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Structural behavior and magnetic properties of coquimbite AlFe33+ (SO4)6(H2O)12·6H2O over a wide temperature range

  • Veronika R. Abdulina , Artem S. Borisov , Oleg I. Siidra ORCID logo EMAIL logo , Victoria A. Ginga , Nicolas Sanchez , Annette Setzer and Astrid Holzheid
Published/Copyright: November 7, 2025
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American Mineralogist
From the journal American Mineralogist Volume 110 Issue 11

Abstract

Hydrated iron sulfate minerals have received considerable attention from the standpoint of environmental science, as well as due to extensive studies on the mineralogy of Mars. In this paper, we report on the thermal evolution of coquimbite AlFe33+SO46H2O12⋅6H2O by single-crystal X-ray diffraction (SCXRD) from −173 to 77 °C. Powder X-ray diffraction (PXRD) was performed in the temperature range of −180 to 740 °C and low vacuum of 600 Pa. Magnetic properties for coquimbite are reported in the range of −271 to 7 °C. It was observed that coquimbite is stable between −180 and + 145 °C and at a low vacuum of 600 Pa. We observed a gradual transition from coquimbite to the amorphous phase at 150 °C, followed by a transition to mikasaite at 225 °C, and a second amorphization at 575 °C, with afterward crystallization to hematite. SCXRD shows that the behavior of coquimbite with increasing temperature can be divided into two stages, with negative and strongly anisotropic thermal expansion at Stage I (−173 to −143 °C) and only positive thermal expansion at Stage II (−133 to 77 °C). All the O-H···O bonds remain virtually intact during Stage I, except for Ow2-H3···O2. The negative thermal expansion observed along the c-axis in the LT range is a result of the simultaneous reduction of several bond lengths and angular distortions: (1) decrease of Ow2-H3···O2 hydrogen bonds oriented approximately along the c-axis; and (2) shrinkage of M3O3(H2O)3 octahedra, evidenced by the decrease in M3-O3 and M3-Ow3 bonds. The nature of the expansion of the coquimbite structure during Stage II is better understood in terms of the orientation of [M2M32(SO4)6(H2O)6]3− clusters along the c-axis. M-O and S-O bonds are only slightly affected by the temperature rise at Stage II, whereas O-H···O angular transformations seem to be the main driving force for the expansion of the coquimbite structure along the α11 direction upon heating.

Coquimbite exhibits distinct magnetic properties compared to other iron sulfates, driven by antiferromagnetic interactions within its M3-M2-M3 trimeric clusters of Fe3+. The presence of Al3+-Fe3+ site mixing in coquimbite introduces structural disorder, partially disrupting its magnetic ordering and contributing to magnetic entropy and magnetization features, such as a 1/3 magnetization plateau.

Keywords: Coquimbite; sulfates; iron; non-ambient single crystal X-ray diffraction; magnetism; non-ambient powder X-ray diffraction; thermal expansion; thermal analysis; Mars

Acknowledgments and Funding

We thank two anonymous reviewers for their comments, which improved the manuscript. Technical support (project# 118201839) by the SPbSU X-ray Diffraction Resource Center is gratefully acknowledged. V.A.G. thanks Alexander A. Tsirlin for stimulating discussions, and his support in analyzing the magnetic properties. V.A.G. was financially supported by DAAD (grant # 91837667).

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Received: 2025-02-09
Accepted: 2025-04-02
Published Online: 2025-11-07
Published in Print: 2025-11-25

© 2025 Mineralogical Society of America

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https://doi.org/10.2138/am-2025-9776
Keywords for this article
Coquimbite; sulfates; iron; non-ambient single crystal X-ray diffraction; magnetism; non-ambient powder X-ray diffraction; thermal expansion; thermal analysis; Mars

Articles in the same Issue

  1. High-resolution analysis of clay minerals and amorphous materials in martian analog environments
  2. Origin and evolution of granitic pegmatite rare metal deposits in the northern Mufushan batholith, South China: Insights from muscovite chemistry
  3. High-energy resolution X-ray absorption spectroscopy study of the state of Pt in pyrite
  4. Nanoscale mapping of ZrSiO4 phases in naturally shocked zircon using electron energy loss spectroscopy
  5. Nanogeochemistry of Ni, Co, and Cu in zoned marcasite-pyrite crystals
  6. Genetic types of Zn-Pb deposits revealed by sphalerite geochemistry
  7. Contribution of Te-Bi melts in gold enrichment at the giant Jiaodong gold province, North China Craton: Insights from the Taishang deposit
  8. Nb-Ta mineralization in a metaluminous-weakly peraluminous magmatic system: Constraints from the chemical compositions and Hf isotopes of columbite-group minerals in China
  9. In situ observation of the subsolidus reactions between petalite and spodumene + quartz in a hydrothermal diamond-anvil cell
  10. Structural behavior and magnetic properties of coquimbite AlFe33+ (SO4)6(H2O)12·6H2O over a wide temperature range
  11. The transformation of magnesium phosphate minerals at atmospheric conditions: Mechanisms, kinetics, and environmental applications
  12. Native tin as solidified molten-metal droplets in a hydrothermal fluid from the epithermal Pukanec deposit (Slovakia)
  13. Wangyanite, PdNi8S8, a new Pd end-member mineral of the pentlandite group from the J-M Reef, Stillwater Complex, Montana, U.S.A.
  14. Crystal chemistry and high-temperature behavior of Al-bearing stishovite and Al-rich phase D: Implications for water storage in the deep mantle
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