Determination of chlorate, perchlorate and bromate anions in water samples by microbore reversed-phase liquid chromatography coupled to sonic-spray ionization mass spectrometry.

RATIONALE: Sonic-spray ionization mass spectrometry (SSI-MS) has recently been shown to provide similar mass spectra to those generated by electrospray ionization mass spectrometry for a wide range of compounds, i.e. from small inorganic species to peptides, proteins and numerous other biomolecules. However, limited information about this new ionization technique, such as sensitivity, limit of detection and quantification accuracy, has been reported. In particular, its coupling to liquid chromatography needs further development and assessment, along with the introduction of a broad range of applications.

METHODS: A high-efficiency glass pneumatic nebulizer, used for decades for sample introduction in atomic spectrometry, was used for the SSI-MS analysis of chlorate (ClO3 - ), perchlorate (ClO4 - ) and bromate (BrO3 - ) anions, following their separation using reversed-phase microbore high-performance liquid chromatography and tandem mass spectrometry (MS/MS) operated in selected reaction monitoring mode.

RESULTS: The developed and optimized microbore HPLC/SSI-MS/MS technique exhibited low limits of detection: 5.3 ng L-1 for chlorate, 10 ng L-1 for perchlorate and 33.7 ng L-1 for bromate, and provided reliable and accurate measurements of chlorate concentrations in water samples as demonstrated when comparing it with Ion Chromatography-Conductivity Detection (IC-CD), the benchmark technique for ion quantitation.

CONCLUSIONS: This is the first time that the use of HPLC/SSI-MS/MS has been reported for the detection and quantitation of chlorate, perchlorate and bromate in water samples. In addition, the exceptionally low LODs achieved using SSI render the technique competitive with the established and dominating electrospray ionization technique. Here, we have demonstrated that a commercially available high-efficiency glass pneumatic nebulizer can also be used, without any further modification, as an efficient gas-phase ion source. Copyright © 2017 John Wiley & Sons, Ltd.