A methodology for the identification of glass panes of different origin in a single stained glass window: Application on two 13th century windows

The chemical composition of 11 glass panes originating from two 13th century non-figurative windows were analyzed by means of Scanning Electron Microscopy–Energy Dispersive X-ray system (SEM-EDX). The windows were discovered in the back-wall of the triforium during the restoration of the choir of the cathedral St. Michael and St. Gudule in Brussels (Belgium). In order to determine if these windows were fabricated with glass of different origin or not, the compositional difference between the panes were compared with the variation in composition as a result of the following causes: (1) compositional fluctuation between panes cut from the same sheet of glass, (2) compositional fluctuation caused when panes are cut from different sheets that were made with the same batch, (3) compositional fluctuation caused when the glass is made from different batches at the same production center, and (4) compositional fluctuation as a result of glass produced at different fabrication centers.     

Black limestone used in Lombard architecture

Black limestone samples from the quarries of Varenna (Lecco, I), Cene (Bergamo, I) and Riva di Solto (Bergamo, I) and widely used in Lombard architecture have been studied in terms of mineralogical, petrographic and chemical properties in order to provide a detailed characterisation and allow an unambiguous determination of their provenance. The inorganic and organic fractions have been separated from each other, and investigated using X-ray powder diffraction, atomic absorption, Hg-porosimetry, high performance liquid chromatography, gas chromatography, nuclear magnetic resonance and Fourier transform infrared spectroscopy. The occurrence of specific mineral phases, some binary chemical patterns (Fe/Mn, Zn/Sr, Zn/Co and Na/Cd) and the carbon chain relative molecular masses has proven to be useful markers to characterise unequivocally the materials studied.     

Protective effect of endolithic fungal hyphae on oolitic limestone buildings

This study presents characterizations of weathering forms of the same oolitic limestone from four quarries and eight monuments exposed on various environmental conditions focusing on the waterproofing effect of endolithic organic matter. Patinas were analyzed by X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDX), capillarity coefficient through weathered and unweathered sides, gypsum content and porous network morphology by epoxy resin molding. Study of weathering forms on old quarries indicates that lichens colonization (Verrucaria nigrescens and Caloplaca aurantia) can fill the superficial porous network with a dense network of lichenised fungal hyphae. Capillary coefficient measurement on natural and calcinated samples showed that endolithic organic matter can waterproof the stone and could act as a sulfate contamination barrier. Similar endolithic organic layer due to ancient lichens growth are found on some antique monuments of the Nîmes downtown and could explain their well-preserved state, unlike decayed 19th century churches that were never colonized by lichens.     

Euganean trachytes: discrimination of quarried sites by petrographic and chemical parameters and by magnetic susceptibility and its bearing on the provenance of stones of ancient artefacts

This paper reports petrographic and chemical data and magnetic susceptibility values for trachytes of quarries recognizable within the Euganean Hills and sets out diagnostic parameters for these rocks. The diagnostic scheme proposed is basic for the definition of provenance of trachytes used in ancient artefacts spread over northern Italy. Trachytes were extensively used by the Romans for paving Via Aemilia, the most important road in the Po Plains connecting Ariminum (present-day Rimini on the Adriatic sea) to Placentia (present-day Piacenza on the Po river). Remains of the trachytic flagstones (basoli) used for paving segments of Via Aemilia crossing Regium Lepidi (present-day Reggio Emilia) and Bononia (present-day Bologna) have been characterised petrographically, chemically and also using magnetic susceptibility data. The discriminating scheme proposed here for the Euganean trachytes has been applied to the data obtained for basoli and thus the provenance of each investigated block has been inferred. The rocks sampled at Regium Lepidi mostly come from Monselice (only a few blocks from Monte Oliveto and Monte Merlo) and those of Bononia come mostly from Monte Merlo and, subordinately, from Monte Oliveto and Monselice (only one sample from Monte San Daniele). The dominant provenance of blocks, which is different in the two colonies distant by less than 50 km, suggests that the two segments of Via Aemilia were not built simultaneously.     

