Paving the Way for Climate Neutral and Resilient Historic Districts.

Climate change is a major global threat to our society's urban areas, with the majority of Europe's population living in cities and their cultural heritage. Historic districts of significant cultural value and the communities connected to these places have an important role to play in fostering location-based identity and economy, social cohesion, innovation, urban regeneration, and climate change adaptation. Thus, it is important to make historic districts climate resilient, by jointly considering climate change adaptation, disaster risk management, heritage management, and sustainable urban development. However, this is often a major challenge for local and regional administrators and relevant stakeholders. This paper constitutes the first major result of the EU R&I Task Force for Climate Neutral and Resilient Historic Urban Districts. It provides an overview of the challenges faced by practitioners and researchers when jointly addressing the needs of resilient historic districts and provides an initial set of recommendations produced by the task force to address these challenges. These challenges cover different issues around five topics (i) data availability, use and its management, (ii) the common responsibility fragmentation in policy and governance, (iii) the challenge on integrating local knowledge and traditions in resilience building, (iv) the difficulties around the co-ownership and co-production in governance and (v) the importance of mainstreaming heritage management in adaptation and resilience policies.

A multi-analytical approach to study the chemical composition of total suspended particulate matter (TSP) to assess the impact on urban monumental heritage in Florence.

In the present paper total suspended particulate matter (TSP) was collected at the S. Marco Museum in Florence during seasonal monitoring campaigns carried out in 2013 and 2014. The analyses focused on the determination of TSP chemical composition: main ions, organic carbon (OC), elemental carbon (EC), water soluble organic compounds (WSOC) and levoglucosa which is considered the specific marker for wood burning. The analysis of TSP composition in Florence historical centre is of interest to assess what the damage caused to the surfaces of the urban monumental heritage could be. TSP higher value has been registered during December 2013 (58,6 µg/m3 ± 7,3 µg/m3) while the lower value has been registered in July 2013 (28,5 µg/m3 ± 2,2 µg/m3). OC and EC were also higher in winter with respect to summer. Sulphate is characterized by quite constant values during all the examined periods while ammonium and nitrate were higher in winter. The seasonal contribution of different sources such as combustion processes (from traffic and wood burning) and soil dust resuspension has been evidenced. In particular during winter a high concentration of levoglucosan, the specific marker for wood combustion, has been determined. Finally, all the data obtained were correlated with those previously determined in another study carried out in 2003 at the Baptistery of San Giovanni in Florence in order to evaluate any possible change in the atmospheric pollution composition.

Air pollution impact on architectural heritage of Morocco: Combination of synchronous fluorescence and ATR-FTIR spectroscopies for the analyses of black crusts deposits.

The work is focusing on air pollution impacts on historical limestone buildings located in urban areas in Morocco. Black crusts sampled on the façades of two ancient limestone monuments, dating back to the 12th and 20th centuries edified in the cities of Salé and Casablanca, have been analyzed by means of ATR-FTIR and synchronous fluorescence spectroscopies. Infrared analyses revealed degradation products, mainly gypsum due to calcite sulphation under wetness and SO2 rich oil fired soot, and oxalates due to ancient biological weathering. Synchronous fluorescence permitted the identification of the most hazardous PAHs along with other non-identified fluorescent organics; this technique appeared efficient and suitable for the analysis of fluorescent pollutants entrapped in black crusts. Such results keeping track of air pollution causing disfigurement of architectural heritage must alarm both cultural heritage and environmental decision makers.

Geochemical caper fingerprints as a tool for geographical origin identification.

The identification of geographical origin of food products is important for both consumers and producers to ensure quality and avoid label falsifications. The caper plant (Capparis spinosa L., Brassicales Capparidaceae), a xerophytic shrub common in the Mediterranean area, produces buds and fruits that are commercialized in brine at high price. Those grown in Italy in the Aeolian Islands are renowned for their high quality. This study is aimed to establish a correlation between the geological and geochemical features of soil and the chemical composition of caper buds grown in two Aeolian Islands, Lipari and Salina. Major and trace elements were investigated by X-ray fluorescence and inductively coupled plasma-mass spectrometry in soil and caper samples from three localities in Lipari and Salina, and data from the three sites were compared by a nonparametric test, a correlation test and multivariate statistics (principal component analysis). The results allowed to discriminate soils according to geolithological characteristics of each area and detect a statistically significant correspondence between soil and caper samples for the elements Co, Fe, Mg and Rb, identifying thus possible geochemical caper fingerprints of origin. These results may also be useful to protect the high quality of Aeolian caper products by a suitable "Made in Italy" trademark and avoid falsifications and frauds.

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.

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.