LC/MS/MS Analysis of Chlorate and Bromate According to Japanese Water Supply Act (JJ-50 2D)

Previously, the Japanese Water Supply Act listed analysis of chlorate only in “Appendix No. 13: Simultaneous analysis by ion (anion) chromatography”. However, from April 1st 2020*, the analysis of chlorate was also added in “Appendix No. 18-2, analysis by LC/MS/MS". In addition to the use of ethylendiamine as an additive for the collected water sample, the use of sodium thiosulfate solution is now also allowed (1 - 2 mL of 0.3 % sodium thiosulfate (w/v) in 1-L water).
In this application, chlorate and bromate were analyzed by an LC/MS/MS method using RSpak JJ-50 4D, a multimode (reversed phase + anion exchange) column modified with quaternary ammonium groups. Calibration curves with good linearities were obtained for chlorate and bromate in the concentration range 0.001 - 0.02 mg/L.

*The version at the time of the application acquisition.

Sample: 5 µL
(Tap water spiked with standards) 10 µg/L each of ClO3-, and BrO3- in tap water containing 0.0003 % sodium thiosulfate (w/v)

  1. 1.ClO3-, Chlorate
  2. 2.BrO3-, Bromate
  3. 3.HS2O32-, Thiosulfate with one hydrogen ion attached

Sample : 5 µL
Tap water containing containing 0.0003 % sodium thiosulfate (w/v)

  1. 1.ClO3-, Chlorate
  2. 2.BrO3-, Bromate
  3. 3.HS2O32-, Thiosulfate with one hydrogen ion attached

Column
Shodex RSpak JJ-50 2D (2.0 mm I.D. x 150 mm)
Eluent
(A); 200 mM HCOONH4 aq./(B); CH3CN
Linear gradient (High pressure); 85 % B (0 min) → 85 % B (8 min) → 50 % B (9 min) → 50 % B (20 min)
Flow rate
0.3 mL/min
Detector
ESI-MS/MS (MRM Negative) for ClO3- and BrO3-
ESI-MS (SIM Negative) for HS2O3-
Column temp.
50 ℃

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