Journal of Hazardous Materials 248–249 (2013) 451–460
Contents lists available at SciVerse ScienceDirect
Journal of Hazardous Materials
journal homepage: www.elsevier.com/locate/jhazmat
Buildings as repositories of hazardous pollutants of anthropogenic origin
N. Prieto-Taboada ∗ , I. Ibarrondo, O. Gómez-Laserna, I. Martinez-Arkarazo, M.A. Olazabal, J.M. Madariaga
Department of Analytical Chemistry, University of the Basque Country (UPV/EHU), Barrio Sarriena s/n, 48940 Leioa, Spain
h i g h l i g h t s
g r a p h i c a l
a b s t r a c t
Building materials act as repositories
of hazardous pollutants.
Raman and XRF spectroscopies are
crucial diagnosing tools of the analytical protocol.
Black crusted samples present the
higher concentrations of hazardous
metals and PAHs.
The accumulation capacity of pollutants of buildings depends on the type
of material.
Buildings could be static indicators of
the pollution suffered in the area.
a r t i c l e
i n f o
Article history:
Received 22 August 2012
Received in revised form 4 January 2013
Accepted 6 January 2013
Available online 11 January 2013
Keywords:
Atmospheric pollution
Pollutant repository
Raman spectroscopy
Polycyclic aromatic hydrocarbons (PAHs)
Chemometric analysis
a b s t r a c t
In the present work the pollutant content of diverse building materials was evaluated by the combination
of spectrometric and chromatographic techniques. A first non-destructive analysis carried out by ␮-XRF
and Raman spectroscopy revealed a high impact of pollutants, which reached depths higher than 6 mm.
The quantitative analyses pointed out that black crust as accumulation nucleus where concentration
values up to 3408 mg/kg of lead, 752 mg/kg of chromium or 220 mg/kg of arsenic, high amounts of diverse
sulphates and nitrates as well as substantial amounts of polycyclic aromatic hydrocarbons (PAHs) of a
clear pyrolytic source were determined. On the other hand, samples without black crust showed also
a surprising soluble salt content up to 5%. Polychlorinated biphenyls (PCB) were found to be absent in
all material types. The chemometric analysis of the quantitative results revealed that the accumulation
capacity and the subsequent pollutant content depends on the type of construction materials, being
mortars the most susceptible.
© 2013 Elsevier B.V. All rights reserved.
1. Introduction
The atmospheric pollution has an important role in the most
important cities of the world due to the heavy and fast industrial
revolution. Moreover, the disordered expansion of industrial and
urban centres increases the problem of the atmospheric pollution
[1,2]. In addition, the emissions derived from combustion processes
such as heating or motor vehicle traffic are the main cause of
atmospheric pollution in urban environments [3]. The atmospheric
pollution is considered the crucial factor in building degradation
∗ Corresponding author. Tel.: +34 94 601 82 94; fax: +34 94 601 35 00.
E-mail address: [email protected] (N. Prieto-Taboada).
0304-3894/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2013.01.008
having cause in some cases a significant loss of cultural heritage
[4–6]. However, the effect of environmental pollution on buildings
without historical relevance is not usually considered [7–9].
Pollutants can be deposited either as gases or as particulate matter. According to the aerodynamic radius of the particle they can
be classified in PM10, PM2.5, PM1. In general, the concentrations
of PM10 and PM2.5 airborne aerosols show good agreement with
traffic-related pollutants and other combustion processes as well
as industry processes [10,11] although soil dust particles should
not be discarded. Depending on their origin, toxic air particles consist of elemental carbon or inorganic core and a large number of
adsorbed substances such as heavy metals, various organic compounds, silicates (Al2 O3 , SiO2 ,...), salts (sulphate, nitrates,...), etc
[7–9,12,13].
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N. Prieto-Taboada et al. / Journal of Hazardous Materials 248–249 (2013) 451–460
Nowadays, most of the studies are focused on the deterioration
capacity of the particulate matter deposited in the building and not
in the accumulation itself of the hazardous pollutant trapped in
the surface. The hazardous air pollutants are defined by the United
State Environmental Protection Agency (EPA) among which we can
find PCBs, PAHs, lead or chrome compounds typically deposited on
buildings located in industrial areas. PCBs belong to a broad family
of man-made organic chemicals that have a range of toxicity and
were used in hundreds of industrial and commercial applications
including electrical and heat transfer equipment, as plasticizers in
paints, plastics, dyes, carbonless copy paper and many other industrial applications [14].
Regarding PAHs, they have a wide variety of sources (natural
emissions, fumes from vehicle exhaust, coal, coal tar, asphalt, wildfires, agricultural burning etc.) although they always form when
burning is not complete [15]. The main sources for heavy metals are
industry and fuel combustion but other sources cannot be discarded
[16–18]. The transport of PAHs, whose carcinogenic and mutagenic properties are well known, from outdoor environments to
the indoor environment has been demonstrated in several studies
[19–21]. In this sense, the determination of toxic pollutants concentration in facades could give also an idea of human exposition
level to hazardous environments.
Although the governments are working to decrease or eliminate (indeed PCBs manufacture was banned in 1979) the emission
of some hazardous pollutants, the buildings can act as repositories
of the past pollution and can show an substantial concentration
of pollutants even after removing the emission source [11]. Generally, buildings accumulate the pollutant at the surfaces in zones
frequently soaked by rainwater but not washed out [11,22]. Greyto-black crust is the most common formation and it is commonly
composed of gypsum crystals and atmospheric depositions, including carbonaceous particles (soot) and heavy metals [3,11,23–25].
