Transylvanian glass icons: A GC/MS study on the binding media

Transylvanian glass icons are very specific heritage items of Romanian folk art, produced from the middle of 18th century until now. The present research reports the results of a study on the organic components of the paint layers, analyzing the binding media of a series of glass icons belonging to three important icon making centers: Nicula, Olt County (?ara Oltului) and Brasov area (?cheii Bra?ovului). The analysis of the binding media has been done by means of gas chromatography coupled with mass spectrometry (GC/MS). The applied analytical procedure allowed the characterization of the proteinaceous, polysaccharide and lipid-resinous content of the binding media starting from a unique microsample. Results showed that a wide range of materials were used by the icons painters, mostly applied as mixtures of a proteinaceous material and a lipid one. The proteinaceous component proved to be mainly egg, though animal glue and casein were ascertained too, and proteins were often mixed; the lipid material was identified as linseed oil. In some of the icons pine resin and saccharide material were found. Data also highlighted that though the materials used in all the glass icons under study are similar, some particularities could be observed in the painting technique of the studied producing centers and icon painters.     

Manufacturing expedients in medieval ceramics in Apulia

A group of 51 shards of medieval polychrome glazed pottery, coming from Canosa castle archaeological site (Bari, Italy), has been investigated through surface analytical techniques, such as Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDS) and elemental ones, such as Inductively Coupled Plasma–Optical Emission Spectroscopy (ICP–OES) and Absorption Atomic Spectroscopy (AAS) by flame and electro-thermal atomisation. The investigation was aimed at defining the elemental composition of pottery findings, identifying pigments and clarifying glaze types. The results of the analytical characterization allowed the identification of materials and technological expedients used for pottery manufacturing, highlighting original features in the production of the investigated pottery.The quantitative analysis performed on ceramic paste, glaze and painted decorations provided a significant number of results, thus enabling their effective exploitation for multivariate statistical techniques, in order to find out possible groups of pottery items with defined similarity within the samples.     

Protein identification and localization using mass spectrometry and staining tests in cross-sections of polychrome samples

The identification and localization of the proteinaceous binders are essential issues in studies of painting materials and techniques, for further proposing valid restoration and conservation treatments of the painted or polychrome works of art. The challenge for analytical chemists and conservation scientists is the availability of methods able to simultaneously identify and map the presence of the binders in the multilayered structure of a sample and the possibility to use a very low amount of sample from the studied art object (considering also the criteria of minimum sampling). These methods should be fast, reproducible in different artefacts and in case of mixture of protein-based binders with other non-proteinaceous constituents (oils, resins, waxes, gums etc.) and also economical (both in terms of materials and time consume). In this context, the present paper proposes an innovative protocol of investigation using two complementary techniques – Matrix-Assisted Laser Desorption/Ionisation – Time of Flight Mass Spectrometry (MALDI-TOF MS) and staining tests (one visible and one fluorescent stain) assisted by Optical Microscopy (OM) on cross-section of samples – for the simultaneous identification and mapping of protein – and oil-based binders in paint materials. The novelty is based on the use of MALDI-TOF MS on cross-sections of paints together with a fluorescent stain for protein identification and mapping (mainly used in the area of proteomics) complementing the use of a traditional visible stain for oil-based material identification. The protocol was successfully applied on several samples taken from a Czech medieval polychrome sculpture, entitled “The Mourning of Jesus Christ” (16th century) belonging to the Moravian Gallery (Brno).     

The analysis of polychrome works of art: 40 years of infrared spectroscopic investigations

In this paper a synthetic chronological survey of analytical applications of infrared spectroscopy for the characterization of the materials of polychrome works of art and archaeology is outlined. Various sampling methods are described and some relevant examples, drawn from the published cases, are presented. The various methods prove to be very effective in characterizing both the inorganic and organic constituents of a wide variety of artworks, giving an insight into the materials and techniques of execution of the artifacts and, in the case of infrared mapping techniques, pinpointing the analytical data within a precise layer of the stratigraphy of the cross-sectioned samples. Overall, the great analytical potential and wide field of application of this technique is fully brought to light.     

