Applied Geochemistry 48 (2014) 122131

Contents lists available at ScienceDirect

Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem

Impact of air pollution in deterioration of carbonate building materials

in Italian urban environments
Donatella Barca a,, Valeria Comite a,b, Cristina M. Belore a,b, Alessandra Bonazza c, Mauro F. La Russa a,c,
Silvestro A. Ruffolo a, Gino M. Crisci a, Antonino Pezzino b, Cristina Sabbioni c
a
Universit della Calabria, Dipartimento di Biologia, Ecologia e Scienze della Terra (DiBEST), Via Pietro Bucci 87036, Arcavacata di Rende (CS), Italy
b
Dipartimento di Scienze Biologiche, Geologiche e Ambientali Sezione di Scienze della Terra, Universit di Catania, Corso Italia 57, 95129 Catania, Italy
c
Istituto di Scienze dellAtmosfera e del Clima, ISAC-CNR, Via Gobetti 101, 40129 Bologna, Italy

a r t i c l e i n f o a b s t r a c t

Article history: This work presents results from a petrographic, morphological and chemical study of the black crusts
Available online 15 July 2014 developing on monuments in three Italian cities, the Cathedral of Milan, the Cathedral of St. Maria del
Editorial handling by M. Kersten 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 spec-
troscopic 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, reecting the severe air pollution of this very large city, which, in
addition to its intense trafc, 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 trafc, 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, expo-
sure, orientation, and the shape of the deposition surface.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
The recent decline in air quality, due to increasing amounts of
anthropogenic pollutants released into the atmosphere of cities,
has had dramatic effects on cultural heritage. Buildings and monu-
ments in city centers are typically blackened, due to the accumula-
tion on their surfaces of atmospheric pollutants. The formation of
black crusts is often due to the growth of gypsum on calcareous
substrates, particularly limestone and marble, sheltered from
water and attacked by an SO2-polluted atmosphere (Moropoulou
et al., 1998).
In addition to gypsum, elemental carbon and organic carbon
compounds are usually the main components of crusts (Ghedini
et al., 2006).
Corresponding author. Tel.: +39 094 493571; fax: +39 0984 493689.
E-mail address: donatella.barca@unical.it (D. Barca).
Many studies have shown the close correlation between envi-
ronmental pollution levels and the formation and development
of black crusts (Ausset et al., 1996; Barca et al., 2010; Del Monte
et al., 1981; Grossi et al., 2003; Rodriguez-Navarro and Sebastian,
1996; Turkington et al., 1997; Zappia et al., 1998). In particular,
study of trace elements, such as heavy metals in the BCs develop-
ing on monuments, provides useful information on pollution
sources (Barca et al., 2010, 2011, 2012; Belore et al., 2013;
Comite et al., 2012; La Russa et al., 2013).
This work presents the results of a systematic mineralogical,
petrographic and chemical examination of BCs and their substrates
on samples from three important monuments in three cities of
central-northern Italy: the Cathedral of Milan, the Cathedral of
St. Maria del Fiore in Florence, and the Vittoriano Monument in
Rome. They were chosen for their historical signicance and
because they offer the possibility of analyzing the BCs developing
in three Italian cities exposed to various sources of pollution. The
air quality in the city centers of Milan, Florence and Rome is known

http://dx.doi.org/10.1016/j.apgeochem.2014.07.002
0883-2927/ 2014 Elsevier Ltd. All rights reserved.
 D. Barca et al. / Applied Geochemistry 48 (2014) 122131 123

