Chemical speciation of trivalent actinides and lanthanides in biological fluids: The dominant in vitro binding form of curium(III) and europium(III) in human urine

Radionuclides represent a serious health risk to humans in case of incorporation. To get a first insight into the transport and metabolism of trivalent actinides in the human organism, we investigated the in vitro speciation of curium(III) in human urine samples using fluorescence spectroscopy. Since in speciation studies trivalent lanthanides are often used as analogs for trivalent actinides, we probed the suitability of this theory by investigating the speciation of europium(III) in human urine, too. Comparison with reference spectra of both heavy metals in model urine and of their complexes with single organic urine constituents then allowed for the determination of the dominant species. Furthermore the chemical composition of all urine samples was analyzed and the parameters affecting the metals’ speciation were determined. Surprisingly the chemical composition of the natural urine samples does not seem to have a great influence on the dominant species. Instead the pH was found to be the most important parameter. For both, the actinide and the lanthanide, two analog species were identified in dependence on the pH: In samples with slight acidic pH a curium(III) and europium(III) citrate complex dominates, respectively, while in samples with near neutral pH a ternary complex with phosphate and citrate as ligands is formed in each case. Comparison with thermodynamic modeling yields some discrepancies especially at higher pH which is due to a lack of data for the ternary species of both heavy metals.