Electron Spin Resonance Studies of Mn²⁺ in Freshwater Snail Shells: Pomacea Canaliculata Lamarck and Fossilized Snail Shell

We study paramagnetic Mn²⁺ ions present in the nowadays shells of univalve freshwater snails of Pomacea canaliculata lamarck (PCL) and the fossilized freshwater snail (FFS), Viviparus. All these shells are abundant in Thailand. The PCL shells were ground into fine powder. A set of seven samples were then separately annealed for 2 h in air atmosphere at different annealing temperatures while the FFS powder was characterized as-received. The PCL shells mainly consist of aragonite and a fraction of calcite. The heat treatments of the PCL powder samples at temperature higher than 450 degrees C resulted in an irreversible phase transformation from aragonite to calcite. However, it is found that the FFS shell is mainly made of calcite, with a minor fraction of aragonite. The crystal structure of the high-temperature-annealed PCL samples are quite similar to that of FFS, which indicates that the metamorphosis (aragonite → calcite) in the FFS shell had occurred but was not yet completed, although it had remained under the pressure and temperature of the Earth's crusts over millions of years. Our detailed ESR spectral analyses of PCL and FFS show that Mn²⁺ ions enter the Ca²⁺ sites during a biomineralization process. Simulated ESR parameters of PCL-500 of Mn²⁺ at a uniaxial site of calcite are reported. It is surprising to find that the ratio of Mn²⁺ concentration present in FFS to those in PCL shells evaluated from ESR spectra is as much as 10:1.