to be very bad for many reasons; they are all large cities character-
ized by very intense trafc (buses, trucks, cars, scooters) and pollu-
tion due to domestic heating (Bonazza et al., 2005; Marcazzan
et al., 2001). In addition, among the three cities, Milan has the
highest level of air pollution, partly because of its position in a
heavily industrialized area, with power plants, reneries, incinera-
tors, and chemical and metallurgical factories in its hinterland
(Marcazzan et al., 2001, 2003).
Several techniques were used for the study, including polarizing
optical microscopy (OM), scanning electron microscopy coupled
with energy-dispersive X-ray spectrometry (SEM-EDS) and Fourier
transform infrared spectroscopy (FTIR), in combination with laser
ablation inductively coupled plasma mass spectrometry (LA-ICP-
MS). The aim of this work was to correlate the morphological, pet-
rographic and geochemical characteristics of the BCs on the stud-
ied monuments with the degree of air pollution, as well as the
exposure and orientation of their deposition surfaces.
2. Materials and methods
2.1. Sampling
Seven BC samples were collected from the surfaces of the three
monuments (gure as Supplementary material). Sampling was car-
ried out by Bonazza et al. (2005) within the framework of the CAR-
AMEL national research project, developed in 2003 by the Institute
of Atmospheric Sciences and Climate (ISAC) of the Italian National
Research Council (CNR) in Bologna. The project aimed at quantify-
ing the carbonaceous fraction within damaged layers of historic
buildings in various European cities.
In this study, three Italian cities, namely Milan, Florence and
Rome, were chosen for their notoriously poor air quality, subjected
as they are to considerable pollution from emissions of gases from
road trafc, domestic heating and industry. In addition, the monu-
ments in each of the above cities were chosen for their historical
and artistic importance and for the stone materials used to build
them (marble and limestone).
The Cathedral of Milan (1419th centuries) is a Late Gothic
building in the center of the city. It was designed by Gian Galeazzo
Visconti in 1386, but work on it lasted until 1894, when the faade
was completed. Milan is a very large city, with many residential
and commercial buildings and intense road trafc; it also lies in
the center of the Po Valley, the most highly industrialized area in
Northern Italy (Marcazzan et al., 2001, 2003). The Cathedral is
now in a pedestrian area (since 1969). The two BC samples studied
here (DM8, DM11) were collected from the south side of the build-
ing at about 40 m from ground level. Two substrate samples of
Candoglia marble were also collected.
The Cathedral of St. Maria del Fiore (1319th centuries) is in a
pedestrian area (since 2009) in the center of Florence, on the site
where the Basilica of St. Reparata, built in the 56th centuries, once
stood. The construction of the Cathedral, directed by Arnolfo di
Cambio, started in 1296 and lasted for nearly ve centuries, ending
in 1884. Four BC samples (DF3, DF4, DF8, DF10) were taken. All
samples and their Carrara marble substrates were collected from
the south-eastern side of the building at a height of about 60 m
from ground level. They were all collected from decorative ele-
ments, except for DF10, which was taken from a horizontal surface
where the crust showed growth oriented in the direction of the
prevailing wind.
The national monument built in honor of Vittorio Emanuele II of
Savoy, known as the Vittoriano Monument, is located in Piazza
Venezia in the center of Rome. Its construction started in 1885
under the direction of the architect Giuseppe Sacconi, and was
completed in 1935. The monument is now entirely surrounded
by roads carrying heavy trafc. One representative sample of black
crust and the relative substrate (Botticino limestone) was collected
from about 20 m from ground level (VR2). Table 1 lists all the
examined BC samples, together with details of sampling location,
shape of deposition surface and information about previous resto-
ration works.
2.2. Analytical methods
Microscopic study of BCs and substrates was carried out on thin
sections by polarizing optical microscopy.
Scanning electron microscopy coupled with energy-dispersive
X-ray spectrometry (SEM-EDS) analyses gave information on BC
micromorphology and chemical composition (major elements).
Analyses were performed on a Tescan Vega LMU scanning electron
microscope equipped with EDAX Neptune XM4 60 microanalysis
working in energy dispersive spectrometry, with an ultrathin Be
window to ensure lower detection limits (to the order of 0.1%)
for all elements analyzed. Operating conditions were set at 20 kV
138 accelerating voltage, 0.2 mA beam current, 100 s acquisition
time, and 3035% dead time. Precision was better than 1% for
major elements and better than 3% for minor elements. Accuracy
was of the same order of magnitude as precision.
FT-IR was used to identify the mineralogical phases of damaged
layers. A Perkin Elmer Spectrum 100 spectrophotometer was used,
equipped with an attenuated total reectance (ATR) accessory.
Infrared spectra were recorded in ATR mode, range 500
4000 cm 1 at a resolution of 4 cm 1.
To determine trace element concentrations, the samples were
analyzed by LA-ICP-MS on an ElanDRCe (Perkin Elmer/SCIEX), con-
nected to a New Wave UP213 solid-state Nd-YAG laser probe
(213 nm). Analytical procedures for acquisition of LA-ICP-MS data
were those tested in the Mass Spectroscopy Laboratory, DiBEST,
University of Calabria (Barca et al., 2010, 2011). After analytical
sequencing, the data were transmitted to a PC and processed by
the GLITTER program (van Achterberg et al., 2001). Constant laser
repetition rate was 10 Hz and uence about 20 J/cm2. Each ablation

Table 1
List of the black crust samples and description of the sampling points (from Bonazza et al., 2005).

Sample Height (m) BC typology Shape of deposition surface Sampling location Past restoration work
Milan Cathedral
DM8 40 Dendritic Horizontal surface, from a decorative element South side None during the last 500 years
DM11 40 Dendritic Concave surface, from a decorative element South side
St. Maria del Fiore Cathedral in Florence
DF3 60 Dendritic Vertical surface, from a decorative element South-east side 1500
DF4 60 Dendritic Horizontal surface, from a decorative element South-east side
DF8 60 Dendritic Horizontal surface, from a decorative element South-east side
DF10 60 Dendritic Horizontal surface, from a decorative element South-east side
Vittoriano Monument in Rome
VR2 20 Compact Horizontal surface, from the basis of a column North side from right propylea None prior to sampling
124 D. Barca et al. / Applied Geochemistry 48 (2014) 122131

crater was generally 50 lm in diameter. For geochemical study, the

samples (about 1 mm thick) were embedded in epoxy resin and
their upper surfaces were polished with a diamond cloth. In partic-
ular, a variable number of spot analyses (from 4 to 11) was carried
out on both BCs and substrates. Calibration was performed on glass
reference material SRM612-50 ppm of the National Institute of
Standards and Technology (NIST), in conjunction with internal
standardization, applying CaO concentrations (Fryer et al., 1995)
from SEM-EDS analyses. In order to evaluate any errors within each
analytical sequence, determinations were also made on an in-
house pressed-powder cylinder of the standard Argillaceous Lime-
stone SRM1d from NIST and on BCR 2G from USGS glass reference
materials, as unknown samples and element concentrations were
compared with reference values from the literature (Gao et al.,
2002; Barca et al., 2011). Accuracy, in terms of the relative differ-
ence compared with reference values, was always better than
10%, and most elements plotted in the range 5%.

3. Results

3.1. Polarizing optical microscopy

3.1.1. Cathedral of Milan

The substrate of samples DM8 and DM11 was Candoglia
marble, composed of calcite crystals and with a granoblastic
heteroblastic texture. The calcite crystals showed Maximum Grain
Size (MGS) of 1.251.75 mm and irregularly lobed contours.
Quartz, muscovite and hematite crystals were present as accessory
minerals.
The substrate appeared to be intensely degraded and the sam-
ples had many micro-cracks containing microcrystalline gypsum
(Fig. 1a).
The typically brown or dark gray BCs mainly consisted of micro-
crystalline gypsum, with single crystals of calcite, quartz and
muscovite embedded in the gypsum matrix (Fig. 1a). They adhered
to the substrate, had irregular morphology, and varied in thickness
from 500 lm to 2 mm. Many black carbonaceous particles, varying
in shape from sub-spherical to spherical and ranging from 30 to
50 lm in size, were observed in both types of samples. Irregularly
shaped iron oxides and hydroxides were also identied in the BCs.

