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.     

Electronic paramagnetic resonance as a tool for studying the blackening of Carrara marble due to irradiation by a Q-switched YAG laser

Several authors or practitioners have remarked that Q-switched lasers have an immediate blackening effect on mineral pigments such as vermilion (HgS), minium (Pb₃O₄), white lead [2PbCO₃. Pb(OH)₂], malachite [Cu₂CO₃.(OH)₂] and yellow ochre (FeOH₂). A similar blackening effect can also be obtained on veined Carrara marble. This stone contains several trace elements, particularly iron and manganese. The latter is responsible for a particular response in electronic paramagnetic resonance spectroscopy (EPRS). We investigated the effect of a Q-switched Nd:YAG laser irradiation on the EPRS trace of Carrara marble. Further experiments were performed with the same analytical tool on synthetic calcite powders that had been doped with iron or manganese. It appeared that no significant change of EPRS trace could be put into evidence after laser irradiation of both bulk Carrara marble or doped calcite powders, although some samples had actually blackened. It is concluded that the blackening effect is not due to an oxidation of manganese ions. Colour measurements were also performed within the framework of this investigation. They showed that the colour shift to black is proportional to the fluence applied to the stone surface     

Diagnosis of weathered Coptic wall paintings in the Wadi El Natrun region,Egypt

This paper deals with the impact of soluble salts on the deterioration of wall paintings in the region of Wadi El Natrun in Egypt, including the identification of the building materials and pigments used. For this purpose we used XRD analysis which proved that the green pigment in the Church of the Virgin, Wadi El Natrun is a mix of malachite and hydrocerussite, and the black pigment is graphite. The results proved that the building materials (stones, mortar, and plaster) in Wadi El Natrun are affected by ground water as they have the same soluble salts at different concentrations. The Wadi El Natrun lakes are the native source of natron salt, which has been used in mummification techniques. Soda lakes represent the major types of naturally occurring highly alkaline environments. The factors leading to the formation of the alkaline saline deposits may be divided into climatic, geological, and topographical. Climatic and topographical factors control the amount of water entering the system as rainfall or surface runoff and the amount leaving by evaporation. Geochemical factors determine which ions enter the system. Solutions of carbon dioxide result in the formation of a weak carbonic acid, which dissolutes the mineral components of the surrounding rocks and archaeological buildings, leading to their ion release.     

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.     

A new class of gels for the conservation of painted surfaces

The application of a new class of organogels as cleaning tools for painted surfaces is described. It combines some of the most attractive features of cleaning liquids and normal gels while diminishing the deleterious characteristics of both. Thus, the ‘latent’ gellant, polyethyleneimine (PEI), reacts with CO₂ at room temperature in solutions of several organic liquids to produce an ammonium carbamate form (PEICO₂). This charged species organizes itself into 3D polymer networks which immobilize the liquids as gels. The properties of the original solution (i.e. a free-flowing liquid) are re-established immediately after addition of a small amount of a weak acid which displaces the CO₂ molecules and makes the PEI chains positively charged. The visual changes are substantiated by rheological analyses. Results from analytical tests to determine the utility of these gels as cleaning tools for painted surfaces of historical and artistic interest, have been obtained from contact angle and FTIR measurements as well as visual comparisons of the surfaces before and after application of the gels. The analyses indicate that the PEICO₂-based organogels were very effective in removing different surface patinas from painted supports. A surface layer of dammar was completely removed from a test canvas with oil paint, an aged painting from the XIX century, and a XV century oil-on-wood panel attributed to Mariotto di Cristoforo. Finally, a surface acrylic polymeric resin (used in a restoration performed during the 1960s) was also successfully removed from Renaissance wall paintings decorating the Santa Maria della Scala Sacristy in Siena, Italy. The isothermally rheoreversible gel approach described in this work represents a new, highly versatile, and very efficient method for removing aged surface patinas from works of art.     

