Manganese speciation in Diplodon chilensis patagonicus shells: A XANES study

X-ray absorption near-edge spectroscopy (XANES) at the Mn K-edge was used to investigate the environment of Mn in situ within the growth increments of the long-lived freshwater bivalve species Diplodon chilensis patagonicus. Single XANES spectra and Mn Kα fluorescence distributions were acquired at submillimetre resolution (up to 100 μm × 50 μm), at Mn concentrations below the weight percent range (100-1000 μg g^-1) in a high Ca matrix. The position and intensity of the pre-edge feature in the shell spectrum resembles best that of the Mn(II)-bearing reference compounds, suggesting that this is the oxidation state of Mn in the bivalve shells. By comparison with the XANES spectra of selected standard compounds, hypotheses about Mn speciation in the shell are also reported. In particular, different factors, such as provenance, ontogenetic age, variable Mn-concentrations or seasonal shell deposition seem not to influence the speciation of the metal in this bivalve species.