Greigite (Fe3S4) Formation in Artificial Sediments via Solid-State Transformation of Lepidocrocite
Авторы: Roud S., Gilder S., Park S.
2022 г.
GGG
Greigite (Fe3S4) is a ferrimagnetic iron-sulfide mineral that forms in sediments during diagenesis.
Greigite growth can occur diachronously within a stratigraphic profile, complicating or overprinting
environmental and paleomagnetic records. An important objective for paleo- and rock-magnetic studies is to
identify the presence of greigite and to discern its formation conditions. Greigite detection remains, however,
challenging and its magnetic properties obscure due to the lack of pure, stable material of well-defined
grain size. To overcome these limitations, we report a new method to selectively transform lepidocrocite to
greigite via the intermediate phase mackinawite (FeS). In-situ magnetic characterization was performed on
discrete samples with different sediment substrates. Susceptibility and chemical remanent magnetization
increased proportionally over time, defining two distinct greigite growth regimes. Temperature dependent and
constant initial growth rates indicate a solid-state FeS to greigite transformation with an activation energy of
78–90 kJ/mol. Low and room temperature magnetic remanence and coercivity ratios match with calculated
mixing curves for superparamagnetic (SP) and single domain (SD) greigite and suggest ∼25% and ∼50% SD
proportions at 300 and 100 K, respectively. The mixing trend coincides with empirical data reported for natural
greigite-bearing sediments, suggesting a common SP endmember size of 5–10 nm that is likely inherited from
mackinawite crystallites. The average particle size of 20–50 nm determined by X-ray powder diffraction and
electron microscopy accords with theoretical predictions of the SP/SD threshold size in greigite. The method
constitutes a novel approach to synthesize greigite and to investigate its formation in sediments.
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