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Carbonated hydroxyapatite is the mineral found in vertebrate bones and teeth, whereas invertebrates utilize calcium carbonate in their mineralized organs. In particular, stable amorphous calcium carbonate is found in many crustaceans. Here we report on an unusual, crystalline enamel-like apatite layer found in the mandibles of the arthropod Cherax quadricarinatus (freshwater crayfish). Despite their very different thermodynamic stabilities, amorphous calcium carbonate, amorphous calcium phosphate, calcite and fluorapatite coexist in well-defined functional layers in close proximity within the mandible. The softer amorphous minerals are found primarily in the bulk of the mandible whereas apatite, the harder and less soluble mineral, forms a wear-resistant, enamel-like coating of the molar tooth. Our findings suggest a unique case of convergent evolution, where similar functional challenges of mastication led to independent developments of structurally and mechanically similar, apatite-based layers in the teeth of genetically remote phyla: vertebrates and crustaceans.

The exoskeleton of the American lobster Homarus americanus is a hierarchical nanocomposite consisting of chitin–protein fibers, reinforced with amorphous calcium carbonate (ACC) and a small amount of crystalline calcite. Crystallographic pole‐figure analysis reveals two texture components of the crystalline α‐chitin in the exoskeleton. One component represents the well‐known twisted plywood structure of chitin–protein fibers within the cuticle plane, and the second component represents fibers oriented roughly perpendicular to the cuticle surface. These perpendicular fibers interpenetrate the open canals of the planar honeycomblike structure originating from the well‐developed pore‐canal system present in this material. The calcite crystallites reveal fiber texture with the crystallographic c‐axis oriented perpendicular to the cuticle surface, suggesting an orientation relationship between calcite and the organic chitin–protein fibers. Local orientation analysis using X‐ray microdiffraction reveals that the crystalline calcium carbonate fraction is associated with the chitin–protein fibers oriented perpendicular to the surface. Calcite is exclusively found in the exocuticle and is mostly restricted to a thin layer in the outermost region, while the major part of the exocuticle and the whole endocuticle contain ACC exclusively. It is therefore speculated that the most likely function of calcite in the exoskeleton of the American lobster is related to impact‐ and wear‐resistance.

In situ X‐ray diffraction during heating of lobster cuticle reveals three regions of thermally induced transformations: 1)Chitin decomposition, 2) amorphous calcium carbonate (ACC) – calcite transformation, and 3) amorphous calcium phosphate (ACP) – hydroxyapatite transformation. These results provide new insights into the stabilization mechanisms of amorphous biominerals based on ACC and ACP.

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