Significance of studying the petrography and mineralogy of the geological environment of old rupestrian churches to prevent their deterioration. A case study from the South Carpathians

This paper provides new insights into understanding the causes of deterioration of the Corbii de Piatra rupestrian church and shows the significance of studying the geological environment of historical rock-cut settlements when undertaking preservation and restoration actions. The Corbii de Piatra church is one of the few rupestrian churches remaining in Romania and is an important part of the country's heritage. The church is carved in a stratum of polymictic sandstone of Oligocene age, which is part of the Getic Depression, located in the southern part of the South Carpathians. In the 14th century the interior walls of the church were decorated with mural paintings of a high artistic value. Over the centuries, the church's walls and mural paintings have been negatively affected by a series of physicochemical processes. These processes were studied through field investigations and laboratory analyses carried out between October 2007 and November 2010. The investigations revealed that tectonic fissuring and the structural anisotropy of the rock facilitate the infiltration of meteoric water through the walls into the interior of the church, from north to south, maintaining a high-level of humidity in the northern wall and in the interior of the church. The most harmful effects observed were: (i) the partial hydrolysis of the feldspars through reaction with water from the pores, producing a friable mass of phyllosilicates which led to a superficial disaggregation of the rock and to a diminished cohesion between the rock and the mortar of the fresco, (ii) the reprecipitation of the gypsum as efflorescences on the northern wall and ceiling, covering the mural painting in localized areas, as a result of the transportation of the gypsum by water from the upper strata, (iii) the alteration of the cinnabar pigment, as a result of water penetration by diffusion through the fresco from the wet rock to the pictorial layer (the secondary effect observed being the formation of sulfuric acid, which further reacted with the carbonate from the fresco to form gypsum), (iv) the development of biotic crusts, predominately algal, on the interior wet walls, which, facilitated by the permanent high humidity and the semi-obscurity of the interior of the church, have covered large surfaces of the fresco. Compared to the interior, the exterior vertical walls have been exposed to prolonged daily and seasonal variations of temperature and humidity. These variations have caused repeated variations in the volume of the sandstone, leading to contraction fissuring and peeling of the vertical walls. Any future procedures that might be used to conserve the church should strive to reduce the humidity of the sandstone in the interior walls.     

An advanced church heating system favourable to artworks: A contribution to European standardisation

The European project Friendly-Heating (FH): comfortable to people and compatible with conservation of artworks preserved in churches addressed the problems caused by the continuous or intermittent heating of historic churches, which disturbs the microclimatic conditions to which the building and the artworks preserved inside have acclimatised. As thermal comfort and the preservation of artworks often conflict with each other, a balance between the two needs is necessary. The proposed heating strategy is to provide a small amount of heat directly to people in the pew area while leaving the conditions in the church, as a whole, undisturbed. This novel heating system is based on some low-temperature radiant emitters mounted in a pew to provide a desirable distribution of heat to the feet, legs and hands of people occupying it. Due to little heat dispersion, this novel system not only significantly reduces the risk of mechanical stress in wooden artworks and panel or canvas paintings, fresco soiling and cyclic dissolution-recrystallization of soluble salts in the masonry, but is energy-efficient. The detailed environmental monitoring was conducted in the church of Santa Maria Maddalena in Rocca Pietore, Italy over a 3-year period to verify the performance of the novel heating system in comparison to the warm-air system that was active earlier in the church. The methodology and results of this comprehensive and multidisciplinary study were included in three draft standards of the European Committee for Standardisation intended for use in the study and control of environments of cultural heritage objects.     

Consolidation and protection by nanolime: Recent advances for the conservation of the graffiti,Carceri dello Steri Palermo and of the 18th century lunettes,SS. Giuda e Simone Cloister,Corniola (Empoli)

Nanolime dispersed in 2-propanol was extensively used for the consolidation of wall paintings. The knowledge of the advances of this methodology dealing with all the possible effects associated with the nanolime new material in conservation is fundamental to assess and improve the technique. In this paper, four different dispersions of Ca(OH)₂ nanoparticles were characterised by Small Angle X-rays Scattering technique (SAXS) and Transmission Electron Microscopy (TEM) in order to achieve information on size, shape, polydispersity, agglomeration, and crystal structure (by SAED patterns) of the particles. Once characterised, the dispersions were tested in two different case studies, the Carceri dello Steri in Palermo with their graffiti and the 18th century lunettes at the SS. Giuda e Simone Cloister, Corniola (Empoli) with their lime-based mural paintings. The treated samples were characterised in relationship to either their morphology and surface chemical composition by Scanning Electron Microscopy coupled with Energy Dispersive X-rays spectroscopy (SEM-EDX), or their water absorption and mechanical properties (resistance to material abrasion). The results obtained showed that all the dispersions were nanometrically structured and their application succeeded in recovering the mechanical properties of the painting or graffito layers, not altering their permeability to water and keeping perfectly the wall transpiration. However, the dispersions constituted of the nanoparticles obtained via a synthesis able to control size and shape of the Ca(OH)₂ particles resulted in a better performance in situ, even if the differences found by SAXS and TEM were slight.     