Teodelinda's tales at Monza Cathedral: A physico-chemical diagnosis of the pictorial cycle

The pictorial cycle “Teodelinda's Tales” at Monza Cathedral, painted by Zavattari and his sons in 1444–1446, has been investigated by optical and SEM-EDS microscopy and microFT-IR spectroscopy. Paint layers, gildings and other metallic decorations have been analysed to elucidate the execution technique, the state of conservation and the possible retouchings in consequence of deterioration processes. Organic binders, coatings and adhesives have been also identified especially by microFT-IR spectroscopy applied directly to the sampled powders or fragments and to their solvent–soluble fractions. The obtained data offer a correct and satisfactory knowledge of the original organic and inorganic materials and those used in the subsequent retouches and restorations, their state of conservation and the painting techniques (fresco, mezzo fresco and secco).The physico-chemical investigations allowed to identify the nature and sometimes the provenance of the employed materials (i.e. ultramarine blue pigments) and some decay markers, particularly useful in understanding and describing the cycle realised by the authors and the modifications suffered along the centuries, and also to propose an integrated methodology for the scientific study of the mural paintings.     

The binding media of the polychromy of Qin Shihuang's Terracotta Army

The “Terracotta Army” is a worldwide known archaeological finding in China. It is a part of the burial complex of the emperor Qin Shihuangdi (259–210 BC), which is still under excavation and study. The fact that the sculptures, chariots and weapons of the First Chinese Emperor's Terracotta Army were originally all painted in bright colours is still not widely known. The chemical characterisation of the paint medium was performed through an analytical procedure based on GC-MS. The proteinaceous binder was identified for the first time through a desalting procedure used in proteomics. The identification of egg as a paint binder is extremely interesting in terms of the historical significance of the work of art itself and important in terms of the method of conservation. Moreover it represents one of the first steps towards an understanding of the painting technique used on ancient sculptures in China, of which – despite their fame – nothing is yet known.     

The Russian avant-garde painting palette: Documentary and physicochemical codification of organic colorants

In the present article an attempt is made to elucidate the organic colorants commonly encountered in the Russian avant-garde painting palette by a combined art historical, documentary and physicochemical investigation, and to examine the influence of environmental factors on the chromatic profile originally sought by the artist. The overall approach based on written sources is confirmed by measurements on relevant paintings. The documentary research deals with the influences of Orthodox iconography, folkloric art, and occidental modernist tendencies on the Russian avant-garde palette, and studies the effects of contradictory historical processes in the chromatic profile of individual paintings. In the experimental section a series of colorants are investigated concerning the effects of accelerated ageing on experimental painting tables, prepared as watercolor and gouache layers on paper ground. The resulting samples are subjected to colorimetric and spectroscopic measurements, and analogous analytical procedures are applied on samples taken from selected paintings. A systematic comparative study of all data permits evaluation of the materials used in terms of their stability towards extrinsic factors, and proposal of degradation routes in order to assist museum curators and conservators in every concrete case related to the broad spectrum of pigments examined.     

An analytical investigation of the painting technique of Italian Renaissance master Lorenzo Lotto

This paper presents the first extensive investigation of the composition of both the organic and inorganic media used by Lorenzo Lotto, one of the outstanding artists of the Italian Renaissance in the early 16th century. By investigating four paintings from The State Hermitage Museum collection (Saint-Petersburg, Russia), new insights into the artist's painting techniques were obtained, which contribute to our understanding of the transition from egg tempera to oil painting techniques that took place in Italian paintings between the 15th to the mid 16th century. Inorganic materials were determined using SEM-EDX and PLM, revealing information on the artist's palette. Of particular note was the powdered colourless glass found in the priming layer of the Madonna delle Grazie, which was most likely used as dryer. Organic materials were analysed in individual paint layers using GC-MS, and revealed a mature use of drying oils as paint binders, skilfully mixed with other organic materials and inorganic driers, to obtain the desired aesthetical and technical qualities of the paint. The study revealed that Lotto used the tempera grassa technique through most of his creative life.     

