Trace elements in natural azurite pigments found in illuminated manuscript leaves investigated by synchrotron x-ray fluorescence and diffraction mapping

Abstract

We present trace-element and composition analysis of azurite pigments in six illuminated manuscript leaves, dating from the thirteenth to sixteenth century, using synchrotron-based, large-area x-ray fluorescence (SR-XRF) and diffraction (SR-XRD) mapping. SR-XRF mapping reveals several trace elements correlated with azurite, including arsenic, zirconium, antimony, barium, and bismuth, that appear in multiple manuscripts but were not always detected by point XRF. Within some manuscript leaves, variations in the concentration of trace elements associated with azurite coincide with distinct regions of the illuminations, suggesting systematic differences in azurite preparation or purification. Variations of the trace element concentrations in azurite are greater among different manuscript leaves than the variations within each individual leaf, suggesting the possibility that such impurities reflect distinct mineralogical/geologic sources. SR-XRD maps collected simultaneously with the SR-XRF maps confirm the identification of azurite regions and are consistent with impurities found in natural mineral sources of azurite. In general, our results suggest the feasibility of using azurite trace element analysis for provenance studies of illuminated manuscript fragments, and demonstrate the value of XRF mapping in non-destructive determination of trace element concentrations within a single pigment.