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The church of San Francesco del Prato in Parma (Italy) is a masterpiece of the Gothic style, dated back to the 13th century. However, its historical and monumental value could not be appreciated for a long time, especially due to the transformation of the building into a city jail. The recent restoration works brought back to light valuable frescos and wall paintings belonging to different periods. An in situ campaign was performed on the 15th-century wall paintings adorning the vault and the walls in the church apse, by using mobile Raman and X-ray fluorescence equipment. The characterization of the art pieces was further carried out with micro-Raman spectroscopy and gas chromatography–mass spectrometry analyses. Overall, a quick and thorough identification of the colours palette of the wall paintings was successfully obtained through the in situ measurements. Laboratory analyses corroborated the understanding of the techniques through the identification of pigments and binders. In addition, micro-Raman analyses highlighted the presence of degradation products. Interestingly, a pigment hierarchy has been noted in relation to the painted contents, enhancing the preciousness of holy figures and their distinctive details.

Since the early 1970′s, enzymes have grown more and more popular among conservators, initially in paper and gradually also in other specialties. Hydrolytic enzymes, or hydrolases, have been most commonly used, for their ability to catalyze hydrolysis of proteinaceous-, polysaccharide- and lipid-based materials that often alter the appearance and the structure of works of art. This action enables the removal of the disturbing materials under milder experimental conditions than would normally be required with more traditional approaches, like organic solvents or alkaline media. Throughout four decades, our knowledge on the mode of action and on the parameters that regulate enzyme activity has steadily made significant progress. Meanwhile, the availability of pure enzymes has also enormously increased. Enzymes can thus be considered useful materials and predictable methods for operators in many disciplines of conservation. This paper reviews the development of the use of enzymes in conservation and presents the state of the art of the current knowledge.

The use of organic solvents in treatments for the removal of varnishes on easel paintings is still a common practice among conservators worldwide. The more polar solvents required for aged, oxidize...

Pagán is an ancient city located in Myanmar that is renowned for the remains of about 4000 pagodas, stupas, temples and monasteries dating from the 11th to 13th centuries. Due to a magnitude 6.8 earthquake in 2016, more than 300 ancient buildings were seriously damaged. As a part of the post-earthquake emergency program, a diagnostic pilot project was carried out on Me-taw-ya temple wall paintings to acquire further information on the materials and on their state of conservation. This article presents our attempts at characterising the painting materials at Me-taw-ya temple using non-invasive portable energy dispersive X-ray fluorescence (ED-XRF), portable Raman spectroscopy and micro-invasive attenuated total reflectance—Fourier transform infrared spectroscopy (ATR-FTIR), micro-Raman spectroscopy (µ-Raman), gas chromatography-mass spectrometry (GC-MS), polarized light microscopy (PLM) and environmental scanning electron microscope—X-ray energy dispersive system (ESEM-EDS) investigations with the aim of identifying the composition of organic binders and pigments. The presence of a proteinaceous glue mixed with the lime-based plaster was ascertained and identified by GC-MS. In addition, this technique confirmed the occurrence of plant-derived gums as binders pointing to the a secco technique. Fe-based compounds, vermillion, carbon black and As-compounds were identified to have been incorporated in the palette of the murals.

An integrated system for the controlled-delivery and micro-aspiration of aqueous solutions for cleaning sensitive painted surfaces has been developed and evaluated. The system relies on a simple syringe-driver device, providing a constant and controllable flow of aqueous solution directly onto the cleaning brush and a surgical micro-aspirator outfitted with a variety of accessories for removing the cleaning solution from the surface through suction. By drastically decreasing the contact time of the aqueous solution, diffusion is greatly reduced, thereby minimizing swelling and possible disruption to sensitive surfaces as well as reducing the risk of the leaching of binding medium components. The aim of this study was to analytically evaluate these risks on an unvarnished oil painting from the late 1970’s. Cotton swabs from aqueous cleaning, applied as per traditional swab rolling and through the controlled delivery/micro-aspiration were analyzed using X-ray Fluorescence (XRF). Untreated and treated (cleaned) paint areas were then sampled and analyzed using Gas Chromatography-Mass Spectrometry (GC/MS) for changes to fatty acid profiles.

