Journal of Cleaner Production 219 (2019) 236e243

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Journal of Cleaner Production

journal homepage: www.elsevier.com/locate/jclepro

Nanoparticles from construction wastes: A problem to health and the

environment
Marcos L.S. Oliveira a, b, Maria Izquierdo c, Xavier Querol c, Roy N. Lieberman c,
Binoy K. Saikia d, Luis F.O. Silva a, *
a
ntico, Colombia
Department of Civil and Environmental, Universidad de la Costa, Calle 58 #55-66, 080002, Barranquilla, Atla
b
Faculdade Meridional IMED, 304- Passo Fundo, RS, 99070-220, Brazil
c
Institute of Environmental Assessment and Water Research (IDAEA-CSIC), C/Jordi Girona 18-26, 08034, Barcelona, Spain
d
Polymer Petroleum and Coal Chemistry Group, Materials Sciences & Technology Division, CSIR-North East Institute of Science and Technology, Jorhat,
785006, India

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

Article history: The present study deals with the nano-mineralogy and geochemistry of ultrafine particles in construc-
Received 9 August 2018 tion waste from the Porto Alegre region in Southern Brazil. Uncontrolled construction waste dumps and
Received in revised form poor management practices in formal disposal sites in the area may increase exposure risks to popu-
8 February 2019
lation. Whilst the physicochemical properties of construction wastes are well documented in the liter-
Accepted 9 February 2019
ature, the characteristics of nanoparticles in their formulations are not well known. Given that
Available online 11 February 2019
degradation of construction materials may unlock and enable further release of nano-particulates pre-
sent, we focused on the <63 mm fraction to examine the geochemistry of inhalable nano-particulates that
Keywords:
Nanoparticles
could cause adverse health impacts on local communities. A particular feature across the studied wastes
Hazardous elements are the numerous aerodynamically favourable, spherical-shaped nanoparticles of magnetite, rutile and
Environmental impacts anatase. The detected nanoparticles contained a number of elements including Al, As, Au, Ca, Cd, Co, Cr,
Civil construction waste Cu, Hg, Na, Fe, K, S, Sn, Si and. An enrichment in metals and metalloids such as As, Co, Cr, Cu, Hg, Fe, Sn or
Ta in particles in the nano-scale range in relation to larger particles was observed. The presence of carbon
nanotubes was also noted. The leaching tests showed that the construction wastes did not reach the
limits for their disposal as hazardous waste according the European Directive. Whilst the majority of
trace elements were highly immobile, the water extractability for oxyanionic-forming metalloids sug-
gests possible migration to surface and groundwater bodies. This work seeks to bring awareness on the
impacts of unsustainable construction waste management, and the relevance of improved regulations
regarding their final disposal.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction 2017). Urbanization increases the emissions of air pollutants and

A recent UN report suggests that over half of the world's pop-
ulation (54%) lives in urban areas and this proportion is expected to
increase to 66% by 2050 (United Nations, 2014). The urbanization
process brings economic and social transformations that are
important drivers of development, but it also brings an enormous
stress on the environment and sustainable development challenges
such as the reduction of green space, greater impermeable coverage
and air and noise pollution (United Nations, 2014; Gredilla et al.,
* Corresponding author.
E-mail address: felipeqma@hotmail.com (L.F.O. Silva).
reduces infiltration of rainwater thus enhancing surface runoff
~ eda et al., 2017). In general, ur-
(Tixier et al., 2011; Agudelo-Castan
ban growth significantly increases the emission of a range of pol-
lutants to surface waters, decreasing quality and increasing threats
to the environment and human health (Ancion et al., 2010).
Population growth brings greater energy and housing demands,
which results in large amounts of construction waste. Construction
and demolition waste generation worldwide reached over 3 billion
tonnes/year until 2012 (Akhtar and Sarmah, 2018). This includes
unused construction materials which result from excess supplies or
mishandling of materials during building construction (Akhtar and
Sarmah, 2018). Regulations in Brazil require waste sorting and se-
lective disposal of different components in specific waste facilities

