Can electrospray mass spectrometry quantitatively probe speciation? Hydrolysis of uranyl nitrate studied by gas-phase methods.

Electrospray ionization of uranyl nitrate dissolved in water generates gaseous species containing either hydroxo-uranyl [UO(2)(OH)](+) or nitrato-uranyl [UO(2)(NO(3))](+) contact ion pairs solvated by up to four water molecules. Furthermore, uranyl clusters of the general type [U(m)O(2m)(X,Y)(2m-1)(H(2)O)(n)](+) (X,Y = OH, NO(3)) with m = 1-5 and n = 2-4 are formed. Collision-induced dissociation experiments are used to probe the structures and the stoichiometries of the uranyl ions generated. A detailed investigation of the concentration-dependent behavior of the formed gaseous uranyl complexes reveals a preference for nitrate- over hydroxide-containing species with increasing concentration of the sprayed solution. This behavior reflects changes in the pH value of the bulk solutions that can be attributed to solvolysis of UO(2)(2+) in water. Further, the tendency for generation of polynuclear cluster ions is amplified with increasing concentration and can be explained by a mechanism which involves the association of cations present in solution with neutral species such as UO(2)(OH)(2), UO(2)(OH)(NO(3)), and UO(2)(NO(3))(2). The observed dependences of the cluster-ion intensities in the mass spectra from the concentration of the solutions fed to the electrospray source are used to suggest a scheme for a quantitative correlation between the gas-phase and solution-phase data. The results inter alia indicate that the effective concentrations of the spraying solution can be several orders of magnitude larger than those of the feed solutions entering the electrospray ionization source.