Mortars and plasters from the Forty Martyrs rupestrian complex (Cappadocia, Turkey) were characterized by means of different and complementary analytical techniques, in order to achieve evidence about the raw materials and the production technologies employed in the site dwelled by some of the first Cappadocian Christian communities. The investigated area is constituted by rooms directly hewn in the volcanic deposits named “Fairy Chimneys” and included in the UNESCO World Heritage List. Archaeological studies attributed different uses to the rooms, i.e. chapels, storages and wineries. The multi-analytical approach means to confirm or to retract the archaeological thesis and to highlight probable differences in the production techniques of the stone materials. In this regard, textural and compositional data of the binder and the aggregate fractions were collected by optical microscopy and electron microscopy coupled with microanalysis. Pigments and binder composition were investigated by Fourier transform infrared and micro-Raman spectroscopy. Lastly, probable traces of organic residues were identified by gas chromatography coupled with mass spectrometry. The obtained results allowed for identifying variations in the technical and compositional characteristics of mortars and plasters which can be related to different uses of the rooms constituting the rupestrian complex.

Casapini’s Herbarium is an 18th century manuscript, belonging to the Palatina Library in Parma and currently stored at the Botanical Garden of Parma University. The Herbarium collects nearly 200 samples of dried plant specimens that have been severely affected by physical, biological and chemical degradation. In 2016 the Inner Wheel Club Italia-Parma Est, an international female association, decided to fund the conservation of this Herbarium in order to preserve it and allow its study. A large team of professionals, including conservators, chemists, physicists and a botanist, has been working on the project to secure this unique but very fragile object. This paper discusses the condition assessment, the identification of degradation processes and the first conservation approach to the Casapini Herbarium. Issues related to the treatment of heavily corroded areas, the resewing of the sections and the future storage of the manuscript are also identified and highlighted for further research.

Wet cleaning of ancient papers is a common treatment performed for the removal of degradation products, external contaminants and salts, which can promote the degradation of cellulose (i.e., hydrolysis, oxidation). In this research, the effects on the mechanical properties of paper samples caused by wet cleaning treatments were evaluated by considering the changes induced in the ultimate tensile strength, deformation at break and flexibility. For this purpose, samples were subjected to different aqueous cleaning treatments such as immersion in deionised water and the application of rigid gels of agar and gellan gum at different concentrations was carried out. Tensile tests were run, and morphological observations of paper by means of light microscopy and scanning electron microscopy were recorded. Contrary to the significant changes in the mechanical properties of paper samples after immersion treatment (an increase in flexibility as the elongation at break), the use of gelled systems caused slight improvement in the mechanical properties of paper (in both the ultimate tensile strength as well as in the breaking strain). Changes in the mechanical properties of paper were also correlated with slight changes in the diameter of the cellulose fibres as a consequence of the swelling action of water molecules, especially in the case of immersion treatment. Finally, the tensile tests performed on the paper samples after thermo-hygrometric accelerated artificial ageing (70 °C and 65 % RH) demonstrated that cleaning treatments by rigid gels did not seem to accelerate any sort of paper degradation in the mid to long term.

A model study on the application of chelating solutions on superficial calcium degradation patinas of wall paintings is presented. For this purpose the solubility of calcium sulfate, carbonate and oxalate in aqueous solutions of the Ca 2 + chelators EDTA and citrate, was evaluated. Both the obtained solutions and their insoluble materials were analyzed by several analytical techniques. These studies revealed that the treatment of solid samples containing calcium sulfate and carbonate as the models of painting patinas resulted in higher solubilities of calcium sulfate and carbonate over that of oxalate. Moreover, our investigations confirmed the higher capacity of EDTA to chelate Ca 2 + compared to that of citrate. All these results were interpreted and discussed on the basis of speciation models, solubility products of the salts and formation constants of the calcium complexes in solution. Finally, we report the characterization of a sodium calcium double citrate salt formed as an unexpected product in the treatment of the calcium sulfate with citrate. Overall our results suggest that the low solubility of calcium oxalate prevents its dissolution upon treatments with chelators, and that the capacity of citrate to dissolve the calcium salts is lower than that of EDTA irrespective of the duration of treatment.

