Rapid analysis of perchlorate, chlorate and bromate ions in concentrated sodium hypochlorite solutions

A sensitive, rapid, and rugged liquid chromatography with tandem mass spectrometry (LC–MS/MS) method for measuring concentrations of perchlorate, chlorate, and bromate ions in concentrated sodium hypochlorite solutions is presented. The LC–MS/MS method offers a practical quantitation limit (PQL) of 0.05 μg L−1 for ClO4−, 0.2 μg L−1 for BrO3−, and 0.7 μg L−1 for ClO3− and a sample analysis time of only 10 min. Additionally, an iodometric titration technique was compared with the LC–MS/MS method for measurement of chlorate ion at high concentration. The LC–MS/MS method was the most reproducible for chlorate concentrations below 0.025 M while the iodometric titration method employed was the most reproducible above 0.025 M. By using both methods, concentrations of chlorate can be measured over a wide range, from 0.7 μg L−1 to 210 g L−1 in hypochlorite ion solutions. Seven quenching agents were also evaluated for their ability to neutralize hypochlorite ion, thereby stopping formation of perchlorate ion in solution, without adversely impacting the other oxyhalide ions. Malonic acid was chosen as the quenching agent of choice, meeting all evaluation criteria outlined in this manuscript.