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

Hirochika Kojima; Shota Kurihara; Yoshito Watanabe; Koki Iwamaru; Kiichi Sato; Kin-Ichi Tsunoda; Hiroki Hotta

doi:10.1002/jms.3731

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

J Mass Spectrom. 2016 Feb;51(2):123-31. doi: 10.1002/jms.3731.

Authors

Hirochika Kojima¹, Shota Kurihara^{1

2}, Yoshito Watanabe^{1

3}, Koki Iwamaru¹, Kiichi Sato¹, Kin-Ichi Tsunoda¹, Hiroki Hotta⁴

Affiliations

¹ Department of Chemistry and Chemical Biology, Gunma University, Tenjin-cho, Kiryu, 376-8515, Japan.
² Nippon Steel & Sumikin Eco-Tech Corporation, Kisarazu, 292-0825, Japan.
³ Moriroku Technology Co., Ltd., Meiwa, 370-0718, Japan.
⁴ Department of Chemistry, Nara University of Education, Takabatake, Nara, 630-8528, Japan.

Abstract

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 (VO3 (-) , CrO4 (2-) , MoO4 (2-) , WO4 (2-) , BO3 (3-) , SiO3 (2-) , SiO4 (4-) , AsO4 (4-) , AsO2 (-) , SeO4 (2-) , SeO3 (2-) and NO2 (-) ), 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 CrO4 (2-) and NTA (m/z 290) and that of SiO4 (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 SiO4 (4-) .

Keywords: carboxylic acids; dehydration reaction; electrospray ionization mass spectrometry; oxyanions.