In paper conservation, wet cleaning treatments are usually performed to remove harmful degradation substances. Although cleaning treatments are fundamental in this field, the use of free water, besides causing an excessive swelling of cellulose fibres and sometimes also strong alterations of graphic media, could induce the extraction of the original sizing agents, resulting in a weakening of the paper structure. Rigid polysaccharide hydrogels (i.e. Gellan gum) can be effectively used to minimize the impact of water on paper. The present study evaluates the rate of gelatine removal from paper artworks comparing two different wet cleaning treatments: washing by immersion in free deionized water and by means of Gellan gum application. After a preliminary characterization of the paper samples through Hertzberg stain test and Fourier transform infrared spectroscopy (FT-IR), the study is carried out using gas chromatography–mass spectrometry analysis (GC–MS). The results showed that Gellan gum was less invasive than immersion treatment since it caused the extraction of lower amounts of gelatine from paper. The gelatine removal was also tested by statistical analysis, in particular principal component analysis (PCA) of amino acids.

Italian photographs, dated between 1890 and 1930, on simple or treated paper support, chosen to be faithful to Italian photographic tradition of those times, were studied with non-invasive techniques. A first investigation by optical microscopy in reflected light put in evidence the surface peculiarity of each different photo types, characteristics and deterioration of the fibres and vegetable biodeteriogens morphology. The study of coatings and supports composition, carried out with Fourier transform infrared micro-spectroscopy in attenuated total reflectance, allowed to recognise the presence of proteinaceous binder and inorganic salts. Moreover, stereomicroscopy, optical microscopy (in reflected and transmitted light) and scanning electron microscope were used for more detailed study of biodeterioration phenomenon. These instrumental techniques have been useful to evaluate cause of chromatic differences on the surface, allowing the identification of different fungi species, and, particularly, a class of them never documented on photographic materials has been detected. Materials identification, deterioration knowledge and formulation of hypothesis on the causes of deterioration are of primary importance to act the better choice for adequate preservation and conservation process. This study shows how non-invasive techniques are completely applicable on photographic materials, field in which diagnostic analyses are still not fully overworked.

The restoration of one of the most famous masterpieces of the Renaissance, the wall paintings regarding the Assumption of the Virgin Mary painted inside the dome of the Cathedral of Parma by Antonio Allegri called Correggio (1489–1534) between 1526 and 1530, allowed an in-depth chemical-physical study of materials. Non-invasive infrared imaging and spectroscopic techniques (reflectance spectrometry in the visible range and in-situ X-ray fluorescence) and micro-invasive analytical techniques (optical microscopy, scanning electron microscopy with energy dispersive X-ray microanalysis, powder X-ray diffraction, micro-FTIR spectroscopy, micro-Raman spectroscopy, and gas chromatography coupled with mass spectrometry) were chosen in order to provide the higher set of significant data, limiting as much as possible sampling. The joined use of different techniques allowed to deeply explore Correggio's palette, on the use of a fresco and/or a secco technique, to study as well degradation products and the diffused and old restoration materials like consolidants. The study allowed the characterization of a wide range of pigments, the identification of the binding media, mainly egg and animal glue, the restoration materials (acrylic resins, paraffin waxes, various pigments) and the degradation products (calcium sulfate dihydrate and calcium oxalate).

This paper presents the results of a comprehensive diagnostic investigation carried out on five paintings (three wood panels and two paintings on canvas) by Lorenzo Lotto, one of the most significant artists of the Italian Renaissance in the first half of 16th century. The paintings considered belong to 1508-1522 period, corresponding to the most significant years of Lotto's evolution. A wide array of non-invasive (reflectance spectrometry and X-ray fluorescence) and micro-invasive analytical techniques (optical microscopy, scanning electron microscopy with energy dispersive spectroscopy, micro-FTIR spectroscopy, micro-Raman spectroscopy, gas chromatography coupled with mass spectrometry and high performance liquid chromatography coupled with photodiode array detection and mass spectrometry) were applied in order to provide a large set of significant data, limiting as much as possible the sampling. This study has proved that Lotto's painting palette was typical of Venetian practice of that period, but some significant peculiarities emerged: the use of two kinds of red lakes, the addition of calcium carbonate and colourless powdered glass, the latter frequently found in pictorial and ground layers. Moreover, the integrated investigation showed that Lotto's technique was sometimes characterized by the use of coloured priming and multi-layer sequences with complex mixtures. Chromatographic analyses allowed to identify in all specimens: azelaic, palmitic and stearic acids, generally referring to the presence of drying oils. The extension of additional non-invasive examination to about 50 paintings by the same author, spanning from 1505 to around 1556, helped to verify the evolution in the use of some pigments, such as the yellow ones, where Pb-Sb yellow was used alongside Pb-Sn yellow.