https://doi.org/10.1016/j.jclepro.2019.02.096
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
 M.L.S. Oliveira et al. / Journal of Cleaner Production 219 (2019) 236e243
for this purpose, with the exception of gypsum plaster. Gypsum
waste cannot be landfilled due to potential formation of toxic gases
upon reaction with organic compounds and therefore it is classified
as recyclable (CONAMA, 2011).
In Southern Brazil, however, poor waste management practices
are not uncommon and these typically low-technology sites often
fail in implementing measures to confine waste and prevent
exposure risks. In addition, proliferation of numerous uncontrolled
clandestine construction/demolition waste dumps appears to be on
the rise (e.g. Fig. 1). Many construction wastes such as concrete,
paints or steel contain nano-size range material in their formula-
tion (Baalousha et al., 2016) and degradation during prolonged
exposure may unlock these nano-particulates. Adverse health im-
pacts on local residents and waste workers may occur following
resuspension of fine particulates and subsequent inhalation.
Although construction and demolition waste (CDW) is relatively
inert, the main environment concern is associated with its high
volume, weight and large worldwide annual production (Akhtar
and Sarmah, 2018; Ga
lvez-Martos et al., 2018). The management
of CDW has been recognised as a major global issue due to the
associated environmental impacts and constitutes a priority for
most environmental programmes worldwide (Ga
lvez-Martos et al.,
2018). In response to this, a range of solutions aimed at increasing
recycling rates have been explored in the past decades. This is re-
flected in the large number of studies on CDW in the literature,
which are largely focused on the physical and mechanical proper-
ties as recycled aggregates for civil engineering applications. Ap-
plications of crushed concrete and bricks include production of
concrete, mortars or tiles, production of cement (Akhtar and
Sarmah, 2018 and references therein), as cemented pasted back-
fill (Chen et al., 2018) or as road pavement material (e.g. Tavira et al.,
2018) among many others.
Extensive research conducted over the past few years has pro-
vided strong evidence that coarse recycled aggregates can be suc-
cessfully used in concrete production, whilst fine particulates <
4 mm have been dismissed due to high pollutant contents and
water absorption (Rodrigues et al., 2013). However increasingly
limited availability of natural aggregates has prompted a growing
interest in potential applications of fine CDW particulates. In a
batch sorption study, Coleman et al. (2005) assessed the ability of
1e2 mm CDW particles to remove heavy metals from aqueous ef-
fluents. Jeli

c et al. (2018) studied the sorption of radionuclides onto
0.3e0.6 mm CDW particles after particle size reduction, whilst no
attempt was made to preserve the original particle size distribu-
tion. The properties of ultrafine particles however remain largely
unknown.
The literature on particulate matter (PM) associated with con-
struction/demolition sites is relatively scarce in relation to other
PM sources such as exhaust emissions. The majority of works
specifically focused on levels of PM emissions whilst the chemical
properties have been overlooked (Dorevitch et al., 2006; Araújo
et al., 2014; Butera et al., 2015). McGee et al. (2003) conducted a
Fig. 1. Uncontrolled building waste dumps in the outskirts of Porto Alegre (Southern
Brazil).
237
comprehensive study of the mineralogical and chemical composi-
tion of settled PM2.5 from the World Trade Center site for a further
toxicological assessment. However in general very little emphasis is
placed on the chemical composition of the ultrafine (PM2.5 and
PM10) particles associated with construction/demolition operations
in the literature and, to our knowledge, the characterisation of
nano-size particles in this waste has not been fully addressed.
In addition, potential recyclability of gypsum plaster waste has
also been addressed in the literature. Emphasis has been placed on
the physical and microstructural aspects of recycled gypsum ob-
tained through calcination-rehydration cycles (Geraldo et al., 2017).