Due to their high specific surface and heavy metal content, black
crusts act as catalytic support to the heterogeneous oxidation of
SO2 [26]. Carbon, present in the alteration crust, may be of three
different origins: calcium carbonate, deriving almost exclusively
from the underlying materials (stones and mortars); deposition
and accumulation of atmospheric particles containing elemental
and organic carbon compounds, and biological weathering due to
the action of micro-organisms [27]. However, although the role of
atmospheric sulphur and nitrogen compounds in stone deterioration is often studied, the importance of carbon compounds cannot
be diminished since they also promote the growth of black crusts
[9].
Once pollutants are deposited, they could be sometimes mobilized by natural factors or during restoration of the building that
involve often cleaning processes. Deposits could be removed and
transported by the action of rain and wind to other environmental
compartments. Concerning wind action, the largest particles likely
redeposit in surrounding areas, whereas the smallest are more hazardous since they can migrate far away and be inhaled sometime.
Unfortunately, the metal concentrations that can be mobilized from
black crusted materials are not usually determined. This issue is
especially important to ensure proper security measurements during processes that could involve PM inhalation. Nowadays, the
cleaning procedures most used for restoration of facades are completely abrasive. This is the case of micro sandblasting (especially
in civil buildings) or laser cleaning and the intervention needs of
both personal and environment security measures to avoid particle
ingestion and inhalation [28,29].
According to the World Health Organization, the current knowledge does not allow specific quantification of the health effects
of emissions from this kind of deposits [30]. Furthermore, the
pollutant content can be a decisive factor when construction materials (coming from restorations or demolitions) are expected to be
Fig. 1. Location of the building and some sampling points of the main facade.
recycled or reused in other fields [31]. However, the fact is that
the amounts of heavy metals and organic toxic compounds often
found in black crusts, should involve managing them as hazardous
residues.
Because of all these facts, it is necessary to analyse both inorganic and organic compounds. Spectroscopic techniques are often
the fastest and even much appropriated [32–34], but they have
disadvantages such as the moderately high concentration needed
to acquire a good spectrum. For this purpose a multianalytical
approach is the best option to obtain valid and complementary
information with other more sensitive analytical techniques [22]. In
this work, non-destructive spectroscopic techniques (Raman spectroscopy and ␮-XRF) were used together with GC/MS and ICP/MS
to quantify the accumulation of soluble salts, PAHs, PCBs and heavy
metals in samples taken from selected areas of a building located in
an urban–industrial area, in an attempt to demonstrate the repository capacity of facades.
2. Materials and methods
2.1. Description of the building and environmental conditions
The studied building was constructed in 1918. It is a big gallery
built to contain a hillside in the town of Getxo, which is located in
the mouth of the Nerbion-Ibaizabal river (50 m away). It is composed of stone pillars, galleries made on cement and presents
masonry ornamentation (see Fig. 1). Concerning the environmental conditions a wide variety of sources found in the bibliography
can be proposed for the target pollutants [35–39]. The building is
located at less than three kilometres far from the Port of Bilbao,
which has been the reference point for industry in Spain as well
as transport and logistics centre in Europe for decades [40]. Many
industries including a thermo power station and a refinery are situated in the surroundings of the port. Furthermore, the studied
gallery suffers an important pollution due to the traffic since it
is placed at the access to the old port, marina and to the beach
which involves a very important tourist and leisure attraction. All
these factors contribute to the presence of PCBs, PAHs and heavy
metals to the environment whose major problem is the PM 10 level
N. Prieto-Taboada et al. / Journal of Hazardous Materials 248–249 (2013) 451–460
Table 1
Brief description of the studied samples.
Code
Material
Description of the samples
M24
M26
Stone
Cement
M28
M29
M30
M31
M32
M33
Mortar
Mortar
Mortar
Mortar
Stone
Mortar
Sandstone with black crust
Piece of cornice with affection of black crust and
efflorescence
Join mortar
Embellishing mortar with efflorescence
Embellishing mortar with very thick black crust
Rendering mortar with efflorescence
Sandstone of the base of the galleries
Embellishing mortar with very thick black crust
that exceeds the permitted values several days a year (50 ␮g/m3 of
PM10) [41].
In addition, the prevailing wind and rain-bearing direction (NW)
affects the main facade of the building. Despite the pollution
problem has considerably decreased in the last decades [42], the
pollution suffered for years has produced in the facade of the studied building black crusts, efflorescences and an important physic
damage accented by the abandonment of the building which has
not been restored or attended since it’s construction.
2.2. Sampling
Different types of materials used in the building were sampled
in the areas with a visible damage of the main facade between 1
and 4 m of height: mortars, cements and stone (see summary in
Table 1). Due to the bad conservation state of the materials, some of
the compiled samples were detached while other fragments were
extracted using a chisel. The thickness of the samples was very different but never less than 6 mm thick, in order to determine the
penetration capacity of pollutants and decaying compounds. Mortar samples were the most affected by black crust, which covered
completely the external surface of the samples.
2.3. Instrumentation
Semiquantitative analysis of the elemental composition was
carried out using an ArtTax model micro X-ray fluorescence spectrometer (␮-XRF) by Röentec (currently Bruker). A 50 kV voltage,
0.6 mA current, 1000s and 0.65 mm Tantalium collimator were used
as measurement parameter values. The equipment has a Mo Xray tube and special Xflash detector (5 mm2 ) and it is provided
with a measuring head implemented on a CCD camera that allows
to focus on the sample by a motorized XYZ positioning unit controlled by the computer. The daily calibration of the equipment was
made with a bronze reference standard of Röntec. The ␮-XRF analysis allows identification of the composition differences among the
external and internal parts of the samples, which allows to identify the original elemental composition of the samples as well as
the elements of anthropogenic source with atomic number higher
than 11.
