The origin of syngenite in black crusts on the limestone monument King's Gate (Belgrade Fortress,Serbia) – the role of agriculture fertiliser

Black crusts formed on limestone built into the King's Gate represent the most important process in stone deterioration that is occurring in this part of the monumental complex of the Belgrade Fortress (Serbia). Of special importance is the association of salts (namely gypsum and syngenite). Syngenite is a common secondary deposit on granite monuments and on medieval stained glass (i.e., on K-containing materials). However, its appearance over calcareous substrates is not apparent, particularly in cases where cement mortar was not used for bounding. The origins of the potassium and sulphate ions required for syngenite formation are related to meteoritic water, which penetrates the soil above the arch of King's Gate. Water dissolves some soil components and becomes enriched with various ions before coming into contact with the limestone blocks. Enriched water contains two times more K⁺ and SO₄^2? ions than pristine meteoritic water does. The source of the required ions is potassium-sulphate that is present in agricultural fertilisers that are used above the monument. The proposed mechanism for syngenite formation was additionally supported with laboratory experiment. The results of X-ray diffractometry and SEM-EDS analyses of limestone treated with potassium-sulphate solution and sulphuric acid suggest the possibility that the syngenite was formed over calcite:CaCO₃ + K₂SO₄ + H₂SO₄ → K₂Ca(SO₄)₂ H₂O + CO₂↑However, the complex mechanisms of gypsum and syngenite formation under natural conditions (variable concentration of potassium and sulphate ions, intermediates phases, temperature changes, humidity, the amount of disposable water etc.) do not exclude the possibility of syngenite formation over gypsum.     

The role of copper on colour of palaeo-Christian glass mosaic tesserae: An XAS study

This work reports mainly the results of an X-ray Absorption Spectroscopy (XAS) study carried out on coloured glass tesserae from the palaeo-Christian mosaic which decorated the votive chapel of St. Prosdocimus (Padova) until its replacement with the current frescoes of Renaissance age, and which is one of the only two known mosaics in the Veneto region (Italy). The study aims at clarifying how the different local structure, oxidation state and quantity of copper influenced colour. Analysis of high-resolution Cu-K edge X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectra showed that copper is present as cuprite (Cu₂O) in orange samples and as metallic copper in red and brown ones. These phases are responsible for both the colour and opacity of the samples. In addition, Cu¹⁺ ions linked to the oxygen atoms of the glass framework were identified in ratios of about 60% and 30% of total copper in orange and red/brown samples, respectively. In blue and green samples, copper is dispersed in the glass matrix as a mixture of Cu¹⁺ and Cu²⁺ ions, and no crystalline phases are visible. In this context, the Cu¹⁺ and Cu²⁺ contents in glass were also quantified thanks to suitable standards, demonstrating that, when Cu²⁺ is the main chromophorous ion, colour intensity is directly correlated to its content in the glass. In particular, in green and blue samples, coloured by copper, Cu²⁺ content varies from 26% to 56% of total copper, and the higher contents of Cu²⁺ are shown by more intensely coloured samples. It should be stressed here that the green colour of the analysed tesserae is given by the physical interaction of blue colour, due to Cu²⁺ ions, and yellow colour, due to Pb antimonates used as opacifiers.     

Evaluation of the effectiveness of treatment products in improving the quality of ceramics used in new and historical buildings

Ceramic samples made with a mixture of 70% ball clay and 30% quartz sand were moulded and then fired at 900 °C in an electric kiln. Samples were then treated with different products and analyses and tests were performed to evaluate the physical changes induced by the application of these products and their effects on the quality of the ceramics. A petrographic study indicated that the ceramics were composed of quartz, small amounts of mullite and sanidine and traces of hematite. Mineral clays (i.e. kaolinite) disappeared during firing. Two consolidating products (Paraloid B72 and Tegovakon V) and one water repellent (Silo 111) were applied to samples by capillarity, and physical changes (colour, water flow, porosity and pore size distribution) were measured. Finally, we carried out salt crystallization tests in order to determine which product improved the quality of the ceramics. Treated samples registered a decrease in porosity and a general increase in pore size. The application of Silo 111 drastically reduced water absorption by immersion and by capillarity. This product was also responsible for a decrease in pore interconnection. Samples treated with Tegovakon V performed better in terms of their overall hydric behaviour. Silo 111 was the only product that did not modify the colour of samples when compared with untreated ones, and after accelerated aging tests, samples treated with this product hindered the absorption of saline solution into ceramic pores and prevented their decay. Paraloid B72 did not improve any of the properties of the ceramics.     