Revival of traditional European dyeing techniques yellow and red colorants

Based on both a historic and documentary and a physicochemical approach, the study is attempting to codify well-adapted antique, medieval and traditional textile dyeing recipes; to reconstruct them through a detailed sequence of simple and reproducible operations; and to optimize the methodology at all stages, i.e. extraction of the colouring principles, as well as mordanting and dyeing; the latter being evaluated through standard light and wash fastness assessments, and on the basis of systematically obtained colorimetric data. As colouring agents are considered saffron, turmeric, weld, Persian berries, henna, safflower, dyer's bugloss, madder, scale insects, sappan and Brazil wood. A variety of mordants, namely FeCl₃, SnCl₂, K₂Cr₂O₇, ZnCl₂, CuSO₄, and KAl(SO₄)₂·12H₂O, is anticipated to meet both early and rather recent options, while being easily available. Based on a large collection of ancient proposals and optimized by means of methodical assessments, the standardized dyeing processes proposed are simple, reproducible, and perfectly reliable for use in the preservation of the relevant tangible heritage, and the revival of traditional arts and crafts; and are consequently beneficial to artistic weavers, as well as conservators and restorers of textile products.     

Microstructure,composition and processing of 15th century Vietnamese porcelains and celadons

Fifteenth century porcelains and celadons are the most interesting ancient Vietnamese ceramics, both from the material and aesthetic points of view. This paper reports on composition, microstructure and technological processing of the Chu Ðâu-My Xa (Hai Duong province) ceramics. Samples come either from the kiln site or from the Cù Lao Chàm (Hôi An) shipwreck. Chemical analysis, scanning electron microscopy, EDX analysis, X-ray diffraction, Raman spectroscopy, thermal expansion/shrinkage and open porosity measurements were systematically performed. The results show the Ca (+K)-based glaze, high-temperature-fired bodies, by one- or multi-step firings. Mullite phase (3Al₂O₃·2SiO₂) was formed in large amount indicating the true porcelain quality of the samples under study. The matrices used for overglaze colouring (e.g., the green, red and metallic-lustre) are lead-based low-firing-temperature glasses. Comparison was made for the structural elements and fluxing agents between the 15th century Vietnamese porcelains and the time-corresponding Chinese ones.     

The impact of electric overhead radiant heating on the indoor environment of historic churches

The impact of electric overhead radiant heaters on the microclimate, air flows, transport and deposition of suspended particulate matter (SPM) was monitored between March 2004 and March 2005 in the historic churches of Saint Michael Archangel in Szalowa and Saint Catherine in Cracow (Poland). The measurements show that although irradiation at the floor level increases temperature and reduces relative humidity in the interior of the church, the effect out of the heated zone and for the surfaces sheltered from irradiation is very limited, i.e. their extent is comparable with natural fluctuations inherent to the local climate of the church. The radiant heaters proved to generate little convectional flow of the air. Therefore, the heating system was not found to increase the concentration of SPM indoors; in particular, no re-suspension of particles already present in the church was observed. This work has demonstrated that the overhead radiant heaters are capable of providing localised heat to the areas where people congregate without adversely affecting painted walls and the works of arts displayed in churches. Care, however, should be taken that sensitive works of art are not exposed to the direct infrared radiation.     

Analysis of calcium acetate efflorescences formed on ceramic tiles in a museum environment

Salt crystallization is a major cause of damage in porous materials such as stone, brick and ceramics. The paper reports results of an analytical study on tiles of glazed ceramics that are seriously damaged by acetate salt crystallization. Measurements of the ionic composition of the salt mixture in the tiles and in the efflorescences were carried out. Based on the available information on the phase equilibria in the system comprising of the main constituents chloride, nitrate, acetate, calcium and sodium, the crystallization pathways of the various solid phases are traced. It is shown that a combination of qualitative XRD analysis of the phases present in the efflorescences together with a quantitative determination of the ionic composition is sufficient for the quantitative analysis of major crystalline species in the efflorescences, i.e. Ca₃(CH₃COO)₃Cl(NO₃)₂ · 7H₂O, thecotrichite, and NaCl, halite. The concentrations of these salts are obtained from a solution of the mass balance by least squares analysis. Their formation from the salt mixtures present in the tiles that are subject to acetic acid vapor attack is consistent with the solubility diagram of the above mentioned quinary system. Finally, the possibilities of preventive conservation of salt contaminated ceramics in typical museum environments are discussed.     

