Instrumental dead-time and its relationship with matrix corrections in X-ray fluorescence analysis

The relationship between instrumental dead-time and the self-absorption coefficients, αsub(ii) in x.r.f. matrix correction by means of influence coefficients, is not generally recognized but has important analytical consequences. Systematic errors of the order of 1% (relative) for any analyte result from experimental uncertainties in instrumental dead-time. Such errors are applied unevenly across a given range of concentration because the error depends on the calibration standards and on the instrumental conditions used. Refinement of the instrumental dead-time value and other calibration parameters to conform with influence coefficients determined elsewhere assumes exact knowledge of dead-time of the instrument used originally, and quite similar excitation conditions and spectrometer geometry for the two instruments. Though these qualifications may not be met, adjustment of any of the parameters (dead-time, reference concentration, background concentration, self-absorption and other influence coefficients) can be easily achieved. (Auth.)