Abstract
High resolution electrospray ionization mass spectrometry (ESI-HRMS) was used to study the speciation of molybdate in interaction with halides (Cl, F, Br). Desolvation during electrospray ionization induced alteration of aqueous species but method optimization successfully suppressed artefact compounds. At low Mo concentrations, chloro(oxo)molybdate and fluoro(oxo)molybdate species were found and in natural samples, MoO3Cl was detected for the first time, to the best of our knowledge. Apparent equilibrium constants for Cl substitution on molybdate were calculated for a range of pH values from 4.5 to 8.5. A minor alteration in speciation during the gas phase (conversion of doubly charged MoO42- to HMoO4-) did not allow investigation of the molybdate acid-base properties; however this could be determined by speciation modeling. This study provides further evidence that ESI-HRMS is a fast and suitable tool to Deceasedassess the speciation of inorganic compounds such as Mo.
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