An analysis of the black crusts from the Seville Cathedral: a challenge to deepen the understanding of the relationships among microstructure, microchemical features and pollution sources.

The Cathedral of Seville is one of the most important buildings in the whole of southern Spain. It suffers, like most of the historical buildings located in urban environments, from several degradation phenomena related to the high pollution level. Undoubtedly, the formation of black crusts plays a crucial role in the decay of the stone materials belonging to the church. Their formation occurs mainly on carbonate building materials, whose interaction with a sulfur oxide-enriched atmosphere leads to the transformation of calcium carbonate (calcite) into calcium sulfate dihydrate (gypsum) which, together with embedded carbonaceous particles, forms the black crusts on the stone surface. To better understand the composition and the formation dynamics of this degradation product and to identify the pollutant sources and evaluate their impact on the stone material, an analytical study was carried out on the black crust samples collected from different areas of the building. For a complete characterization of the black crusts, several techniques were used, including laser ablation inductively coupled plasma mass spectrometry, Fourier transform infrared spectroscopy, micro infrared spectroscopy, optical and scanning electron microscopy. This battery of tests provided information about the nature and distribution of the mineralogical phases and the elements within the crusts and the crust-substrate interface, contributing to the identification of the major pollution sources responsible for the deterioration of the monument over time. In addition, the results revealed a relation among the height of sampling, the surface exposure and the concentration of heavy metals. Finally, information has been provided about the origin of the concentration gradients of some metals.

Assessment of air pollutant sources in the deposit on monuments by multivariate analysis.

A proper recognition of the pollutant sources in atmospheric deposit is a key problem for any action aiming at reducing their emission, being this an important issue with implications both on human health safeguard and on the cultural heritage conservation in urban sites. This work presents the results of a statistical approach application for the identification of pollutant sources in deposits and damage layers on monuments located in different European sites: Santa Maria del Fiore, Florence (Italy), Cologne Cathedral, Cologne (Germany), Ancient ramparts, Salè (Morocco), National Museum, Cracow (Poland) and National Gallery, Oslo (Norway). For this aim, the surface damage layers on monuments and historical buildings of the selected sites were collected and analyzed, in terms of ionic and elemental composition, through application of ion chromatography and induced coupled plasma-optical emission spectroscopy. The achieved results were processed by multivariate analyses such as correlation matrix and principal component analysis in order to identify the possible origin of pollutants affecting the state of conservation of the monuments. This allowed us to assume that in all case studies the traffic emission is the main pollutant source. In the case of Ancient ramparts, Salè (Morocco), and National Gallery, Oslo (Norway), the surfaces are also under influence of marine aerosols. Moreover, concerning the Cologne Cathedral, the strong impact of the pollutants emitted by railway station was also revealed.

Mapping the impact of climate change on surface recession of carbonate buildings in Europe.

Climate change is currently attracting interest at both research and policy levels. However, it is usually explored in terms of its effect on agriculture, water, industry, energy, transport and health and as yet has been insufficiently addressed as a factor threatening cultural heritage. Among the climate parameters critical to heritage conservation and expected to change in the future, precipitation plays an important role in surface recession of stone. The Lipfert function has been taken under consideration to quantify the annual surface recession of carbonate stone, due to the effects of clean rain, acid rain and dry deposition of pollutants. The present paper provides Europe-wide maps showing quantitative predictions of surface recession on carbonate stones for the 21st century, combining a modified Lipfert function with output from the Hadley global climate model. Chemical dissolution of carbonate stones, via the karst effect, will increase with future CO(2) concentrations, and will come to dominate over sulfur deposition and acid rain effects on monuments and buildings in both urban and rural areas. During the present century the rainfall contribution to surface recession is likely to have a small effect, while the increase in atmospheric CO(2) concentration is shown to be the main factor in increasing weathering via the karst effect.

Carbon in black crusts from the Tower of London.

This paper investigates the origin, fluxes, and transformation of carbon compounds within black crusts on the stone walls of the Tower of London. The crusts were analyzed for elemental and organic carbon, including the water soluble fraction. Elemental carbon and low solubility compounds such as oxalates appeared to be conserved because of long residence times. Conversely, more soluble ions, like chloride and formate would be removed from the layers relatively quickly by rainfall. At higher organic carbon concentrations acetic acid may be produced within the crusts from biological transformations. Currently, traffic sources contribute to increasingly organic rich crusts. The deposition of elemental carbon to buildings darkens surfaces and has important aesthetic implications. The increased organic content may have further aesthetic consequence by changing the color of buildings to warmer tones, particularly browns and yellows. Management of historic buildings requires us to recognize the shift away from simple gypsum crusts to those richer in organic materials.

Did smoke from the Kuwait oil well fires affect Iranian archaeological heritage?

The combustion of crude oil produces a wide range of pollutants, including gases, volatile organic compounds, polycyclic aromatic hydrocarbons, acid compounds (e.g., sulfuric acid), and soot. Several of these pollutants have been linked with the deterioration and blackening of monuments. The paper reports the results of an investigation on the causes of the soiling of cultural remains at important archaeological sites in the provinces of Khuzestan and Fars, in southern Iran, assumed to be an effect of the Persian Gulf oil well fires of 1991. Different analytical techniques were applied to characterize the mineralogical composition of the damage layers, investigate the deposition of atmospheric particles, measure the anion concentrations, and identify and quantify the carbon components. The results showed that the black deposits on the surfaces of the Iranian monuments considered are mainly microbiotic crusts produced by cyanobacterial growth. No evidence was found of the deposition of particulate matter (smoke) produced by the Kuwait oil fires during the Gulf War.

Chemical-thermal quantitative methodology for carbon speciation in damage layers on building surfaces.

The issue of environment protection, including the conservation of the monumental heritage worldwide, is related to atmospheric pollution, and its future therefore depends on air pollutant reduction. Carbonaceous particles emitted by combustion processes are the main factors responsible for the blackening of buildings. The identification and evaluation of the carbon species constituting the noncarbonate fraction of total carbon in damage layers, particularly in urban areas, are required in orderto investigate atmospheric deposition on building surfaces. Since noncarbonate carbon contains organic and elemental carbon originating from various human activities, its measurement and speciation are crucial to the protection and conservation of monuments and ancient masonry, playing an important role both in the proposal of mitigation strategies and in the definition of conservation treatments. The availability of a correct, accurate, and reproducible analytical method for a complete carbon balance is essential in studying the effects of atmospheric pollutants on the environment, including those affecting cultural heritage. A chemical-thermal methodology was set up, and its sensitivity, accuracy, repeatability, and reproducibility were tested on appropriate standard samples of composition similar to the black crusts on stones and mortars. The results indicate thatthe technique satisfactorily distinguishes among carbon species, particularly those of anthropogenic origin, allowing a reliable evaluation of their quantities in damage layers. In view of the difficulties encountered in applying the thermo-optical methods adopted for the measurement of carbon filters, the proposed methodology contributes to filling the current gap in suitable and reliable analytical procedures in the field of cultural heritage protection.