Bromide/bromate speciation by NTI-IDMS and ICP-MS coupled with ion exchange chromatography

Two different mass spectrometric methods, negative thermal ionization isotope dilution mass spectrometry (NTI-IDMS) and inductively coupled plasma mass spectrometry (ICP-MS), off-line and on-line coupled with anion exchange chromatography, have been developed for simultaneous bromide and bromate determinations in water samples. The detection limits of these methods are in the range of 0.03-0.09 mu g/L using a 50 mL sample. The results are independent of the content of other anions, which could be demonstrated by the analyses of six mineral waters containing chloride and sulfate of up to 160 mg/L and 1500 mg/L, respectively. Bromide has been analyzed by the NTI-IDMS method in the range of 10-500 mu g/L and bromate in the range of 1-50 mu g/L with relative standard deviations of 0.3-1.2% and 0.4-6%. Quantification for the ICP-MS method was carried out by the standard addition technique, which resulted in relative standard deviations of 5.5% for bromide at the 500 mu g/L level and of 13% for bromate at the level of about 3 mu g/L. These results are compared with those described in the literature for ion chromatographic (IC) and other methods and those obtained in this work by IC using UV detection, which allows high concentrations of chloride in the bromate fraction. The detection limits of this IC method are 6 mu g/L for bromide and 30 mu g/L for bromate. NTI-IDMS and ICP-MS therefore fit the recommendations of the European Union (detection limit < 2.5 mu g/L; precision and accuracy better than 25% at the 10 mu g/L level) for methods analyzing the carcinogenic bromate much better than IC and other methods applied up to now. As a definitive but time consuming method, NTI-IDMS is preferably applicable as a calibration technique, whereas ICP-MS, with relatively short analysis times, due to on-line coupling with chromatography, can be used as a sensitive and powerful routine method for trace bromide and bromate species in water samples.