A study of the effect of the wavelength in the Q-switched Nd:YAG laser cleaning of gilded wood

The removal of a brass-based paint (purpurin) used in painting gilded wood to cover losses of gold leaf, represents today a difficult task to conservators, who may have to resort to toxic chemical solvents in order to clean the painted surface. This action, due to its nature, is unsuitable for both the conservator and the artwork itself. In this study, a Q-switched Nd:YAG laser system outputting 1 064 nm (infrared), 532 nm (visible, green) and 266 nm (ultra-violet) radiation was used to study the interaction of these wavelengths in a gilded sample surface painted with purpurin. All tested wavelengths interacted differently with the tested surface and, also, the several layers that form the gilded surface (purpurin, varnish and gold) showed different interactions to each wavelength. The ultra-violet radiation (266 nm), in a multi-pulse mode at low fluences, was found to be the most efficient wavelength in cleaning the painted gilded surface.     

Innovative uses of 3D digital technologies to assist the restoration of a fragmented terracotta statue

This paper describes how some innovative methodologies have been designed and employed to support the restoration of the Madonna of Pietranico, a terracotta statue severely damaged in the 2009 earthquake. The statue, fragmented in many pieces, has undergone a complex restoration performed by a multidisciplinary working group. The contribution of digital technologies was planned from the very beginning, since the complexity of this restoration originated the design of innovative procedures for managing the reassembly and restoration process. The Madonna test bed was therefore an example of how technology innovation could be pushed by clear application needs. A first important contribution was the study of the recombination hypothesis of the fragments. This initial phase was performed on digitized 3D models of the statue fragments, with the aim of reducing fragments manipulation, preventing further damages and increasing the capabilities to rehearse and evaluate different reassembly options. The accuracy of the 3D scanned models and the new recombination procedure introduced in this paper allowed to manage this phase in the digital domain with successful results. The digital 3D models were also used to design and produce an innovative supporting structure, constructed with a rapid prototyping device. Another important contribution concerned the study and virtual restoration of the polychrome decoration of the statue; our aim was to reproduce and restore in the virtual 3D domain the very complex original polychrome decoration, on the base of the remaining traces. Consequently, new virtual painting functionalities have been designed on the MeshLab platform (an open-source tool for 3D models visualization and manipulation) for reproducing pictorial decorations over digital 3D models and have been assessed on this specific test bed. This allowed us also to investigate the complexity of the virtual repainting process and to identify further technology enhancements. Finally, computer graphics technologies have been also used to produce a video that tells the story of the restoration.     

Pollution monitoring by dosimetry and passive diffusion sampling for evaluation of environmental conditions for paintings in microclimate frames

Pollutants and their potential degradation of paintings have been measured for the first time in microclimate frames (mc-frames), which are used to protect paintings. The pollutants that were measured include both inorganic pollutants, which originate mainly from external sources, and organic pollutants from mainly internal sources. Those originating from the outdoors enter rooms and subsequently mc-frames at a rate depending on the ventilation rates (air exchange rates) of the mc-frames. The concentration of gaseous pollutants emitted within the mc-frames will depend on net emission rates of the materials used to make the mc-frames, their design, and their ventilation rates. In the EU PROPAINT project measurements of gaseous air pollutants and climatic conditions were performed at various locations both inside and outside different state-of-the-art mc-frames. Diffusive passive pollution gas samplers were used together with different types of dosimeters. Results show that the dosimeters respond to either the photo-oxidizing conditions or the level of volatile organic acids in the environments both in the museums and within the mc-frames. Two dosimeters, the Early Warning Organic (EWO) made from a synthetic polymer and the Resin Mastic coated Piezo electric Quartz Crystals (RM-PQC) respond to photo-oxidation and showed higher values outside than inside the mc-frames. Two other dosimeters, the Glass Slide Dosimeter (GSD) and the Lead coated Piezo electric Quartz Crystals (L-PQC) respond to volatile organic acids and yielded higher values inside than outside the mc-frames. This study emphasizes the need for further work to determine environmental damage functions for paintings, in particular for the effects of organic acids. Such information is essential for the evaluation of the protective effects of mc-frames for paintings. The use of mc-frames is increasing and it is very important to know that this protective measure does not introduce new risks.     

