Kinetic calibration for automated hollow fiber-protected liquid-phase microextraction

Recently, a kinetic calibration method was developed for the quantification of microextraction. In this study, we proved that the sample volume and sampling time do not affect the feasibility of the calibration method, theoretically. The new theoretical considerations of the kinetic calibration method were validated through the investigation of the kinetics of the absorption and desorption processes of hollow fiber-protected liquid-phase microextractrion (HF-LPME). The kinetic calibration method for HF-LPME was successfully used to correct the matrix effects in the carbaryl analysis of a red wine sample. This research extends the kinetic calibration approach to fast sampling and some in-vial analyses, whereby the sample volume is not much larger than the product of the distribution coefficient and the volume of the extraction phase. HF-LPME technique was successfully automated with a CTC CombiPal autosampler, and a new device was designed for the automation of HF-LPME in this study. All steps of the HF-LPME technique, including the filling of the extraction solvent, sample transfer and agitation, withdrawing the solvent to a syringe, and introducing the extraction phase into the injector, were automated by a CTC autosampler. The fully automated HF-LPME technique is more convenient and more accurate. The good reproducibility of the fully automated HF-LPME technique eliminates the need for an internal standard to improve the analytical precision. The automated HF-LPME technique can be also used to obtain the distribution coefficient between the sample matrix and the extraction phase. The distribution coefficients of carbaryl and (13)C-carbaryl between 1-octanol and red wine, at 25 degrees C, were obtained with this technique.