Preliminary Assessment of Potential for Metal–Ligand Speciation in Aqueous Solution via the Liquid Sampling–Atmospheric Pressure Glow Discharge (LS-APGD) Ionization Source: Uranyl Acetate

The determination of metals, including the generation of metal–ligand speciation information, is essential across a myriad of biochemical, environmental, and industrial systems. Metal speciation is generally affected by the combination of some form of chromatographic separation (reflective of the metal–ligand chemistry) with element-specific detection for the quantification of the metal composing the chromatographic eluent. Thus, the identity of the metal–ligand is assigned by inference. Presented here, the liquid sampling–atmospheric pressure glow discharge (LS-APGD) is assessed as an ionization source for metal speciation, with the uranyl ion–acetate system used as a test system. Molecular mass spectra can be obtained from the same source by simple modification of the sustaining electrolyte solution. Specifically, chemical information pertaining to the degree of acetate complexation of uranyl ion (UO₂²⁺) is assessed as a function of pH in the spectral abundance of three metallic species: inorganic (nonligated) uranyl, UO₂Ac­(H₂O)_n(MeOH)_m⁺, and UO₂Ac₂(H₂O)_n(MeOH)_mH⁺ (n = 1, 2, 3, ...; m = 1, 2, 3, ...). The product mass spectra are different from what are obtained from electrospray ionization sources that have been applied to this system. The resulting relationships between the speciation and pH values have been compared to calculated concentrations of the corresponding uranyl species: UO₂²⁺, UO₂Ac⁺, UO₂Ac₂. The capacity for the LS-APGD to affect both atomic mass spectra and structurally significant spectra for organometallic complexes is a unique and potentially powerful combination.