3.1.2. Cathedral of St. Maria del Fiore, Florence

The substrate is of Carrara marble with characteristic polygonal
granoblastichomeoblastic fabric. It is composed of calcite crystals
of nearly isometric shape, with MGS of 0.50.75 mm; 120 triple
junctions are frequent, and rare, small quartz crystals were identi-
ed as accessories. The substrate is severely degraded, and all sam-
ples had many cracks in which microcrystalline gypsum had
penetrated and was growing.
All samples had a yellowish-brown, homogeneous layer 80
200 lm thick, developing at the contact between crust and sub-
strate. All the BCs had irregular external proles; they varied in
thickness from 400 to 800 lm in DF4 and DF8 (Fig. 1b), up to
1 mm in DF3, and up to 2 mm in DF10. All the BCs were composed
of microcrystalline gypsum showing acicular habit in DF4 and DF8,
and acicular habit arranged radially in DF10; single crystals of cal-
cite, quartz and muscovite embedded in the gypsum matrix were
also identied.
Many black carbonaceous particles and iron oxides and hydrox-
ides were observed, homogeneously distributed within the BCs of
DF3, DF4 and DF8, but heterogeneously distributed in that of
DF10. The carbonaceous particles varied in shape from spherical
to sub-spherical and prismatic, and were from 15 to 80 lm in size
(Fig. 1b).
Fig. 1. Photomicrographs representative of the investigated substrates (Sub) and
relative black crusts (BC) (plane polars light). DM8 = Milan Cathedral; DF8 = St.
Maria del Fiore Cathedral (Florence); VR2 = Vittoriano Monument (Rome).
3.1.3. Vittoriano Monument, Rome
The substrate of sample VR2 is a Botticino limestone composed
of mainly microcrystalline calcitic mud (crystal size 4 lm). Allo-
chemical components were bioclasts and rare iron oxides. The sub-
strate appeared compact, only slightly degraded, with primary
porosity of about 1% and no secondary porosity (Fig. 1c). On the
basis of these characteristics, the rock will be classied as a biomi-
crite or a mudstone, according to Folk (1959) and Dunham (1962),
respectively.
The crust adhered well to the substrate, with regular morphol-
ogy and little thickness (80700 lm); it was composed of micro-
crystalline gypsum with rare single quartz crystals embedded in
the matrix. Iron oxides and hydroxides and a few black carbona-
ceous particles, spherical to sub-spherical in shape with diameters
of about 40 lm, were also prevalently distributed in the outer
portion of the crust (Fig. 1c).
 D. Barca et al. / Applied Geochemistry 48 (2014) 122131 125

3.2. SEM-EDS analysis
SEM-EDS morphological and microchemical analyses were car-
ried out on the BCs of the three monuments.
Those of the Cathedral of Milan (Fig. 2a and b) showed irregular
dendritic morphology, ranging between 200 lm and 2 mm in
thickness. The layer was rmly attached to the substrate, which
was severely degraded, with many micro-cracks into which gyp-
sum had penetrated.
The substrate from the Cathedral in Florence was also severely
degraded (Fig. 2cf) with many micro-cracks in which BCs were
found. Samples DF3 and DF10 (Fig. 2c and f) had BCs between 1
and 2 mm thick, with indented, heterogeneous morphology and
alternating light and dark areas. On the other hand, the BCs of
DF4 and DF8 (Fig. 2d and e) were thin (250800 lm), with irregu-
lar external proles and rather homogeneous morphology.
The BC of the Vittoriano Monument (Fig. 2g) adhered to the
substrate and was thin, with irregular external proles and rather
homogeneous morphology.
All the BCs were composed of acicular gypsum crystals, with
single fragments of the substrate embedded within the crust and
variable quantities of combustion particles distributed throughout