Quantitative analysis of some of the elements identified by
␮-XRF was carried out by ICP-MS. Prior to the analysis, an acid
digestion was performed by an adaptation of EPA 3051 protocol
[43] in a microwave digestion system Multiwave 3000 (Anton Paar,
Graz, Austria) provided with a 8XF-100 microwave digestion rotor
and 100 mL fluorocarbon polymer (PTFE) microwave vessels. ICPMS standard solutions were prepared from Alfa Aesar (Specpure® ,
Plasma standard solution, Germany) stock solutions and argon
(99.999%, Praxair, Spain) was used as carrier gas in the ICP-MS measurements by an Elan 9000 ICP-MS (Perkin-Elmer, Ontario, Canada)
provided with a Ryton cross-flow nebulizer, a Scott-type double pass spray chamber and standard nickel cones. Preparation of
calibrates as well as analysis of samples was carried out in a clean
453
room (class 100). The ELAN 3.2 software was used to analyse the
results.
The determination of the molecular composition of the surface of the samples was carried out by Raman spectroscopy. A
Raman microprobe Renishaw inVia Raman spectrometer coupled
to a Leica DMLM (UK) microscope with a diode laser at 785 nm excitation wavelength and a Peltier cooled CCD detector was used for
this purpose. The equipment was periodically calibrated with the
520.5 cm−1 silicon band. In order to avoid thermal decomposition
of the samples, the laser power (350 mW) was varied at 1%, 10% and
100% depending on measurements. The spectra were taken with a
resolution of 1 cm−1 in the range of 2200–200 cm−1 , accumulating
several scans from each spectrum to improve the signal-to-noise
ratio. The microscope lens 20× was used to perfect focusing of the
laser beam thanks to a TV microcamera. Data acquisition was carried out by the Wire 3.0 software package of Renishaw and the
analysis of the results undertaken by the Omnic 7.2 software (Nicolet). The e-visart and e-visarch dispersive Raman and FT-Raman
spectral databases were used for the interpretation of the results
[44,45].
The analysis of organic compounds (PAHs and PCBs) was carried out using a 6890 N gas chromatograph coupled to a HP 5973 N
mass spectrometer with a 7683 autosampler (Agilent Technologies, Avondale, PA, USA) after application of a microwave assisted
extraction method described elsewhere [46]. The extraction and
elution with analysis of both compound families is possible to
accomplish simultaneously thanks to a protocol optimized for
this purpose. Prior to the analysis Florisil® cartridges and elution with n-hexane:toluene (4:1) were used as clean-up technique
[46].
Finally, the quantification of soluble salts was carried out by a
Dionex ICS 2500 suppressed ion chromatograph with a conductivity detector ED50. An IonPac AS23 (4 × 250 mm) column and
IonPac AG23 (4 × 50 mm) precolumn were used for the separation
of anions. 4.5 mM Na2 CO3 /0.8 mM NaHCO3 , 25 mA and 1 mL/min
were used as mobile phase, suppression current and flow respectively in the quantification of the anions. The quantification of
cations was conducted by using an IonPac CS12A (4 × 250 mm) column and IonPac CG-12 A (4 × 50 mm) precolumn from Vertex. A
20 mM CH4 SO3 as mobile phase, 75 mA of suppression current and
1 mL/min flow were used for cations measurement. The samples
were treated following an ultrasound assisted extraction method
[47], as a less time consuming and efficient alternative to the currently most used UNI 11087/2003 [48,49] for extraction of soluble
salts from buildings materials.
Replicates were carried out when enough sample material was
available (M28 and M29) in order to determine the method repeatability of the quantitative analyses for each of the analytes.
3. Results and discussion
3.1. X-ray fluorescence analysis
In order to establish the penetration level of the deposited
metals, both interior and external surfaces of the samples were analysed. Generally, P, S, Ca, K, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Sr and Pb were
identified in all the samples. Sn, Ba, Cl, Br and Co were sometimes
identified as minor elements and finally, Cd (M30), As (M28 and
M32), Sb (M30), Pd (M30) and Hg (M32) signals only were present
in the exterior surface of the samples. In all samples Ca and Fe were
the major elements, which is logical taking into account the nature
and origin of the raw material used for the masonry, likely being
the quarries of the area [50,51].
The identification of sulphur is usually related with decaying
products formed due to the attack of sulphuric aerosols coming
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N. Prieto-Taboada et al. / Journal of Hazardous Materials 248–249 (2013) 451–460
from the reaction among SOx combustion gases and the original
materials. In the same way, the presence of high amounts of chlorine is due to the impact of marine aerosols in the facade [22,52].
However, both aspects were studied in depth by means of Raman
spectroscopy and ion chromatography. Pb, Cu and Cr were identified, related to the presence of black crust. The origin of these
compounds is supposed to be the combustion of fuels and emissions associated to the port activities as well as traffic (marine
and road) [43,53]. In addition, these elements can react with acid
gases forming the corresponding decaying compounds like lead
sulphate for example. In any of their chemical forms that they are
accumulated in building materials, the fact is that some of the identified elements are considered dangerous from the environmental
and health points of view. Moreover, the knowledge on the metal
content of building materials can help to establish intervention
procedures or security measures in case of restoration (or demolition) of the building takes place. Even more, the pollutant content
can be a decisive factor when construction materials are expected
to be recycled or reused in other fields [31]. Therefore, the elemental composition was determined by means of ICP-MS specially
focusing on heavy metals.