rez et al. (2016) found
In a study of life cycle of recycled gypsum, Sua
that recycled gypsum production may have respiratory effects due
to emissions of PM to air associated with gypsum crushing. How-
ever the geochemistry of these potentially inhalable (thoracic)
gypsum particles is still unclear.
It is widely known that coal combustion fly ash may contain
potential hazardous elements (PHEs) such as As, Ba, Cd, Cr, Hg, Sb,
Pb, Zn and Mn that can cause damage to the environment and
human health (Yang et al., 2016). US Clean Air Act Amendments (US
EPA, 1990) have considered many of these elements as elements of
serious environmental impact and are regulated by the European
Union (EU) (EMEP/EEA, 2009). To address this issue, potential al-
ternatives for recycling have been extensively studied, being the
addition to cement/concrete the main application. In addition,
other ultrafine particulates such as carbon nanotubes, SiO2, TiO2,
Fe2O3, Cu or Ag nanoparticles are increasingly used in multiple
applications in construction owing to their ability to improve the
physical, chemical and mechanical performance of concrete,
ceramic, steel or paint (Lee et al., 2010). However these rarely have
been examined embedded in a building material matrix. Despite
their unique properties and potential benefits, their release to the
environment could bring adverse biological and toxicological ef-
fects including cell and DNA damage, inflammatory and immune
responses or ROS-induced oxidative stress among others (Lee et al.,
2010). Other more abundant and widespread construction mate-
rials can also be of concern to an extent e.g. gypsum and calcite are
known to cause irritation of the mucus membranes of the eyes and
respiratory tract, and therefore inhalation of high doses of these
species in ultra-fine particle form (e.g. PM2.5) could potentially have
toxic respiratory effects McGee et al. (2003).
Growing needs for waste management in Southern Brazil pose a
challenge to municipal authorities and there is a lack of under-
pinning experimental data to adequately assess the potential
exposure pathways and risk associated with inadequate construc-
tion waste dumping. The objective of this work is to study the
occurrence, composition and solubility of nanoparticles from the
most common construction wastes collected from uncontrolled
deposits. This work does not intend to provide an exhaustive
characterisation of nanoparticles across the building waste sites in
Brazil. Rather, our aim is to provide preliminary data on the
occurrence of nanoparticulate matter and the relationships be-
tween concentrations of trace elements, solubility and particle size
in building waste. Ultimately, this work seeks to bring awareness on
the impact of unsustainable construction waste management,
particularly on the most vulnerable, socioeconomically disadvan-
taged communities that face greatest potential exposure, and
provide a basis for future work supporting decision-making.
2. Material and methods
2.1. Sample collection and preparation
A total of 33 samples of concrete slabs, concrete roofing tiles and
plasterboards (x11 samples each type) were collected from 5
238 M.L.S. Oliveira et al. / Journal of Cleaner Production 219 (2019) 236e243
clandestine waste dumps located in the city of Porto Alegre,
Southern Brazil (Fig. 1). These dumps primarily consist of relatively
recent construction waste whilst the proportion of demolition
waste appears to be marginal. Each sample consisted of approx.
10 kg material collected with a plastic shovel and stored in plastic
bags. The samples were then combined and homogenised to pro-
duce a 110 kg composite sample for each waste i.e. concrete, tiles
and plasterboard. Representative ca. 10 kg sub-samples of each
specific waste component were obtained with the aid of an
industrial-size riffle splitter. Further representative sub-samples for
the different analyses were obtained with a bench-top riffle sample
splitter. The samples were dried at 40
C for 48 h and subsequently
transferred to desiccators containing silica gel to remove residual
moisture. After 4 days, the samples were sieved over a 63 mm mesh
