U.S. Department of Energy


Date of this Version



Published in J. Phys. Chem. B, Vol. 112, No. 41, 2008.


Many biominerals, including mollusk and echinoderm shells, avian eggshells, modern and fossil bacterial sediments, planktonic coccolithophores, and foraminifera, contain carbonates in the form of biogenic aragonite or calcite. Here we analyze biogenic and geologic aragonite using different kinds of surface- and bulksensitive X-ray absorption near-edge structure (XANES) spectroscopy at the carbon K-edge, as well as highresolution scanning transmission X-ray microscopy (STXM). Besides the well-known main π* and σ* carbonate peaks, we observed and fully characterized four minor peaks, at energies between the main π* and σ* peaks. As expected, the main peaks are similar in geologic and biogenic aragonite, while the minor peaks differ in relative intensity. In this and previous work, the minor peaks appear to be the ones most affected in biomineralization processes, hence the interest in characterizing them. Peak assignment was achieved by correlation of polarization-dependent behavior of the minor peaks with that of the main π* and σ* peaks. The present characterization provides the background for future studies of aragonitic biominerals.