Spiking of an analyte is performed to validate a sensor’s performance rather than using HPLC or ICP method to measure the concentration of the targeted analyte?
Because you are validating the sensor and not the HPLC method which is very complex and expensive (see ICH Q2). In addition HPLC separates and resolves the targeted analyte in the sample matrix, while the sensor must operate successfully within the sample matrix.
Sensor performance is usually a function of either UV or IR lamp's age which reduces as the lamps age. Spiking a sample validates your calibration curve with the relative recovery. Other option is to use a certified reference material for a particular analyte and method. Ideally it depends upon your application.
Calibration of the sensor with "clean standard" may not be valid if there are any matrix effects originating from the sample matrix. To verify that one good way is to spike the sample with a known concentration (of few spikes with a series of concentrations) of the analyte and calibrate the sensor "in the sample matrix", which is equivalent to the method of standard addition. Spiking may also be useful to test the linearity within the matrix, any such suspected behavours unique to the matrix.
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