Chemical and structural aspects of fresh and fossil marine mollusc shells investigated by mid-infrared and near-infrared spectroscopy with the support of statistical and multivariate methods

Mecozzi, Mauro; Fratte, Riccardo Delle; Pietroletti, Marco; Novelli, Fabrizio; Scacco, Umberto

Chemical and structural aspects of fresh and fossil marine mollusc shells investigated by mid-infrared and near-infrared spectroscopy with the support of statistical and multivariate methods

2022

Mecozzi, Mauro | Fratte, Riccardo Delle | Pietroletti, Marco | Novelli, Fabrizio | Scacco, Umberto

In the present study, we applied Fourier transform infrared (FTIR) and Fourier transform near infrared (FTNIR) spectroscopy to investigate some specific structural aspects of Patella caerulea, Mytilus edulis, Ostrea edulis, and Calista chione shells sampled in different sites. Moreover, for Ostrea edulis and Calista chione, the present study also included fossil samples. As far as FTIR spectroscopy is concerned, the support of statistical and multivariate methods such as the average spectrum (AV), spectral deconvolution, and two-dimensional correlation analysis (2DCOS) allowed to detect structural differences existing within the same mollusc species as a function of the sites they come. These differences can be reasonably linked to the local environmental conditions, which affect the biomineralization pattern of shell formation and growth. These structural differences are related to the calcite, aragonite, Mg-calcite contents, and interactions, as presently observed for fresh and fossil shells. The application of 2DCOS and deconvolution to FTIR spectra also showed the role of the amorphous calcium carbonate (ACC) in the structural characterization of shells, then suggesting the use of a new parameter, the calcite and aragonite to ACC (CAACC) ratio, as a new measurement for the structural characterization of shells. At last, FTNIR spectroscopy allowed detecting the presence of α-helix and β-sheet protein structures in the shells. The results of this study show that also FTIR and FTNIR spectroscopy are able to discern differences in structural characteristics of mollusc shells, a field of environmental studies where scanning electron microscopy and X-ray diffraction are the more widely used methods.

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