Curium(III) Speciation in Aqueous Solutions of Bacterial Siderophores

Actinides have been and will be introduced into shallow and deep groundwater environments via various human activities. The process of interaction between naturally occurring chelating substances and metals may influence the migration behavior of hazardous actinides in the environment once they have been released. Siderophores are chelating substances produced by microorganisms under iron-deficient conditions. For example, Powell et al. [1] demonstrated the occurrence of hydroxamate siderophores produced by microorganisms in concentrations ranging from 10-7 to 10-8 M in a variety of soils. In general catechol and hydroxamate groups in siderophores are the main functional groups involved in binding with actinides. As an example, Pseudomonas species are ubiquitous soil and groundwater bacteria that synthesize bacterial pyoverdin-type [2-5] and hydroxamate siderophores [6]. The observed mobilization effects of siderophore molecules on radionuclides probably due to the formation of strong soluble species motivated detailed investigation of their complexation characteristics, using a radionuclide suitable for spectroscopic methods.
To overcome the lack of information about actinide(III) siderophore interactions, we thus present findings regarding the complexation of curium(III) with pyoverdins (PYO) and desferrioxamine B (DFO), obtained using time-resolved laser-induced fluorescence spectroscopy (TRLFS). The excellent luminescence properties of curium(III) were used to explore its complexation behavior with the two different bioligands at environmentally relevant curium(III) concentrations.
(A) PYO: Pseudomonas fluorescens (CCUG 32456) cells isolated from the granitic rock aquifers at the Äspö Hard Rock Laboratory (Äspö HRL), Sweden, secreted a pyoverdin mixture containing 4 main components [5].
(B) DFO: Desferrioxamine B (DFO) is a microbial produced trihydroxamate siderophore which is commercially available and could occur naturally in soils. Recently Essen et al. [6] could show the production of desferrioxamine siderophors by Pseudomonas stutzeri (CCUG 36651). This strain was also isolated at the Äspö Hard Rock Laboratory.

We explored the unknown luminescence properties, lifetimes and individual luminescence emission spectra of the formed Cm(III) species. The strength of the complex formation of the two bioligands will be discussed on the basis of the spectroscopic properties obtained in their individual systems. The results of this study increase our understanding of the mobilization of actinides by siderophores secreted by resident bacteria in a natural environment.

[1] Powell, P.E., et al., Nature 287 (1980) 833-834.
[2] Budzikiewicz H., Fortschr. Chem. Org. Naturst. 87 (2004) 83-237 .
[3] Kalinowski B.E., et al., Geomicrobiol. J. 23 (2006) 157-164.
[4] Moll, H., et al., BioMetals 21 (2008) 219-228.
[5] Moll, H., et al., Geomicrobiol. J. 25 (2008) 157-166.
[6] Essen, S.A., et al., Appl. Environ. Microbiol. 73 (2007) 5857-5864.