Provenance study of ancient Iranian luster pottery using PIXE multivariate statistical analysis

Although luster potteries are frequently excavated at archeological sites in Iran, a thorough scientific study of their provenance has not yet been performed. In this work, 43 pieces of Iranian luster pottery (bowl, dish and tile) excavated from Rayy, Kashan, Maragheh, Alamoot, Takht-i-Sulayman and Jiroft were analyzed in order to investigate their origin. The luster shards which belong to Seljuks and Il-Khanids dynasties (12th–13th centuries) were analyzed using proton induced X-ray emission (PIXE) technique. To classify the fragments according to their location and origin, principal component analysis (PCA) and hierarchical cluster analysis (HCA) were applied to the chemical compositions of the body of the shards. We were able to classify the samples into three distinct groups using PIXE.     

Methodology of analytical study for provenance determination of calcitic,calcite–dolomitic and impure marbles from historical quarries in the Czech Republic

The present provenance study was focused on marbles from historical quarries of one geological unit (Bohemian Massif, Czech Republic) exhibiting complex polyphase geological evolution. A combination of mineralogical–petrographic, geochemical and physical methods has been tested i.e. optical microscopy (OM) of the whole rock, X-ray diffraction (XRD) of the insoluble residues, petrographic image analysis (PIA) of carbonate grains, cathodoluminescence (CL) of microfacies, stable isotope ratio analysis (SIRA) of carbonates in the groundmass and secondary veins, Raman microspectrometry (RM) of the carbonaceous matter and bulk magnetic susceptibility (MS) of the whole rock.Based on the results of historical quarries and the artefacts from Pernštejn Castle and Prague Castle, the most effective way for provenance determination of marbles seems to be a combination of petrographic methods (including quantitative approaches), cathodoluminescence, and stable isotope study. Less conventional methods (e.g. Raman microspectrometry or physical properties like bulk magnetic susceptibility) are very useful for provenance studies on impure calcitic and dolomitic marbles that include carbonaceous matter, magnetic minerals or silicates. For the first time, Raman data on reduced carbonaceous matter permitted differentiation amongst marbles of different origin.     

Elemental analyses by laser induced breakdown spectroscopy as restoration test on a piece of ordnance

Laser induced breakdown spectroscopy was used to investigate the composition of a gun found in the Adriatic seabed and kept in the “S. Castromediano” Provincial Museum in Lecce (Italy). Optical emission spectra of the laser-induced plasma from the surface of the piece of ordnance were recorded before and after its restoration. The metal alloy of the gun was determined through the identification of characteristic atomic emissions and confirmed through microanalysis carried out by energy dispersion X-ray spectroscopy. Experimental results evidenced that the gun is of bronze and revealed that elements composing the encrustation and noxious for the object conservation, such as calcium, were removed successfully during the cleaning operation. Performed elemental analyses confirmed that laser induced breakdown spectroscopy is a useful diagnostic tool to test the restoration degree of artworks.     

Application of Laser Ablation ICP-MS for characterization of obsidian fragments from peri-Tyrrhenian area

This paper presents the results of a geochemical study on obsidian fragments by Inductively Coupled Plasma Mass Spectrometry associated with Laser Ablation (LA-ICP-MS). This analytical method, almost non-destructive, has proven to be a powerful tool for “in situ” determination of trace elements, and is very useful in characterizing and determining the provenance of obsidian fragments of archeological interest. Its major advantage is that 29 trace and rare earth elements can be analysed in a very short time, without any sample manipulation.Analyses were carried out on 27 representative obsidian samples, collected from the main geological outcrops of Sardinia and the minor islands of Lipari, Pantelleria and Palmarola, in the peri-Tyrrhenian area, and on eight obsidian fragments recovered from three different Italian archeological sites of Neolithic age. The geological samples show variable trace element and REE compositions, and differences in Cs, Y, Zr, Nb, Ba, La, Nd, Ho, Er and Yb were great enough to allow the various source areas to be distinguished. The fragments fall into seven compositional groups. Three, which are homogeneous but clearly distinct from each another, include the Lipari, Palmarola and Pantelleria samples. The other four groups refer to the obsidian of Monte Arci in Sardinia, already known in the literature as SA, SB1, SB2 and SC. LA-ICP-MS established the definite origin and source areas of the artefacts.Analytical results indicate that, for obsidian samples from the peri-Tyrrhenian area, significant geochemical differences exist in their trace and REE compositions, which identify their source areas and establish their provenance for archeometric purposes.     