to segregate the fine fraction for further analyses whilst the
retained fraction was discarded. No grinding was applied as we
intended to obtain ultrafine samples as they may naturally occur in
the environment.
2.2. Determination of total and leachable concentrations of
elements
All samples were digested using a multiple-step method
devised to retain to volatile elements during dissolution of solid
samples (Querol et al., 1997). This consisted of a first extraction of
0.1 g of sample with concentrated trace element grade HNO3 during
8 h at 90
C in closed PFA bombs, followed by a concentrated trace
element grade HF:HNO3:HClO4 acid digestion on a hot plate at
160
C until dryness. The solid was re-dissolved with HNO3 and
MilliQ water to a volume of 100 mL solution (5% HNO3). A certified
standard reference material (NIST SRM 1633b) and blanks were
also digested following the same procedure to test the accuracy of
the analytical and digestion methods.
The water solubility of elements was studied following the
compliance leaching test EN 12457-2 (EN 2002). This is a single
batch-leaching test performed at a liquid to solid ratio of 10 L/kg
with 24 h of agitation time and MilliQ water as leachant. The sus-
pensions were centrifuged, filtered and acidified to 1% HNO3 prior
to analysis. The concentrations of minor and trace elements in the
acid digests and leachates were determined using a Thermo X-Se-
ries 2 ICP-MS (Thermo Fisher Scientific, Bremen, Germany.
2.3. Mineralogical analysis
The X-ray diffraction analyses were carried out using a Bruker
diffractometer, model D8 Advanced. Experimental conditions were
Cu Ka monochromatic radiation, slit fixed at 12 mm, 20 mA and
40 kV (De Vallejuelo et al., 2017; Oliveira et al., 2018). Samples were
run at a speed of 0.3
2q/min (5e65
).
2.4. Electron microscopy analysis
The morphology and chemical composition of microparticles,
nanoparticles and minerals were analysed using a Zeiss ULTRA plus
field emission scanning electron microscope (FE-SEM) with charge
compensation for all applications on conductive (Civeira et al.,
2016a, b) for particles larger than 100 nm. The conditions of SEM
equipment were accelerating voltage of 20 KV; beam current of
1010A and detector was coupled with an energy dispersive X-ray
microanalysis system (EDX). Non-conductive samples were ana-
lysed using a 200-keV JEOL-2010F high resolution transmission
electron microscope (HR-TEM) equipped with an Oxford energy
dispersive X-ray detector and a scanning (STEM) unit (Silva et al.,
2009). The FE-SEM was equipped with an energy-dispersive X-
ray spectrometer (SEM-EDS), and the mineral identifications were
made on the basis of morphology and grain composition using both
secondary electron and back-scattered electron modes. Different
organic solvents such as hexane, acetone, dichloromethane and
methanol, were selected to prevent possible mineralogical alter-
ations. The suspension consisted of 10 mL of each of the solvents
mixed with 0.5 g of dried and sieved waste sample. The suspension
was stirred for ~1 min and then pipetted onto carbon films sup-
ported by Cu grids (Giere
et al., 2006). The suspension was left to
evaporate before inserting the sample into the TEM. This method
may have led to agglomeration but is a widely used standard pro-
cedure for most minerals, including metal sulphates (Kan et al.,
2003).
3. Results and discussion
3.1. Mineralogical characterisation of construction waste
Due to the limited XRD sensitivity to trace levels, only the major
crystalline species present were detected. Quartz (SiO2, JCPDS file
00-046-1045) and calcite (CaCO3, 00-005-0586) were the domi-
nant species in the concrete and tile samples, with traces of feld-
spars (Ca(Al2Si2O8, 00-041-1481) and dolomite (Ca,Mg(CO3)2, 00-
036-0426) reflecting the presence of multiple components in the
parent concrete mixtures. This mineral association and their rela-
tive abundances is in good agreement with the findings of Engelsen
et al. (2009) for CDW from Norway, Evangelista et al. (2015) and
Rodrigues et al. (2013) for <63 mm CDW fraction from Portugal and
Jeli