3.2. Quantitative elemental analysis by ICP-MS
A first semiquantitative screening was carried out to define the
metals to be quantified. Owing to the low amount of sample, it
was not possible to perform a separated analysis of the internal
and external surface. Sc, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Sr, Mo,
Ag, Cd, Sn, Sb, Ba, Hg and Pb were determined from the entire
grinded samples. The content of other elements was determined
as soluble salts by ion chromatography. According to the results
summarized in Table 2, samples showing a black crust (M26, M30
and M33) were the ones having the highest concentration values
for the most hazardous elements. For example, the mean concentrations of lead and arsenic found in the building were of 806 and
53 mg/kg respectively, having observed concentration values up to
3408 and 220 mg/kg in black crusted samples. With regard to their
origin, Pb, As, Cu, Zn, Cr, Ni, Cd, Mn, Ba, and Sr can be related to
traffic pollution and the nearby industry [11,43]. In this sense, the
nearby thermal power station of the port and the steel factories
situated in the river are the most probable sources since they emit
Pb, As, Cu, Zn, Cr, Cd, Ni, Hg and PM10 according to the data of
the European Pollutant Emission Register (EPER). Barium is usually found as a consequence of traffic contamination due to wheel
wear [52,54]. Concerning manganese and strontium, they are not
considered by the EPER, whereas the rest of elements were found
at lower concentration levels in general terms.
3.3. Raman spectroscopy analysis
The inner surfaces of the samples were analysed in an attempt to
have an idea of the original molecular composition of each building
material. According to the measurements on the extracted samples,
calcite (CaCO3 main Raman bands at 1085, 712 and 281 cm−1 ) was
identified as the main original compound in all the sampled materials. The CaCO3 polymorph aragonite (Raman bands at 1085, 705
and 205 cm−1 ) was also occasionally identified. In addition, iron (III)
oxides were identified, as limonite (FeO(OH)n ·H2 O, Raman bands at
552, 394, 297 and 240 cm−1 ) and hematite (␣-Fe2 O3 , 612, 410, 293
and 226 cm−1 ) in major percentage. These findings agree with the
high Ca and Fe amounts determined by ␮-XRF analyses. Titanium
oxide in the rutile tetragonal form (TiO2 , detected Raman bands at
608 and 447 cm−1 ) was identified in mortars and in brookite rhombic form (TiO2 , detected Raman bands at 623, 496, 410, 317 and
245 cm−1 ) in the case of stone samples, as original compounds. In
addition, samples showed a mixture of silicates as obsidian (main
Raman bands at 1645, 1518 and 1333 cm−1 ), quartz (SiO2 , detected
Raman bands at 464 cm−1 ) or micas with main Raman bands in the
range of 1700–1100 cm−1 . Finally, vitrified carbon was also identified by its two characteristic sharp bands at 1600 and 1325 cm−1
[55,56], as part of the original composition of the stone samples
(grey calcites from the quarries around). Concerning the samples
presenting black crusts, they showed broad Raman bands centred
at 1640 and 1300 cm−1 likely due to the presence of soot particles
(amorphous carbon) trapped into the surface [55,56].
In only one sample of stone (M24), pyrite (FeS2 ) was identified
by the Raman bands at 373 and 339 cm−1 . Due to the location of
the pyrite grain, this compound was considered a deposition compound; the building is located less than 3 km far and in the direction
of the winds coming from the discharge area of the port of Bilbao, where pyrite was (and still is) a common goods discharged
[40,57,58].
With regard to the degradation products, gypsum (CaSO4 ·2H2 O,
identified by Raman bands at 1132, 1008, 493 and 412 cm−1 ), anhydrite (CaSO4 , Raman bands at 1148, 1017, 675, 627, 609, 500 and
417 cm−1 ) and thenardite (Na2 SO4 , detected Raman bands at 1148,
1128, 1100, 991, 644, 632, 628, 464 and 451 cm−1 ) were clearly
identified; these compounds are formed as a results of the attack of
Table 2
Concentration of the individual elements in mg/kg and method RSD (relative standard deviation) repeatabilities obtained by ICP-MS for each of the samples. Results given
for M28 and M29 are mean values of three replicates.
M24
Ag
As
Ba
Cd
Co
Cr
Cu
Fe
Mn
Mo
Ni
Pb
Sb
Sn
Sr
Zn
M26
−3
5.7 × 10
<LOD
<LOD
1.15
2.00
58
10.3
1.64 × 104
2.30 × 102
3.5 × 10−1
6.7
7.2 × 102
<LOD
<LOD
20.0
1.46 × 102
<LOD
14.0
3.5 × 102
10.2
5.9
7.5 × 102
58
1.61 × 104
3.2 × 102
5.9
82
4.63 × 102
1.6
5.2
8.3 × 102
8.6 × 102
LOD: limit of detection.
LOQ: limit of quantification.