Efflorescence of mirabilite,epsomite and gypsum traced by automated monitoring on-site

Short crystallisation and deliquescence cycles of mirabilite, epsomite and gypsum are identified by using an automated monitoring system on-site. It consists of digital cameras and RH/T sensors which are computer-controlled and connected to the Internet. Digital images are processed to form a time-lapse movie, so that surface alterations are easily recognised. High resolution imaging (6 mega pixels) in combination with various lenses (12–24 mm zoom, 28–105 mm zoom, 20 mm inversed) results in a wide range of precise observation from 7 to 500 mm width of image. That is essential for discriminating phase transitions of single crystals at the same time as monitoring the evolution of the efflorescence as a whole. Crystallisation-deliquescence cycles are induced by small temperature and humidity variations. Mirabilite and epsomite undergo phase changes from crystallisation to deliquescence and vice versa at about 83% RH (15–20 °C). These equilibrium relative humidities are considerably reduced compared to the pure salt systems as a consequence of mixed salt solutions. Observations confirm predictions by ECOS simulation based on chemical analyses of water extracts from the site. Dehydration of mirabilite is observed when the relative humidity drops below 65% RH. Mirabilite exhibits the most pronounced and rapid phase changes in response to indoor climate variations. As an example, whisker crystals of 1–3 mm length grow within one up to some days. Epsomite responds fainter and slower. Crystallisation of gypsum is distinguished by the growth of new crystals on the stone surface. They have a size of about 10 μ – which is close to the image resolution – when they appear on the image. Crystallisation is associated with an increased granular disaggregation of the stone surface. Rhythmical crystallisation of gypsum appears to correlate with small relative humidity variations of ±2–5% within a band from 65 to 75% RH in the room. However, this needs to be clarified in detail.     

Excimer laser removal of beeswax from galician granite monuments

The paper presents the use of laser radiation for cleaning of beeswax treated granite stone. In the early sixties, prestigious restorers decided to apply molten beeswax on the granite surface of valuable monuments with the aim of preventing the erosive action of atmospheric agents. An interesting example of this treatment is the Renaissance Frieze in the Cloister of the Cathedral of Santiago de Compostela in Galicia (Northwest Spain). With time, salt accumulation beneath the beeswax layer has caused an intense surface disintegration of granite. Conventional cleaning methods can destroy sculptured details of these emblematic monuments. For this reason, excimer laser cleaning has been chosen as a promising non contact, selective and environmentally friendly cleaning technique to be studied.The cleaning tests have been carried out using an excimer laser (ArF, 193 nm), with fluences between 0.5 and 2 J cm⁻² pulse⁻¹ and a spot area of 0.025 cm². Samples representing beeswax films over Roan granite have been irradiated and their degree of cleaning has been studied as a function of the number of pulses and the laser fluence.Cleaning efficiency has been evaluated by FT-Raman Spectroscopy, allowing to establish the beeswax ablation threshold and the ablation rate.Excimer laser cleaning allows a progressive and controlled removal of a few tenths of micrometers of beeswax per pulse without damaging the underlying granite stone.     

Nanoparticles of calcium hydroxide for wood deacidification: Decreasing the emissions of organic acid vapors in church organ environments

Acetic and formic acid vapors emitted from woodwork in historical organs are very important corrosive agents for lead pipes. These acids are slowly released from the wood both during playing and when the pipes are silent. To inhibit this emission process, the wood surface can be modified, by creating a protective layer with alkaline features. However, a coating of wood is not recommended since this could modify the appearance and create a layer not perfectly compatible with the substrate. For this reason, we propose to use some innovative nanotechnology that has been successfully applied for the deacidification of wood samples coming from the Vasa shipwreck. Application of calcium (or magnesium) hydroxide nanoparticles, with sizes ranging from 30–150 nm, allowed a homogeneous distribution of particles through the surface layer of wood simply by soaking (or spraying) it in a alcoholic (or mixed with less polar solvents) dispersion of nanoparticles. Nanoparticles do not modify the wood appearance and distribute randomly within the first layers of wood. The small size of particles accounts for the high reactivity with CO₂ from the air, to give the alkaline reserve of carbonates that provide high efficacy in the neutralization of gaseous acids. The emission of volatile organic compounds (VOC) from the treated wood was determined by using an emission test cell, Field and Laboratory Emission Cell (FLEC). The results show that the emissions of acetic acid vapor from nanoparticles treated wood was very low (< 70 μg/m² h) during the first 13 month. In contrast, untreated wood emitted high concentrations of acetic acid vapor (200–400 μg/m² h).     