c et al. (2018) for <4 mm CDW from Serbia. These authors also
noted the absence of ordinary Portland cement-derived phases and
hydration by-products in XRD spectra i.e. portlandite (Ca(OH)2) or
calcium silicate hydrates (CSH). Concrete ageing and prolonged
exposure to atmospheric conditions may cause (i) decalcification
and silicate polymerisation; and (ii) carbonation of portlandite
(Jeli

c et al., 2018). The plasterboard waste consisted primarily of
gypsum (CaSO₄$2H₂O, 00-033-0311) followed by low amounts of
quartz (00-046-1045).
3.2. Chemical characterisation
As expected, concrete and concrete tiles are compositionally
similar (Fig. 2). A large number of trace elements are present in
concentrations >1 mg g1 including potentially hazardous elements
such as As and Co (5e10 mg g1), Pb, Cu, Ni, Cr, La, Ce, Nd
(10e50 mg g1), V and Zn (100e200 mg g1). Titanium was the most
enriched trace element with concentrations ca. 3000 mg g1. Similar
Co and Ni concentrations (4e8 and 21e30 mg g1 respectively) were
reported for construction waste from a residential area in Serbia
(Jeli

c et al., 2018). By contrast, gypsum-rich plasterboard is depleted
in environmentally relevant trace elements with the exception of
W, Zr and Zn (20e50 mg g1). As shown in Fig. 2, concrete and tile
components are the primary contributors of hazardous elements to
the potentially inhalable ultrafine particles from construction
waste.
3.3. Trace element solubility
The pH of the leachates ranged between 9.4 and 11.0 reflecting
the alkaline nature and strong buffering capacity of Portland
cement-based products. This is in line with the findings of other
authors for concrete-rich waste (Galvín et al., 2014). Leaching tests
revealed that most elements in the studied construction wastes
were highly immobile. The leachable concentrations of potentially
harmful metals and metalloids such as Be, Sc, Se, Y, Cd, Sn, Cs, REE,
Tl, Pb, Bi or U among others (Fig. 3) were <0.001 mg g1. This may be
attributed to the alkaline nature of the leachates given that the
 M.L.S. Oliveira et al. / Journal of Cleaner Production 219 (2019) 236e243 239

total concentra on (μg g-1) 10000

1000
100
10
1
0.1
0.01
0.001
Se Cd Bi Tl Sb W Be Sc Mo Ta U Ge Hf Sn Cs Th Nb As Co Ga Y Li Pb Cu Rb Ni Cr V Zr B Zn Mn Sr Ba Ti

concrete le plasterboard

100
total concentra on (μg g-1)

80
60
40
20
0
La Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

concrete le plasterboard
Fig. 2. Total concentration of trace elements in concrete, tile and plasterboard waste particles <63 mm. All values are in mg g1 on a dry bulk basis.

100
n (μg g-1)

10

1
total concentra

0.1

0.01

0.001
Be Sc Mn Ge Se Y Zr Nb Cd Sn Hf Ta Tl Pb Bi Th U Cs Sb Ni As W Zn Co Ti Cu Ga Mo Li Ba Cr Rb V B Sr

2003/33/CE concrete le plasterboard

Fig. 3. Leachable concentration of trace elements in concrete, tile and plasterboard waste particles <63 mm. All values are in mg g1 on a dry bulk basis. Columns denote the
maximum limit values for acceptance at non-hazardous waste landfills (Council Decision 2003/33/CE).