M28
M29
−2
6.0 × 10
14.7
5.7 × 101
4.6 × 10−1
2.51
3.0
8.2
1.74 × 104
1.77 × 102
7.4 × 10−1
8.4
13.2
1.6 × 10−1
2.9 × 10−1
4.7 × 102
26.1
M30
−2
5.5 × 10
24.8
1.07 × 102
1.32
2.19
6.2
12.9
7.6 × 103
1.39 × 102
9.1 × 10−1
9.5
47.0
3.1 × 10−1
1.03
5.5 × 102
49
M31
−1
3.9 × 10
1.99·102
3.7 × 102
8.2 × 10−1
3.67
55
1.45 × 102
2.09 × 104
2.4 × 102
18.9
52
3.26 × 103
15
34
4.5 × 102
4.8 × 102
M32
−1
1.19 × 10
10.2
1.58 × 102
7.9 × 10−1
3.19
23
23.3
7.3 × 103
1.70 × 102
7.9 × 10−1
12.6
58
2.4 × 10−1
1.5
6.9 × 102
1.43 × 102
M33
−1
1.23 × 10
10.6
19.1
1.89 × 10−1
2.31
4.64
5.9
3.5 × 104
25
2.78 × 10−1
7.2
29.3
8.4 × 10−1
<LOD
9.0
70
RSD (%)
−1
3.7 × 10
2.20·102
3.4 × 102
5.3 × 10−1
2.55
40
89
1.66 × 104
1.73 × 102
16.6
39
3.41 × 103
19
43
5.7 × 102
2.59 × 102
5
2
3
4
2
5
3
4
4
3
3
2
9
7
3
3
LOD
LOQ
−6
6.5 × 10
3.8 × 10−4
4.9 × 10−2
2.0 × 10−6
1.9 × 10−4
9.8 × 10−4
1.4 × 10−4
8.2 × 10−3
4.7 × 10−5
1.1 × 10−4
5.9 × 10−4
5.3 × 10−6
2.7 × 10−4
9.4 × 10−5
3.7 × 10−6
3.0 × 10−2
1.5 × 10−5
1.5 × 10−3
5.8 × 10−2
1.3 × 10−5
2.2 × 10−4
2.4 × 10−3
9.6 × 10−4
1.4 × 10−2
1.6 × 10−4
1.4 × 10−4
1.1 × 10−3
1.5 × 10−4
2.9 × 10−4
1.6 × 10−4
1.5 × 10−4
3.7 × 10−2
N. Prieto-Taboada et al. / Journal of Hazardous Materials 248–249 (2013) 451–460
Fig. 2. Raman spectra of gypsum (1) and thenardite (2) found mainly in black crust
and efflorescence respectively.
the sulphuric acid aerosols to the original compounds (see Fig. 2).
Sodium nitrate is known to be one of the most hazardous sulphate
salts due to the transformation from thenardite (Na2 SO4 anhydrous, 2.70 g/cm3 ) to mirabilite (Na2 SO4 ·10H2 O, 1.49 g/cm3 ). That
is, these salts promote the damage of building materials not only
by crystallization but also due to the hydration–dehydration cycles
that change significantly the volume of the molecule. The physical stress caused within material pores results on the formation of
cracks and even material loss. In this way, thenardite was found
as the responsible for the detachments of some embellishing and
rendering mortars (M29 and M31). Other degradation compounds
found related to the effect of SOx were barium sulphate (BaSO4 ,
main Raman bands at 991, 626 and 457 cm−1 ) and iron sulphate
in the (para)-coquimbite form (Fe2 (SO4 )3 ·9H2 O, detected Raman
bands at 1198, 1092, 1025, 598 and 497 cm−1 ) [59]. The samples
showing iron sulphate (all mortars except M28) were always those
having high amounts of iron according to the ␮-XRF analysis. This
finding agrees with bibliography because coquimbite is referenced
to be formed by the free sulphate ions (coming from sulphuric acid
present in the polluted atmospheres) attack to the iron deposition,
following a mechanism described elsewhere [11,60].
Regarding the degradation compounds related to NOx gases,
nitratine (NaNO3 ) was identified in the sample M26 by its main
Raman band at 1067 cm−1 during the curve fitting procedure performed on a broad band in which calcite and silicates were also
present (see Fig. 3). This nitrate compound could be the result of the
interaction of the original calcite with the atmospheric nitric acid
in presence of the marine aerosol [61,62]. However, owing to the
location of the building, a direct deposition from marine aerosols
cannot be ruled out in this case [63]. In any case, the presence of NOx
Fig. 3. Raman spectra of nitratine (1) and scytonemin (2) determined in cement
sample (M26).
455
in the atmosphere is more important in areas close to ports, since
these gases are emitted during combustion of ships fuels. Indeed,
high amount of nitrates have been found in previous studies performed on buildings located in coastal areas with marine traffic
[22].
Finally, the affection by microorganisms was also evidenced not
only in areas where lichen colonies wear visible but also by the
identification of carotenoids with the Raman spectrum bands at
1520, 1336 and 1141 cm−1 and scytonemin (C36 H20 N2 O4 , Raman
bands at 1590, 1578, 1553, 1433, 1384, 1322, 1169, 1096, 1023,
983, 753, 575, 494 and 270 cm−1 ), as shown in Fig. 3.2 in stone and
cement samples (M24 and M26). Scytonemin is a brown-yellow
pigment excreted by cyanobacteria to shelter from UV radiation.
However, a recent study revealed that this pigment is also synthesized under highly polluted environmental conditions to protect
the colony from acid pollutants [64].
Regarding the depth reached by pollutants into the studied
substrates, it should be mentioned that decaying compounds as
gypsum and (para-)coquimbite were found in the internal side of
the mortars samples (M30, M31 and M33), which indicates that at
least 6 mm depth (the minimum thickness sampled) was reached.
In addition, the semiquantitative comparison of the internal and
external side of samples by ␮-XRF showed that heavy metals mobilize from the surface and accumulate even in the interior in some
cases.
3.4. PAHs and PCBs analysis by GC–MS
16 PAHs and 11 PCBs picked up in the EPA list of priority compounds (see Table 3) and classified as hazardous substances by the
Agency for Toxic Substances and Disease Registry (ATSDR) were
analysed [65,66]. As can be seen in Table 3, all the samples had total
PAH concentrations higher than 100 ng/g, which is the maximum
value accepted in soils according to local legislation. Furthermore,
the concentration of FLT exceeds the limit in all samples according to Spanish legislation [67,68]. However, black crusted mortar
samples (M30 and M33) gave the most worrying results since they
exceeded even the local VIE-B limit (a human health and environment hazardous compounds limit values for soil secure uses
established in the Basque legislation), for B(a)P, B(a)A, PY, B(b)F,
D(a,h)A and IP. According to European legislation, B(a)P should be
used as a marker for the carcinogenic risk of PAHs in ambient air,
being 1 ng/m3 the limit value (mean value in PM10 present in air
over calendar year) [69]. However, most of the analysed PAHs are
known to have or promote carcinogenic and/or mutagenic effects
as already mentioned [65,66,70]. In this sense, total concentration values of more than 5900 ng/g in B(a)A, Chry, B(b)F, B(k)F,
B(a)P, IP, D(a,h)A and B(ghi)P were found in the samples, that are
a negligible fraction of the whole facade. Such high concentration
values must be taken into account to design safety measures for
worker’s protection when acting on those facades for cleaning or
other restoration purposes. On the contrary, all samples showed
PCBs (and the individual PAHs indicated with ** at the end of
Table 3) concentrations below the detection limit (generally around
30 ng/g).
