title: Investigation of polynuclear Zr(IV) hydroxide complexes by nanoelectrospray mass-spectrometry combined with XAFS.
abstract: Polynuclear species of zirconium in acidic aqueous solution are investigated by combining X-ray absorption spectroscopy (XAFS) and nanoelectrospray mass spectrometry (ESI-MS). Species distributions are measured between pHC 0 and pHC 3 for [Zr]=1.5-10 mM. While the monomer remains a minor species, with increasing pH the degree of polymerization increases and the formation of tetramers, pentamers, octamers, and larger polymers is observed. The high resolution of the mass spectrometer permits the unambiguous determination of polynuclear zirconium hydroxide complexes by means of their isotopic patterns. The relative abundances of mononuclear and polynuclear species present simultaneously in solution are measured, even if one of the species contributes only 0.1% of the Zr concentration. For the first time it has been directly observed that the hydrolysis of polynuclear Zr species is a continuous process which leads to charge compensation through the sequential substitution of water molecules by hydroxide ligands until doubly charged polymers dominate at conditions (H+ and Zr concentrations) close to the solubility of Zr(OH)4(am). The invasiveness of the electrospray process was minimized by using very mild declustering conditions, leaving the polynuclear species within a solvent shell of approximately 20 water molecules.
authors.affiliation: Institut für Nukleare Entsorgung, Forschungszentrum Karlsruhe, Postfach 3640, 76021, Karlsruhe, Germany. walther@ine.fzk.de
authors.forename: Clemens
authors.initials: C
authors.lastname: Walther
authors.forename: Jörg
authors.initials: J
authors.lastname: Rothe
authors.forename: Markus
authors.initials: M
authors.lastname: Fuss
authors.forename: Sebastian
authors.initials: S
authors.lastname: Büchner
authors.forename: Sergei
authors.initials: S
authors.lastname: Koltsov
authors.forename: Thorald
authors.initials: T
authors.lastname: Bergmann