Wood modification with siloxanes bearing amino groups with copper-linking function was carried out by a sol-gel process. Tetraethoxysilane (TEOS) and 3-aminopropyltriethoxysilane (APTES) were the main components. Two different procedures were followed: a two-step process (impregnation with the TEOS/APTES mixture followed by dipping into a copper sulphate solution) and a one-step process (impregnation with a homogeneous sol mixture of TEOS, APTES and copper (II) chloride). The obtained materials were characterized by infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and energy dispersive X-ray microanalysis. The determination of copper content before and after leaching was performed by atomic absorption spectroscopy. The efficacy against the brown rot fungus Coniophora puteana was tested by an accelerated procedure. SEM analyses showed that silicon penetrated into wood, while copper is effectively drawn into wood only in the one-step treatment. Copper fixation to the silica gel proved to be adequately strong. Both sol-gel treatments gave good protection against Coniophora puteana.

Powdered pigments found in bowls from the Pompeii archaeological site and some wall-painting fragments from the Vesuvian area (conserved in the National Archaeological Museum of Naples) were investigated by microscopic Raman and FTIR spectroscopies, X-ray diffraction and scanning electron microscopy-energy dispersive X-ray. Brown, red and yellow pigments are common ochres based on goethite and haematite. The blue pigment is Egyptian blue: the presence of tridymite and cristobalite indicates firing temperatures in the 1000–1100 °C range. Pink pigments were prepared both with purely inorganic materials, by mixing haematite and Egyptian blue (violet hue), or presumably by adding an organic dye to an aluminium-silica matrix. A white powder found in a bowl is composed mainly of the unusual pigment huntite (CaMg3(CO3)4). Celadonite is found in the green samples from the wall paintings, together with Egyptian blue and basic lead carbonate, while the heterogeneous green pigment in a bowl shows malachite mixed with goethite, Egyptian blue, haematite, carbon, cerussite and quartz. Copyright © 2010 John Wiley & Sons, Ltd.

During the restoration plan of the famous painting “Madonna col Bambino e S. Giovannino” by Sandro Botticelli, located in the Museo Civico of Piacenza (Italy), a study on painting materials was carried out. The pigments, the binders and the materials used for the application of ground and priming layers were studied using micro-Raman spectroscopy, gas chromatography coupled with mass spectrometry (GC/MS), optical and electronic microscopies. Gypsum and anhydrite were found in the ground layer, while carbon black and lead white were used in the priming layers. The precious pigments of the artist's palette and the binders used (egg and animal glue) were determined.

The Cathedral of St. Giorgio in Ragusa Ibla like the majority of historic buildings in the Ragusa area is constructed mainly from locally outcropping calcarenite belonging to the Ragusa Formation. Through the years, the cathedral has undergone diverse restoration procedures using different protective products, the nature of which was determined by means of Fourier transform infrared spectroscopy (FT-IR) and gas chromatography coupled with mass spectrometry (GC–MS). Regardless of these interventions, the materials used today are still subject to diverse forms of alterations and degradation (alveolitation, differential degradation, decohesions, chromatic alterations and the formation of biological patinas correlated to lichen activity), which cause considerable damage to the facade. In this paper, three protective products were tested on the calcarenite of the Ragusa Formation taken from a quarry: a fluorurated elastomer, a fluorurated anionic polyurethane and linseed oil. The protective efficiency was determined, after undergoing UV radiation aging by means of capillary water absorption, porosimetric and colorimetric procedures. The results highlighted a good and persistent protective capability of both the elastomer and the fluorurated polyurethane, whereas, the linseed oil not only provoked strong chromatic variations but also quickly lost its hydro-repellant capacity with aging.

