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The investigation of an ancient Chinese ceramic served to further develop and validate fundamental parameter-based quantitation procedures in reference-free x-ray fluorescence (XRF) analysis. The XRF measurements of this sample were performed at the four-crystal monochromator beamline of the Physikalisch-Technische Bundesanstalt (PTB) at the BESSY II synchrotron radiation facility employing different excitation energies. The parallel processing of the XRF spectra recorded at different excitation energies provides a means to simultaneously evaluate relevant fundamental parameters and secondary enhancement processes such as those induced by photoelectrons. Employing well-characterized and absolutely calibrated instrumentation, all experimental parameters involved in XRF are known for small relative uncertainties allowing for a completely reference-free quantitation. Apart from traces of rare earth elements, the analytical results of the Chinese ceramic achieved by reference-free XRF are in line with target values given within a proficiency test of the International Atomic Energy Agency (IAEA) involving atomic and nuclear methods.