According to bibliography, the relations of some of the individual PAHs could provide information about their source: pyrolytic,
petrogenic or biogenic source [71–74]. The mean relations between
PHE/AN and FLT/PY were 2.5 and 1.2 respectively, which would
indicate a pyrolytic source, principally combustion of fuel-oils. This
is consistent with the high concentration of 202 molecular weight
isomers found [75]. These relations were always similar except for
M33 whose phenanthrene concentration was higher (and the subsequent PHE/AN relation the most elevated), showing a pyrolytic
source with some effect of the petrogenic compounds. Therefore,
according to this ratio analysis, the influence of the traffic and
456
N. Prieto-Taboada et al. / Journal of Hazardous Materials 248–249 (2013) 451–460
Table 3
Concentration (in ng/g) and method repeatability obtained by GC–MS for each of the individual PAHs in each sample. Results given for M28 and M29 are mean values of
three replicates.
Phenanthrene (PHE)
Anthracene (AN)
Fluoranthene (FLT)
Pyrene (PY)
Benzo(a) anthracene (B(a)A)
Chrysene (Chry)
Benzo(b)fluoranthene (B(b)F)
Benzo(k) fluoranthene (B(k)F)
Benzo(a) pyrene (B(a)P)
Indenopyrene (IP)
Dibenzo (a,h) anthracene (D(ah)A)
Benzo (g,h,i) perylene (B(ghi)P)
PCBs
M24
M26
M28
M29
M30
M31
M32
M33
RSD (%)
LOD
LOQ
98
<LOQ
1.1 × 102
56
<LOQ
17.1
11.6
<LOD
<LOQ
<LOQ
<LOQ
<LOQ
<LOD
71
7.8
1.2 × 102
85
30.3
74
84
28
43
37
<LOQ
34
<LOD
27
<LOD
55
39
<LOQ
6.2
<LOQ
<LOD
<LOQ
<LOQ
<LOD
<LOD
<LOD
37
<LOD
74
51
12.6
23.3
28
<LOQ
16
14
<LOQ
13
<LOD
5.1 × 102
1.53 × 102
9 × 103
7.4 × 103
2.22 × 102
3.4 × 102
4.9 × 102
1.6 × 102
2.7 × 102
2.4 × 102
1.06 × 102
2.3 × 102
<LOD
19
<LOD
59
46
<LOQ
17.8
21
<LOQ
<LOQ
<LOQ
<LOD
<LOQ
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
<LOD
8.9 × 102
67
2.5 × 103
1.8 × 103
3.06 × 102
7.7 × 102
7.9 × 102
2.8 × 102
3.5 × 102
3.6 × 102
1.5 × 102
3.7 × 102
<LOD
6
3*
11
7
3
3
7
11*
9
20
7*
12
-
3.6
3.5
5.8
5.3
6.7
4.8
5.8
9.1
11.0
8.8
17.2
10.3
<33.7
11.8
11.7
19.2
17.7
22.5
16.0
19.4
30.3
36.7
29.5
57.4
34.2
<1.1 × 102
*
Repeatability of the measurement.
** Naphthalene (NP), acenaphtylene (AL), acenaphtene (AE) and fluorene (FL) are below detection level in all samples (<75 ng/g).
heating systems of the city, as well as the close industrial influence of the port of Bilbao are the sources for the target pollutants.
It is remarkable that other authors claim that the ratios are useful only when the sample (better if this is air sample) is close to
the emission source [76,77]. However, due to the location of the
building, ratios study has been taken into account in any case.
3.5. Analysis of soluble salts by ionic chromatography
Fluoride, sulphate, nitrite, chloride, calcium, sodium, potassium
and magnesium content were determined in entire samples by suppressed ion chromatography, except for M30 and M33, where black
crust composition was analysed after scraping crusted surfaces.
According to the results summarized in Table 4, sulphate was the
major component of the soluble fraction together with calcium. Sulphate achieved concentrations up to 7.04 × 105 mg/kg in strongly
black crusted samples (M31 and M33) whereas calcium maximum
concentration was found to be of 2.20 × 105 mg/kg in M33. On the
other hand, soluble sulphate and calcium maximum concentrations
found in samples without black crust (M28, M29, M31 and M32)
were found to be of 2.0 × 104 (M28) and 1.93 × 104 mg/kg (M31),
respectively. This means that high sulphate concentrations are not
exclusive of black crusted samples. In fact, thenardite was demonstrated to be probably the responsible for the detachment of M29
and M32.
According to the correlation analysis carried out on these results,
calcium and sulphate are strongly correlated (0.894), indicating
that they are likely forming as gypsum. Indeed this result agrees
with Raman spectroscopy findings. This means that the mean
gypsum amount represents around the 43% of soluble salt content of the samples and thus, this sulphate may be considered as
the major decaying compound of the analysed materials. However, taking into account the concentrations found for sulphate
and calcium and their molar ratio in a gypsum molecule, it can be
concluded that this is not the only sulphate formed. For instance,
(para-)coquimbite and thenardite (iron and sodium sulphates,
respectively) found by Raman spectroscopy could explain such sulphate excess in the black crusted samples (M30 and M33). Taking
into account that the formation of gypsum inside the materials
needs a previous H2 SO4 penetration and the fact that gypsum was
found in the most internal part of the samples, the impact of an acid
atmosphere for years is demonstrated.