minimum solubility of most trace metals is typically attained reported by Galvín et al. (2014) suggesting that the water solubility
within the pH 7e10.5 range. Low overall solubility of these ele- typically remains <0.5 mg g1 and may not pose a major concern in
ments has been reported for other alkaline wastes with similar pH terms of releases to surface water bodies.
e.g. municipal solid waste incineration ash (Izquierdo et al., 2002, Fig. 3 shows that special attention should be directed to
2008) or coal combustion ash (Izquierdo and Querol, 2012). Ex- oxyanionic-forming metalloids such as As and Mo (up to
ceptions are elements such as Li, Ba, Cs, Rb and Sr, likely associated 0.05 mg g1 leachable), Cr and W (up to 0.2 mg g1), V (up to
with major elements in chlorides, sulphates, carbonates and hy- 0.8 mg g1) and B (reaching 14 mg g1 in plasterboard). In terms of
droxides in the construction waste, which may be relatively soluble extractable proportion, these values indicate that approx. 1e2% of
across the pH range. Their leachable concentrations ranged be- the total concentration of these elements can be readily solubilised
tween 0.01 and 2.1 mg g1, which indicates that 0.1e2% of their total by water, although this proportion reached 16% leachable B for
content is water soluble for all the studied wastes regardless of the plasterboard waste. The above listed elements were found to be
pH. Concentrations of up to 1.4 mg g1 leachable Ba were also re- highly mobile in other alkaline wastes given that their solubility
ported for concrete-rich CDW in Spain following the same leaching peaks within the pH 7e10 range (Izquierdo and Querol, 2012).
protocol (Galvín et al., 2014). Chromium was identified by Galvín et al., (2014) as the most
The leachable concentrations of Co, Cu, Ni and Zn ranged be- conflictive trace element in CDW in terms of water leaching. The
tween 0.01 and 0.07 mg g1. These metals are highly immobile (i.e. presence of Cr in concrete waste is attributed to the raw materials
<0.01 mg g1) under near neutral conditions but their solubility used in cement production i.e. clay, limestone, Fe additives and
may increase at pH > 10 due to their amphoteric behaviour additions such as blast furnace slag, pozzolans or fly ash. In a study
(Izquierdo and Querol, 2012). Leachable concentrations in the of different commercial cement types in Slovakia, Estokova
et al.
0.01e0.1 mg g1 range for these elements in CDW were also (2012) estimated that 50e90% Cr in cement is hexavalent Cr and
240 M.L.S. Oliveira et al. / Journal of Cleaner Production 219 (2019) 236e243
forms readily soluble compounds. These authors determined
water-soluble proportions between 0.2 and 1.4% depending on the
cement type which are consistent with our observations for Cr
(0.1e1.2% leachable Cr). Chromium in its hexavalent form has been
reported to be harmful and has the potential to penetrate human
skin causing Cr dermatitis (Estokova
et al., 2012). However, the
leachable concentrations of the studied elements remained below
the maximum limit values for waste acceptance at landfills for non-
hazardous waste according the Council Decision 2003/33/CE
(Fig. 3).
It is worth noting that the leaching test performed used MilliQ
water as leachant and had no pH control. This may provide valuable
information on the potential release of pollutants from exposed
construction waste at the disposal site following a rain event.
However the results obtained may not provide a reliable estimate of
the bioaccessibility of these elements i.e. physiological solubility of
an element in the body gateway following ingestion or inhalation.
Greater dissolution rates and absorption across the membranes may
be expected due to differences in the media e.g. gastro-intestinal
tract, characterised by acidic pH. In addition greater quantities of
leached elements may be anticipated due to longer contact times, as
nanoparticles may be retained in vital organs for >24 h.
3.4. Detection and characterisation of nanoparticles
SEM and TEM analysis of the <63 mm fractions of the collected
samples confirmed the presence of ultra-fine and nanometric
particles in all kinds of waste, which may be re-suspended and
inhaled by population exposed. Our observations evidenced that
the particles in the nano-size range are compositionally and
mineralogically different than the bulk < 63 mm sample suggesting
that mineralogy is strongly particle-size dependent and therefore
possibly controlled by the source.
A key feature is the large number of spherically-shaped nano-
particles in the samples under study. Coal combustion fly ash
cenospheres of up to 15 mm diameter were particularly abundant in
concrete samples (Fig. 5). Other authors have reported the presence
of relict fly ash particles in concrete waste (Evangelista et al., 2015).
This suggests that a number of ash cenospheres may remain
unhydrated and virtually unaltered during concrete life cycle.
Extensive and widespread addition of CFA to cement blends has
been reported in Southern Brazil (Oliveira et al., 2018). Dumping
unused cement bags containing up to 40% CFAs appears to be
frequent in the area. Improper cement disposal enhances resus-
pension processes of this fine powder thus increasing exposure and
