Abundance and Impact of Doubly Charged Polyatomic Argon Interferences in ICPMS Spectra.

Doubly charged molecular ions of alkaline earth metals and argon could be identified as spectral interferences in an inductively coupled plasma mass spectrometer. These molecular ions were found to occur at abundances reaching about 10(-4) relative to the alkaline earth atomic ion abundances. They can thus substantially affect ultratrace analyses and, when present at similar concentration as the analyte elements, also isotope ratio measurements. For the case of Cu and Zn isotope ratio analyses, the same mass concentration of Sr was found to alter the measured (63)Cu/(65)Cu and (64)Zn/(66)Zn isotope ratios by -0.036‰ to -0.95‰ due to SrAr(2+), appearing at m/Q 63 and 64. BaAr(2+) can affect Sr isotope analyses, MgAr(2+) may impair S isotope ratio measurements, while CaAr(2+) may cause interference to Ca(+) isotopes. The abundances of the doubly charged molecular ions were higher than those of the corresponding singly charged species, which is in accordance with their generally higher bond dissociation energies. The relative abundances were found to depend significantly on the inductively coupled plasma (ICP) operating conditions and generally increase with increasing carrier gas flow rates or lower gas temperature of the ICP. They also increase by about an order of magnitude when a desolvated aerosol is introduced to the ICP.