A nano to macroscale study on structure-mechanics relationships of archaeological oak

Mechanical properties of wood at different length scales of its hierarchical structure are governed by structural and compositional properties on smaller length scales. This opens up the possibility to use microstructural data for estimating mechanical properties, which are difficult to assess by conventional, destructive testing but are nevertheless of high relevance for conservation practice. Herein, we investigate such microstructure-mechanics relationships for a particular example, namely the load bearing archaeological oak of the Oseberg Viking ship, displayed at the Viking Ship Museum in Oslo, Norway. In order to identify the effects of degradation on the mechanical behavior and their relations to the microstructure, recent oak specimens of different geographical origin (Norway and Austria) are investigated as well. Wood exhibits a cellular structure. Its cell walls are composed of an amorphous polymer matrix consisting of lignin and hemicelluloses and embedded, stiff cellulose fibers. At the cell level, experimental studies comprised microscopic investigations of the cellular structure, chemical analyses of the composition of the cell walls, as well as nanoindentation tests on single cell walls. The same samples were also analyzed on the macroscopic level, where additionally mass density and annual ring data were measured together with ultrasonic stiffnesses. The chemical data clearly indicate deterioration in the archaeological oak, affecting mainly hemicelluloses and amorphous cellulose. At the cell wall scale, however, this does not necessarily lead to a weaker material behavior. The nanoindentation modulus, as a measure of the cell wall stiffness, was found to even increase. This is counterintuitive to our understanding of the effects of chemical degradation. It might be due to possible modification of lignin in the Oseberg oak, and thus have a stronger effect on the indentation modulus than the concurrent weakening of the interfaces between the load-carrying cellulose fibers and the connecting cell wall matrix when analyzing wood at the microscopic level. A similar effect is also observed for the transversal stiffness of macroscopic samples, which increases. In tension-dominated loading modes, however, the degradation of the interfaces is the dominant effect, resulting for example in a considerable reduction of the macroscopic stiffness in longitudinal direction. This underlines the utmost relevance of the loading condition on the remaining load-carrying capacity of degraded wood. On the macroscale, effects of the geographical origin (i.e. growth conditions) on ring characteristics of the oak tissues override the effects of degradation on the mechanical behavior. They have to be carefully extracted in order to come up with conclusions on the effect of degradation from macroscopic test results. The identified microstructure-mechanics relationships provide the basis for–in further research steps–building mathematical models describing the relations between microstructural characteristics and macroscopic mechanical properties and, thereon, for structural analyses of historical wooden objects.     

Technological features of the ‘Cotto Variegato’: a petrological approach

The ‘Cotto Variegato’ are tiles used in Lombardy, between the XVII and XIX centuries as flooring for several historical buildings. Tiles are produced by the processing of two compositionally distinct clays. The main stylistic character of these tiles is a banded texture producing a veined aspect, in which white and red bands are also folded. The artefacts were hand crafted using two clayey raw materials of different composition, that are only partially mixed before the firing. The colour differences are produced during the firing. In all samples white and red portions are always composed of Ca-rich and Ca-poor clay, respectively. The multi-layered texture was obtained by a multiple folding and pressing process of the mixture. The interference of fold limbs with the tile surface gives the ‘variegato’ style to tiles. The paper explains how basic petrological knowledge can be applied to the study of ceramic artefacts in order to define provenance of the raw material, firing technology and how ancient craftsmen transformed the natural clayey materials into floor tiles. The methodological approach is that commonly applied to the study of the rocks and consists of textural analyses, at a different observational scale, combined with X-ray powder diffraction, X-ray fluorescence and microprobe analyses.     

英国圣保罗大教堂重建时期石材采运研究(1675-1710年)

基于历史档案资料,追述了伦敦大火后英国圣保罗大教堂重建时期石材采运的历史,揭示了各类石材的开采与运输方式、建造中引发的问题,并首次对石材的供应情况进行了定量分析,呈现了石材采运如何成为圣保罗大教堂的重建历时35年之久的主要原因之一。圣保罗大教堂的石材采运问题并非独特案例,同类型的石材在同时期其他建筑中曾被广泛运用,因此对研究那个时代的砖石建筑具有更普遍的参考意义。     

Spectroscopic and chromatographic studies of sculptural polychromy in the Zhongshan Grottoes (R.P.C.)