risk to the population (Martinello et al., 2014; Wilcox et al., 2015).
Evidence for DNA damage induced by intra-tracheal instillation of
coal ash in mice has been found (Leo
n-Mejía et al., 2018).
Spherical nanoparticles of magnetite (Fe3O4) were also abundant
in concrete and tiles (Fig. 4). Magnetite is widely used for the
manufacture of steel and it is a common mineral in coal fly ash used
for the cement manufacture. It is acknowledged that the Fe in nano-
magnetite can induce the formation of reactive oxygen species,
promoting the oxidative stress of cells; it is also thought to play a role
in the extent to which hydrogen-free radicals attack DNA, resulting
in mutation and malignant transformations (Grazuleviciene et al.,
2009).
The relative abundance of spherical TiO2 nanoparticles in con-
crete and tiles is also worth noting. These were present different
crystalline forms such as anatase and rutile (Fig. 4). Currently, it is
estimated that 10e30% of TiO2, 30% of ZnO, 5e10% of CeO2 used in
paint and coatings are formulated as ultrafine particles close to the
nanometric scale (Piccinno et al., 2012). Even traditional pigments
such as TiO2 contain a nanometric fraction, from which about 36%
of the particles are <100 nm (Weir et al., 2012).
The species discussed above primarily occurred in nano-sized,
spherical aerodynamically favourable forms in concrete, tile and
gypsum samples. This is of particular relevance in terms of health
risk due to their potential to enter the respiratory tract and pene-
trate into the deepest alveolar area of the lung. However irregular-
shaped particles enriched in metals were also found in concrete
and tiles (e.g. Fig. 6). Although a number of metal-rich (Cd, Pb, Sn)
spheres were detected in plasterboard, metals primarily occurred
in irregular-shape nanoparticles (Fig. 7).
In general, the nanoparticles detected in the studied wastes
contained a number of elements including Al, As, Au, Ca, Cd, Co, Cr,
Cu, Hg, Na, Fe, K, S, Sn, Si and Ta (e.g. Figs. 6 and 7), some of them
potentially harmful to human health. For example, Cr reacts with
natural reductants such as thiols and ascorbate, producing reactive
oxygen species such as superoxide ions, peroxide, and hydroxyl
radical, leading to oxidative stress of the cell (Stohs and Bagchi,
2005), whilst Cu has been found to cause mitochondrial damage
(Arciello et al., 2005). An enrichment in metals and metalloids
including As, Co, Cr, Cu, Hg, Fe, Sn or Ta in particles in the nano-scale
range in relation to larger particles was noted.
In addition, the presence of carbon nanotubes in elongated and
amorphous forms was reported in concrete samples (Fig. 8). Carbon
nanotubes are widely used in a broad range of commercial prod-
ucts. A key exposure pathway is the inhalation of nanotube-rich
aerosols, with the respiratory tract as portal of entry. This raises
concerns on human health given that experimental animal studies
revealed asbestos-like effects associated with C nanotubes
(Oberdo € rster et al., 2015).
3.5. Environmental implications
The geochemistry of nanoparticles in construction waste has not
been extensively studied before and therefore this study may help
bring more attention to this issue and assist regulators in decision
making regarding the monitoring, and particularly the long-term
management of these waste materials. Studies on construction
materials reported an exponential decrease in the release of
nanoparticles over time (Kaegi et al., 2010) whilst other authors
found no particular time-dependent trend (Al-Kattan et al., 2013).
The release of nanoparticles from construction materials into the
environment is often associated with ageing of coatings, enhanced
by weathering during exposure to atmospheric conditions. Degra-
dation of organic polymer layer on the surface unlocks inorganic
nanoparticulates retained in polymer networks (Al-Kattan et al.,
2013). The uncontrolled disposal of construction waste in uncon-
fined, open sites may therefore result in direct and diffuse path-
ways for nanoparticles into the environment and the surrounding
population.
A first key exposure pathway are re-suspension processes of
ultrafine particles by the action of wind, traffic or waste handling,
enabling direct PM inhalation. Waste dumps with unrestricted or
relatively easy access are attractive sources of valuable construction
material that can be re-used. Local lower-income communities may
be particularly vulnerable to this issue as recycling practices
through waste-picking are widespread in the area. Informal recy-
cling practices are often associated with poor environmental and
safety awareness that can aggravate environmental contamination
of air, soil and water and increase the exposure to a range of pol-
lutants. Evidence for improper handling, transport and storage
without protective equipment has been observed (e.g. Fig. 1). This
can release high levels of airborne pollutants and have an impact
not only on the local community but on the wider environment due
to uncontained transportation practices (Fig. 1).
A second key pathway includes migration of pollutants to
aquatic ecosystems via surface runoff after a rain event, either in
 M.L.S. Oliveira et al. / Journal of Cleaner Production 219 (2019) 236e243 241