Fig. 2. BSE-SEM microphotographs of the examined samples: DM8 (a), and DM11 (b) = Milan Cathedral; DF3 (c), DF4 (d), DF8 (e) and DF10 (f) = St. Maria del Fiore Cathedral
in Florence; VR2 (g) = Vittoriano Monument in Rome. The holes caused by LA-ICP-MS spot analyses (carried out on black crusts = BC and substrates = Sub) are also visible.
126 D. Barca et al. / Applied Geochemistry 48 (2014) 122131
the thickness. In particular, several types of particles were found to
vary in shape (from spherical and sub-spherical to irregular), sur-
face morphology (smooth, porous or rough) and size (1550 lm).
SEM-EDS results for the BCs showed CaO and SO3 as major com-
ponents, with lesser amounts of SiO2, Al2O3 and Fe2O3 followed by
MgO, K2O and Na2O.
3.3. FTIR-ATR analysis
The infrared spectra of all BCs taken from the damaged layers
(Fig. 3) showed the same characteristic absorption peaks of gyp-
sum, centered at 1109, 667 and 596 cm 1, together with the OH
stretching and bending vibrations of calcium carbonate, with peaks
at 1409, 871 and 710 cm 1. The presence of oxalates in samples
DM11 and VR2 was revealed by peaks centered at 1630 and
1320 cm 1.
3.4. LA-ICP-MS analysis
Trace element concentrations were determined by LA-ICP-MS
on the BCs and underlying substrates of all samples from the three
monuments studied here. The ppm concentrations of chemical ele-
ments, determined for each spot analysis, are reported as elec-
tronic Supplementary material. LA-ICP-MS analyses were
generally performed along selected crust-substrate proles, but
when the crust was very thin, LA-ICP-MS analyses were carried
out along the crust layer.
3.4.1. Cathedral of Milan
The spatial variability of element concentrations within the BCs
of Milan was checked in eleven spot analyses on the crust of DM8
and on six on those of DM11; a total of nine spot analyses were car-
ried out on the substrate.
Both DM8 and DM11 showed higher concentrations of all heavy
metals than the substrate. In particular, the following elements in
the BCs were found to be particularly enriched: As maximum value
91 ppm, minimum value 1.2 ppm; Cr 37.3 to 2.4 ppm; Cu 213 to
56 ppm; Ni 79 to 5 ppm; Pb 15651 to 133 ppm; Sb 28 to
3.7 ppm; Sn 46.6 to 4.9 ppm; V 152 to 3.8 ppm; Zn 3256 to
31 ppm. It was interesting to note that Pb and Zn contents of
DM11 BC were almost always higher than those of DM8. In the
substrate, As average is 1.45 ppm; Cr 3.79 ppm; Cu 3.47 ppm; Ni
0.9 ppm; Pb 23.9 ppm; Sb 0.16 ppm; Sn 0.56 ppm; V 1.05 ppm;
Zn 29.5 ppm.
3.4.2. St. Maria del Fiore, Florence
Trace element concentrations of BCs and substrate by LA-ICP-
MS were determined on four samples from St. Maria del Fiore. In
Fig. 3. FTIR spectra of samples DM11 = Milan Cathedral; DF8 = St. Maria del Fiore Cathedral in Florence; VR2 = Vittoriano Monument in Rome.
particular, ve spot analyses were carried out on the BCs of sam-
ples DF3 and DF4, eleven on those of DF8 and eight on those of
DF10. A total of thirteen spot analyses were carried out on the
substrate.
The BCs showed general enrichment in most of heavy metals
with respect to the substrate, except for Pb and Zn whose concen-
trations in some spot analyses of the stone (S-1, S-6, S-9) are com-
parable with those in the BCs (cfr. Supplementary material). In
detail, heavy metal contents varied in the BCs as: As from 118 to
7.2 ppm; Cr 56.7 to 6.3 ppm; Cu 203 to 33 ppm; Ni 27 to
3.5 ppm; Pb 840 to 30 ppm; Sb 12 to 2.4 ppm; Sn 20.4 to
2.3 ppm; V 68.3 to 5.5 ppm; Zn 213 to 11.9 ppm; in the substrate,
average values are as follows: As 2.22 ppm; Cr 4.79 ppm; Cu
11.5 ppm; Ni 1.67 ppm; Pb 29.9 ppm; Sb 1.27 ppm; Sn 0.7 ppm;
V 2.12 ppm; Zn 18.3 ppm.
3.4.3. Vittoriano Monument, Rome
Four spot analyses of BCs and ve of the substrate of this mon-
ument were carried out by LA-ICP-MS. In the BCs, all heavy metals
had higher concentrations than the substrate. In particular, con-
tents varied as follows: As from 71 to 33 ppm, Cr 38 to 22.6 ppm;
Cu 120 to 75 ppm; Ni 32 to 10 ppm; Pb 569 to 309 ppm; Sb 10 to
5.7 ppm; Sn 103 to 13.7 ppm; V 90 to 43 ppm; Zn 150 to
107 ppm; in the substrate, average values are as follows: As
1.84 ppm; Cr 13.54 ppm; Cu 7.95 ppm; Ni 0.87 ppm; Pb
84.6 ppm; Sb 0.33 ppm; Sn 0.42 ppm; V 7.26 ppm; Zn 54.8 ppm.
4. Discussion
Petrographic, morphological and chemical characterization
(major elements) obtained with OM and SEM-EDS analytical tech-
niques, yielded information on the BCs and the state of conserva-
tion and extent of deterioration of the substrates of the three
monuments studied here.
Different degrees of substrate deterioration were observed in
the three sites. The Candoglia and Carrara marbles, used in the
cathedrals of Milan and Florence respectively, showed frequent
deep penetration of alteration products along micro-cracks, in
which microcrystalline gypsum was growing with its typical acic-
ular habit. On the other hand, the substrate of the Vittoriano Mon-
ument in Rome, composed of biomicrite, was only slightly
damaged.
In all three monuments, the BCs were composed of microcrys-
talline gypsum and adhered to their substrates, though their mor-
phology varied according to the different times of accumulation
(see Table 1). Specically, the BCs collected in Milan and Florence
were very thick, with irregular, dendritic morphologies; those from
Rome were thinner and had regular, compact morphology. In
 D. Barca et al. / Applied Geochemistry 48 (2014) 122131 127

general, all samples contained iron oxides and hydroxides and air-
borne combustion particles, varying in shape from spherical to
sub-spherical and in size from 15 to 50 lm. In particular, the high-
est quantities were observed in the BCs of the cathedrals.
FTIR results showed that the mineralogical composition of all
samples consists of gypsum, calcite, and, in some cases, calcium
oxalate. Gypsum is the main component of BC, while the presence
of calcite is ascribable to substrate. Regarding calcium oxalate, its
presence within black crusts has been widely debated by the scien-
tic community (Del Monte and Sabbioni, 1983). The occurrence of
calcium oxalate is generally due to the partial oxidation of organic
carbon (Rampazzi et al., 2005; Sabbioni and Zappia, 1991) that
could come from organic protective products applied during previ-
ous restoration work, or from the activity of microorganism colo-
nies, or from environmental pollutants (Barone et al., 2008;
Belore et al., 2010; Bonazza et al., 2007; Gulotta et al., 2013;
Lluveras et al., 2008; Monte, 2003). Since the examinated monu-
ments did not undergo any restoration work, both biological activ-
ity and pollutans depostion can be reasonably considered as the
major responsible for calcium oxalate formation.
LA-ICP-MS data for spot analyses of the BCs were useful in eval-
uating the environmental air pollution of the cities of Milan, Flor-
ence and Rome. In terms of trace element concentrations, the
BCs are clearly distinguishable from their substrates: the results
show general enrichment in BCs in most of trace elements, partic-
ularly in some heavy metals (As, Cr, Cu, Ni, Pb, Sb, Sn, V, and Zn).
The boxplots of the above trace elements (Fig. 4) show the
medians and the statistical distribution of concentrations of these
elements measured in the BCs and substrates. In all three monu-
ments, Pb and Zn have greater dispersion. BCs of Milan Cathedral

