In this work, a visual colorimetric method based on headspace-single drop microextraction (HS-SDME) was developed for the non-chromatographic speciation analysis of nitrite and nitrate. The method adequately exploited the individual chemical vapor conditions of nitrite and nitrate that were converted to NO by specific reductants. Gaseous NO underwent a diazotization reaction with chromogenic reagent through the HS-SDME process to change from colorless to purplish-red. Instead of using large, time-consuming and relatively complicated chromatographic equipment for separation, the species of nitrite and nitrate could be analyzed by simply changing the reagents. Meanwhile, the extraction method effectively mitigated the matrix interference of solution and improved the sensitivity of method, with intuitive discrimination of color by the naked eye. The limits of detection were 0.07 μg/mL for nitrite and 0.2 μg/mL for nitrate, respectively. This method has been applied to analysis of real environmental water samples, which also effectively extended the application scope of HS-SDME device.
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