Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. II: insights from STEM-EDXS and DFT calculations

Yokosawa, Tadahiro; Prestat, Éric; Polly, Robert; Bouby, M.; Dardenne, Kathy; Finck, N.; Haigh, Sarah J.; Denecke, Melissa A.; Geckeis, Horst

doi:10.1007/s11356-018-1904-7

Cited by 5 publications

(6 citation statements)

References 59 publications

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“…In sample T2, particles have sizes of about 100-200 nm and in T2 super needles have about 10-30 nm in diameter and < 500 nm in length. These values are consistent with those obtained by transmission electron microscopy (Yokosawa et al 2018).…”

Section: Morphology Mineralogical and Elemental Compositionssupporting

confidence: 92%

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Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. I: insights from ICP-OES, XRD, ESEM, AsFlFFF/ICP-MS, and EXAFS spectroscopy

Finck

Bouby

Dardenne

2018

Environ Sci Pollut Res

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Two-line ferrihydrite (2LFh) was aged for 12 years under ambient conditions and sheltered from light in the presence of Lu(III) used as surrogate for trivalent actinides. 2LFh aging produced hematite rhombohedra with overgrown acicular goethite particles. Analysis of the homogeneous suspension by asymmetrical flow field-flow fractionation (AsFlFFF) coupled to ICP-MS indicated that particles have a mean hydrodynamic diameter of about 140 nm and the strong correlation of the Fe and Lu fractograms hinted at a structural association of the lanthanide with the solid phase(s). Unfortunately, recoveries were low and thus results cannot be considered representative of the whole sample. The suspension was centrifuged and X-ray absorption spectroscopy (XAS) at the Lu L -edge on the settled particles indicated that Lu(III) is sixfold coordinated by oxygen atoms, pointing to a retention by structural incorporation within particles. This result is consistent with AsFlFFF results on the same suspension without centrifugation. The detection of next nearest Fe and O atoms were consistent with the structure of goethite, ruling out incorporation within hematite. After centrifugation of the suspension, only nanoparticulate needle-like particles, very likely goethite, could be detected in the supernatant by ESEM. AsFlFFF data of the supernatant were comparable to that obtained for the homogeneous suspension, whereas XAS indicated that Lu(III) is predominantly present as dissolved species in the supernatant. Results from both techniques can be interpreted as a major fraction of Lu present as aqueous ions and a minor fraction as structurally incorporated. Findings from this study are corroborated by STEM-HAADF data and results from DFT calculations in a companion paper.

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Section: Morphology Mineralogical and Elemental Compositionssupporting

confidence: 92%

“…Information on the retention mode and on the nature of the host phase was obtained by X-ray absorption spectroscopy at the Lu L 3 -edge. Complementary STEM-HAADF investigations on the same sample and DFT calculations will be presented in an companion paper (Yokosawa et al 2018).…”

Section: Introductionmentioning

confidence: 99%

Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. I: insights from ICP-OES, XRD, ESEM, AsFlFFF/ICP-MS, and EXAFS spectroscopy

Finck

Bouby

Dardenne

2018

Environ Sci Pollut Res

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“…Similarly, Sun et al carried out DFT calculations using different cluster models for the brucite layer. Our theoretical approach to investigate radionuclide interaction with GR is a continuation of previous theoretical attempts on similar systems (see, for example, refs and ).…”

Section: Introductionmentioning

confidence: 99%

First Principle Investigation of the Incorporation of Trivalent Lanthanides and Actinides in Hydroxycarbonate and Hydroxychloride Green Rust