(A) (B)

(C) (D)

Fig. 4. Spherical NPs of rutile (A) and anatase (B) in tiles (HR-TEM image) and spherical nano-magnetite in tiles (C) and concrete waste (D) (EDS-TEM image).

Cu
Co
Sn
Al
Au

Fig. 5. FE-SEM image of a coal combustion fly ash particle in the concrete sample. Fig. 6. FE-SEM image of an submicronic and ultrafine clay particle detected in the
concrete sample and containing Co, Al, Au, Cu and Sn.
242 M.L.S. Oliveira et al. / Journal of Cleaner Production 219 (2019) 236e243

potentially reaching underlying aquifers is also likely. The absence

of composite liners and leachate collection systems in informal
disposal sites can severely affect the quality of surface and
groundwater.
Ca Improved regulations and implementation of measures to safely
contain CDW would be advisable to minimise exposure risks to the
K population. Organised and supported informal waste recycling
A
Au Gypsum could help decrease the environmental burden associated with the
Cu use of natural resources whilst effectively contribute to reduce
poverty and, crucially, address the public health challenges posed
by uncontrolled dumping of construction waste.
Cu
Na Au Ta 4. Conclusions

This work confirms the existence of numerous nanoparticles in

C K construction waste. Evidence of potentially suspendable and
inhalable TiO2 and Fe3O4 (magnetite) nanoparticles with spherical
shape and other ultra-fine particles including carbon nanotubes
was reported. An enrichment in metals and metalloids including
As, Co, Cr, Cu, Hg, Fe, Sn or Ta in particles in the nano-scale range in
relation to larger particles was observed, and this was apparent
Fig. 7. FE-SEM image of metal-bearing gypsum nanoparticles detected in the plas-
across the studied wastes. Thus, numerous particles contained in
terboard sample.
construction wastes have the morphology, size and elemental
composition to be regarded as potentially dangerous for human
health and pose a threat in case of irreversible retention following
inhalation. Our findings emphasize the need for (i) further work to
systematically study toxicological aspects of particulate matter
associated with construction waste; and (ii) improved regulations
and implementation of measures to contain construction waste and
minimise exposure risks to the population.
Low overall water solubility of the studied wastes was reported.
The leachable concentrations of most potentially harmful elements
e.g. Be, Sc, Se, Y, Cd, Sn, Cs, REE, Tl, Pb, Bi or U among others was
below the detection limit probably due to the alkaline nature of the
wastes. Higher mobility was reported for oxyanionic-forming
metalloids including As, Mo, Cr, W, W and B. Approx. 1e2% of the
total concentration of these elements can be readily solubilised by
water and this proportion reached 16% leachable B for plasterboard
waste. Whilst the leachable concentrations may not necessarily
suggest a risk of acute exposure, sustained releases in contact with
rainwater and subsequent migration to surface and groundwater
bodies may be of concern in the long term. The conclusions of this
work are expected to raise awareness on the potential impact of
construction wastes and the relevance of improved regulations
regarding the final disposal of these wastes.

Acknowledgments

This study was supported by grants from Conselho Nacional

gico (CNPq), Brazil.
para o Desenvolvimento Científico e Tecnolo

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