Efficiently capturing large,complex cultural heritage sites with a handheld mobile 3D laser mapping system

Accurate three-dimensional representations of cultural heritage sites are highly valuable for scientific study, conservation, and educational purposes. In addition to their use for archival purposes, 3D models enable efficient and precise measurement of relevant natural and architectural features. Many cultural heritage sites are large and complex, consisting of multiple structures spatially distributed over tens of thousands of square metres. The process of effectively digitising such geometrically complex locations requires measurements to be acquired from a variety of viewpoints. While several technologies exist for capturing the 3D structure of objects and environments, none are ideally suited to complex, large-scale sites, mainly due to their limited coverage or acquisition efficiency. We explore the use of a recently developed handheld mobile mapping system called Zebedee in cultural heritage applications. The Zebedee system is capable of efficiently mapping an environment in three dimensions by continually acquiring data as an operator holding the device traverses through the site. The system was deployed at the former Peel Island Lazaret, a culturally significant site in Queensland, Australia, consisting of dozens of buildings of various sizes spread across an area of approximately 400 × 250 m. With the Zebedee system, the site was scanned in half a day, and a detailed 3D point cloud model (with over 520 million points) was generated from the 3.6 hours of acquired data in 2.6 hours. We present results demonstrating that Zebedee was able to accurately capture both site context and building detail comparable in accuracy to manual measurement techniques, and at a greatly increased level of efficiency and scope. The scan allowed us to record derelict buildings that previously could not be measured because of the scale and complexity of the site. The resulting 3D model captures both interior and exterior features of buildings, including structure, materials, and the contents of rooms.     

Non-destructive assessment of a buried rainwater cistern at the Carthusian Monastery ‘Vall de Crist’ (Spain, 14th century) derived by microgravimetric 2D modelling

The microgravity method is one of the geophysical tools used in engineering and environmental and archaeological researches, where the detection of subsurface cavities or buried structures is essential. In this study, this technique has been revealed to be an efficient and respectful tool for use in Cultural Heritage restoration studies, such as those carried out in the restoration of historical sites in which the elements to be examined are beneath a shallow coating of material. Therefore, the aim of this microgravimetric survey is to define the exact position and dimensions of a subsurface structure (rainwater cistern) through microgravity response of the medium.For this purpose, the subsurface structure of San Gerónimo Cloister of the Vall de Crist Carthursian Monastery (14th century) has been researched. This monastery was known to be the largest Carthusian Monastery in the region of Valencia (Spain) and one of the most remarkable of the ancient Corona de Aragón. A rectangular grid of microgravity measurement station points was designed to cover the entire surface of the cloister. In addition, a microgravimetric profile was acquired along a hillside close to the Carthusian buildings in order to obtain the density value of the medium.The study was performed using a LaCoste&Romberg D203 gravimeter to detect and to map the shallow subsurface rainwater cistern that probably exits beneath it. This gravimeter has a sensitivity of approximately 1 μgal (μgal = 1.10⁻⁸ ms⁻²) and an accuracy of 3–5 μgal for relative gravity measurements.Two contour maps were calculated (observed gravity and Bouguer gravity values) in order to improve the interpretation results. On these maps we can observe the shape of the body that is causing the perturbation in gravity values. And what is more, it led us to deduce that the central area of the cavity is deeper than the border area. In addition, we can asses that the cavity is 8 m wide and 12 m long, and is symmetrical along its longitudinal axis, but not along its transversal axis.Also, a microgravimetric inversion was performed and the subsurface is split into 7 prisms and the depth and height of each is to be estimated separately. As a result of this inversion we can estimate that the ceiling of the cistern is located about 1 m under the cloister pavement and the cistern floor at a depth of 4 m. The cistern is slightly inclined towards one of its edges by about 20 cm.Finally, the 2D modelling derived by microgravimetric data has allowed us to determinate the shape, dimensions and location of the cistern accurately. In addition we have calculated the cistern capacity (288 m³, that is, 2880 Hl). This capacity was quite enough for the water necessities of 13 monks who lived there permanently, even for making it through the drought periods frequent in this kind of Mediterranean areas.     