et al. 2022

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In this work, we present first principle density functional theory calculations on hydroxycarbonate and hydroxychloride green rust. Green rust is a layered mineral, with brucitelike layers of Fe(OH) 2 . It is an important corrosion product of iron present in the near field of a nuclear waste disposal site. Substitution of a part of the Fe 2+ by Fe 3+ creates a layer charge, which is compensated by interlayer anions (e.g., carbonate or chloride). The simultaneous presence of Fe 2+ /Fe 3+ in the brucite layer of green rust is a considerable theoretical challenge due to the open shell ground states of Fe 2+ /Fe 3+ . We fully characterized the lattice parameters and the internal coordinates of pure hydroxycarbonate and hydroxychloride green rust and reproduced the available experimental structural data to a very high accuracy. Based on these results, we investigated the incorporation of trivalent lanthanides and actinides into the brucite layer of green rust by replacing Fe 3+ and obtained internuclear distances in agreement with available experimental results. We show that the incorporation in all investigated green rust variants is structurally possible. The Am 3+ −O distances are in good agreement with experimental data [Finck, N.; Nedel, S.; Dideriksen, K.; Schlegel, M. L. Trivalent Actinide Uptake by Iron (Hydr)oxides. Environ. Sci. Technol. 2016, 50, 10428], whereas the agreement of the calculated and measured Am 3+ −Fe distances is less satisfactory. We demonstrated that DFT+U is a very reliable theoretical method for the theoretical investigation of hydroxycarbonate and hydroxychloride green rust and the incorporation of trivalent lanthanides and actinides into these layered double hydroxides.

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“…Along with phase transformation, various metal ions are often associated with ferrihydrite, leading to the variation of stability and mobility of metals in terrestrial environments. Aging studies of ferrihydrite with metals (e.g., Cd(II), Mn(II), Ni(II), and Pb(II)) showed that the transformation reactions were influenced by the structural incorporation of metals into recrystallized oxides. , A few studies showed that the phase transformation of ferrihydrite was also affected by adsorbed REEs (e.g., Lu(III)). , However, the mechanisms responsible for the suppressed ferrihydrite transformation by REEs are not clearly understood.…”

Section: Introductionmentioning

confidence: 99%

“…25,26 A few studies showed that the phase transformation of ferrihydrite was also affected by adsorbed REEs (e.g., Lu(III)). 27,28 However, the mechanisms responsible for the suppressed ferrihydrite transformation by REEs are not clearly understood.…”

Section: ■ Introductionmentioning

confidence: 99%

Ferrihydrite Transformation Impacted by Adsorption and Structural Incorporation of Rare Earth Elements

Yang

Liang

Liu

et al. 2021

ACS Earth Space Chem.

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Understanding the association of rare earth elements (REEs) with iron (oxyhydr)oxides is of great interest in the recovery of REEs from regolith and weathered soils in the world. The objective of this study was to understand the effects of 1 mg L–1 REEs on the ferrihydrite transformation process. Ferrihydrite was synthesized at pH 5 and 7 in the presence of REEs, and the transformation products were characterized using X-ray diffraction, Fe K-edge X-ray absorption spectroscopy, and transmission electron microscopy. During the phase transformation process after 60–120 days, the retention of REEs varied with the REE atomic number. In general, heavy REEs preferably partitioned in aged (≥90 days) ferrihydrite more than light REEs, especially at pH 5. At pH 5, the transformation of ferrihydrite to goethite was retarded by ∼12% when REEs were present. The average structural substitution of REEs was as high as ∼550 mg kg–1, and the substitution of heavy REEs such as Yb and Lu was a critical factor to suppress the ferrihydrite transformation. At pH 7, the formation of hematite was retarded by ∼10%, and the structural incorporation of REEs was more important than adsorbed REEs during the first 30 days. There was no REE-specific retention in aged iron (oxyhydr)oxides at pH 7. The results of this study may explain the association of REEs with iron (oxyhydr)oxides, especially heavy REEs in mildly acidic regolith and weathered soils. This study advanced our understanding of the aqueous geochemical behavior of REEs in iron (oxyhydr)oxide-rich supergene environments.

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Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. II: insights from STEM-EDXS and DFT calculations

Cited by 5 publications

References 59 publications

Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. I: insights from ICP-OES, XRD, ESEM, AsFlFFF/ICP-MS, and EXAFS spectroscopy

Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. I: insights from ICP-OES, XRD, ESEM, AsFlFFF/ICP-MS, and EXAFS spectroscopy

First Principle Investigation of the Incorporation of Trivalent Lanthanides and Actinides in Hydroxycarbonate and Hydroxychloride Green Rust

Ferrihydrite Transformation Impacted by Adsorption and Structural Incorporation of Rare Earth Elements

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