Times Cited: 16; International audience; Cattle domestication from wild aurochsen was among the most important innovations during the Neolithic agricultural revolution. The available genetic and archaeological evidence points to at least two major sites of domestication in India and in the Near East, where zebu and the taurine breeds would have emerged independently. Under this hypothesis, all present-day European breeds would be descended from cattle domesticated in the Near East and subsequently spread during the diffusion of herding and farming lifestyles. We present here previously undescribed genetic evidence in contrast with this view, based on mtDNA sequences from five Italian aurochsen dated between 7,000 and 17,000 years B.P. and > 1,000 modern cattle from 51 breeds. Our data are compatible with local domestication events in Europe and support at least some levels of introgression from the aurochs in Italy. The distribution of genetic variation in modern cattle suggest also that different south European breeds were affected by introductions from northern Africa. If so, the European cattle may represent a more variable and valuable genetic resource than previously realized, and previous simple hypotheses regarding the domestication process and the diffusion of selected breeds should be revised.

Micro-Raman spectroscopy and gas chromatography combined with mass spectrometry (GC–MS) were employed to investigate the materials used in the wall paintings by the older Parmigianino (Francesco Mazzola, 1503–1540) on the arch over the main altar in the church of Santa Maria della Steccata in Parma, Italy. The pigments used by the artist and those added by later restorations are characterized by micro-Raman spectroscopy. GC–MS identified the organic binding media in the paint samples and revealed the presence of polysaccharides in the plaster. These investigations may be useful for a comparison with the technique of the young Parmigianino, author of wall paintings in the church of S. Giovanni Evangelista in Parma in the 1520s. Copyright © 2004 John Wiley & Sons, Ltd.

During the late Pleistocene, early anatomically modern humans coexisted in Europe with the anatomically archaic Neandertals for some thousand years. Under the recent variants of the multiregional model of human evolution, modern and archaic forms were different but related populations within a single evolving species, and both have contributed to the gene pool of current humans. Conversely, the Out-of-Africa model considers the transition between Neandertals and anatomically modern humans as the result of a demographic replacement, and hence it predicts a genetic discontinuity between them. Following the most stringent current standards for validation of ancient DNA sequences, we typed the mtDNA hypervariable region I of two anatomically modern Homo sapiens sapiens individuals of the Cro-Magnon type dated at about 23 and 25 thousand years ago. Here we show that the mtDNAs of these individuals fall well within the range of variation of today's humans, but differ sharply from the available sequences of the chronologically closer Neandertals. This discontinuity is difficult to reconcile with the hypothesis that both Neandertals and early anatomically modern humans contributed to the current European gene pool.

Archaeological bones contain only small amounts of DNA due to post-mortem DNA degradation and the changes endogenous DNA is subjected to during diagenesis. An important step before undertaking such time-consuming and costly analyses as ancient DNA investigation is to predict the presence of DNA in ancient samples. To date, the leading screening method has been amino acid racemization; however, other analytical techniques can also be used to assess the degree of bone preservation.The aim of the present study was to relate the presence of DNA with bone preservation in order to select samples potentially suitable for ancient DNA analysis.Bones collected from several archaeological sites, different locations (cave, rockshelter or sub divo) and diachronic periods were selected for analytical and spectroscopic analysis in order to correlate bone tissue preservation with the presence of DNA. Different techniques were combined to assess the degree of preservation of organic and inorganic components.As determined by different analytical methods, preservation of the inorganic component was best associated with the presence of DNA.Evaluation of the bone preservation state may be an efficient step to predict the presence of DNA in ancient samples prior to aDNA analysis.