The presence of trapped carbon dioxide in lapis lazuli and its potential use in geo-sourcing natural ultramarine pigment

The source of the previously unassigned weak band at 2340 cm⁻¹ that is occasionally observed in the infrared spectrum of natural lapis lazuli pigment is here attributed conclusively to CO₂ trapped in the β-cage of lazurite. In addition, the geo-sourcing potential of this infrared feature for lapis lazuli is tested and found to be more ambiguous than previously suggested. The CO₂ absorption band is in fact observed in lapis lazuli samples from numerous disparate geographic locales including Afghanistan, Canada, Myanmar, Siberia, Tajikistan, and the Ural Mountains, as well as mineral hauyne samples from Germany and Italy. The spectral feature was absent from lapis lazuli samples from California, Chile, Colorado, and New York. Furthermore, poor quality lapis lazuli samples, regardless of locale, highly processed natural pigment samples, and all samples of synthetic ultramarine blue, green, and violet pigments were devoid of encapsulated CO₂.     

Photoluminescence of the inorganic pigments Egyptian blue, Han blue and Han purple

The room-temperature photoluminescence spectra of various samples of Egyptian blue (CaCuSi₄O₁₀) are presented, discussed and compared with those of recently synthesized compounds corresponding to the ancient pigments Han blue (BaCuSi₄O₁₀) and Han purple (BaCuSi₂O₆). All the samples of Egyptian blue show identical spectra, in spite of their very different origin. The spectra of Han blue and Han purple are significantly different. Since the Cu²⁺ ion may be considered the only luminescent centre in the spectral range under investigation, the differences between the spectra of the various pigments are ascribed to a ligand-field change. This can be related to the larger size of the Ba²⁺ ion with respect to Ca²⁺. The use of PL spectra for the identification of these pigments in works of art is proposed.     

Use of ZnO nanoparticles for protecting oil paintings on paper support against dirt,fungal attack,and UV aging

Zinc oxide nanoparticles were prepared and used for surface treatment of oil paintings painted on paper supports. The prepared coating mixture containing 2% of ZnO nanoparticles showed excellent transparency. The effect of coating on protecting the paper support and paintings against microbial attack by Trichoderma reesei and Aspergillus niger, dirt accumulation, and UV aging was studied. Coatings containing ZnO nanoparticles enhanced the durability of linseed oil-based paintings toward UV aging regarding the change in color. Coatings containing ZnO nanoparticles improved resistance to microbial attack when subjected to inoculums containing T. reesei or A. niger fungi. In addition, coatings containing ZnO nanoparticles reduced accumulation of dirt on oil paintings when left in open air for 6 months; cleaning of paintings was quite easy compared to the non-coated paintings or those coated with the varnish without ZnO nanoparticles.     

The conservation of the Vecchietta's wall paintings in the Old Sacristy of Santa Maria della Scala in Siena: The use of nanotechnological cleaning agents

In the present article we report a study on some sodium dodecyl sulphate/propylene carbonate based aqueous micellar solutions developed with the aim of setting up a nanotechnological cleaning system to remove naturally aged polymeric acrylic layers from the surface of the wall paintings in the Old Sacristy of Santa Maria della Scala in Siena (15th century). Being these systems mainly composed of water (more than 70% by weight), the cleaning of the painted surface have been performed with low environmental impact, due to the small amount of the pure organic solvents used (always less than 25% by weight). Furthermore, the aqueous phase constitutes a hydrophilic barrier to the penetration of the hydrophobic acrylic materials into the porous support. Fourier Transform InfraRed spectroscopy (FTIR), Scanning Electron Microscopy coupled with Energy Dispersive X-rays analysis (SEM/EDX) and in situ capillary water adsorption measurements indicated the efficacy of this cleaning procedure. Finally, the chemical diagnostics investigation enabled to ascertain the presence of both salts (nitrates and gypsum) and the acrylic polymeric material.     

