The method of trace element analysis by X-ray fluorescence detection has been improved to an especially efficient multielement method for the ng to pg range in matrices containing light elements by the use of synchrotron radiation for excitation. It was necessary to determine the intensity and polarisation of the synchrotron radiation quantitatively. Inclusion of the vertical electron beam diameter and the divergence into the calculation, and definition of an effective vertical beam diameter by fitting the calculated polarisation spectrum leads to quantitative agreement between experimental and calculated absolute intensity spectra of scattered and fluorescent radiation of well-defined samples. This means that absolute mass determinations are in principle possible. The physical limits of detection calculated with these data agree very well with the experimental results. The limits of detection for special elements can be optimised by using different absorbers in the primary beam. They range from 0.05 to 0.2 μg for organic matrix. This implies an absolute physical detection limit of 0.1 to 0.4 pg for a diameter of the primary beam of 0.5 mm and a sample of 1 mg/cm 2.