The relevance of a risk assessment of the built heritage was clearly justified due to the fact that it acts as a pollutant repository and hazardous pollutants have the capacity to penetrate into materials. However, the limitation of the sampling processes due to the high value of the built heritage makes a correct evaluation difficult. For that reason, in the present work, the potential of agar gels as non-invasive samplers of built heritage deterioration products, like crusts and patinas, was evaluated. Different gels of agar and Carbopol® (as control gel) were applied on these built surfaces considering several factors: the treatment time, the effectiveness of the addition of EDTA (ethylenediaminetetraacetic acid, C10H16N2O8) and its concentration and the use of a buffer at pH 7.5. All these factors were evaluated in order to determine the capacity of these gels as sampling systems under non-controlled atmospheric conditions. The results obtained in the assays were evaluated by visual examination, by evolution of pH and by the most important techniques used in the risk assessment analysis of the built heritage (Raman spectroscopy, scanning electron microscope (SEM)/energy dispersive X-ray (EDX) and inductively coupled plasma mass spectrometry (ICP-MS)). In this evaluation, the agar gels showed an intrinsic capacity as sampler with respect to the gel Carbopol® and thus, the best option between the studied gels consisted on agar gels with 2 % of EDTA and the longest application time. On the whole, the agar gels showed an interesting potential as non-invasive samplers of built heritage deterioration materials which should be studied more in depth.

During the last restoration of the six paintings by Raffaele Rinaldi (1851-1916), located in the church of Maria SS. Annunziata (Marano Principato, Cosenza, Italy), made between 1890 and 1903, several scientific investiga- tions were carried out on them. The present work aims at classifying the painting in terms of its materials and tech- nical particularities. The goal of this study was to charac- terise the painting technique of the painter, its evolution and possible additions made during previous restorations. Pig- ments, binder media and raw materials used for the appli- cation of the ground and the paint layers were studied us- ing electronic microscopy equipped with energy dispersive spectroscopy qualitative microanalysis (SEM-EDS), infra- red spectroscopy (FTIR) and gas chromatography coupled with mass spectrometry (GC/MS). Furthermore, a complete analysis of the state of preservation of these paintings rep- resents a scientific aid and guide for its restoration, taking into account the severe damage not exclusively due to natu

Mineralogical, petrographic and chemical analyses were performed on sherds of transport amphorae (VI–III century B.C.) excavated at Locri Epizephiri, as well as on specimens of local manufacture. Examination of thin sections by the polarizing microscope and of X-ray powder diffraction patterns suggested that most of the amphorae could be assigned to local workshops since fossils and minerals as well as rock fragments are compatible with the crystalline basement of the Calabrian-Peloritanian arc. Chemical analysis, performed by ICP and flame atomic emission spectroscopy followed by multivariate treatment of data, further suggested that three groups of composition may gather most of the amphorae and the local reference products. These results point to a wide local production of transport amphorae in Locri, thus indicating that the ancient town was self-sufficient in producing agricultural foodstuffs, with limited dependence on imported goods.

Technological features of sherds of Roman terra sigillata were studied. The sherds analysed represented products of workshops which were most probably located in Gaul, central Italy, north-west Italy and the plain of the river Po. Equivalent firing temperatures were estimated by colour measurement, X-ray diffraction and thermal expansion measurement; in addition, the chemical and morphological features of the red sintered slips were investigated using scanning electron microscopy coupled with energy dispersive X-ray microanalysis. The combined results suggest that, relative to northern Italian products, terra sigillata from Gaul and central Italy was made by potters who were more successful in modifying slip composition and controlling firing temperature to obtain highly sintered slips. Northern Italian potters seem to have worked their clays less successfully and fired them at temperatures which were too low to overcome the limited presence of fluxes in the slip.

Researches on environmental radioactivity in the Ross Sea — Terra Nova Bay area have been carried out with the aim of evaluating the role of different abiotic and biotic matrices in the cycling of radio-nuclides in the marine and lacustrine ecosystems. The transfer of Sr-90, Cs-137, Pu-238 and Pu-239(240) from the water to the benthic organisms and the sediment layer has been investigated. Contamination levels in both ecosystems and biogeochemical cycles of the main fission and transuranic products are therefore presented and discussed. A comparison of radioecological data from different areas of the Antarctic Ocean and the Mediterranean Sea is given. In the framework of the data obtained, concentrations of the natural radionuclides K-40, Th-232 and U-238 in the sediment samples, are also presented.