Interpreting the age of the ruins of St. John the Baptist's church with multivariate analysis

Two multivariate statistical tools – principal components analysis and cluster analysis – were applied to aid in the interpretation of the historical development of St. John the Baptist's church (?i?e, Slovenia). With these methods it was possible to distinguish between the types of mortar used in the Romanesque and Gothic time periods. The investigated structure is a ruin with poorly preserved fragments of historical mortars, so tracing the individual stages of its construction proved to be a demanding task. Its chemical composition was determined by inductively coupled plasma mass spectrometry (ICP-MS) and the results of the content of various oxides were statistically evaluated to interpret the age of the southern wall of the church.     

Comparison of hot-air and low-radiant pew heating systems on the distribution and transport of gaseous air pollutants in the mountain church of Rocca Pietore from artwork conservation points of view

The concentrations of CO₂, CO, formaldehyde (H₂CO) and water vapour were simultaneously monitored in various sections of a mountain church situated in the village of Rocca Pietore in the Italian Alps. The performance of a conventional, hot-air heating system and a novel design for heating the church, consisting of low-temperature heating elements, such as electrically heated pews and carpets, were compared for the supply, transport and removal of gases, the deposition and/or transformation of which may affect the preservation of displayed works of art. Experiments with sulphur hexafluoride (SF₆) tracer-gas showed a considerable influx of external air through the hot air carrier ducts of the old heating system, and also the leakage of the internal air mostly via the apertures of the doors. The ventilation rates for the total volume of the church with the hot-air heating system (on for 1.5 h), the new heating system (on for 2 h), and without heating were calculated to be 0.25, 0.18, and 0.13 h⁻¹, respectively. Without heating, a nearly homogeneous distribution of gases has been observed along both the horizontal and the vertical cross-sections of the church. Immediately after switching on the hot-air heating system, the levels of CO₂ and water vapour showed a sharp increase. After turning this system off, the levels of gases showed a slow fall and they developed a highly non-homogeneous spatial distribution indoors for many hours. In the upper region of the church, being airtight, higher concentrations of the pollutants could be detected. The low levels of CO and H₂CO, mostly originating from incense burning during services, were correlated to that of CO₂. The hot-air heating system has been proved to present a potential deterioration risk to artworks, as it increases the supply, transport and deposition probability of air pollutants. On the other hand, the novel, symmetrical heating system eliminates these undesirable effects, thus its application is advantageous to all churches involved in the preservation of works of art.     

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.     

Effectiveness of crystallization inhibitors in preventing salt damage in building materials

Salt crystallization in porous materials constitutes one of the most frequent causes of decay of buildings in a wide range of environments. Up to now no definitive solution exists to limit salt crystallization damage, unless of removing either the salt or the moisture. The possibility of making the process of salt crystallization less harmful by means of crystallization inhibitors has only recently been considered. Crystallization inhibitors are known to delay nucleation and to modify the growth rate of the crystals in bulk solution, but their possible application for the prevention of salt decay in porous material is still controversial.The present paper reports a series of systematic investigations performed on three different materials (a limestone, a sandstone and a brick) contaminated with two types of salt (sodium chloride and sodium sulphate) and two types of inhibitors (sodium-ferrocyanide and diethylenetriaminepentakis methylphosphonic acid). Drying experiments have been performed to study the effect of the inhibitors on the salt solution transport. Accelerated crystallization experiments have investigated the possible consequences of the application of the inhibitor on salt crystallization damage (quantified as material loss).Environmental Scanning Electron Microscope (ESEM) has been used to study how the presence of inhibitors affects the crystallization morphology of salt in the material.The results show that the effect of the inhibitor strongly depends on the type of substrate. NaFeC, when applied on NaCl contaminated limestone and brick was able to enhance the drying and to favour the appearance of efflorescences, whereas the effect on the sandstone was very limited. DTPMP enhanced the drying of Na₂SO₄ laden sandstone, but had no influence on the drying of both brick and limestone. These different have been attributed to the properties of the materials, in particular pore size distribution and composition.The effects of the inhibitor on salt crystallization damage were less evident: no differences in surface damage, quantified as material loss, were observed between specimens with and without inhibitor.     

