Valeria Comite

Application of spectrometric analysis to the identification of pollution sources causing cultural heritage damage

Black crusts are recognized to have been, up to now, one of the major deterioration forms affecting the built heritage in urban areas. Their formation is demonstrated to occur mainly on carbonate building materials, whose interaction with an SO2-loaded atmosphere leads to the transformation of calcium carbonate (calcite) into calcium sulfate dihydrate (gypsum) which, together with embedded carbonaceous particles, consequently forms the black crusts on the stone surface. An analytical study was carried out on black crust samples collected from limestone monumental buildings and churches belonging to the European built Heritage, i.e., the Corner Palace in Venice (Italy), the Cathedral of St. Rombouts in Mechelen (Belgium), and the Church of St. Eustache in Paris (France). For a complete characterization of the black crusts, an approach integrating different and complementary techniques was used, including laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), Fourier transform infrared spectroscopy, optical and scanning electron microscopy. In particular, the application of LA-ICP-MS permitted to obtain a complete geochemical characterization in terms of trace elements of the black crusts from the inner parts to the external layers contributing to the identification of the major combustion sources responsible for the deterioration over time of the monuments under study. In addition, the obtained results revealed a relation between the height of sampling and the concentration of heavy metals and proved that the crust composition can be a marker to evaluate the variation of the fuels used over time.

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.

Advanced mortar coatings for cultural heritage protection. Durability towards prolonged UV and outdoor exposure

In the present work, two kinds of hybrid polymeric–inorganic coatings containing TiO2 or SiO2 particles and prepared starting from two commercial resins (Alpha®SI30 and Bluesil®BP9710) were developed and applied to two kinds of mortars (an air-hardening calcic lime mortar [ALM] and a natural hydraulic lime mortar [HLM]) to achieve better performances in terms of water repellence and consequently damage resistance. The two pure commercial resins were also applied for comparison purposes. Properties of the coated materials and their performance were studied using different techniques such as contact angle measurements, capillary absorption test, mercury intrusion porosimetry, surface free energy, colorimetric measurements and water vapour permeability tests. Tests were also performed to determine the weathering effects on both the commercial and the hybrid coatings in order to study their durability. Thus, exposures to UV radiation, to UV radiation/condensed water cycles and to a real polluted atmospheric environment have been performed. The effectiveness of the hybrid SiO2 based coating was demonstrated, especially in the case of the HLM mortar.

Diagnostic analysis of bricks from the underwater archaeological site of Baia (Naples, Italy): preliminary results

In this multidisciplinary contribution, several diagnostic tests were carried out in order to characterize the archaeological materials, as well as the alteration and degradation products, present in the submerged archaeological site of Baia (Naples, South Italy). Founded by the Romans in the 1st century B.C., this archaeological area represents one of the greatest evidence of Roman architecture and it includes ancient ruins whose structures range from maritime villas and imperial buildings. Fragments of bricks belonging from walls of a monumental villa, called Villa con ingresso a protiro, were studied with different and complementary techniques. In particular, polarized optical microscopy and X-ray diffraction were performed in order to characterize the raw materials employed for their production, while to evaluate the state of conservation and identify the biodeteriogen agents, samples were studied under a stereomicroscope and scanning electron microscopy. Analytical data highlighted that: a) different types of bricks were used in the ancient roman city of Baia; b) the presence of several degree of biological colonisation is mainly correlated to the type of temper used for their production.