EXAFS investigations of uranium (VI) interaction with bacteria

Mobilization of heavy metals in the environment due to industrial activities is of serious concern due to the toxicity of these metals in humans and other forms of life. Uranium is an example of these metals, and is considered one of the most seriously threatening heavy metals mainly because of its high toxicity, not so much radioactivity. Activities associated with the nuclear industry, mining and wastewater treatment have brought excessive amounts of uranium into the environment. In uranium deposits a number of acidophilic chemolithoautotrophic ( Acidithiobacillus ferrooxidans, for instance) bacteria have been identified which are able to oxidise sulphide minerals, elemental sulfur, ferrous iron. Sequence analysis of the 16S rRNA genes of several reference strains and uranium mining waste pile isolates of A. ferrooxidans revealed specific signatures which distinguish three types within the species. These types differ in their capability to accumulate and tolerate uranium /1/.
Uranium (VI) complexes formation at cell surfaces of A. ferrooxidans types was studied using uranium LIII-edge Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. In all samples uranium is coordinated by two axial oxygen atoms (Oax) at distance of 1.77-1.78 Å. The average distance between uranium and the equatorial oxygen atoms (Oeq) is 2.35 Å. The coordination number for Oeq is 5-6.
Using U-C and U-P phase and amplitude functions, the third and the fourth peak in the FT of A. ferrooxidans give a distance of 2.91 and 3.58 ± 0.02Å, respectively. The latter is the same U-P bond distance as for the organic uranyl phosphate (U(VI)-ATP complex). But we do not exclude the possibility of implication of sulfur because these 2 elements (P and S) are close each other in the periodic system of elements and EXAFS can not distinguish between them. In addition, the P (or S) is bonded in a monodentate mode to the uranyl ion. A bidentate bounding would give a atomic distance of approximately 3.2 Å.
Moreover, no structural differences were observed between the uranium complexes formed by the 3 types of A. ferrooxidans. However, the EXAFS spectra are indicating a formation of uranium complexes which are different from those formed by Bacilli /2/.

/1/ M. Merroun et al., Interaction of three types of Acidithiobacillus ferrooxidans with uranium, Biometals (in preparation).
/2/ C. Hennig et al., EXAFS investigation of uranium(VI) complexes formed at Bacillus cereus and Bacillus sphaericus surfaces, Radiochim. Acta (in press).