RATIONALE: In this review, works published in the past 25 years for fluorine, chlorine, bromine, and iodine determination in several matrices by inductively coupled plasma mass spectrometry (ICP-MS) were covered. Usually, the determination of halogens has been performed by ICP-MS using a previous sample preparation step or, more recently, by direct analysis of solid or liquid samples. METHODS: Methods based on combustion, extraction, pyrohydrolysis, sample dilution in organic or aqueous medium, and wet digestion, among others, are discussed. Moreover, the recent applications of methods based on laser ablation (LA) and electrothermal vaporization (ETV) coupled to ICP-MS are discussed. RESULTS: The main challenge for methods using sample preparation has been to obtain a final solution compatible with ICP-MS, as well as to overcome problems related to analyte losses and contamination. Interferences due to the presence of dissolved organic compounds in solution, enhancement or suppression of ionization of analytes, and related matrix effects have been of concern when using ICP-MS. For the determination of halogens by ICP-MS using LA and ETV systems, some limitations related to the difficulty of calibration are pointed out, impairing the widespread use of this approach. CONCLUSIONS: A critical view is presented for further halogen determination by ICP-MS, mainly for matrices considered difficult to digest using conventional protocols.
RATIONALE: In this review, works published in the past 25 years for fluorine, chlorine, bromine, and iodine determination in several matrices by inductively coupled plasma mass spectrometry (ICP-MS) were covered. Usually, the determination of halogens has been performed by ICP-MS using a previous sample preparation step or, more recently, by direct analysis of solid or liquid samples. METHODS: Methods based on combustion, extraction, pyrohydrolysis, sample dilution in organic or aqueous medium, and wet digestion, among others, are discussed. Moreover, the recent applications of methods based on laser ablation (LA) and electrothermal vaporization (ETV) coupled to ICP-MS are discussed. RESULTS: The main challenge for methods using sample preparation has been to obtain a final solution compatible with ICP-MS, as well as to overcome problems related to analyte losses and contamination. Interferences due to the presence of dissolved organic compounds in solution, enhancement or suppression of ionization of analytes, and related matrix effects have been of concern when using ICP-MS. For the determination of halogens by ICP-MS using LA and ETV systems, some limitations related to the difficulty of calibration are pointed out, impairing the widespread use of this approach. CONCLUSIONS: A critical view is presented for further halogen determination by ICP-MS, mainly for matrices considered difficult to digest using conventional protocols.