New insight on spatial localization and microstructures of calcite-aragonite interfaces in adult shell of Haliotis tuberculata: Investigations of wild and farmed abalones by FTIR and Raman mapping

Abstract

In the present study, we investigated the shell microstructures of the gastropod European abalone Haliotis tuberculata in order to clarify the complex spatial distribution of the different mineral phases. Our studies were carried out with a standardized methodology on thirty adult European abalone H. tuberculata (5–6 cm long) composed of 15 wild individuals and 15 individuals taken from the France Haliotis hatchery. The macroscopic (binocular) and microscopic observations coupled with Fourier Transform Infrared Spectroscopy (FTIR) and Raman vibrational analysis allowed to unambiguously detect, identify and localize calcite and aragonite. For the first time it has been shown that calcite is present in 100% of farmed and wild adult shell. The microstructural details of the calcite-aragonite interfaces were revealed by using both confocal micro-Raman mapping and Scanning Electron Microscopy (SEM) observations. Calcite zones are systematically found in the spherulitic layer without direct contact with the nacreous layer. The calcite area - nacreous layer interface is made of a thin spherulitic layer with variable thickness from a few micrometers to several millimeters.In order to contribute to a better understanding of the biomineralization process, a model explaining the hierarchical arrangement of the different phases of calcium carbonate is presented and discussed. Finally, it has been shown that these calcitic zones can be connected to each other within the shells and that their spatial distributions correspond to streaks perpendicular to the direction of length growth.