Trace Analysis of Bromate, Chlorate, Iodate, and Perchlorate in Natural and Bottled Waters

A simple and rapid method has been developed to simultaneously measure sub-μg/L quantities of the oxyhalide anions bromate, chlorate, iodate, and perchlorate in water samples. Water samples (10 mL) are passed through barium and hydronium cartridges to remove sulfate and carbonate, respectively. The method utilizes the direct injection of 10 μL volumes of water samples into a liquid chromatography−tandem triple-quadrupole mass spectrometry (LC−MS/MS) system. Ionization is accomplished using electrospray ionization in negative mode. The method detection limits were 0.021 μg/L for perchlorate, 0.045 μg/L for bromate, 0.070 μg/L for iodate, and 0.045 μg/L for chlorate anions in water. The LC−MS/MS method described here was compared to established EPA methods 300.1 and 317.1 for bromate analysis and EPA method 314.0 for perchlorate analysis. Samples collected from sites with known contamination were split and sent to certified laboratories utilizing EPA methods for bromate and perchlorate analysis. At concentrations above the reporting limits for EPA methods, the method described here was always within 20% of the established methods, and generally within 10%. Twenty-one commercially available bottled waters were analyzed for oxyhalides. The majority of bottled waters contained detectable levels of oxyhalides, with perchlorate ≤0.74 μg/L, bromate ≤76 μg/L, iodate ≤25 μg/L, and chlorate ≤5.8 μg/L. Perchlorate, iodate, and chlorate were detectable in nearly all natural waters tested, while bromate was only detected in treated waters. Perchlorate was found in several rivers and reservoirs where it was not found previously using EPA 314.0 (reporting limit of 4 μg/L). This method was also applied to common detergents used for cleaning laboratory glassware and equipment to evaluate the potential for sample contamination. Only chlorate appeared as a major oxyhalide in the detergents evaluated, with concentrations up to 517 μg/g. Drinking water treatment plants were also evaluated using this method. Significant formations of chlorate and bromate are demonstrated from hypochlorite generation and ozonation. From the limited data set provided here, it appears that perchlorate is a ubiquitous contaminant of natural waters at trace levels.