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Identification of Mackinawite and Constraints on Its Electronic Configuration Using Mössbauer Spectroscopy

Title data

Schröder, Christian ; Wan, Moli ; Butler, Ian B. ; Tait, Alastair ; Peiffer, Stefan ; McCammon, Catherine:
Identification of Mackinawite and Constraints on Its Electronic Configuration Using Mössbauer Spectroscopy.
In: Minerals. Vol. 10 (2 December 2020) Issue 12 . - No. 1090.
ISSN 2075-163X
DOI: https://doi.org/10.3390/min10121090

Abstract in another language

The Fe(II) monosulfide mineral mackinawite (FeS) is an important phase in low-temperature iron and sulfur cycles, yet it is challenging to characterize since it often occurs in X-ray amorphous or nanoparticulate forms and is extremely sensitive to oxidation. Moreover, the electronic configuration of iron in mackinawite is still under debate. Mössbauer spectroscopy has the potential to distinguish mackinawite from other FeS phases and provide clarity on the electronic configuration, but conflicting results have been reported. We therefore conducted a Mössbauer study at 5 K of five samples of mackinawite synthesized through different pathways. Samples show two different Mössbauer patterns: a singlet that remains unsplit at all temperatures studied, and a sextet with a hyperfine magnetic field of 27(1) T at 5 K, or both. Our results suggest that the singlet corresponds to stoichiometric mackinawite (FeS), while the sextet corresponds to mackinawite with excess S (FeS1+x). Both phases show center shifts near 0.5 mm/s at 5 K. Coupled with observations from the literature, our data support non-zero magnetic moments on iron atoms in both phases, with strong itinerant spin fluctuations in stoichiometric FeS. Our results provide a clear approach for the identification of mackinawite in both laboratory and natural environments.

Further data

Item Type: Article in a journal
Refereed: Yes
Keywords: mackinawite; iron sulfide; lepidocrocite; polysulfide; Mössbauer spectroscopy; electronic configuration; magnetic hyperfine field; quadrupole splitting; Debye model
Institutions of the University: Faculties > Faculty of Biology, Chemistry and Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Earth Sciences
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Earth Sciences > Chair Hydrology
Faculties > Faculty of Biology, Chemistry and Earth Sciences > Department of Earth Sciences > Chair Hydrology > Chair Hydrology - Univ.-Prof. Dr. Stefan Peiffer
Result of work at the UBT: Yes
DDC Subjects: 500 Science > 500 Natural sciences
500 Science > 550 Earth sciences, geology
Date Deposited: 23 Dec 2020 08:03
Last Modified: 23 Dec 2020 08:03
URI: https://eref.uni-bayreuth.de/id/eprint/61383