Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals

TL;DR

This study reveals that nanoparticle-mediated nucleation introduces imperfections in anhydrite crystals, leading to mesocrystalline disorder while maintaining overall single crystal properties, providing insights into mineral formation processes.

Contribution

It demonstrates how non-classical nucleation pathways create structural imperfections in natural anhydrite crystals, linking nanoscale processes to macroscopic crystal features.

Findings

Nanoparticle misalignment propagates across scales.

Imperfections lead to mesocrystalline disorder.

Crystals retain single crystal characteristics despite defects.

Abstract

In recent years, we have come to appreciate the astounding intricacy of the formation process of minerals from ions in aqueous solutions. In this context, a number of studies have revealed that nucleation in the calcium sulfate system is non-classical, involving the aggregation and reorganization of nanosized prenucleation particles. In a recent work we have shown that this particle-mediated nucleation pathway is actually imprinted in the resultant single micron-sized CaSO4 crystals. This property of CaSO4 minerals provides us with an unique opportunity to search for evidence of non-classical nucleation pathways in geological environments. In particular, we focused on the quintessential single crystals of anhydrite extracted from the Naica mine in Mexico. We elucidated the growth history from this mineral sample by mapping growth defects at different length scales. Based on these data we argue that the nano-scale misalignment of the structural sub-units observed in the initial calcium sulfate crystal seed propagate through different length-scales both in morphological, as well as strictly crystallographic aspects, eventually causing the formation of large mesostructured single crystals of anhydrite. Hence, the nanoparticle mediated nucleation mechanism introduces a 'seed of imperfection', which leads to a macroscopic single crystal, in which its fragments do not fit together at different length-scales in a self-similar manner. Consequently, anisotropic voids of various sizes are formed with very well-defined walls/edges. But, at the same time the material retains its essential single crystal nature. These findings shed new light on the longstanding concept of crystal structure.