Headspace Solid-Phase Microextraction Following Chemical Vapor Generation for Ultrasensitive, Matrix Effect-Free Detection of Nitrite by Microplasma Optical Emission Spectrometry.

A new chemical vapor generation method coupled with headspace solid-phase microextraction miniaturized point discharge optical emission spectrometry (HS-SPME-μPD-OES) for the sensitive and matrix effect-free detection of nitrite in complex samples is described. In an acidic medium, the volatile cyclohexene was generated from cyclamate in the presence of nitrite, which was volatilized to the headspace of the container, efficiently separated, and preconcentrated by HS-SPME. Consequently, the SPME fiber was transferred to a laboratory-constructed thermal desorption chamber wherein the cyclohexene was thermally desorbed and swept into μPD-OES for its sensitive quantification via monitoring the carbon atomic emission line at 193.0 nm. As a result, the quantification of nitrite was accomplished through the determination of cyclohexene. The application of HS-SPME as a sampling technique not only simplifies the experimental setup of μPD-OES but it also preconcentrates and separates cyclohexene from N2 and sample matrices, thus eliminating the interference from water vapor and N2 and significantly improving the analytical performance on the determination of nitrite. Under the optimum experimental conditions, a limit of detection of 0.1 μg L-1 was obtained, which is much better than that obtained by conventional methods. The precision, expressed as relative standard deviation, was better than 3.0% at a concentration of 10 μg L-1. The proposed method provides several advantages of portability, simplicity, high sensitivity, and low energy consumption and eliminates expensive instruments and matrix interference, thus retaining a promising potential for the rapid, sensitive, and field analysis of nitrite in various samples.