It is also remarkable the nitrate and chloride content found
in some of the samples, especially the ones not having a black
crusted surface. For example, the maximum nitrate concentration
was found in M28 (8.1 × 102 mg/kg), whereas M29 showed the
highest chloride concentration (7.4 × 103 mg/kg). The presence of
these salts can promote a substantial material loss due to their
high solubility and thus they are considered more hazardous than
sulphates in terms of material integrity.
On the other hand, the deterioration level of the construction
materials of the studied building was quantified in terms of the total
soluble salts content. The soluble salts content was found to be in
the range between 0.1 and 5% w/w (related to the entire sample)
depending on the material type. The stone materials were the less
affected followed by cement and, finally, mortars. Among the latter, the embellishing mortars M30 and M33 showed a 69% and 93%
w/w salt content (related to the total mass of the scrapped crust),
respectively. According to the previous discussion, the salts formed
are not significantly health hazardous, but such a high salt content
limits material reusing in other fields. As an example, regarding
European legislation, the maximum sulphate concentration value
for road filling is 0.7% w/w which is achieved in most of the
samples, whereas chlorides exceeded in the half of the samples
the maximum (0.1% w/w) concentration accepted for road filling
or for cultural heritage in France [31].
In terms of conservation state of the building materials, the soluble salt amount found as well as their nature, indicated a high
Table 4
Concentration values in mg/kg and method repeatabilities obtained by ionic chromatography for each of the analytes and samples, and total soluble salt content (referred to
sample weight). Results given for M28 and M29 are mean values of 3 replicates.
Chloride
Nitrate
Sulphate
Sodium
Potassium
Magnesium
Calcium
% Soluble salts w/w
*
M24
M26
M28
M29
M30
M31
M32
M33
RSD
LOD
LOQ
1.93 × 102
24.0
2.62 × 102
46.4
<LOD
<LOD
1.82 × 102
0.07%
1.24 × 103
33
9.01 × 102
2.52 × 103
1.5 × 102
1.08 × 102
1.32 × 104
2%
6.3 × 103
8.1 × 102
2.00 × 104
7.3 × 103
8.7 × 102
98
1.49 × 104
5%
7.4 × 103
3.8 × 102
8.78 × 103
9.9 × 103
2.2 × 103
48
1.00 × 104
4%
6.6 × 102
<LOD
6.66 × 105
1.31 × 102
<LOD
<LOD
2.4 × 104
69%
1.61 × 103
3.9 × 102
1.00 × 104
2.98 × 103
2.8 × 102
<LOD
1.93 × 104
3%
5.9 × 102
11.9
1.47 × 103
3.07 × 102
28
34
7.4 × 102
0.3%
8.7 × 102
<LOD
7.04 × 105
1.54 × 103
2.3 × 102
<LOD
2.20 × 105
93%
2%
3%
1%
2%
8%
4%
4%
–
2.2 × 10−1 *
2.7 × 10−2 *
1.2*
1.4 × 10−1
1.4 × 10−1
2.3 × 10−1
1.4 × 10−1
–
5.1 × 10−1 *
1.4 × 10−1 *
3.5*
4.7 × 10−1
4.6 × 10−1
7.6 × 10−1
4.7 × 10−1
–
Value of the maximum LOD and LOQ obtained in the different calibrates.
N. Prieto-Taboada et al. / Journal of Hazardous Materials 248–249 (2013) 451–460
deterioration level, which can get worse since soluble salts can be
dissolved by rainfalls. As a consequence, a new original material
is again exposed so can be transformed into soluble compounds,
closing the decaying cycle.
3.6. Principal component analysis of the results
The multivariate analysis of the data was used in order to
obtain further information on the correlation among the studied
compounds, material type and the affection found. As already mentioned, the samples were analysed by ␮-XRF for both internal and
external surfaces, with the objective to compare the accumulation
level of the pollutants in both sides. The Unscrambler® v9.2 [78]
software was used to determine whether there was any difference
among the spectra got in the external and internal surface of the
samples. For this purpose, the comparison of the spectral areas
obtained for each of the elements was carried out. The Principal
Component Analysis (PCA) carried out on the semiquantitative data
(see Fig. 4.1) suggested that pollutants penetrated more than 6 mm
depth (the total thickness of the extracted samples) because there
was not any grouping of the results got for measurements on the
surface (measurements labelled as ex) or in the interior (labelled
457
as in) of the samples. This means that there was not any significant
compositional difference between the external and internal surface. However, in this analysis the number of principal components
needed to explain the 90% of variance was high (eight Principal
Components (PC) were necessary to explain 90.24% of variance) so
the model is quite difficult to be interpreted.
On the other hand, the PCA of the quantitative results obtained
by ICP-MS, GC–MS and IC showed some trends according to the
three types of materials: stone, mortar and cement. The PC1 versus
PC2 representation of the results obtained by the three analytical
techniques showed that the samples having the highest amounts
of hazardous elements and/or compounds were all mortars (see
Fig. 4.2). This PCA, which explained the 82.6% of variance with
the first three principal compounds, revealed that the totally black
crust samples (M30 and M33) were completely different from the
rest, in terms of concentrations found for the following analytes:
Pb, As, Ba, Cu, F− , Ca2+ , SO4 2− and some of the individual PAHs.
