Biomineralization by particle attachment in early animals

Significance The mechanisms by which organisms form mineralized skeletons have been a major research focus for the last 50 y and remain so today. Among the most surprising discoveries is the recent observation that different animals use the same mechanisms, and precisely the same amorphous precursors, to form biomineralized structures as diverse as coral skeletons, molluscan shells, and sea urchin spines. In living animals, skeletal biomineralization from amorphous precursors correlates with a distinctive nanoparticulate texture that can be preserved in fossils, enabling us to probe mechanisms of skeletal formation in early animals. We document nanoparticulate texture in some of the oldest known carbonate skeletons, which strongly suggests that skeletons formed from amorphous precursors throughout the recorded history of animals. Crystallization by particle attachment (CPA) of amorphous precursors has been demonstrated in modern biomineralized skeletons across a broad phylogenetic range of animals. Precisely the same precursors, hydrated (ACC-H2O) and anhydrous calcium carbonate (ACC), have been observed spectromicroscopically in echinoderms, mollusks, and cnidarians, phyla drawn from the 3 major clades of eumetazoans. Scanning electron microscopy (SEM) here also shows evidence of CPA in tunicate chordates. This is surprising, as species in these clades have no common ancestor that formed a mineralized skeleton and appear to have evolved carbonate biomineralization independently millions of years after their late Neoproterozoic divergence. Here we correlate the occurrence of CPA from ACC precursor particles with nanoparticulate fabric and then use the latter to investigate the antiquity of the former. SEM images of early biominerals from Ediacaran and Cambrian shelly fossils show that these early calcifiers used attachment of ACC particles to form their biominerals. The convergent evolution of biomineral CPA may have been dictated by the same thermodynamics and kinetics as we observe today.