~23.6 and, additionally, a most probably polynuclear complex. The readily dissolved EuL− species with a log β of ~11.2 is formed at alkaline pH. A six-membered chelate ring is the key motif in all solution structures. The equilibrium between the Eu(III)–HEDP species is influenced by several parameters, i.e., pH, M:L, total Eu(III) and HEDP concentrations, and time. Overall, the present work sheds light on the very complex speciation in the HEDP–Eu(III) system and indicates that, for risk assessment of potential decorporation scenarios, side reactions of HEDP with trivalent actinides and lanthanides should also be taken into account.",
keywords = "ATR-FT-IR, complexation, DFT, ESI-MS, lanthanides, NMR, speciation, TRLFS",
author = "Anne Heller and Christian Senwitz and Harald Foerstendorf and Satoru Tsushima and Linus Holtmann and Bj{\"o}rn Drobot and Jerome Kretzschmar",
note = "Funding Information: This work is funded by the German Federal Ministry of Education and Research (BMBF) under grant number 02NUK057B and is part of the joint project RADEKOR. L.H. acknowledges funding received from BMBF, grant number 02NUK057D, and J.K. acknowledges funding received from the German Federal Ministry for the Environment, Nature Conversation, Nuclear Safety and Consumer Protection (BMUV) within the GRaZ II project, grant number 02E11860B.",
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day = "31",
doi = "10.3390/molecules28114469",
language = "English",
volume = "28",
journal = "MOLECULES",
issn = "1420-3049",
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Download

TY - JOUR

T1 - Europium(III) Meets Etidronic Acid (HEDP)

T2 - A Coordination Study Combining Spectroscopic, Spectrometric, and Quantum Chemical Methods

AU - Heller, Anne

AU - Senwitz, Christian

AU - Foerstendorf, Harald

AU - Tsushima, Satoru

AU - Holtmann, Linus

AU - Drobot, Björn

AU - Kretzschmar, Jerome

N1 - Funding Information: This work is funded by the German Federal Ministry of Education and Research (BMBF) under grant number 02NUK057B and is part of the joint project RADEKOR. L.H. acknowledges funding received from BMBF, grant number 02NUK057D, and J.K. acknowledges funding received from the German Federal Ministry for the Environment, Nature Conversation, Nuclear Safety and Consumer Protection (BMUV) within the GRaZ II project, grant number 02E11860B.

PY - 2023/5/31

Y1 - 2023/5/31

N2 - Etidronic acid (1-Hydroxyethylidene-1,1-diphosphonic acid, HEDP, H4L) is a proposed decorporation agent for U(VI). This paper studied its complex formation with Eu(III), an inactive analog of trivalent actinides, over a wide pH range, at varying metal-to-ligand ratios (M:L) and total concentrations. Combining spectroscopic, spectrometric, and quantum chemical methods, five distinct Eu(III)−HEDP complexes were found, four of which were characterized. The readily soluble EuH2L+ and Eu(H2L)2− species with log β values of 23.7 ± 0.1 and 45.1 ± 0.9 are formed at acidic pH. At near-neutral pH, EuHL0s forms with a log β of ~23.6 and, additionally, a most probably polynuclear complex. The readily dissolved EuL− species with a log β of ~11.2 is formed at alkaline pH. A six-membered chelate ring is the key motif in all solution structures. The equilibrium between the Eu(III)–HEDP species is influenced by several parameters, i.e., pH, M:L, total Eu(III) and HEDP concentrations, and time. Overall, the present work sheds light on the very complex speciation in the HEDP–Eu(III) system and indicates that, for risk assessment of potential decorporation scenarios, side reactions of HEDP with trivalent actinides and lanthanides should also be taken into account.

AB - Etidronic acid (1-Hydroxyethylidene-1,1-diphosphonic acid, HEDP, H4L) is a proposed decorporation agent for U(VI). This paper studied its complex formation with Eu(III), an inactive analog of trivalent actinides, over a wide pH range, at varying metal-to-ligand ratios (M:L) and total concentrations. Combining spectroscopic, spectrometric, and quantum chemical methods, five distinct Eu(III)−HEDP complexes were found, four of which were characterized. The readily soluble EuH2L+ and Eu(H2L)2− species with log β values of 23.7 ± 0.1 and 45.1 ± 0.9 are formed at acidic pH. At near-neutral pH, EuHL0s forms with a log β of ~23.6 and, additionally, a most probably polynuclear complex. The readily dissolved EuL− species with a log β of ~11.2 is formed at alkaline pH. A six-membered chelate ring is the key motif in all solution structures. The equilibrium between the Eu(III)–HEDP species is influenced by several parameters, i.e., pH, M:L, total Eu(III) and HEDP concentrations, and time. Overall, the present work sheds light on the very complex speciation in the HEDP–Eu(III) system and indicates that, for risk assessment of potential decorporation scenarios, side reactions of HEDP with trivalent actinides and lanthanides should also be taken into account.

KW - ATR-FT-IR

KW - complexation

KW - DFT

KW - ESI-MS

KW - lanthanides

KW - NMR

KW - speciation

KW - TRLFS

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U2 - 10.3390/molecules28114469

DO - 10.3390/molecules28114469

M3 - Article

AN - SCOPUS:85161638522

VL - 28

JO - MOLECULES

JF - MOLECULES

SN - 1420-3049

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