Radioecological Aspects on the Interaction of Radionuclides and Heavy Metals with Biomass: Methods for Speciation and Structural Information

A more detailed survey of modern methods for characterizing radionuclides and heavy metals in the environment and for elucidating the mechanisms of their interaction with biomolecules is given.
Laser-induced spectroscopies, including Time-Resolved Laser Fluorescence (TRLFS), Photoacustic (LIPAS), Thermal Lensing (LITLS) and Photothermal Deflection Spectroscopy (LIPDS) provide the identification of the chemical species of radionuclides and heavy metals in environmental media in concentrations down to the micro-molar range and even lower. This includes information on the oxidation state, the stöchiometry, and the structure of ions and dissolved complexes, including the discrimination between ionic and polynuclear or colloidal species that may preferentially be built with thorium, uranium and plutonium.
The complexes formed with the biomolecules as the result of the metal incorporation can be studied by X-ray absorption spectroscopies using synchrotron radiation, such as X-ray Absorption Near Edge Spectroscopy (XANES) and Extended X-ray Absorption Fine Structure. These methods give information on the valency and the coordination of the central ion as well as on the bond length to neighboring atoms, leading to an initial understanding of the spatial orientation and structure. This knowledge is essential to describe the interaction of radionuclides, such as U, Th, Ra, Np, Pu, Am, Cm, Zr, Sr, Cs and Tc with biomolecules and biomass. The selenium uptake by the soil bacterium Bacillus subtilis is cited as an example: from XANES spectra, the absorption process could be proved as an incorporation into the cell membrane under reduction of selenium(IV) to zerovalent selenium. From both the identified species and the characterized final complex, conclusions can be drawn regarding the overall absorption mechanism. These information are essential for selecting and optimizing biomolecular systems intended for environmental remediation purposes.