Preservation of aged paper using borax in alcohols and the supercritical carbon dioxide system

Selecting an appropriate paper deacidification agent is very important for the deacidification of paper. The use of three deacidification agents (i.e., iso-butylamine, calcium propionate, and borax) is studied for the deacidification of paper using the immersion treatment by investigating the paper surface pH, alkaline residue, paper whiteness, strength, and other performance indicators. Results show the deacidification by borax solution not only results in the promotion of a proper pH range, high level of alkali reserves, and ignorable influence to paper appearance, but also to the enhancement of the mechanical intensities of paper even after artificial aging. Supercritical carbon dioxide (CO₂SCF), as a solvent system, is used in the deacidification of acidic papers using the borax solution of water and alcohol. CO₂SCF improved the deacidification process by significantly improving the pH value and the base residual value. The borax in supercritical fluids can be better combined with cellulose hydroxyl to improve the mechanical properties of paper substantially. The treatment of borax in CO₂SCF could be an alternative for acidic papers. Aside from improving the pH and depositing a sufficient alkaline residual, CO₂SCF also strengthens the mechanical properties of treated papers.     

Mapping the corrosion impact of air pollution on the historical peninsula of Istanbul

This paper presents the most comprehensive study conducted so far for evaluating the corrosion levels related to air quality and the seasonal pollutant (NO₂, SO₂, and O₃) exposure levels over 50 monitoring stations distributed on the historical peninsula of Istanbul. Istanbul has been one of the most important as well as most populated major cities in the world during all the ages. Today, owing to its historical and cultural structures, the historical peninsula of Istanbul has become an attraction point of tourism and is one of the most unique and ancient urban settlement areas in the world. However, the cultural heritage stocks in the peninsula are under the risk of corrosion and critical air pollution level exposure caused by chemical reactions under the multi-pollutant situation of the air pollutants, principally SO₂, NO₂, and O₃, as well as meteorological factors, e.g. humidity and temperature. In the present study, seasonal exposure of NO₂, SO₂, and O₃ pollutants were monitored using passive samplers, and corrosion attack values were calculated using dose-response functions. The geostatistical analyst tool of ArcGIS^® 9.1 was then used for generating GIS-based surface pollution and corrosion distribution maps. Subsequently, two hotspots were clearly identified, the tip of the peninsula and the area around the Ataturk Bridge, which fall under serious corrosion risks for copper, cast bronze, and carbon steel materials. However, no significant risk was identified for cultural heritage materials made of limestone in the peninsula.     

Microanalytical identification of Pb-Sb-Sn yellow pigment in historical European paintings and its differentiation from lead tin and Naples yellows

The work is focused on identification of lead tin yellow types I and II, Naples yellow, and also on discrimination of a less common, distinct yellow pigment, the ternary Pb-Sb-Sn oxide.The knowledge about all those Pb-based yellows was in fact forgotten after introduction of modern synthetic yellows in 19th century. As late as in the last decade of the 20th century, the existence of Pb-Sb-Sn yellow and its production have been rediscovered, and only then it has been identified in colour layer of artworks.Pb-Sb-Sn yellow has recently been identified in colour layer of 17th century Italian paintings by Sandalinas and Ruiz-Moreno [C. Sandalinas, S. Ruiz-Moreno, Lead tin-antimony yellow, historical manufacture, molecular characterization and identification in seventeenth-century Italian paintings, Stud. Conserv. 49 (2003) 41–52], and here we report the finding of this pigment in Mid-European painting of the 18th and 19th centuries. Lead tin yellows, lead antimony yellow (Naples yellow), and lead antimony tin yellow were synthesized in laboratory following historical recipes, their colour was analyzed, and their structure was confirmed to provide a basis for their routine identification in microsamples of artworks by X-ray microdiffraction. Unequivocal identification of Pb-based yellows could help in authentication of traditional European paintings, because their use was temporally and also geographically specific. Combination of elemental microanalysis (X-ray fluorescence electron microanalysis) and X-ray powder microdiffraction were found very efficient in the microanalysis of colour layers of artworks with Pb-based yellows and their unequivocal identification.