Alessandra Bonazza

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.

Organic anions in damage layers on monuments and buildings

Abstract This article is focused on small (C1–C2) organic anions present in the damage layers on historic monuments and buildings. Formate, acetate and oxalate are consistently found in black crusts, where atmospheric deposition accumulates along with the products of the chemical transformation of stone and mortars. While sulphation processes affecting building materials have been extensively studied, the importance of carbon compounds in black crusts is only recently being realised. Recent data show carbon to be the second most important airborne element after sulphur in damage layers on building exteriors. Total carbon is composed of carbonate-, organic-, and elemental carbon. The organic fraction includes formate, acetate and oxalate; these are always detected in black crusts. Their origin, role and measurement in the atmosphere and in the museum environment have been the subject of many studies, but little has been reported concerning their presence in building exterior damage layers. This paper presents data on these anions in damage layers on stones and mortars sampled on monuments and buildings at different urban, suburban and rural European sites. Oxalate encountered in black crusts likely originates from the metabolism of micro-organisms and protective treatments on surfaces. Primary and secondary atmospheric pollutants are likely the main sources of formate and acetate anions.

An integrated approach to assess air pollution threats to cultural heritage in a semi-confined environment: The case study of Michelozzo's Courtyard in Florence (Italy)

An example of an integrated approach to assess air pollution threats to cultural heritage in a semi-confined environment is presented in this work, where the monitoring campaign carried out at the Michelozzos Courtyard (in Palazzo Vecchio, Florence, Italy) is used as a case study. A wide research project was carried out, with the main aim of obtaining the first quantitative data on air quality and microclimate conditions inside the Courtyard, and, if possible, identifying the main causes of degradation and suggesting appropriate conservation strategies. The investigation adopted a holistic approach involving thermographic measurements on the wall paintings, microclimatic analysis, gaseous pollutant monitoring, atmospheric particles characterisation and dry deposition compositional analysis. Attention was focused on the wall painting depicting the city of Hall because of its anomalous and critical conservation conditions, which are visible at a glance, due to the contrast between a wide darker zone around the central subject of the painting and external lighter areas.

Damage on hydraulic mortars: the Venice Arsenal

Abstract Very few scientific studies have been performed so far on ancient and modern hydraulic mortars. The effects of atmospheric multi-pollutants on hydraulic mortars used in monuments and historic buildings in urban areas, especially those linked to dry and wet carbon and sulphur deposition, remain in need of thorough investigation. In the literature, studies on damage typology identification, composition and origin and relative quantitative data are both scarce and rather poor in quality. While the sulphate source from marine spray deposition and water capillary rising are known, atmospheric sulphur effects on mortars still require elucidation. Ancient and modern hydraulic mortars have been collected from the Arsenal of Venice. The original material characterisation and the evaluation of the surface damage due to atmospheric pollution are presented along with a comparison of the data obtained for the cement and cocciopesto mortars.

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.

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.

Innovative consolidating products for stone materials: field exposure tests as a valid approach for assessing durability

The impact of climate on cultural heritage surfaces leads to several damage processes and the protection and the preservation of works of art is a challenge for conservation scientists and restorers. Traditional and innovative products are used in consolidating treatments in order to reduce the effects of the interaction environment-materials. The EC NANOMATCH Project aims at the development of innovative consolidating agents for carbonate matrices, wood and glass whose features should result in high compatibility, efficiency and long-lasting effect. In this project, metal alkoxides, molecular precursors for the deposition of metal carbonate are synthesized, characterized, tested and proposed as an alternative to traditional consolidating agents as well as to calcium hydroxide nanoparticles. This paper gives an overall description of the methodological approach adopted for the in field evaluation of durability taking into account the environmental impact. Preliminary results of the analyses carried out on carbonate stones aimed at investigating the features of the consolidating treatment are here presented and discussed.

Durability assessment to environmental impact of nano-structured consolidants on Carrara marble by field exposure tests.

The EU policy of reducing the emissions of combustion generated pollutants entails climate induced deterioration to become more important. Moreover, products applied to preserve outdoor built heritage and their preliminary performance tests often turn out to be improper. In such context, the paper reports the outcomes of the methodology adopted to assess the durability and efficiency of nano-based consolidating products utilized for the conservation of carbonate artworks, performing field exposure tests on Carrara marble model samples in different sites in the framework of the EC Project NANOMATCH. Surface properties and cohesion, extent and penetration of the conservative products and their interactions with marble substrates and environmental conditions are here examined after outdoor exposure for eleven months in four different European cities and compared with the features of undamaged and of untreated damaged specimens undergoing the same exposure settings.

Deterioration estimation of paintings by means of combined 3D and hyperspectral data analysis

Deterioration of artwork, in particular paintings, can be produced by environmental factors such as temperature fluctuations, relative humidity variations, ultraviolet radiation and biological factors among others. The effects of these parameters produce changes in both the painting structure and chemical composition. While well established analytical methodologies, such as those based in Raman Spectroscopy and FTIR Spectroscopy require the extraction of a sample for its inspection, other approaches such as hyperspectral imaging and 3D scanning present advantages for in-situ, noninvasive analysis of artwork. In this paper we introduce a novel system and the related methodology to acquire process, generate and analyze 4D data of paintings. Our system is based on non-contact techniques and is used to develop analytical tools which extract rich 3D and hyperspectral maps of the objects, which are processed to obtain accurate quantitative estimations of the deterioration and degradation present in the piece of art. In particular, the construction of 4D data allows the identification of risk maps on the painting representation, which can allow the curators and restorers in the task of painting state evaluation and prioritize intervention actions.