Using 3D digital models for the virtual restoration of polychrome in interesting cultural sites

In most cases, the polychrome paintings that decorated heritage buildings no longer exist or are reduced to mere remnants. These facts decontextualize the sites in their historical and artistic evolution, distort the intention under which they were conceived, and hamper their accomplishment. Current recovery methods are restricted to the stabilization of the remains in their present status, requiring a lot of completely manual work that is expensive and almost unrelated to the use of new technologies. Three-dimensional digitalization and modelling is proved to be the basis for the virtual recovery of paintings in a significant edifice. To do so, an innovative methodology is presented that allows the 3D geometric information of a site (captured using a laser scanner) to be combined with specially designed 2D artistic images. The resulting 3D digital models can then be focused, with high efficiency projectors, on the equivalent area of the original site, and also used as raw material to compose a video-projection without perspective effects to emulate, with due rigour, the primitive appearance, its evolution along time, the effects of the deterioration, or other interesting aspects. The results obtained at Sta. María de Mave (Palencia, Spain) are presented, supporting the potential of this new methodology not only as a scientific way to discuss possible restoration hypotheses with experts or as a didactic tool for narrating the historical evolution of a monument, but also as a spectacular show for tourists.     

Mortars,pigments and binding media of wall paintings in the ‘Carrera del Darro’ in Granada,Spain

The Carrera del Darro is a street within the city of Granada, Spain, which is emblematic owing to the architectural value of its buildings, to its significance for the urban structure of the city and to the implications it has for the surroundings of the Alhambra. Our study concerns the chemical analysis of the mural paintings on four façades, corresponding to numbers 23, 25, 27 and 29 of the Carrera del Darro. From the analysis of the mortar, it may be concluded that the composition is very similar, though not identical, in the four paintings studied: a limestone mortar. Ochre, white, black and red were used for the decoration of the four façades; green pigment was also observed in the second decoration of no. 29. The results of the morphological examination and EDX microanalysis of the paint samples are shown. By means of the thermogravimetric analysis we established the existence of an organically derived compound. After the existence of an oleaginous binder had been discounted by gas chromatography/mass spectrometry (GC/MS) analysis, we continued with the extraction and determination of proteins by spectrophotometry analysis, detecting low levels of proteins in the paint on the four façades analysed. The study was completed by evaluating the influence on the deterioration of the paintings by the possible surface presence of salts (such as nitrates or chlorides) and organic compounds.     

Efficiency of antibiotics and gamma irradiation in eliminating Streptomyces strains isolated from paintings of ancient Egyptian tombs

Forty-six Streptomyces strains were isolated from paintings and stone surfaces from Tell Basta and Tanis tombs (80 km south-east Cairo, Egypt). Eight of these strains were selected to determine their sensitivity against 13 antibiotics. In general, high levels of resistance could be observed. Gentamycin, spiramycin and doxycycline were the most effective antibiotics against the majority of strains under study. Due to the observed antibiotic resistances, gamma irradiation was studied as a possible alternative to inhibit microbial growth. Isolated bacteria were exposed to different doses of gamma irradiation (5, 10, 15, 20 and 25 kGy). The growth of all Streptomyces isolates except S. canarius was completely inhibited at 25 kGy. The applied doses of gamma irradiation did not cause any observable alterations or colour changes to pigments and binding media (arabic gum, animal glue and egg-yolk) used in the paintings.     

