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  • Review Article
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Molecular-level understanding of metal ion retention in clay-rich materials

Nature Reviews Earth & Environment volume 3, pages 461–476 (2022)Cite this article

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Abstract

Clay minerals retain or adsorb metal ions in the Earth’s critical zone. Rocks, sediments and soils rich in clay minerals can concentrate rare earth elements (REEs) in ion adsorption-type deposits (IADs) and are similarly effective at metallic contaminant remediation. However, the molecular-scale chemical and physical mechanisms of metal ion retention remain only partly understood. In this Review, we describe the nature, location and energy requirements of metal retention at clay mineral surfaces. Retention originates mainly from electrostatic interactions during cation exchange at low pH and chemical bonding in surface complexation and precipitation at neutral and high pH. Surface complexation can induce surface redox reactions and precipitation mechanisms including neoformation of clay mineral layered structures. In IADs, outer-sphere adsorption is the major retention mechanism of REE ions. By contrast, the use of clay minerals in pollution control relies on various mechanisms that can coexist, including cation exchange, surface complexation and nucleation growth. To more effectively leverage clay mineral–metal interactions in resource recovery and contaminant remediation, complex mechanisms such as surface precipitation and redox reactions must be better understood; for instance, by utilizing advances in quantum mechanical calculations, close combination between synchrotron and simulation techniques, and upscaling of molecular-level information in macroscopic thermokinetic predictive models.

Key points

  • Clay minerals have a diverse array of chemical structures and layer types that lead to a range of metal ion retention mechanisms in Earth’s critical zone. The metal retention capabilities of clay minerals can concentrate rare earth elements (REEs) in ion adsorption-type deposits (IADs) and can also be exploited for metallic industrial waste disposal.

  • Basic metal ion–clay mineral interaction mechanisms include cation exchange, surface complexation, ligand exchange, structural incorporation, surface precipitation (with or without epitaxial growth of neoformed minerals) and precipitation induced by surface redox reactions.

  • Such diversity of retention mechanisms originates from the distinct structures and properties of basal and edge surfaces. Cation exchange on basal surfaces occurs mainly through electrostatics whereas other mechanisms occur through chemical bonding on edge surfaces.

  • REEs in IADs are mainly physically adsorbed on basal surfaces, which are responsible for the high REE extractability (>50%) through ion exchange.

  • Both cation exchange and surface complexation processes occur during the retardation of metallic pollution plumes in waste management applications (radioactive and conventional industrial wastes as well as landfill leachate).

  • Understanding and quantification of the multifaceted and multiscale nature of clay mineral–metal ion interactions necessitate the close combination of experimental and modelling techniques at the molecular level.

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Fig. 1: Clay mineral sheet, layer and particle structures.
Fig. 2: Interaction mechanisms of metal ions with clay minerals.
Fig. 3: Upscaling of information in modelling of radionuclide storage.
Fig. 4: Ion adsorption-type rare earth element deposits.

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Acknowledgements

X.L. was supported by the National Natural Science Foundation of China (Nos. 42125202 and 41872041). C.T., S.G. and M.M.F. acknowledge funding from the EC Horizon 2020 project European Joint Programme on Radioactive Waste Management (EURAD) under Grant Agreement 847593 (WP FUTURE). Research by C.T. at Lawrence Berkeley National Laboratory (LBNL) was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, through its Geoscience programme at LBNL under Contract DE-AC02-05CH11231. C.T. acknowledges a grant overseen by the French National Research Agency (ANR) as part of the ‘Investissements d’Avenir’ Programme LabEx VOLTAIRE, 10-LABX-0100 at Institut des Sciences de la Terre d’Orléans (ISTO). S.G. acknowledges partial funding by an in-house BRGM grant. A.G.K.acknowledges the financial support of the industrial chair ‘Storage and Disposal of Radioactive Waste’ at the IMT-Atlantique, funded by ANDRA,Orano and EDF.

