Analytical contributions to the evaluation of painting authenticity from Princely church of Curtea de Arges

The present study contains the analyses performed for pigment samples taken from the Princely church of Curtea de Arges, one of the oldest churches in Romania. The results of our investigations have shown the source of these samples, thus being identified the pigments: natural ultramarine, cinnabar, red earth, and calcium carbonate in the painting from the 14th century, the pigments: lead white, zinc white, and Prussian blue in the repainting from the 19th century and the pigments zinc white, titanium dioxide white, bone white, yellow ochre, red ochre, green earth, artificial ultramarine, and mars red in the interventions carried out in the 20th century. The analyses consisted of light microscopy (LM) and microchemical tests, as well as energy dispersive X-ray (EDX) analysis. This system of analyses allows one to precisely determine the authenticity of certain pigments, thus avoiding the dating errors for different interventions carried out on the original mural painting from the Saint Nicholas Princely church of Curtea de Arges.     

Thermal desorption/gas chromatography/mass spectrometry approach for characterization of the volatile fraction from amber specimens: A possibility of tracking geological origins

Research on the chemical composition of fossil resins has evolved during the last decades as a multidisciplinary field and is strongly oriented toward the correlation with their geological and botanical origin. Various extraction procedures and chromatographic techniques have been used together for identifying the volatile compounds contained in the fossil resin matrix. Hyphenation between thermal desorption (TD), gas chromatography (GC) and mass spectrometry detection (MS) has been chosen to investigate the volatile compounds fraction from ambers with a focus on Romanite (Romanian amber) and Baltic amber species. A data analysis procedure was developed for the main purpose of fingerprinting ambers based on the MS identity of the peaks generated by the volatile fraction, together with their relative percentual area within the chromatogram. Chromatographic data analysis was based entirely on Automated Mass Spectral Deconvolution & Identification System (AMDIS) software to produce deconvoluted mass spectra which were used to build-up a mixed mass spectra and relative retention scale library. Multivariate data analysis was further applied on AMDIS results with successful discrimination between Romanite and Baltic ambers. A special trial was conducted to generate pyrolysis “like” macromolecular structure breakdown to volatile compounds by gamma irradiation with a high absorbed dose of 500 kGy. Contrary to our expectations the volatile fraction fingerprints were not modified after irradiation experiments. A complementary non-destructive new approach by ESR spectroscopy was also proposed for discriminating between Romanite and Baltic ambers.     

Spectroscopic evaluation of painted layer structural changes induced by gamma radiation in experimental models

The degradation of cultural heritage objects by insects and microorganisms is an important issue for conservators, art specialists and humankind in general. Gamma irradiation is an efficient method of polychrome wooden artifacts disinfestation. Color changes and other modifications in the physical chemical properties of materials induced by gamma irradiation are feared by cultural heritage responsible committees and they have to be evaluated objectively and precisely. In this paper FTIR and FT-Raman spectroscopy methods were used to investigate the structural changes in some experimental models of tempera paint layers on wood following 11 kGy gamma irradiation at two dose rates. Radiation chemistry depends on the particular pigment, matrix formed by protein, resin (in case of varnished samples) and water presence. For the majority of painted layer in experimental models very small spectral variations were observed. Small changes in the FTIR spectra were observed for the raw sienna experimental model: for the higher dose rate the egg yolk protein oxidation peaks and the CH stretching bands due to lipids degradation products increased.     

TD-GC-FID based approach for monitoring indoor borne styrene and optimization of irradiation conditions for radiopolymerization in consolidated artifacts

Styrene induces various adverse health impacts. Due to its wide applications, the quantification of personal exposure level is of great importance, especially in places that attract a large number of people daily, like museums. The aim of this study was to develop a TD-GC-FID based approach to assay the level of residual indoor borne styrene from artifacts consolidated through radio-polymerization. Optimization of the irradiation conditions and the minimum absorbed dose for total radio-polymerization were also investigated through the proposed methodology. Styrene’s assay was performed using a thermal desorption instrument coupled to a gas chromatograph equipped with a flame ionization detector (TD-GC-FID). Specific TD protocols were optimized for both declared objectives. Thermogravimetry/differential scanning calorimetry (TG/DSC) was used for optimization of the TD operational parameters. It was demonstrated that an adsorbed dose of 30 kGy ensures an almost complete radio-polymerization process. Less than 1.746?ppm of styrene is delivered from artifacts and may be inhaled by a person situated in its close proximity, a level placed within the accepted limits imposed by OSHA regulations. It was demonstrated that the TD-GC-FID approach might be useful to assess the occupational exposure to gaseous residual indoor borne styrene from museums exhibiting consolidated artifacts.