Technetium Complexation with Multidentate Carboxylate-Containing Ligands: Trends in Redox and Solubility Phenomena

DiBlasi, Nicole A.; Dardenne, Kathy; Prüssmann, Tim; Duckworth, Sarah; Altmaier, Marcus; Gaona, Xavier

doi:10.1021/acs.est.2c09360

Technetium Complexation with Multidentate Carboxylate-Containing Ligands: Trends in Redox and Solubility Phenomena

Journal Article · Fri Feb 24 00:00:00 EST 2023 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.2c09360· OSTI ID:1960196

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Karlsruhe Inst. of Technology (KIT) (Germany)

The chemistry of technetium (t_1/2(⁹⁹Tc) = 2.11 × 10⁵ years) is of particular importance in the context of nuclear waste disposal and historic contaminated sites. Polycarboxylate ligands may be present in some sites and are potentially capable of strong complexing interactions, thus increasing the solubility and mobility of ⁹⁹Tc under environmentally relevant conditions. This work aimed to determine the impact of five organic complexing ligands [L = oxalate, phthalate, citrate, nitrilotriacetate (NTA), and ethylenediaminetetraacetate (EDTA)] under anoxic, alkaline conditions (pH ≈ 9–13) on the solubility of technetium. X-ray absorption spectroscopy confirmed that TcO₂(am,hyd) remained the solubility-controlling solid phase in undersaturation solubility experiments. Ligands with maximum coordination numbers (CN) ≥ 3 (EDTA, NTA, and citrate) exhibited an increase in solubility from pH 9 to 11, while ligands with CN ≤ 2 (oxalate and phthalate) at all investigated pH and CN ≥ 3 at pH ≈ 13 were outcompeted by hydrolysis reactions. Though most available thermodynamic values were determined under acidic conditions, these models satisfactorily explained high-pH undersaturation solubility of technetium for citrate and NTA, whereas experimental data for Tc(IV)–EDTA were highly overestimated. Finally, this work illustrates the predominance of hydrolysis under hyperalkaline conditions and provides experimental support for existing thermodynamic models of Tc–L except Tc–EDTA, which requires further research regarding aqueous speciation and solubility.

View Accepted Manuscript (DOE)

Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: German Federal Ministry for Economic Affairs and Climate Action (BMWK); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1960196

Report Number(s):: LA-UR-22-33017

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 9 Vol. 57; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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complexation
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thermodynamics

Technetium Complexation with Multidentate Carboxylate-Containing Ligands: Trends in Redox and Solubility Phenomena

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