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

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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. Bd. 10 (2020) Heft 12 . - 1090.
ISSN 2075-163X
DOI: https://doi.org/10.3390/min10121090

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Abstract

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.

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Publikationsform: Artikel in einer Zeitschrift
Begutachteter Beitrag: Ja
Keywords: mackinawite; iron sulfide; lepidocrocite; polysulfide; Mössbauer spectroscopy; electronic configuration; magnetic hyperfine field; quadrupole splitting; Debye model
Institutionen der Universität: Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften
Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Geowissenschaften
Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Geowissenschaften > Lehrstuhl Hydrologie
Fakultäten > Fakultät für Biologie, Chemie und Geowissenschaften > Fachgruppe Geowissenschaften > Lehrstuhl Hydrologie > Lehrstuhl Hydrologie - Univ.-Prof. Dr. Stefan Peiffer
Fakultäten
Titel an der UBT entstanden: Ja
Themengebiete aus DDC: 500 Naturwissenschaften und Mathematik > 500 Naturwissenschaften
500 Naturwissenschaften und Mathematik > 550 Geowissenschaften, Geologie
Eingestellt am: 23 Dec 2020 08:03
Letzte Änderung: 30 Aug 2023 13:21
URI: https://eref.uni-bayreuth.de/id/eprint/61383