Calibration in SPME

One of the important aspects of any analytical method is its calibration and, therefore, much effort has been put into SPME calibration. As it is not always practicable to employ traditional calibration methods (external standards, internal standards, and standard addition) owing to the sometimes significant matrix effects in complex samples, equilibrium calibration has been suggested as an alternative. In SPME, however, it would normally take rather a long time to achieve equilibrium calibration. If sensitivity were not a concern in an analysis, reduction of extraction time would be desirable, that is, the extraction could be stopped before equilibrium but this would thus demand a new approach to calibration. In this regard, as a way of circumventing matrix effects in environmental analysis, several diffusion-based calibration methods have been recently developed for quantification in SPME.30 

One of these methods is called kinetic calibration, in which analyte absorption from the sample to the liquid coating (PDMS) on the fiber is related to analyte desorption from the coating to the sample. The isotropy of absorption and desorption in the kinetic calibration has been described by Chen et al.31 In kinetic calibration, also called in-fiber standardization, desorption of a radio-labeled standard (preloaded on the fiber coating) into the sample is used to calibrate the extraction (absorption/adsorption in the case of a liquid/solid coating) of analyte from the sample into the fiber. This calibration approach considerably facilitates the use of SPME for the on-site field sampling of water, where the control of flow velocity or addition of a standard to the matrix is very difficult. 

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