Local strain heterogeneity associated with Al/Si ordering in anorthite, CaAl₂Si₂O₈, with implications for thermodynamic mixing behavior and trace element partitioning in plagioclase feldspars

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Atkinson, Alison J. ; Boffa Ballaran, Tiziana ; Carpenter, Michael A.:
Local strain heterogeneity associated with Al/Si ordering in anorthite, CaAl₂Si₂O₈, with implications for thermodynamic mixing behavior and trace element partitioning in plagioclase feldspars.
In: American Mineralogist. Bd. 109 (2024) Heft 7 . - S. 1292-1302.
ISSN 1945-3027
DOI: https://doi.org/10.2138/am-2023-9197

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Abstract

Hard Mode IR powder absorption spectroscopy has been used to characterize local strain relaxation associated with Al/Si ordering in a suite of synthetic anorthite samples with structural states that vary from a high degree of Al/Si order through a metastable incommensurate structure at intermediate states of order to long-range order with I1 symmetry. The dominant feature accompanying the changing structural states is line broadening, which has been quantified by autocorrelation analysis and is attributed to local heterogeneous strain variations on a length scale of at least 1–5 unit cells. The autocorrelation results are consistent with contributions to the line broadening as being due to order parameters for both the C1 → I1 and I1 → P1 transitions, which couple biquadratically, λQod2Qdispl2. Close correlation with enthalpy variations from previously published calorimetric data indicates that the driving force for ordering can be understood in terms of elimination of strain fields arising from accommodating more or less rigid AlO4 and SiO4 tetrahedra in the feldspar framework. The metastable incommensurate structure of anorthite is closely analogous to the stable incommensurate structure that develops at intermediate compositions in the plagioclase solid solution, confirming that the same strain relaxation mechanism dominates the properties and behavior of all structural states across the solid solution. Elimination of strain heterogeneity by ordering on the basis of I1 symmetry determines the form of non-ideal mixing shown by the solid solution at high temperatures, and changes in elastic properties may contribute to a break in the slope of partitioning of trace elements between crystals and melt.