A novel method for determination of inorganic oxyanions by electrospray ionization mass spectrometry using dehydration reactions

Kojima, Hirochika; Kurihara, Shota; Watanabe, Yoshito; Iwamaru, Koki; Sato, Kiichi; Tsunoda, Kin‐ichi; Hotta, Hiroki

Novel methods for the determination of inorganic oxyanions by electrospray (ES) ionization mass spectrometry have been developed using dehydration reactions between oxyanions and carboxylic acids at the ES interface. Twelve oxyanions (VO(3) (−), CrO(4) (2−), MoO(4) (2−), WO(4) (2−), BO(3) (3−), SiO(3) (2−), SiO(4) (4−), AsO(4) (4−), AsO(2) (−), SeO(4) (2−), SeO(3) (2−) and NO(2) (−)), out of 16 tested, reacted with at least one of four aminopolycarboxylic acids, i.e. iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), trans‐1,2‐diaminocyclohexane‐N,N,N′,N′‐tetraacetic acid and triethylenetetramine‐N,N,N′,N″,N′″,N′″‐hexaacetic acid, at the ES interface to produce the dehydration products that gave intense mass ion responses, sufficient for trace analysis. As examples, trace determinations of Cr(VI) and silica in water samples were achieved after online ion exchange chromatography, where the dehydration product of CrO(4) (2−) and NTA (m/z 290) and that of SiO(4) (4−) and IDA (m/z 192) were measured. The limits of detection of the respective methods were 17 nM (0.83 ng Cr/ml) for Cr(VI) and 0.17 μM (4.8 ng Si/mL) for SiO(4) (4−). Copyright © 2016 John Wiley & Sons, Ltd.