The macroscopic behaviour of minerals is not always directly related to their crystalline structure at the atomic scale but often depends explicitly on mesoscopic (nanometer–micrometer) features. This paper reviews various cases where the macroscopic phenomena differ from those of the bulk, with structural and chemical variations related to: domain walls, leading to enhanced or reduced transport properties; surfaces controlling growth morphologies; and radiation-damaged minerals where the interface between the amorphous and crystalline phase is believed to play a key role in hydrothermal leaching behaviour. Minerals explicitly discussed are: quartz, agate, hydroxylapatite, cordierite and metamict zircon.

A brief review is given of the ways in which the local structure in glass can influence the microstructure that supports ionic transport. This in turn contributes to the co-operative nature of ion dynamics and ways in which this underpins the ‘mixed alkali effect’ are discussed. Glass microstructure too is expected to affect glass fracture as well as the chemistry of glass surfaces. In melts, though, these restrictions appear to vanish as the rigidity of intermediate range order is lost.