Abstract
Fe(II) only occupies octahedral sites in phyllosilicates, whereas Fe(III) can occupy both octahedral and tetrahedral sites. The controls on Fe(III) distribution between tetrahedral and octahedral sites have been a matter of great interest to understand the interplay between formation environment (Fe abundance, redox conditions) and crystal-chemical factors (stability of the crystal lattice) during crystallization of Fe-phyllosilicates. Here, for the first time, we present a model of Fe(III) distribution in 2:1 phyllosilicates. We investigated 21 samples of 2:1 phyllosilicates of submarine hydrothermal origin using XRD, chemical analysis, and Mössbauer spectroscopy (and other supporting techniques not presented here). An additional data set of 49 analyses of 2:1 phyllosilicates from the literature was also used. Overall, the data cover a wide range of dioctahedral and trioctahedral phyllosilicates, including end-member minerals and interstratified phases. Dioctahedral phyllosilicates have a steric control whereby tetrahedral Fe(III) is only allowed if at least five out of six octahedral atoms are larger than Al (typically Fe[III], Fe[II], Mg) that produces an expanded structure where tetrahedral sites can accommodate Fe(III). After this threshold, further Fe(III) atoms occupy tetrahedral sites preferentially (~73% of further Fe[III] atoms) over octahedral sites. In trioctahedral 2:1 phyllosilicates there is no steric hindrance to tetrahedral Fe(III) because the crystal dimensions are such that tetrahedral sites can accommodate Fe(III). On average, Fe(III) enters tetrahedral and octahedral sites in similar proportion, and the only apparent control on tetrahedral Fe(III) abundance is Fe(III) availability during crystallization. This model allows to predict Fe(III) distribution between structural sites, provides an avenue for further exploration of the thermodynamic stability of phyllosilicates using cationic size, and provides a tool to better describe stability/reactivity of Fe-rich phyllosilicates, the most reactive of phyllosilicates and very relevant in geochemical and biological processes.
Acknowledgments and Funding
This study was funded by the IEF Marie Curie program of the EC (Hydro-Mars). E.A. Breves and M. Nelms are thanked for help with Mössbauer data processing. The comments of A. Baldermann and an anonymous reviewer greatly helped to improve this article.
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Artikel in diesem Heft
- Crossroads in Earth and Planetary Materials
- Computer modeling of apparently straight bond angles: The intriguing case of all-silica ferrierite
- Composite materials based on zeolite stilbite from Faroe Islands for the removal of fluoride from drinking water
- The Italian Solfatara as an analog for Mars fumarolic alteration
- Change of crackling noise in granite by thermal damage: Monitoring nuclear waste deposits
- Constraining the timing and character of crustal melting in the Adirondack Mountains using multi-scale compositional mapping and in-situ monazite geochronology
- Melting in the Fe-FeO system to 204 GPa: Implications for oxygen in Earth’s core
- Controls on tetrahedral Fe(III) abundance in 2:1 phyllosilicates
- Stability, composition, and crystal structure of Fe-bearing Phase E in the transition zone
- Enrichment of manganese to spessartine saturation in granite-pegmatite systems
- Al and Si diffusion in rutile
- Sound velocity of neon at high pressures and temperatures by Brillouin scattering
- A Cr3+ luminescence study of natural topaz Al2SiO4(F,OH)2 up to 60 GPa
- Two generations of exsolution lamellae in pyroxene from Asuka 09545: Clues to the thermal evolution of silicates in mesosiderite
- Crystallographic and fluid compositional effects on the halogen (Cl, F, Br, I) incorporation in pyromorphite-group minerals
- Diffusion of F and Cl in dry rhyodacitic melt