The sculptural polychromy in the Zhongshan Grottoes, sited in northwest China, has been investigated in terms of chemical composition of employed materials and pigments, state of conservation and painting technique. Raman analysis, Fourier-transform infrared analysis, analysis through energy-dispersive X-ray spectrometry coupled to scanning electron microscopy and pyrolysis coupled to gas chromatography and mass spectrometry were applied. Six analyzed samples showed silicates and kaolin as main components of the ground layers. Also lead white has been found in these layers. Minium, red-earth and mercury sulfide are the red pigments detected in the polychromy. A mixed use of malachite and atacamite has been detected in three green samples. Optical characteristics of atacamite and malachite found in the samples indicate a synthetic origin. The presence of a synthetic organic pigment such as phthalocyanine chlorinated pigment was also revealed. Ultramarine blue pigment, obtained by purification of lapis lazuli, has been detected in the blue sample. As for the binders used, fatty materials and siccative oil were found.     

Chemical and textural characterisation of medieval slags from the Massa Marittima smelting sites (Tuscany,Italy)

During the 13th and 14th centuries, the commune of Massa Marittima successfully exploited the nearby base-metal mines (copper, lead and silver). Several smelting sites were active. Twenty-seven slag specimens were sampled at Marsiliana, Arialla and Rocchette Pannocchieschi. Slags have been analysed by X-ray fluorescence spectrometry, X-ray powder diffraction, optical microscopy, scanning electron microscopy and energy dispersive X-ray spectrometry. The slags from the three sites differ in chemical composition. The most abundant pyrometallurgic phases in the glassy matrix are calcic clinopyroxene, kirschsteinite, melilite, accompanied by spinel, wüstite, sulphides, metals and metal alloys. The three sites produced more than 2000 t of copper, 6000 t of lead and 2 t of silver. Copper was mostly smelted at Marsiliana, and silver-bearing lead was smelted at Arialla and Rocchette Pannocchieschi. The minerals underwent only a mild roasting prior to smelting. Flux lime was added to the mineral charge, and the resulting viscosity index of the melts (from 0.9 to 3.7) assured effective metal segregation. Furnace temperatures reached 1150–1300 °C.     

An analysis of building methods: chemical-physical and archaeological analyses of micro-layer coatings on medieval facades in the centre of Genoa

The present research is an attempt to create a link among different disciplines and to confirm stratigraphic observations through chemical analyses. It involved detailed colorimetric examination and in-depth chemical-physical study of the samples taken from the historical centre of Genoa, which enabled connections to be made among many data. This led to the creation of an analytical method that is applicable to various geographical sites. Examinations involved several experimental techniques: X-ray diffractometry, scanning electron microscopy, optical microscopy and infrared spectroscopy; the data were compared with those from the stratigraphic examination. A detailed investigation of the Ligurian climate, including data kindly supplied by the Environment Department of the Provincia di Genova, allowed us to explain the presence of particular chemical substances and suggested how they might have been formed.     

Investigation of a naturally patinated bronze artifact originating from the outdoor statuary group of Mathias Rex

The present work aims to investigate the morphology and composition of natural patina formed after long-term atmospheric exposure (∼100 years) on the bronze screws used in assembling the statuary group of Mathias Rex, placed in the center of Cluj-Napoca, Romania. The chemical composition of the bronze and of the natural patina, formed on the screws’ surface were determined by X-ray fluorescence analysis, and the morphology of the latter was determined by SEM - EDX cartographies.     

Mineralogical and chemical composition of transport amphorae excavated at Locri Epizephiri (southern Italy)

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.     

Characterisation of wall paintings in the Sos Furrighesos necropolis (Anela,Italy)

The Sos Furrighesos necropolis (Anela) is considered to be one of the most important funerary monuments in Sardinia. The hypogeum consists of various graves, called Domus de Janas, which are decorated with Neolithic mural paintings and sculptures. This work was undertaken in order to clarify which techniques were used in the past, through the identification of pigments and binding media. The samples, scraped off from the paint surface, were studied by using various analytical techniques in order to characterise both the pigments and the binding media. The main problems concerning the characterisation were due to the small sizes (1–5 mg) of the samples and their complex nature. As regards pigments, X-ray diffraction and scanning electron microscopy-energy dispersive X-ray spectrometry analyses were performed on the samples. These techniques are well suited to the characterisation of inorganic pigments and have led to the identification of the red pigment as haematite. In order to characterise the organic binders, the samples were analysed by a procedure based on a gas chromatography–mass spectrometry technique, which allows proteinaceous and lipidic media determination in the same sample. In most of the samples, the presence of egg was suggested.     