Fig. 4. Box plots showing the variation of concentrations (in ppm) of heavy metals measured in all spot analyses performed respectively in DM (Milan Cathedral) samples, DF
(St. Maria del Fiore Cathedral in Florence) samples and VR2 (Vittoriano Monument (Rome) sample. Bc = black crust, S = substrate.
128 D. Barca et al. / Applied Geochemistry 48 (2014) 122131

have the highest Cu, Pb, Sb and Zn, whereas high As, Cr, Ni, Sn and
V were found in those of the Vittoriano Monument (Fig. 4). The
medians of concentrations measured in the samples from Florence
were generally lower than those registered in the BCs from the
other two buildings, particularly for Cu, Ni, Pb, Sn, V, and Zn.
All the substrates were generally poorer in heavy metals than
the BCs. However, different behavior was observed in St. Maria
del Fiore regarding Pb and Zn. Concentrations of these two ele-
ments measured in the substrate are, in some cases, comparable
with those measured in the relative BCs (cfr. Supplementary mate-
rial). For this, in both boxplots of Pb and Zn (Fig. 4), the upper hinge
and whiskers in the positive direction of the substrate show the
same values as the whiskers in the negative direction of the BCs.
Such high Pb and Zn concentrations found in some portions of
the substrate can be explained by the high geochemical mobility
(in certain environmental conditions) of Zn2+ and Pb2+ cations,
whose strong afnity with calcite causes their migration towards
the carbonate substrate (La Russa et al., 2013; McAlister et al.,
2005, 2006, 2008). Here they act as continuous catalysts for the
formation of new crust at the expense of the substrate, which in
fact resulted to be intensely degraded (cfr. Sections 3.1 and 3.2).
For information on the variability of BC composition in all sam-
ples, the Enrichment Factor (EF) was calculated, and the mean val-
ues of element concentrations in BCs were normalized to those of
the corresponding substrate. In the logarithmic spider-diagrams
(Fig. 5), EF differences among samples collected from the same
monument and among samples from all three monuments are
clear-cut. In the Milan samples, many elements (As, Cu, Pb, Sb,
Sn, V, and Zn) were strongly enriched in the BCs, generally yielding
EF values between 10 and 100. An exception may be observed for
Cr, which has an EF ranging between 4 and 5. Nevertheless, sample
DM11 has greater enrichment in Pb and Zn with respect to DM8. As

