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This chapter provides a short review of results that have been obtained on the structure and chemistry of mineral solid solutions using diffraction methods. It is written to provide a simple, sometimes even colloquial, discussion of tie type of information, loosely termed long-range, that can be determined in the study of complex chemical/structural systems such as minerals. Different aspects will be illustrated through the extensive crystal-chemical studies made at the CNR-CSCC in Pavia, Italy, combining X-ray single-crystal structure refinements with in situ electron-microprobe and ion-microprobe analysis. The same general approach can be applied to structural data obtained by other long-range techniques (e.g., powder diffraction and neutron and electron scattering measurements).

For a review of the theory and the practical aspects relating to crystal-structure analysis, the reader is referred to the IUCr text Fundamentals of crystallography (edited by C. Giacovazzo, 1992). For questions related to refinement procedures, one can consult the review regarding difficult refinements by Watkin (1994) and the proper chapter of the International tables for crystallography (Albinati et al., 1992). The website of the IUCr ( also provides a mine of useful information. Further references on crystallographic studies of solid solutions and more detailed discussion can be found in individual works or by use of search programs for the mineralogical literature.

The formation of a mineral solid solution results from the interplay between a chemically complex environment and the ability of many structures to incorporate different ions at the same structural site.

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