Non invasive analysis of miniature paintings: proposal for an analytical protocol.

The characterisation of palettes used in manuscript illumination is a hard analytical task, due to value and fragility of the analysed items. Analysis on miniatures must be necessarily non-invasive and fast and requires the use of several techniques since no single technique is able to provide all information needed. In this work a four-step analytical protocol is proposed for non-invasive in situ characterisation of miniature paintings. The protocol allows the identification of coloured materials through the use in sequence of complementary techniques, so as to fully exploit the information given by each instrument. Preliminarily to the instrumental investigations on ancient books and miniatures is the compilation of spectroscopic databases obtained from "standard" samples prepared on parchment, according to recipes described in medieval artistic treatises. The protocol starts with an extensive investigation with UV-visible spectrophotometry in reflectance mode, collecting spectra from all the most significant painted areas in the manuscript; chemometric classification is then performed on the spectra to highlight areas possibly containing the same materials. The second step involves in-depth inspection of miniatures under optical microscopy that guides the interpretation of reflectance spectra. XRF spectrometry is then performed to characterise pigments and metal layers, to verify the presence of overlapping layers, to identify mordants in lakes and to recognise minor components that may yield information concerning provenance; in addition, chemometric classification can be performed on element concentrations to highlight similar areas. Finally, Raman spectroscopy is used to shed light on the uncertain cases, if still present. Such a procedure offers a wealth of information without causing stress to the manuscripts under analysis.

Room-temperature study of iron gall ink impregnated paper degradation under various oxygen and humidity conditions: time-dependent monitoring by viscosity and X-ray absorption near-edge spectrometry measurements.

Many western manuscripts were written using iron gall inks. These inks can damage the paper via two major mechanisms: (a) acid hydrolysis, enhanced by humidity, and (b) oxidative depolymerization provoked by the presence of oxygen and free iron(II) ions. The degradation of unsized Whatman paper impregnated with different combinations of iron sulfate, gallic acid, and gum arabic was studied at room temperature in order to assess the relative importance of each mechanism. The samples were stored in various environments including a dry and/or an oxygen-free atmosphere. The cellulose depolymerization was monitored by viscometry and related to changes in the oxidation state of iron, determined by X-ray absorption near-edge spectrometry. The results indicate that residual amounts of oxygen (less than 0.1%) promote cellulose depolymerization, whereas the level of relative humidity has no impact. The cellulose depolymerization also appears closely correlated to oxidative mechanisms. Regarding the oxidation of iron, it only occurs in the simultaneous presence of oxygen and moisture, suggesting the occurrence of rustlike oxidative mechanisms. Finally, the presence of gallic acid has a strong influence, which is only partially explained by its capacity to reduce iron(III) to iron(II).