Fig. 5. Spider diagrams (logarithmic scale) of mean values of trace elements in black crusts normalized to the substrate (EF = Enrichment Factor) for: (a) samples DM8 and
DM11 from Milan Cathedral, (b) DF3, DF4, DF8 and DF10 samples from St. Maria del Fiore Cathedral (Florence), (c) sample VR2 from Vittoriano Monument (Rome).
 D. Barca et al. / Applied Geochemistry 48 (2014) 122131
highlighted by several authors (Barca et al., 2010; Belore et al.,
2013; Comite et al., 2012; Kukkonen et al., 2005; La Russa et al.,
2013; Marcazzan et al., 2003; Metallo et al., 1995; Perrino et al.,
2008a, 2008b), the EF variations observed in the BCs of the same
monument can be ascribed to several factors, such as: height of
sampling, morphology of deposition surfaces (vertical, horizontal,
concave and convex), exposure to atmospheric agents and wash-
out. Considering that the two DM samples were collected at the
same height and on the same south side of the Cathedral (see
Table 1), the observed variations can be ascribed to the shape of
the deposition surface. Indeed, lower EF values were measured in
DM8 sample collected from a horizontal surface and the higher
ones on DM11 collected from a concave surface which may likely
favor the deposition of particulate richer in heavy metals (Barca
et al., 2010).
In the Vittoriano Monument the VR2 sample shows a maximum
EF value (ca. 90) for Sn and moderate values (2030) for As, Ni and
Sb. However, the impossibility of analyzing more than one sample,
does not allow to evaluate the compositional variability of the
black crusts developed on the monument.
The spider-diagrams of DF samples (Florence) showed similar
trends, with low trace elements enrichment with respect to the
substrate (EF ranging from 4 to 23). All four DF samples were col-
lected from decorative elements in a restricted area in the south-
eastern side of the Cathedral, at the same height from the ground
(60 m). The small differences in EF patterns can be correlated to
the shape of deposition surface and their different exposure to
atmospheric agents. Specically, both DF3 sample, collected from
a vertical surface in a protected area, and sample DF10, collected
Fig. 6. Pb vs. Cu (a) and Zn vs. V (b) binary diagrams for black crusts (bc) and substrates (s) of all samples analyzed by LA-ICP-MS. Literature data used for comparison refer to
black crusts collected from: the San Cosimato Cloister in Rome and a sculpture in Milan (Barca et al., 2010); and the Cathedral of St. Maria del Fiore in Florence (Ozga et al.,
2014).
129
from a prominent horizontal surface (where the crust shows a
growth oriented in the direction of the prevailing wind), show EF
values for As, Cr, Ni, Pb, Sn, and V lower than the other two samples
(DF4 and DF8) collected from a horizontal surface in an area pro-
tected from the atmospheric agents.
The binary diagrams Zn vs. V and Pb vs. Cu in Fig. 6 conrm the
inuence of the exposure and the surface morphology in the depo-
sition of particulate and the consequent heavy metals enrichment
of BCs. In the same diagrams, literature data relative to black crusts
from the same cities were also plotted for comparison. Specically,
the data used refer to BCs collected from: (a) the Cloister of S. Cos-
imato in Rome and a sculpture in Pessano con Bornago near Milan
(Barca et al., 2010); and (b) the Cathedral of St. Maria del Fiore in
Florence (Ozga et al., 2014). Here samples were collected on the
northern site at a height of 2.50 m (DF38 sample) and 35 m
(DF41 and DF42 samples), as well as on the southwestern balus-
trades at a height of 35 m (DF34 sample). The comparisons reveal
good overlap between our results and the literature data referred
to the same cities (Fig. 6).
In general, the highest concentrations of heavy metals and par-
ticularly of Pb and Zn have been measured in the BCs of Milan
(Cathedral, sculpture). In the Pb vs. Cu diagram, the values mea-
sured in BCs of sculpture overlap the values measured in the BCs
of DM11 in the Zn vs. V diagram, concentrations of these two ele-
ments in the sculpture overlap those in DM8 sample.
Such high contents of heavy metals in the Milan Cathedral may
be explained by a combination of various anthropogenic sources of
pollution, such as domestic heating and emissions from road trafc
(Cachier et al., 2004; Marinoni et al., 2003). Although the Cathedral
130 D. Barca et al. / Applied Geochemistry 48 (2014) 122131
of Milan is located in a pedestrian area since 1969, a large number
of vehicles are authorized to circulate nearby, and therefore con-
tribute to increase the atmospheric pollution level around the
building. In general, road trafc is very heavy throughout the city
center (about 1.8 million vehicles: buses, taxis, cars, trucks,
motor-bikes and scooters; Bonazza et al., 2005). In addition, in
view of the sampling height (40 m; see Table 1), the pollution from
heavy industry in the Milanese hinterland (Marcazzan et al., 2001,
2003), which release large quantities of As, Cu, Pb, Sb, Sn, V and Zn
into the atmosphere (Harmens et al., 2007; Harmens and Norris,
2008), certainly also contributes to the high heavy metal concen-
trations measured in the BCs. This is also conrmed by the similar-
ity with the high concentrations measured on the BCs of the
sculpture located in a small industrial town near Milan (Barca
et al., 2010).
Regarding the Vittoriano Monument, the agreement between
our data and literature values measured in the BCs of the Saint Cos-
imato Cloister (Barca et al., 2010), allow for the hypothesis that the
causes of air pollution in Rome are mainly related to vehicular traf-
c. Indeed, the monument is located in Piazza Venezia, in the city
center, a transit area between the old city and Campo Marzio,
where trafc is so much heavy almost 24 h a day and the direct
impact of vehicle emissions is particularly severe. The high con-
tents of As, Cr, Ni, Pb, Sn and V may be ascribed to the combustion
of fossil fuels (Geller et al., 2006; Rodriguez-Navarro and Sebastian,
1996), the attrition and friction of mechanical parts of vehicles
(Harmens and Norris, 2008) and wear and tear on asphalt
(Winther and Slent, 2010). In detail, Pb, and Zn are associated
with leaded petrol (Zou and Hooper, 1997), in use until the
1990s; Cu, Ni, Cr and V are also generally due to mineral oil com-
bustion; Cu, Sb and Ni are emitted into the atmosphere due to
brake pad wear and Zn and Sn by worn tires of all types of road
vehicles (Harmens and Norris, 2008). In addition, since As is
released into the atmosphere from carbon combustion, the high
concentration of this element in the BC of the Vittoriano Monu-
ment can be ascribed to the carbon used in the past for domestic
heating. Due to the absence of industries in the hinterland of Flor-