Spectroscopic analyses of Hellenistic painted plasters from 2nd century B.C., Sicily (South Italy)

In the present work, an analytical characterization of painted plaster samples coming from ancient buildings dated back to 2nd cent. B.C., located in Licata (Sicily, Southern Italy), has been carried out. The investigation has been performed through different spectroscopic techniques: X-ray fluorescence (XRF) using an handheld energy-dispersive XRF analyzer, scanning electron microscopy equipped with an Energy Dispersive Spectrometry microanalysis detector (SEM-EDS) and Fourier transform infrared absorbance spectroscopy (FT-IR). The main goal is to identify the plaster and pigments material. In particular, the XRF investigation of surfaces is the first step for a preliminary elemental characterization. Then, through SEM-EDS measurements, a quantitative analysis of the chemical composition of the plaster and the pigmenting agents along with eventual components related to deterioration processes has been obtained. Finally, FT-IR absorbance spectra have proven to be a useful tool to investigate the molecular nature of the used materials.     

Study on some sorption properties of treated bentonites for their potential use as a moisture regulating system for the preservation of historical wooden elements

We report the first results of a research study aimed at developing a new strategy for the conservation of wooden structural elements present in historical buildings, based on moisture regulating systems. As has been happening for artefact preservation in museums, the idea is to develop systems based on the ability of some highly hygroscopic materials to moderate variations in relative humidity. These materials could adsorb and release moisture to reduce the extreme values of humidity in the micro-climate, for example between wooden beams and masonry. In order to experimentally verify this possibility using current, low cost and easy handling building materials, 5 bentonite samples were laboratory processed to improve their adsorbing properties by means of treatment with sodium carbonate at 3 concentrations: 2, 3 and 4% by weight. The effectiveness of ion exchange between sodium carbonate and bentonite was controlled by measuring the swelling volume of the bentonites. All the samples (n = 15) were tested for their hygroscopic properties. Adsorption isotherms were measured at 25 °C, using desiccators with silica gel, saturated salt solutions and bi-distilled water. A comparison between isotherms of one of the lower hygroscopic treated sample of bentonite and of a sample of wood and of a sample of brick and some numerical analyses with the Delphin code were made in order to evaluate the potential use of this bentonite as a moisture regulating system for the preservation of historical wooden elements. Results show that it seems to be possible to use bentonites as a moisture buffering material in order to reduce moisture content in wooden beams at least during their adsorption phase. It remains to investigate their desorption phase and their behaviour if they be in a saturation condition. Further studies are currently under way.     

Damage mechanism in Tournai limestone – The case of the tomb of Admiral Tromp in the Old Church of Delft (The Netherlands)

The funeral monument of Maarten Tromp, in the Old Church of Delft (the Netherlands), is partially built with Tournai stone, a grey-blackish limestone from the Wallonia region (Belgium). This stone is suffering a severe delamination and scaling, which has, in the course of the centuries, led to a considerable material loss from the surface of some of the stone elements. In order to identify the damage process and define a sound basis for the conservation of the monument, a research plan was set-up including, next to the tests and analyses on the stone, a 1-year monitoring of the microclimate in the church and the investigation of the structure of the monument as well as its connections to the adjacent walls. First of all, the stone type was identified by macroscopic features and by thin section microscopy. The moisture distribution in the monument and in the adjacent walls was gravimetrically determined on samples taken at different height and depths. The content and type of salt in the Tournai stone from the monument were determined by X-ray diffraction and ion chromatography, and the results compared to those obtained for the fresh stone. The analyses showed the presence of considerable amount of gypsum, together with a low content of soluble salts (chlorides and nitrates). The SEM-EDS observations showed that gypsum is mainly crystallizing in cracks between the layers of the material. The damage mechanism and the influence of salt on the decay were further investigated by combining hygroscopic moisture uptake, hygric dilation (RH cycles between 50% and 95% RH) measurements and SEM-EDS observations; all measurements were performed both on stone sampled from the monument and, as comparison, on fresh stone specimens. The results show that gypsum is the main salt present, but its role in the damage is not significant. The naturally thin laminated structure of the stone together with the considerable hygric dilation seem to be the main causes of the delamination observed in this stone.