Startseite Synthesis of ferrian and ferro-saponites: Implications for the structure of (Fe,Mg)-smectites formed under reduced conditions
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Synthesis of ferrian and ferro-saponites: Implications for the structure of (Fe,Mg)-smectites formed under reduced conditions

  • Hiroshi Sakuma ORCID logo , Koki Morida , Yoshio Takahashi , Keisuke Fukushi , Natsumi Noda , Yasuhito Sekine und Kenji Tamura
Veröffentlicht/Copyright: 29. September 2022
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American Mineralogist
Aus der Zeitschrift American Mineralogist Band 107 Heft 10

Abstract

Clay minerals are widely distributed on the surface of Earth, Mars, and Ceres in the solar systems. Among numerous clay minerals, smectites can record the history of the environment through the exchange of interlayer cations with those in water or through redox reactions with the atmosphere. Therefore, characterization of chemical compositions and crystal structures of smectites is crucial for revealing the paleoenvironment. For instance, the crystal structure within octahedral sheets of iron-bearing smectites changes to trioctahedral sheets under reduced or dioctahedral sheets under oxidizing conditions. Orbital infrared and X‑ray diffraction (XRD) analyses by Mars orbiters/rovers revealed the presence of (Fe,Mg)-smectites on the surface of Mars; however, it has been difficult to characterize the properties of these (Fe,Mg)-smectites, which are rare on the surface of Earth. In this study, we synthesized ferrian (ferric ion-rich) and ferrous (ferrous ion-rich) (Fe,Mg)-saponite and revealed the effect of valence states and iron contents on the crystal structures. These saponites were synthesized using a hydrothermal method under reduced conditions. The crystal structures and valence states of iron were analyzed by XRD, Fourier-transform infrared spectroscopy, transmission electron microscopy, Mössbauer spectroscopy, and X‑ray absorption near edge measurements. The synthesized clays were trioctahedral swelling clays and were identified as saponites. The valence state of iron in these synthesized saponites is altered by oxygen and a reducing agent in water; however, the trioctahedral structures are maintained under both oxidizing and reduced conditions, following a reversible reaction. This mechanism can be interpreted by the desorption and adsorption of hydrogen in the hydroxyls of the octahedral sheets of the smectite layers. The maximum basal spacing of the (02l) lattice plane in the octahedral sheets was defined by compiling various smectite data. When the basal spacing of (02l) is larger than the maximum in dioctahedral smectites, smectite can be identified as trioctahedral smectite. The redox state of iron in the octahedral sheet cannot be determined from the basal spacing of (02l). We revealed that the iron content in the trioctahedral sheet has a linear relationship with lattice parameter b. This provides a method to estimate the iron content in saponite from XRD data. The XRD profiles of smectites found at the Yellowknife Bay on Mars can be explained only by trioctahedral smectites, and the iron content in the octahedral sheet is roughly estimated to be 0.5–1.7 in a half-unit cell. These results indicate that the presence of (Fe,Mg)-saponite implies a reduced environment during the formation and that this iron-bearing saponite has both oxidation and reduction capabilities depending on the environment.

Keywords: Reduction; oxidization; smectites; XRD; XANES; clay mineralogy; Mars

Acknowledgments and Funding

We thank M. Mitome, K. Kurashima, and Y. Owada (NIMS) for collecting and interpreting the TEM data, and A. Iwanade (NIMS) for his assistance with the wet chemical analysis. Comments on the experiments by K. Hashi (NIMS) are also appreciated. This work was supported by JSPS KAKENHI (Grant Number JP17H06458).

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Received: 2021-07-27
Accepted: 2021-10-19
Published Online: 2022-09-29
Published in Print: 2022-10-26

© 2022 Mineralogical Society of America

Artikel in diesem Heft

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https://doi.org/10.2138/am-2022-8231
Schlagwörter für diesen Artikel
Reduction; oxidization; smectites; XRD; XANES; clay mineralogy; Mars

Artikel in diesem Heft

  1. Experimentally derived F, Cl, and Br fluid/melt partitioning of intermediate to silicic melts in shallow magmatic systems
  2. Spectroscopic study on the local structure of sulfate ( S O 4 2 − ) incorporated in scorodite (FeAsO4·2H2O) lattice: Implications for understanding the Fe(III)-As(V)- S O 4 2 − -bearing minerals formation
  3. Oxidation of arcs and mantle wedges by reduction of manganese in pelagic sediments during seafloor subduction
  4. Raman scattering and Cr3+ luminescence study on the structural behavior of δ-AlOOH at high pressures
  5. Jadeite and related species in shocked meteorites: Limitations on inference of shock conditions
  6. Pressure-induced C23–C37 transition and compression behavior of orthorhombic Fe2S to Earth’s core pressures and high temperatures
  7. Estimating ferric iron content in clinopyroxene using machine learning models
  8. Pyradoketosite, a new, unexpected, polymorph of Ag3SbS3 from the Monte Arsiccio mine (Apuan Alps, Tuscany, Italy)
  9. Pyrite geochemistry and its implications on Au-Cu skarn metallogeny: An example from the Jiguanzui deposit, Eastern China
  10. Synthesis of ferrian and ferro-saponites: Implications for the structure of (Fe,Mg)-smectites formed under reduced conditions
  11. Natural cubic perovskite, Ca(Ti,Si,Cr)O3–δ, a versatile potential host for rock-forming and less-common elements up to Earth’s mantle pressure
  12. Nazarovite, Ni12P5, a new terrestrial and meteoritic mineral structurally related to nickelphosphide, Ni3P
  13. Zinconigerite-2N1S ZnSn2Al12O22(OH)2 and zinconigerite-6N6S Zn3Sn2Al16O30(OH)2, two new minerals of the nolanite-spinel polysomatic series from the Xianghualing skarn, Hunan Province, China
  14. Tracing structural relicts of the ikaite-to-calcite transformation in cryogenic cave glendonite
  15. Oxygen-fugacity evolution of magmatic Ni-Cu sulfide deposits in East Kunlun: Insights from Cr-spinel composition
  16. New Mineral Names
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