ence, such as in the case of Rome, enrichment of As, Cr, Ni and V in
the BCs in St. Maria del Fiore can be attributed to air pollution pro-
duced by domestic heating and, to a lesser extent, by the road traf-
c. On the other hand, the relatively low concentrations of heavy
metals are due to the fact that the BCs studied here were collected
at high height (60 m) from the south-eastern side of the Cathedral.
The comparison with BCs collected from the same monument and
analyzed by Ozga et al. (2014) through ICP-OES technique demon-
strates that, within the same monument, the concentrations of pol-
lutants decrease with the height; indeed, the DF38 sample
collected at a height of 2.5 m from the ground shows higher con-
centrations of Cu, Pb and Zn than BCs collected at 35 m (Ozga
et al., 2014) and our samples taken at 60 m from the ground.
5. Conclusions
In this work, black crusts and substrates collected from monu-
ments located in the cities of Milan, Florence and Rome were ana-
lyzed. The high concentrations of heavy metals observed in the
three monuments indicate that the trace element composition of
the black crusts is greatly inuenced by the different degrees and
causes of anthropogenic pollution affecting the three cities.
The concentrations of most heavy metals in the BCs collected
from the Cathedral of Milan were particularly high, as a result of
the combination of various anthropogenic sources (industrial
activity, domestic heating, road trafc), which contribute to the
air pollution of the city. The BCs of Florence and Rome show a dif-
ferent trend of Enrichment Factors in heavy metals, indicating that
atmospheric pollution in the two cities is mainly due to domestic
heating and road trafc.
In addition, the study demonstrates that many factors play an
important role in the accumulation of heavy metals in BCs, such
as the shape and exposure of deposition surfaces. Specically,
results highlighted that within the same monument the concave
surfaces accumulate greatest amounts of particulate rich in heavy
metal than the horizontal ones, as in the case of Milan Cathedral
where sample DM11 registered higher trace elements concentra-
tions than DM8. Similarly, in Santa Maria del Fiore in Florence,
horizontal surfaces (DF4 and DF8) resulted to be more enriched
in heavy metals than the vertical one (DF3). In addition, the
obtained data conrmed the importance of exposure of the depo-
sition surfaces to the atmospheric agents in the formation of BCs
and accumulation of pollutants. As an example, in the Florence
Cathedral sample DF10 taken from a horizontal surface exhibited
lower concentrations than the other samples also collected from
horizontal elements due to its exposure to the prevailing winds.
In conclusion, the geochemical approach used proved to be a
powerful tool in the study of black crust genesis, allowing the iden-
tication of specic sources of environmental pollutants.
Acknowledgements
The authors would like to thank the editors and the two review-
ers for their positive comments and suggestions, which certainly
increased the quality of the manuscript.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apgeochem.2014.
07.002.
References
Ausset, P., Crovisier, J.L., Del Monte, M., Furlan, V., Girardet, F., Hammecker, C.,
Jeannette, D., Lefevre, A., 1996. Experimental study of limestone and sandstone
sulphation in polluted realistic conditions: the Lausanne Atmospheric
Simulation Chamber (LASC). Atmos. Environ. 30, 31973207.
Barca, D., Belore, C.M., Crisci, G.M., La Russa, M.F., Pezzino, A., Ruffolo, S.A., 2010.
Application of Laser Ablation ICP-MS and traditional techniques to the study of
black crusts on building stones: a new methodological approach. Environ. Sci.
Pollut. Res. 17, 14331447.
Barca, D., Belore, C.M., Crisci, G.M., La Russa, M.F., Pezzino, A., Ruffolo, S.A., 2011. A
new methodological approach for the chemical characterization of black crusts
on building stones: a case study from the Catania city centre (Sicily, Italy). J.
Anal. At. Spectrom. 26, 10001011.
Barca, D., Belore, C.M., Crisci, G.M., La Russa, M.F., Pezzino A., Ruffolo, S.A., 2012.
Genesis of black crusts on building stones from three Italian cities: relations
with environmental pollution. In: Critelli S., Muto F., Perri F., Petti F.M., Sonnino
M., Zuccari A. (Eds.), Rendiconti online della Societ Geologica Italiana (86
Congresso Nazionale della Societ Geologica Italiana, Arcavacata di Rende, 18
20 Settembre 2012), vol. 21, pp. 644645.
Barone, G., La Russa, M.F., Lo Giudice, A., Mazzoleni, P., Pezzino, A., 2008. The
Cathedral of S. Giorgio in Ragusa Ibla (Italy): characterization of construction
materials and their chromatic alteration. Environ. Geol. 55, 499504.
Belore, C.M., La Russa, M.F., Pezzino, A., Campani, E., Casoli, A., 2010. The baroque
monuments of Modica (Eastern Sicily): assessment of causes of chromatic
alteration of stone building materials. Appl. Phys. A 100, 835844.
Belore, C.M., Barca, D., Bonazza, A., Comite, V., La Russa, M.F., Pezzino, A., Ruffolo,
S.A., Sabbioni, C., 2013. Application of spectrometric analysis to the
identication of pollution sources causing cultural heritage damage. Environ.
Sci. Pollut. Res. 20, 88488859.
Bonazza, A., Sabbioni, C., Ghedini, N., 2005. Quantitative data on carbon fractions in
interpretation of black crusts and soiling on European built heritage. Atmos.
Environ. 39, 26072618.
Bonazza, A., Brimblecombe, P., Grossi, C.M., Sabbioni, C., 2007. Carbon in black
crusts from the Tower of London. Environ. Sci. Technol. 41, 41994204.
Cachier, H., Sarda-Estve, R., Oikonomou, K., Sciare, J., Bonazza, A., Sabbioni, C.,
Greco, M., Saiz-Jimenez, C., Hermosin, A., Reyes, J., 2004. Aerosol
characterisation and sources in different European urban atmospheres: Paris,
Seville, Florence and Milan. In: Saiz-Jimenez, C. (Ed.), Air Pollution and Cultural
Heritage. Balkema, Lisse, pp. 314.
 D. Barca et al. / Applied Geochemistry 48 (2014) 122131
Comite, V., Barca D., Belore C.M., Bonazza A., Crisci G.M., La Russa M.F., Pezzino A.,
Sabbioni C., 2012. Potentialities of spectrometric analysis for the evaluation of
pollution impact in deteriorating stone heritage materials. In: Critelli S., Muto
F., Perri F., Petti F.M., Sonnino M., Zuccari A. (Eds.), Rendiconti online della
Societ Geologica Italiana (86 Congresso Nazionale della Societ Geologica
Italiana, Arcavacata di Rende, 1820 Settembre 2012), vol. 21, pp. 652653.
Del Monte, M., Sabbioni, C., Vittori, O., 1981. Airborne carbon particles and marble
deterioration. Atmos. Environ. 15, 645652.
Del Monte, M., Sabbioni, C., 1983. Weddellite on limestone in the Venice (Italy)
environment. Environ. Sci. Technol. 17, 518522.