The scientific investigation for the study and conservation of the wooden model of S. Maria della Consolazione's church (Todi,Italy)

The focus of this work is the wood polychrome model of the church of S. Maria della Consolazione in Todi, an artefact whose author and historical events are not completely known except a general reference to the construction period of the church (1508–1607 AD). In this study, original and additional materials were examined in order to provide a deeper understanding of the painting and assembly techniques, and a greater awareness of how well preserved the object is, as well as an analysis of previous preservation and conservation interventions. The samples from the painted surfaces were examined by means of micro-Raman spectroscopy, fourier transform infrared (FTIR) spectrometry and internal microstratigraphic analysis. Thin sections of the wood samples were examined under an optical transmission light microscope in order to identify the botanical species. The results shown in this paper suggest the possibility that the original painted layers are made of calcium carbonate white, red ochre and indigo and they were applied by protein binder without any ground layer. Some non-original pigments were found on the model surface like Prussian blue and chrome yellow. Concerning wood components, poplar was characterized both in the original and non-original parts of the model whereas pine species were detected only in the restoration elements.     

Spectroscopic methods for the analysis of celadonite and glauconite in Roman green wall paintings

One set of samples from wall paintings of the X^th Regio of Italy containing green colours was analysed exploiting different spectroscopic techniques, aiming to identify the pigments used. The possibility to distinguish between glauconite and celadonite, the most common green pigments used in such paintings, was of particular interest. Samples of celadonite from Monte Baldo and glauconite from Belgium were considered as standard materials for comparison. The results obtained using FTIR, EDS, AAS, Colorimetry, Raman and EPR spectroscopies were compared for the identification of the green pigments.     

Identification of a fungal community on gilded wood carved heritage

During restoration activities, a fungal reddish area was noted on a gilded wood carved ceiling decoration from a sacristy of a church in Aveiro, Portugal. The protocols used to identify the fungal community present in this wooden material included the classical culturing methods and a molecular biology protocol based on the ability of denaturing high performance liquid chromatography (DHPLC) to separate fungal DNA from several species. This last method complemented the results obtained with the traditional culturing method approach and the overall study revealed three fungal species: Serpula lacrymans (Wulfen) P. Karsten, Paecilomyces lilacinus (Thom) Samson and Penicillium chrysogenum Thom. This is, to the author's knowledge, the first documented case of S. lacrymans in Portuguese built cultural heritage. Despite the antifungal solution applied and the dryer environment recommended, the water activity (Aw) levels recorded on location are still dangerously high and may allow fungal regrowth. Periodic inspections were advised.     

Characterisation of 15 century red and black pastes used for wall decoration in the Qijmas El-Eshaqi mosque (Cairo, Egypt)

The use of coloured pastes for inlaying marble and limestone wall panels is one of the ornamental techniques that were widely used during the Mamluk period in Egypt (1250–1516 AD). Red and black pastes from Qijmas El-Eshaqe mosque (1482 AD) in Cairo were studied to identify their main components. The study of the samples involved the identification of the pigments, additive materials and organic binding media. The study was performed using various analytical methods such as polarising microscopy (PLM), scanning electron microscopy equipped with energy dispersive X-ray analyser (SEM-EDX), inductively-coupled plasma (ICP-AES), X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR). These complementary analytical techniques provide precise identification of inorganic and organic substances used in the pastes. The results indicated that the red pigment is mainly obtained from red ochre containing hematite, whereas amorphous carbon (bone black and charcoal) was used to obtain the black colour. Both samples contain calcium sulphate, which was used to give some hardness to the pastes. Beeswax was used as an organic medium in both pastes. The study provides the information required for the conservation of the coloured paste ornaments.