Cleaning is one of the most important, delicate, and at the same time controversial processes in the conservation treatment of paintings. Although a strict definition of cleaning would be the removal of dirt, grime, or other accretions (surface cleaning), in the conservation field, cleaning is used in the broader meaning to include thinning/removing altered or “unwanted layers” of materials without damaging or altering the physicochemical properties of the surfaces to be preserved. The cleaning of unvarnished paintings is one of the most critical issues that are currently discussed. Several studies exist regarding different cleaning tools, such as gels, soaps, enzymes, ionic liquids, and foams, as well as various dry methods and lasers, but only a few have been performed on the risk associated with the use of water and organic solvents for the cleaning treatments in relation to the original paint binder. The aim of the study is to verify analytically the behavior of water gelling agents during cleaning treatments and the interaction of the following elements: water or organic solvents applied for the removal of gel residues with the original lipid paint binder. For this purpose, the study was conducted on a fragment of canvas painting (sixteenth to seventeenth century) of Soprintendenza per i Beni Storici, Artistici ed Etnoantropologici del Friuli Venezia Giulia (Superintendence for the Historical, Artistic and Ethno-anthropological Heritage of Friuli Venezia Giulia), Udine by means of Fourier transform infrared spectroscopy, gas chromatography/mass spectrometry, and scanning electron microscopy.

In the conservation field, the original morphology and texture of the paper surface represent an important aspect to be preserved as historical evidence of the papermaking process. The aim of this preliminary research is to evaluate the effects of aqueous (cellulose ethers, rigid gels of Agar and Gellan gum) and not aqueous cleaning treatments (a typical dry cleaning treatment with wishab sponge) on the original surface morphology of late nineteenth century paper. Nineteenth century newspaper paper was chosen because it is strongly affected by cellulose oxidation and depolimerization due to the rough materials (wood pulp) and the papermaking process used at the time and to the environmental conditions (light, humidity, temperature) to which such paper has been subjected. A preliminary characterization of the paper with Herzberg and Phloroglucinol reactives and Fourier Transform infrared Spectroscopy analysis was performed to understand the paper composition and the type of inorganic fillers used. The paper surface microtopography was then measured by contact profilometry to analyze the effects of the cleaning treatments on paper surface roughness. The effects of the cleaning action was qualitatively evaluated by means of stereo microscopy and scanning electron microscopy. Preliminary results suggest that the treatments which are most respectful of the original surface micromorphology of the paper are those based on the use of rigid gels (Agar and Gellan gum), because they determine the smallest variation in the roughness of surface paper, unlike the application of cellulose ethers by brush. This finding was confirmed by statistical analysis of the roughness results by means of ANOVA and Tukey HSD post hoc test.

During the last restoration (2008-2011) of the polychrome terracotta altarpiece called Coronation of Virgin between Saints Rocco, Sebastian, Peter martyr and Antonio abbot, located in the collegiate church of S. Maria Assunta in Montecassiano (Macerata, Italy), scientific investigations were carried out to acquire detailed information about the painting technique. The identification of materials allowed a correct restoration. The altarpiece is almost entirely realized by Marco della Robbia (Fra Mattia), dates back to the first half of the XVI century and represents an interesting example of painted terracotta produced by using two different techniques: glazed polychrome terracotta and the "cold painting" technique. The characterization of the samples' material constituents was obtained by analysing the cross-sections and the fragments by different techniques (optical, SEM-EDS and ATR-FTIR microscopy as well as GC-MS), as the real nature of a component is often difficult to assess with one single technique. The optical microscope examination of paint cross-sections shows the presence of many layers, indicating the complexity of the paint stratigraphic morphologies. The original polychromy of della Robbia's masterpiece is constituted of cinnabar, red lake, red lead, orpiment, red ochre, lead white, lead tin yellow, green earth and raw umber. Two different types of gilding technique have been distinguished. The first one presents a glue mordant, and the second one shows an oil mordant composed by a mixture of red lead, red ochre, cinnabar and orpiment. The GC-MS analysis allowed the characterisation of linseed oil and a mixture of animal glue and egg as binding media stratigraphically located by the use of ATR-FTIR mapping microscopy. The analytical results of the painted terracotta integrated investigations show that original technique adopted is characterised by the application of pigments in an oil-binding medium directly applied on the substrates, probably treated with oil and animal glue. A large number of overpaintings above the original scheme of polychromy was found, which could be ascribed to almost three different interventions; the absence of modern pigments suggests that they could be realized long ago.