Dunham, R.J., 1962. Classication of carbonate rocks according to depositional
texture. In Classication of carbonate rocks. Assoc. Pet. Geol. Mem. 1, 18 (W.E.
Ham (Ed.), Tulsa, Oklahoma p. 108).
Folk, R.L., 1959. Practical petrography classication of limestones. Am. Assoc. Pet.
Geol. Bull. 43, 138.
Fryer, B.J., Jackson, S.E., Longerich, H.P., 1995. 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. Can. Mineral. 33, 303312.
Gao, S., Liu, X., Yuan, H., Hattendorf, B., Gunther, D., Chen, L., Hu, S., 2002.
Determination of forty-two major and trace elements in USGS and NIST SRM
glasses by laser ablation-inductively coupled plasma mass spectrometry.
Geostand. Newslett. Geostand. Geoanal. Res. 26, 181196.
Geller, M.D., Ntziachristos, L., Athanasios Mamakos, A., Zissis, Samaras Z., Schmitz,
D.A., Froines, J.R., Sioutas, C., 2006. Physicochemical and redox characteristics of
particulate matter (PM) emitted from gasoline and diesel passenger cars.
Atmos. Environ. 40, 69887004.
Grossi, G.M., Esbert, R.M., Diaz-Pache, F., Alonso, F.J., 2003. Soiling of building stones
in urban environments. Build. Environ. 38, 147159.
Ghedini, N., Sabbioni, C., Bonazza, A., Gobbi, G., 2006. Chemical-thermal
quantitative methodology for carbon speciation in damage layers on building
surfaces. Environ. Sci. Tecnol. 40, 939944.
Gulotta, D., Bertoldi, M., Bertolotto, S., Fermo, P., Piazzalunga, A., Toniolo, L., 2013.
The Angera stone: a challenging conservation issue in the polluted environment
of Milan (Italy). Environ. Earth Sci. 69 (4), 1085.
Harmens, H., Norris, D.A., Koerber, G.R., Buse, A., Steinnes, E., Rhling, A., 2007.
Temporal trends in the concentration of arsenic, chromium, copper, iron, nickel,
vanadium and zinc in mosses across Europe between 1990 and 2000. Atmos.
Environ. 41 (31), 66736687.
Harmens, H., Norris, D.A., 2008. The Participants of the Moss Survey, Spatial and
Temporal Trends in Heavy Metal Accumulation in Mosses in Europe (1990
2005), ICP Vegetation Programme, Coordination Centre, Centre for Ecology &
Hydrology/Natural Environment Research Council
Kukkonen, J., Pohjola, M., Sokhi, R.S., Luhana, L., Kitwiroon, N., Fragkou, L.,
Rantamaki, M., Berge, E., Odegaard, V., Slrdal, L.H., Denby, B., Finardi, S.,
2005. Analysis and evaluation of selected local-scale PM10 air pollution
episodes in four European cities: Helsinki, London, Milan and Oslo. Atmos.
Environ. 39, 27592773.
La Russa, M.F., Belore, C.M., Comite, V., Barca, D., Bonazza, A., Ruffolo, S.A., Crisci,
G.M., Pezzino, A., 2013. Study of black crusts as a diagnostic tool in cultural
heritage. Appl. Phys. A 113, 11511162. http://dx.doi.org/10.1007/s00339-013-
7912-z.
Lluveras, A., Boularand, S., Roqu, J., Cotte, M., Girldez, P., Vendrell-Saz, M., 2008.
Weathering of gilding decorations investigated by SR: development and
distribution of calcium oxalates in the case of Sant Benet de Bages (Barcelona,
Spain). Appl. Phys. A 90, 2333.
McAlister, J.J., Smith, B.J., Neto, J.B., Simpson, J.K., 2005. Geochemical distribution
and bioavailability of heavy metals and oxalate in street sediments from Rio de
131
Janeiro, Brazil: a preliminary investigation. Environ. Geochem. Health 27, 429
441.
McAlister, J.J., Smith, B.J., To } ro
}k, A., 2006. Element partitioning and potential
mobility within surface dusts on buildings in a polluted urban environment,
Budapest. Atmos. Environ. 40, 67806790.
} ro
McAlister, J.J., Smith, B.J., To }k, A., 2008. Transition metals and water-soluble ions
in deposits on a building and their potential catalysis of stone deca. Atmos.
Environ. 42, 76577668.
Marcazzan, G.M., Vaccaro, S., Valli, G., Vecchi, R., 2001. Characterisation of PM10
and PM2.5 particulate matter in the ambient air of Milan (Italy). Atmos.
Environ. 35, 46394650.
Marcazzan, G.M., Ceriani, M., Valli, G., Vecchi, R., 2003. Source apportionment of
PM10 and PM2.5 in Milan (Italy) using a receptor modeling. Sci. Total Environ.
317, 137147.
Marinoni, N., Pellizon Birelli, M., Rostagno, C., Pavese, A., 2003. The effects of
atmospheric multipollutants on modern concrete. Atmos. Environ. 37, 47014712.
Metallo, M.C., Poli, A.A., Diana, M., Persia, F., Cirillo, M., 1995. Air pollution loads on
historical monuments: an air quality model application to the marble Arch of
Titus in Rome. Sci. Total Environ. 171, 163172.
Monte, M., 2003. Oxalate lm formation on marble specimens caused by fungus. J.
Cult. Heritage 4, 255258.
Moropoulou, A., Bisbikou, K., Torfs, K., Van Grieken, R., Zezza, F., Macri, F., 1998.
Origin and growth of weathering crusts on ancient marbles in industrial
atmosphere. Atmos. Environ. 32 (6), 967982.
Ozga, I., Ghedini, N., Giosu, C., Sabbioni, C., Tittarelli, F., Bonazza, A., 2014.
Assessment of air pollutant sources in the deposit on monuments by
multivariate analysis. Sci. Total Environ. 490, 776784.
Perrino, C., Canepari, S., Cardarelli, E., Catrambone, M., Sargolini, T., 2008a. Inorganic
constituents of urban air pollution in the Lazio region (Central Italy). Environ.
Monit. Assess. 136, 6986.
Perrino, C., Catrambone, M., Pietrodangelo, A., 2008b. Inuence of atmospheric
stability on the mass concentration and chemical composition of atmospheric
particles: a case study in Rome, Italy. Environ. Int. 34, 621628.
Rampazzi, L., Andreotti, A., Bonaduce, I., Colombini, M.P., Colombo, C., Toniolo, L.,
2005. Analytical investigation of calcium oxalate lms on marble monuments.
Talanta 63, 966977.
Rodriguez-Navarro, C., Sebastian, E., 1996. Role of particulate matter from vehicle
exhaust on porous building stones (limestone) sulfation. Sci. Total Environ. 187,
7991.
Sabbioni, C., Zappia, G., 1991. Oxalate patinas on ancient monument: the biological
hypothesis. Aerobiologia 7, 3137.
Turkington, A.V., Smith, B.J., Whalley, W.B., 1997. Short-term stone surface
modication; an example from Venice. In: Proceedings of the 4th
International Symposium on the Conservation of Monuments in the
Mediterranean Basin, Technical chamber of Greece, Rhodes, vol. 1, pp. 359372.
van Achterberg, E., Ryan, C.G., Jackson, S.E., Grifn, W.L., 2001. Data reduction
software for LA-ICPMS: appendix. In: Sylvester, P.J. (Ed.), Laser Ablation-ICP-
Mass Spectrometry in the Earth Sciences: Principles and Applications.
Mineralogical Association of Canada (MAC) Short Course Series, vol. 29, pp.
239243.
Winther, M., Slent, E., 2010. Heavy Metal Emissions for Danish Road Transport. In:
Neri, (Ed.). Technical Report, National Environmental Research Institute, Aarhus
University, No. 780.
Zappia, G., Sabbioni, C., Riontino, C., Gobbi, G., Favoni, O., 1998. Exposure tests of
building materials in urban atmosphere. Sci. Total Environ. 224, 235244.
Zou, L.Y., Hooper, M.A., 1997. Size-resolved airborne particles and their morphology
in central Jakarta. Atmos. Environ. 31, 11671172.