Calcium and sulphate are mainly related to the black crusted samples due to typical gypsum (CaSO4 ·2H2 O) massive presence in this
kind of formations. However, the PAHs and metals, such as lead,
have been described as component of black crusts as well [22].
The mortar samples without black crust (M28 and M29) grouped,
Fig. 4. PCAs carried out by Unscrambler where A groups corresponds to the black samples and B group to the samples without black crust. (1) Representation of PC1 vs.
PC2 of the PCA of the results obtained by ␮-XRF were differences between the internal (represented with blue colour and in letters) and the external (represented with red
colour and ex letters) side of samples are not observed. (2) PCA of the all results obtained by ICP-MS + CI + GC–MS. (For a better interpretation of the references to colour in
the artwork, the reader is referred to the web version of the article.)
458
N. Prieto-Taboada et al. / Journal of Hazardous Materials 248–249 (2013) 451–460
among others, with nitrates. Nitrates are very soluble salts that give
rise to material loss, especially when they are result of the transformation of the cement (commonly carbonate) by the action of acid
gases [22,79]. That is, the absence of the black crust although aesthetically better, is not indicative of a good state of conservation.
Finally, the rest of the samples appeared (M24, M26, M31 and M32)
grouped with a great influence of iron and chromium. It is remarkable that the materials involved in this group are sandstones (M24
and M32), cement (M26) and rendering mortar (M31); that is, they
are not embellishing mortars, as this is the case of the rest of the
samples. However, it is difficult to find a common source for the
elements influencing the grouping since the cited samples are of
different nature. For instance, the effect of iron could be due to
the fact that two of the samples are stone, and therefore rich in
iron. However, the fact that coquimbite was identified (the only
sample were coquimbite was not detected by Raman spectroscopy
was M28) and taking into account the conditions for its formation,
deposition of iron rich particulate matter cannot be ruled out. With
regard to chromium, it was considered a pollutant element, in
agreement with XRF analyses.
Focusing on the ICP-MS results, the representation of PC1 versus
PC2 (the first three PCs explain the 83% of the variance), the relation
of the metals with the different kind of materials can be more
clearly observed (see Fig. 5.1). For instance, sample M26 is shown to
be separated from the last group mentioned (M31, M32 and M24),
because of its high chromium content, which is the highest of the
samples. In general terms, this sample is closer to the most polluted
samples M30 and M33 due to its total metal content.
The joint PCA of the results obtained by IC and GC–MS (Fig. 5.2)
explained the 91% of variance with the first three principal components and the results revealed again a clear difference in the
absorption and reactivity of the building materials studied. For
instance, apart from the most referenced presence of gypsum, also
high PAH contents were found to be typical of the black crust composition.
Finally, the chemometric analysis shows that marine aerosols
have impacted mainly the mortar samples. According to the results,
mortar and cement samples are related with potassium, chloride, sodium and nitrate which may be related to very soluble
compounds as nitratine (NaNO3 ) found by Raman spectroscopy or
NaCl and KCl, also common in marine environments.
On the whole, the results confirm that building materials behave
in a different way against pollutants and that mortars are the most
susceptible for suffering from atmospheric attack. A detailed study
Fig. 5. PCAs carried out by Unscrambler where A group corresponds to the black samples and B group to the samples without black crust. (1) PCA of the result of ICP-MS
where the different types of construction materials are grouped according to their metal content. (2) PCA of the chromatographic results.
N. Prieto-Taboada et al. / Journal of Hazardous Materials 248–249 (2013) 451–460
of this behaviour could allow to determine the most suitable materials for construction of buildings depending on the environmental
conditions.
4. Conclusions
The results shown in this work demonstrate that buildings
are repositories of hazardous compounds that remain even after
removing the emission source. Although the number of samples
is not high enough to be representative of such a large building,
we could assume that the pollutants found accumulate in a similar way on every kind of building materials. Hazardous compounds
were found principally in the black crust, which corroborates its
high role as accumulation nucleus. The near port of Bilbao affected
directly the facade by deposition of particulate material, which in
most of the cases showed a high content of toxic compounds as
PAHs or heavy metals. Moreover, the high penetration capacity of
the contaminants has been shown to depend on the building material. In an attempt to determine the depth reached, other sampling
strategies (as micro drillings) should be taken into consideration in
future analysis.
Besides, soluble salt content is up to 5% of the sample weight.
The main component affecting to the building materials were sulphates in agreement with other authors. However, high amounts
of nitrates and chlorides were also determined. According to the
results obtained in this work, the samples showing the highest
concentration values for these salts were those that did not show
any crust. Therefore, the absence of black crust should not be the
only factor to consider when establishing the conservation state of
building materials.
In conclusion, it is remarkable that building materials are acting as passive samplers (a static indicator) of pollution suffered
by the ecosystem over the years. Thus, the results of this survey
will provide an indication of the chronic or persistent pollution
in the sampling area. Portable non-destructive techniques such as
␮-XRF and Raman spectroscopy provide a first screening of the
affection of the materials and are a suitable tool to design the sampling [71–74]. In any case, the combination of different analytical
techniques allows us to obtain essential information to perform a
complete risk assessment of building materials.
Acknowledgements
This work has been financially supported by the project DEMBUMIES from the Spanish Ministry of Economy and Competitiveness
(MINECO) (ref: BIA2011-28148). N. Prieto-Taboada acknowledges
her grant from the Spanish Ministry of Science and Innovation
MICINN (ref: BES2009-013639). I. Ibarrondo and O. Gómez-Laserna
acknowledge their grants from the University of the Basque Country. Technical support provided by the Raman-LASPEA Laboratory
of the SGIker (UPV/EHU, MICINN, GV/EJ, ERDF and ESF) is gratefully
acknowledged.
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