A GC-MS method is proposed for the characterization of binding media in paint works of art. The basic methodology relied on the determination of amino acids and fatty acids after hydrolysis with HC1 and derivatization with 2-propanol and trifluoroacetic anhydride, and on the comparison with reference materials. The use of fused-silica capillary columns coated with methylphenylsilicone phases allowed to separate amino acid and fatty acid derivatives in a single analytical run. The method was applied to identify binding media used in ground and paint layers of polychrome sculptures of the eighteenth century.

Fifty-six sherds of fine ware from Locri Epizephiri were analysed by inductively coupled plasma optical emission spectroscopy (ICPOES) and flame emission spectroscopy (FES). The sherds had been excavated on the archaeological areas of Marasa Sud, Centocamere and San Cono, and represent local and imported products from the seventh to the second century BC. The samples were dissolved by fusion with lithium metaborate and analysed for nine elements (Al, Fe, Ca, Mg, Ti, Mn, Sr, Ba and Cr) by ICPOES, while Na and K were determined by FES. The analytical data were subjected to hierarchical agglomerative clustering and principal components analysis to classify the sherds into compositional groups. The results obtained indicated that Corinthian, Attic and Ionian products or imitations may be classified in a few separate groups, while most local products are found in a unique, large group.

Proteinaceous organic materials used as ancient painting media were investigated by capillary gas chromatography (GC) and capillary gas chromatography — mass spectrometry (GC/MS). Medieval wall paintings made by the tempera technique were considered and their binding media were studied by the characterization of their main chemical components. The basic methodology is based on the determination of amino acids in samples of paint layers after hydrolysis and derivatization and on the comparison with reference proteinaceous materials. Multivariate chemometric techniques were used to facilitate the recognition of the protein source from chromatographic data. To characterize the binders further, a method was developed for the determination of fatty acids, present as minor components, by GC/MS. The use of fused-silica capillary columns coated with selected stationary phases allowed the separation of amino acid and fatty acid derivatives in a single analytical run.

Background The present research concerns the Roman wall paintings preserved at Insula del Centenario (IX, 8), the important Pompeian block situated in the Regio IX, along Via di Nola. Results The aims of this research are two: to verify the presence of lipidic and proteinaceous material to spread the pigments, and to identify organic matter in painting materials owing to previous restoration works. The samples collected from the wall paintings of different rooms have been investigated by Fourier Transform Infrared Spectroscopy (FT-IR), and Gas Chromatography/ Mass Spectrometry (GC/MS). Conclusions The analytical results show that these Roman wall paintings were realized without the use of lipidic and proteinaceous materials, supposedly in fresco technique. Moreover, it was detected that wax, egg, and animal glue were used in previous restoration works for protective purpose and to restore the wall paintings to their original brilliant colours.

Fifty-five fragments of Roman glass from Augusta Praetoria (Aosta, Italy) were analysed by inductively coupled plasma optical emission spectroscopy determining 15 elements (Si, Na, Ca, Al, Fe, Mg, Mn, Ti, Sr, Ba, Cr, Ni, Cu, Co and Pb) on dissolved samples; in addition, potassium was determined by flame atomic absorption spectroscopy. The analytical results indicate that all the fragments, with one exception, are silica-soda-lime glasses; (he exception is a potash glass. Cluster analysis was performed on the analytical data by accounting for either 14 (all the elements searched for but Ni and Pb) or eight elements (after further removal of Si, Fe, Mn, Cr, Cu and Co from the data set). The results obtained indicate that, once colouring and decolouring agents are removed, the classification of the glasses seems to be mainly determined by chronology; separate groups within coeval fragments may indicate different provenances.

Supervised and unsupervised pattern recognition techniques were used to classify 48 sherds of Roman pottery (terra sigillata), analysed by inductively coupled plasma atomic emission spectrometry and atomic absorption spectrometry for seven major and minor elements (Al, Fe, Ca, Mg, K, Ti and Mn). Hierarchical agglomerative clustering and principal component analysis were used to classify the studied material into compositional groups which could account for different centres of production; soft independent modelling of class analogy (SIMCA) was used to solve questions regarding doubtful assignments. The results indicate that, in the case study, a throughout statistical treatment can allow one to discriminate wares produced in different geographical areas on the basis of the seven elements accounted for.