Accelerated hydrothermal degradation of fibres of Phormium tenax (New Zealand flax)

Solid-phase microextraction (SPME)–gas chromatography (GC)–mass spectrometry (MS) has been applied to the analysis of acetic acid and furfural that are emitted from the fibres of Phormium tenax (Xanthorrhoeaceae) [New Zealand flax] during degradation. Accelerated hydrothermal ageing of fibres of the Ruawai cultivar of P. tenax for 55 days at 70 °C resulted in the production of acetic acid at a level greater or equal to 1.65 mg g^–1 fibre. This corresponds to only 8.5% of the acetyl groups present in the fibres. These groups are an important source of acetic acid, which is capable of damaging the fibres. The rate of production of acetic acid suggests that a heritage object made from the fibres of P. tenax, that was stored in damp ambient conditions, would undergo significant deterioration after a relatively short period. Other volatile products released during ageing included furfural, a series of short to medium chain aliphatic aldehydes that were derived from the oxidation of long chain unsaturated fatty acids on the fibres and a small group of products that were derived from carotenoids. The levels of furfural were determined to be approximately 0.75% of the potential production but at these levels, furfural could contribute to unpleasant odours from unventilated items. Fibres from six cultivars of P. tenax were found to release acetic acid and furfural all at the same rate. The levels of acetic acid that can be generated from these fibres are sufficiently high that low moisture levels and continuous change of air is required to minimize degradation of cultural objects that are made from these fibres and displayed in museum halls.     

Future pest status of an insect pest in museums,Attagenus smirnovi: Distribution and food consumption in relation to climate change

The brown carpet beetle Attagenus smirnovi, Zhantiev 1973 (Coleoptera: Dermestidae) is an important pest of objects of organic origin in museums of cultural and natural history in Europe. Future climate changes are expected to lead to increasing temperatures, which will affect the pest status of this species. In the present study a laboratory investigation was conducted to elucidate the effect of temperature and humidity on the amounts of organic material consumed by larvae of A. smirnovi. In the case of new and old skin, consumption was approximately twice as high at 28 °C compared to 20 °C. Wool was consumed in the greatest amounts: 169 mg of wool was consumed in three months by 30 A. smirnovi larvae. The expected future climate changes in Scandinavia are assumed to lead to higher temperatures in museums and stores where climate is not regulated. Updated data on the present distribution of A. smirnovi in Europe show that it is widespread and common, also in regions with a climate that does not support its survival out of doors. Thus, dispersal of this pest probably only rarely occurs by flight, but usually with human activity. Due to the widespread distribution of A. smirnovi, it is likely that damages in museums and collections in Scandinavia due to this pest will increase as climate changes come into effect.     

The genesis and characterisation of ‘Marmor Misium’ from Kozak (Turkey), a granite used in antiquity

‘Marmor Misium’ was one of the most used granites of antiquity, especially for the manufacture of columns and slabs. It was quarried in the area of Kozak (Turkey) and used locally from the Late Hellenistic period and later, probably at the end of the 1st century AD, exported to Rome and other important Roman towns of the Mediterranean sea. It seems that ‘Marmor Misium’ continued to be quarried until the Early Byzantine time; it is now still quarried for local use (road paving, etc.). In spite of its historical importance and geological interest, this granite has never been the subject of detailed petrological studies. That is why in this work it has been sampled from various outcrops of the plutonite and in abandoned ancient quarries and characterised petrographically and geochemically. From the petrographic point of view, the plutonites of Kozak are medium-grained biotite-hornblende granite and granodiorite composed of 34.2–53 % (modal) zoned plagioclase, 23.7–35.4 % K-feldspar, 21.4–29 % anhedral quartz, 4.9–10 % brown biotite and 7.7 % green hornblende. These rocks are I-type metaluminous granitoids of high-k calc-alkaline orogenic series forming a crystallised body at a depth of about 10 km. The positive distinction between ‘Marmor Misium’ and two other granites used in antiquity and macroscopically very similar to it, those from the Elba and Giglio islands (Italy), is easily made by considering the absence of hornblende, the peraluminous character and the lower Sr and Ba and higher Rb contents for the latter.     

Trees as natural barriers against heavy metal pollution and their role in the protection of cultural heritage

Leaves of common deciduous trees: the horse chestnut (Aesculus hippocastanum) and linden (Tilia spp.) from the park, near one of the most important cultural institutions, the National Library of Serbia, were studied as bioaccumulators of heavy metal (Cr, Fe, Ni, Zn, Pb, Cu, V, As and Cd) air pollution. The leaf samples were collected from the urban park exposed to the exhaust of heavy traffic. The May–September heavy metal accumulation in the leaves, and their temporal trends, were assayed in a multi-year period (2002–2006). Comparing the obtained concentration of the investigated elements from the beginning to the end of growing seasons, a significant rate of accumulation was determined for a majority of measured elements, and it was concluded that these tree species (horse chestnut and linden) can be used as bioaccumulators of the investigated heavy metals. The SEM-EDAX analysis of individual particles deposited on the leaves showed that the 50–60% belong to a class of fine particles (D < 2 μm), mainly of anthropogenic origin. Thus, the investigated tree species could be grown as a natural barrier against urban air pollution in the vicinity of libraries, museums and other buildings for cultural heritage storage.     

