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The qualitative and quantitative investigation of historical iron-gall inks using micro-XRF spectrometry is a suitable method for analyzing composition fingerprints of different ink types. The quantitative analysis is based on a model that takes into account the inhomogeneity and the layer structure of archaeometric samples. Starting from these composition fingerprints, it is possible to characterize distinguishable inks of one artist to classify different chronological ink types and, further, to date unknown fragments that have not so far been integrated into the lifework of an artist. The first qualitative and quantitative investigations of the manuscript Faust I and II and of the music composition The Magic Flute demonstrate impressively the identification of J. W. v. Goethe's and W. A. Mozart's artistic work with modern scientific methods. Further investigations on A. v. Arnim's manuscript Studien zu Naturwissenschaften provide evidence that the diversity of various degradation mechanisms of iron-gall inks could be mainly caused by different inorganic compositions.
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.