A rapid and green GC-MS method for the sampling of volatile organic compounds in spices and flowers by concurrent headspace single-drop microextraction and solid-phase microextraction.

The equilibrium rather than the exhaustive nature of headspace single-drop microextraction (HS-SDME) and headspace solid-phase microextraction (HS-SPME) allowed the concurrent sampling of volatile organic compounds (VOCs) on the same sample in the same vial in a dual extraction configuration. This has avoided the necessity of conducting a separate set of experiments and was found to produce results in the time duration of a single sample preparation experiment. The results obtained by HS-SDME were validated against those found by the standard method of HS-SPME. Rectilinear calibration was made for certain VOCs tested as analytes over the range of 0.01-8 µg g-1, and the average values of R2, LOD and LOQ were found to be, respectively, 0.9992, 1.9 ng g-1 and 5.7 ng g-1 in HS-SDME, and 0.9991, 3.1 ng g-1 and 9.1 ng g-1 in HS-SPME. The spiked recoveries and RSD were, respectively, 100.5% and 3.3% in HS-SDME and 98.1% and 3.6% in HS-SPME. HS-SDME is convenient to perform and produce results in a much cheaper way than HS-SPME and free from the inconveniences of memory effects. With GC-MS, this method has also been implemented as a rapid, reliable and green procedure (by GAPI and AGREE tools) for the sampling of VOCs in real samples of spices, flowers, and a beetle nut chewing sample illicitly containing tobacco.

Combined liquid phase microextraction and fiber-optics-based cuvetteless micro-spectrophotometry for sensitive determination of ammonia in water and food samples by the indophenol reaction.

The Berthelot reaction for ammonia is revisited with the aim of miniaturization and addressing interferences as encountered with food and water samples. Headspace single drop microextraction of ammonia in phosphoric acid served to attain selectivity in complex matrices, and liquid-liquid microextraction of red or blue indophenol species into 1-octanol-isooctane (60:40, v/v) resulted into high sensitivity. Fiber-optics-based cuvetteless micro-spectrophotometry has been used for colorimetric determination on microliter volumes of extract. The linear dynamic range, limit of detection and enrichment factor have been found to be 0.2-3 mg kg-1, 0.14 mg kg-1 and 38, respectively, measuring red species for milk, cheese and beer (4.9-5.5% error; 4.8-6.3% RSD; n = 5); and 5-400 µg L-1, 0.4 µg L-1 and 137, respectively, measuring blue species for water samples (3.3-5.7% error; 3.6-6.8% RSD; n = 5). A plausible reaction scheme has been proposed for nitroprusside catalysis in indophenol reaction.