Synthesis of Ca(OH)2 nanoparticles with the addition of Triton X-100. Protective treatments on natural stones: Preliminary results

Calcium hydroxide is typically used in Cultural Heritage conservation for superficial protective treatments thanks to its conversion into calcium carbonate. Calcium carbonate is, in fact, compatible with many carbonate-based architectonic surfaces, because its characteristics are similar to those of the restored materials. In order to improve calcium hydroxide treatments, Ca(OH)₂ particles with sub-micrometric dimensions (nanolimes), are synthesised by a chemical precipitation process: a sodium hydroxide solution, used as precipitator, is added, drop by drop, to a calcium chloride one. In this paper, a nanometric calcium hydroxide, to be used in stones treatment, is produced adding in the initial solutions a surfactant agent (Triton X-100); the solutions are then mixed together simultaneously, drastically reducing the time needful for preparation. Different contents of surfactant are employed, and the influence on particles dimension and carbonatation process is analysed too. The obtained Ca(OH)₂ nanoparticles are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and electron diffraction (ED). The Ca(OH)₂ nanoparticles are regularly shaped, hexagonally plated and with side dimensions less than 200 nm: in particular, increasing the surfactant content, the particle dimension reaches values until 20 nm. Comparing nanolime suspensions obtained without and with the addition of the surfactant agent, the last ones have comparable, if not better, performances in terms of average particle size and morphology, crystallinity and reactivity. Afterwards, the alcoholic nanolime suspension obtained by using Triton X-100 is applied on some natural stones; in fact, the aim of this section is to compare the obtained results with those achieved using a nanolime synthesised without the surfactant agent. To evaluate the treatment effectiveness in a preliminary way, standard tests are performed and compared with the same tests previously obtained by the nanolime synthesised without the surfactant agent: “Scotch Tape Test” and capillarity test.     

Defects induced by gamma irradiation in historical pigments

The paper presents our results concerning a complex investigation by reflectance spectroscopy (RS) and Electron Paramagnetic Resonance (EPR) of the defects induced by gamma irradiation in 22 different historical pigments. Gamma irradiation is used to destroy microflora and insects which are involved in biodeterioration processes of art works such as paintings. At the same time, it can induce defects i.e. color centers which are likely to modify the original painting colors by altering the embedded pigments. Accordingly, RS was used to quantify, by means of CIELAB color space, the contribution of irradiation defects to the pigments color changes, while EPR spectroscopy, in view of paramagnetic properties of color centers, was used to confirm their presence after irradiation. Our investigations showed that, excepting marble dust whose color alteration was still observable after 3 months, color changes induced by irradiation in all other pigments disappeared after about 30–40 days. In addition, RS as well as EPR measurements suggest that color changes are related to irradiation color centers, this finding being confirmed by the coincidence, within experimental uncertainties, of the half-life time color changes as obtained by these methods.     

Validating chemical and structural changes in painting materials by principal component analysis of spectroscopic data using internal mineral standards

This work shows the capability of principal component analysis (PCA) to detect molecular, chemical and mineralogical changes in historic painting materials subjected to a thermal ageing test (< 250 °C). To simulate the heat-induced alterations an ageing accelerated process was performed on two sets of samples containing two mineral phases (hydroxyapatite and quartz) and two organic compounds (collagen and albumin). The chosen minerals behaved as internal standards during the tests since they are stable and chemically inert at the tested temperatures. Raman microscopy (RM) was applied to characterise one set of samples made of bone, containing ca. 70% hydroxyapatite and 30% collagen. Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy was used to study the other set of samples made of four different quartz/albumin mixtures with quartz contents of 30%, 50%, 70% and 90% (w/w). The aim was to identify the ideal proportion of internal standard to be validated by ATR-FTIR and PCA, determined to be 70%. PCA analyses detected changes in the molecular structures of the organic components while the internal mineral standard remained stable. Moreover, the internal standard IR/Raman bands were constant during the tests and confirmed that the results of PCA analyses were independent of instrumental and technical factors, as well as sample collecting and handling. This demonstrates the potential benefits of our approach to study historical painting materials, which have suffered any type of heat-induced alteration.