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Authors and Affiliations

  1. State Key Laboratory for Mineral Deposits Research, School of Earth Sciences and Engineering, Nanjing University, Nanjing, China

    Xiandong Liu

  2. Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing, China

    Xiandong Liu

  3. Institut des Sciences de la Terre d’Orléans, Université d’Orléans−CNRS−BRGM, Orléans, France

    Christophe Tournassat

  4. Earth and Environmental Sciences Area, Lawrence Berkeley National Laboratory, Berkeley, CA, USA

    Christophe Tournassat

  5. BRGM, Orléans, France

    Sylvain Grangeon

  6. Laboratoire SUBATECH, Institut Mines-Télécom Atlantique, Nantes, France

    Andrey G. Kalinichev

  7. Department of Earth and Planetary Science, The University of Tokyo, Tokyo, Japan

    Yoshio Takahashi

  8. Laboratory for Waste Management, Paul Scherrer Institute, Villigen, Switzerland

    Maria Marques Fernandes

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  2. Christophe Tournassat
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  3. Sylvain Grangeon
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Contributions

X.L. and C.T. were responsible for the design and compilation of the article. All authors contributed to the writing and editing.

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Correspondence to Xiandong Liu or Christophe Tournassat.

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Nature Reviews Earth & Environment thanks J. Kubicki, B. Sarkar and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Glossary

Clay minerals

A class of hydrated phyllosilicates making up the fine-grained fraction of rocks, sediments and soils.

Metal ions

Metal cations (M) in aqueous solution with the chemical formula [M(H2O)n]z+, metal ions include rare earth elements (REEs), actinides, transition metals, and alkaline and alkaline earth metals.

Earth’s critical zone

The thin layer at Earth’s surface and shallow subsurface, spanning from the canopy to the bottom of groundwater, where soil, water, air and the living interact.

Clay-rich materials

Materials containing clay minerals, such as sediments, soils and weathered rocks, and with physical and chemical properties dominated by their clay mineral fraction.

Complex

A compound consisting of a central atom or ion that is bonded to other atoms or ions, which are called ligands.

Octahedral sheet

A 2D sheet formed by octahedral units, each consisting of a metal cation coordinated by six oxygen atoms, linked to six neighbouring octahedra by shared edges.

Tetrahedral sheets

2D sheets formed by tetrahedral units, each consisting of a metal cation coordinated by four oxygen atoms and linked to three neighbouring tetrahedra by shared oxygen.

2:1 Layers

Structural clay mineral layers made of one octahedral sheet sandwiched by two tetrahedral sheets.

Epitaxial nucleation

The formation of a crystalline nucleus on a substrate, where the new crystalline phase forms with one or more well-defined crystallographic orientations fixed by that of the substrate lattice.

Neutron diffraction

An experimental technique used to probe the crystallographic properties of materials, including the position of hydrogen atoms, notably by taking advantage of the contrasting interactions of neutrons with hydrogen and deuterium.

Synchrotron X-ray reflectivity

An experimental technique used to study the detailed surface properties of solids, based on the analysis of X-rays reflected by a surface.

X-ray absorption spectroscopy

An experimental technique used to study the oxidation state and local environment of an atom in a sample, based on analysis of variations in X-ray absorption over a range of photon energies.

Smectite

A group of 2:1-type clay minerals with expandable interlayer space

Illite

A group of 2:1-type clay minerals with non-expandable interlayer space.

Inner-sphere complex

A complex where the cation is adsorbed on a clay layer with direct chemical contact to the mineral layer surface.

Outer-sphere complexes

Complexes where the cation is adsorbed on a clay layer surface, but is separated by one or more water molecules.

Ligand exchange

A type of reaction in which a ligand of a complex is replaced by a different ligand.

Dioctahedral

A common type of octahedral sheet where most of the metal cations are of +3 valence; two-thirds of the octahedra are occupied whereas the other third is vacant.

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Liu, X., Tournassat, C., Grangeon, S. et al. Molecular-level understanding of metal ion retention in clay-rich materials. Nat Rev Earth Environ 3, 461–476 (2022). https://doi.org/10.1038/s43017-022-00301-z

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