Impact of air pollution in deterioration of carbonate building materials in Italian urban environments

Abstract This work presents results from a petrographic, morphological and chemical study of the black crusts developing on monuments in three Italian cities, the Cathedral of Milan, the Cathedral of St. Maria del Fiore in Florence, and the Vittoriano Monument in Rome. Black crusts (BCs) were studied with traditional techniques such as optical microscopy (OM), scanning electron microscopy coupled with energy-dispersive X-ray spectrometry (SEM-EDS) and infrared spectroscopic techniques (FT-IR), in combination with laser ablation inductively coupled mass spectrometry (LA-ICP-MS), which has shown itself to be particularly useful in determining concentrations of heavy metals in BCs. Although the BCs of the three monuments show general enrichment in heavy metals with respect to the substrate (S), interesting differences were observed among them. The BCs from Milan are the richest in heavy metals, particularly Pb and Zn, reflecting the severe air pollution of this very large city, which, in addition to its intense traffic, is located in the most highly industrialized area of Northern Italy. The BCs from the south-eastern side of the Cathedral of St. Maria del Fiore in Florence, facing a pedestrian area, show little enrichment in heavy metals, and those from the Vittoriano Monument in Rome, which is exposed to intense road traffic, display variable enrichment, attributable to mobile emission sources. Results show that the various enrichment trends in heavy metals observed in the BCs of these three monuments are due to many factors: various sources of anthropogenic pollution, sampling height, exposure, orientation, and the shape of the deposition surface.

[1]  M. Vendrell-Saz,et al.  Weathering of gilding decorations investigated by SR: development and distribution of calcium oxalates in the case of Sant Benet de Bages (Barcelona, Spain) , 2007 .

[2]  G. M. Crisci,et al.  A new methodological approach for the chemical characterization of black crusts on building stones: a case study from the Catania city centre (Sicily, Italy) , 2011 .

[3]  J. Kukkonen,et al.  Analysis and evaluation of selected local-scale PM10 air pollution episodes in four European cities: Helsinki, London, Milan and Oslo , 2005 .

[4]  Cinzia Perrino,et al.  Influence of atmospheric stability on the mass concentration and chemical composition of atmospheric particles: a case study in Rome, Italy. , 2008, Environment international.

[5]  Peter Brimblecombe,et al.  Carbon in black crusts from the Tower of London. , 2007, Environmental science & technology.

[6]  P. Mazzoleni,et al.  The Cathedral of S. Giorgio in Ragusa Ibla (Italy): characterization of construction materials and their chromatic alteration , 2008 .

[7]  H. Longerich,et al.  The design, operation and role of the laser-ablation microprobe coupled with an inductively coupled plasma-mass spectrometer (LAM- ICP-MS) in the Earth sciences , 1995 .

[8]  Cristina Sabbioni,et al.  Airborne carbon particles and marble deterioration , 1981 .

[9]  L. Zou,et al.  Size-resolved airborne particles and their morphology in Central Jakarta , 1997 .

[10]  A Andreotti,et al.  Analytical investigation of calcium oxalate films on marble monuments. , 2004, Talanta.

[11]  C. Saiz-Jimenez,et al.  Aerosols characterization and sources in different European urban atmospheres: Paris, Seville, Florence and Milan , 2004 .

[12]  Cristina Sabbioni,et al.  Quantitative data on carbon fractions in interpretation of black crusts and soiling on European built heritage , 2005 .

[13]  H. Harmens,et al.  Temporal trends in the concentration of arsenic, chromium, copper, iron, nickel, vanadium and zinc in mosses across Europe between 1990 and 2000 , 2007 .

[14]  S. A. Ruffolo,et al.  Application of spectrometric analysis to the identification of pollution sources causing cultural heritage damage , 2013, Environmental Science and Pollution Research.

[15]  Morten Winther,et al.  Heavy metal emissions for Danish road transport , 2010 .

[16]  Leonidas Ntziachristos,et al.  Physicochemical and redox characteristics of particulate matter (PM) emitted from gasoline and diesel passenger cars , 2006 .

[17]  A. Bonazza,et al.  Chemical-thermal quantitative methodology for carbon speciation in damage layers on building surfaces. , 2006, Environmental science & technology.

[18]  The Baroque monuments of Modica (Eastern Sicily): assessment of causes of chromatic alteration of stone building materials , 2010 .

[19]  J. B. Neto,et al.  Geochemical Distribution and Bioavailability of Heavy Metals and Oxalate in Street Sediments from Rio de Janeiro, Brazil: A Preliminary Investigation , 2005, Environmental geochemistry and health.

[20]  Bernard J. Smith,et al.  Element partitioning and potential mobility within surface dusts on buildings in a polluted urban environment, Budapest. , 2006 .

[21]  R. J. Dunham.  Classification of Carbonate Rocks According to Depositional Textures , 1962 .

[22]  C. Sabbioni,et al.  Oxalate patinas on ancient monuments: the biological hypothesis , 1991 .

[23]  Cristina Sabbioni,et al.  Assessment of air pollutant sources in the deposit on monuments by multivariate analysis. , 2014, The Science of the total environment.

[24]  D. Günther,et al.  Determination of Forty Two Major and Trace Elements in USGS and NIST SRM Glasses by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry , 2002 .

[25]  Franca Persia,et al.  Air pollution loads on historical monuments: an air quality model application to the marble Arch of Titus in Rome , 1995 .

[26]  Eduardo Sebastian,et al.  Role of particulate matter from vehicle exhaust on porous building stones (limestone) sulfation , 1996 .

[27]  D. Barca,et al.  Geochemical study of black crusts as a diagnostic tool in cultural heritage , 2013 .

[28]  Francisco J. García Alonso,et al.  Soiling of building stones in urban environments , 2003 .

[29]  C. Perrino,et al.  Inorganic constituents of urban air pollution in the Lazio region (Central Italy) , 2007, Environmental monitoring and assessment.

[30]  Antonia Moropoulou,et al.  Origin and growth of weathering crusts on ancient marbles in industrial atmosphere , 1998 .

[31]  C. Sabbioni,et al.  Weddellite on limestone in the Venice [Italy] environment. , 1983, Environmental science & technology.

[32]  Bernard J. Smith,et al.  Transition metals and water-soluble ions in deposits on a building and their potential catalysis of stone decay , 2008 .

[33]  Alessandro Pavese,et al.  The effects of atmospheric multipollutants on modern concrete , 2003 .

[34]  G. M. Crisci,et al.  Application of laser ablation ICP-MS and traditional techniques to the study of black crusts on building stones: a new methodological approach , 2010, Environmental science and pollution research international.

[35]  Lucia Toniolo,et al.  The Angera stone: a challenging conservation issue in the polluted environment of Milan (Italy) , 2013, Environmental Earth Sciences.

[36]  G Valli,et al.  Source apportionment of PM10 and PM2.5 in Milan (Italy) using receptor modelling. , 2003, The Science of the total environment.

[37]  R. Vecchi,et al.  Characterisation of PM10 and PM2.5 particulate matter in the ambient air of Milan (Italy) , 2001 .

[38]  M. Monte.  Oxalate film formation on marble specimens caused by fungus , 2003 .

[39]  V. Furlan,et al.  Experimental study of limestone and sandstone sulphation in polluted realistic conditions: The Lausanne Atmospheric Simulation Chamber (LASC) , 1996 .

[40]  Cristina Sabbioni,et al.  Exposure tests of building materials in urban atmosphere , 1998 .