Evidence for a Liquid Precursor to Biomineral Formation

Abstract

The crystals in animal biominerals, such as sea urchin spines, mollusk shells, and coral skeletons, form by attachment of amorphous particles that subsequently crystallize. Do these solid amorphous precursor particles have liquid precursors? Polymer-induced liquid precursors (PILP) or prenucleation clusters coalescing into a liquid precursor to calcium carbonate crystallization have been observed extensively in synthetic systems. Molecular dynamics simulations also predict liquid-liquid phase separation. However, evidence for liquid precursors in natural biominerals remains elusive. Here, we present Scanning or PhotoEmission Electron Microscopy (SEM or PEEM) evidence consistent with a dense liquid-like precursor in regenerating sea urchin spines. The observed precursor originates in tissue and ultimately transforms into a single crystal of calcite (CaCO3) with complex stereom morphology.