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The lack of an appropriate methodology makes numerous important issues related to miniature paintings unresolved-despite the fact that the portrait miniatures of the seventeenth to the nineteenth century represent a highly specific and significant field of European fine art. One of these issues is represented by chemical degradation of miniatures and its analytical evidence. Fragility, variability of the employed materials, and detailed execution make their analysis highly challenging-since no sampling is usually allowed and any change on their surface is immediately noticeable. Therefore, this study focused on finding a fully non-invasive multi-analytical approach to describe degradation processes resulting from the interaction of lead pigments and oils. For this purpose, a representative set of miniature portraits on various supports (ivory, metal, glass) has been selected. For the first time, Pb carboxylates (lead soaps) have been evidenced in miniatures painted in oil and also in a combined technique (gum + oil). Their distribution and crystallinity was described by a combination of X-ray-based (X-ray fluorescence and X-ray diffraction) and micro-spectroscopic methods. At the same time, a number of new findings about the employed painting technique and involvement of various pigments in the degradation processes were obtained. For example, a possible saponification of a mixed Pb-Sn-Sb yellow was indicated for the first time. Although the degradation is clearly at an advanced stage, it has not shown yet any visible symptoms that might warn restorers and curators. Therefore, without targeted analysis, it would remain overlooked.

Application of X-ray diffraction (XRD)-based techniques in the analysis of painted artworks is not only beneficial for indisputable identification of crystal constituents in colour layers, but it can also bring insight in material crystal structure, which can be affected by their geological formation, manufacturing procedure or secondary changes. This knowledge might be helpful for art historic evaluation of an artwork as well as for its conservation. By way of example of kaolinite, we show that classification of its crystal structure order based on XRD data is useful for estimation of its provenance. We found kaolinite in the preparation layer of a Gothic wall painting in a Czech church situated near Karlovy Vary, where there are important kaolin deposits. Comparing reference kaolin materials from eight various Czech deposits, we found that these can be differentiated just according to the kaolinite crystallinity. Within this study, we compared laboratory powder X-ray micro-diffraction (micro-XRD) with synchrotron radiation X-ray diffraction analysing the same real sample. We found that both techniques led to the same results.

The uniqueness and limited amounts of forensic samples and samples from objects of cultural heritage together with the complexity of their composition requires the application of a wide range of micro-analytical methods, which are non-destructive to the samples, because these must be preserved for potential late revision. Laboratory powder X-ray micro-diffraction (micro-XRD) is a very effective non-destructive technique for direct phase analysis of samples smaller than 1 mm containing crystal constituents. It compliments optical and electron microscopy with elemental micro-analysis, especially in cases of complicated mixtures containing phases with similar chemical composition. However, modification of X-ray diffraction to the micro-scale together with its application for very heterogeneous real samples leads to deviations from the standard procedure. Knowledge of both the limits and the phenomena which can arise during the analysis is crucial for the meaningful and proper application of the method. We evaluated basic limits of micro-XRD equipped with a mono-capillary with an exit diameter of 0.1 mm, for example the size of irradiated area, appropriate grain size, and detection limits allowing identification of given phases. We tested the reliability and accuracy of quantitative phase analysis based on micro-XRD data in comparison with conventional XRD (reflection and transmission), carrying out experiments with two-phase model mixtures simulating historic colour layers. Furthermore, we demonstrate the wide use of micro-XRD for investigation of various types of micro-samples (contact traces, powder traps, colour layers) and we show how to enhance data quality by proper choice of experiment geometry and conditions.

Correct identification of pigments and all accompanying phases found in colour layers of historical paintings are relevant for searching their origin and pigment preparation pathways and for specification of their further degradation processes. We successfully applied the analytical route combining non-destructive in situ X-ray fluorescence analyses with subsequent laboratory investigation of micro-samples by optical microscopy, scanning electron microscopy/energy-dispersive spectroscopy and X-ray powder micro-diffraction (micro-XRD) to obtain efficiently all the data relevant for mineralogical interpretations of the copper pigments origin. Cu salts (carbonates, chlorides, sulphates, etc.) used as pigments exist in a range of polymorphs with similar or identical composition. The efficiency of the micro-XRD for direct identification of such crystal phases present in micro-samples of colour layers was demonstrated in the presented paper. A new, until now unpublished, type of copper pigment--cumengeite, Pb(21)Cu(20)Cl(42)(OH)(40)--used as a blue pigment on a sacral wall painting in the Czech Republic was found by means of micro-XRD. Furthermore, azurite, malachite, paratacamite, atacamite and posnjakite were identified in fragments of colour layers of selected Gothic wall paintings. We found Cu-Zn arsenates indicating the natural origin of azurite and malachite; artificial malachite was distinguishable according to its typical spherulitic crystals. The corrosion of blue azurite to green basic Cu chloride was clearly evidenced on some places exposed to the action of salts and moisture-in a good agreement with the results of laboratory experiments, which also show that oxalic acid accelerates the corrosion of Cu pigments.

Sixteen samples of orange-red and yellow Fe-oxide earthy pigments mainly from bole grounds of Baroque paintings were studied by elemental and phase analysis and voltammetry. Fe, K, and Ti content were found to be suitable for further classification of those earthy pigments. According to the chemical and phase composition the yellow grounds were natural yellow ochres formed by intense chemical weathering in a moderate climate. Very similar phase and elemental composition of part of the orange-red boles indicated their similar geological origin or even their formation by calcination of yellow ochres. Part of the orange-red boles differed significantly from the yellow boles, especially in their increased content of Ti, indicating their relation to end products of intense weathering, e.g. laterites formed in a tropical climate. Analogous materials with a correspondingly large Ti content are not currently commercially available and their geological origin (provenance) is not clear. In several orange-red boles the intentional addition of rather coarse-grained haematite to natural ochre by the painters was assumed on the basis of Fe oxide content and crystallinity.