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Ecotoxicology and Environmental Safety 159 (2018) 198–204

Contents lists available at ScienceDirect

Ecotoxicology and Environmental Safety


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

Street dust from a heavily-populated and industrialized city: Evaluation of T


spatial distribution, origins, pollution, ecological risks and human health
repercussions

R. Urrutia-Goyesa, N. Hernandezb, O. Carrillo-Gamboab, K.D.P. Nigamb,c, N. Ornelas-Sotob,
a
Departamento de Ciencias de la Energía y Mecánica, Universidad de las Fuerzas Armadas ESPE, Av. Gral. Rumiñahui s/n, P.O. Box 171-5-231B, Sangolqui 171103,
Ecuador
b
Laboratorio de Nanotecnología Ambiental, Tecnologico de Monterrey, Escuela de Ingeniería y Ciencias, Ave. Eugenio Garza Sada 2501, Monterrey, N.L. 64849, México
c
Department of Chemical Engineering at Indian Institute of Technology, Delhi, India

A R T I C LE I N FO A B S T R A C T

Keywords: Emissions from vehicles include particles from tire and brake wearing that can settle down and join industrial
Street dust discharges into street dust. Metals present in street dust may create ecological and health threats and their
Heavy metals analysis is of great environmental relevance. The city of Monterrey, Mexico is an industrial pillar of the country
XRF and shows an increasing fleet during the last years, which has yielded higher traffic and emissions. This study
Human health
analyzes 44 street dust samples taken across the city for total element concentrations by using X-ray fluores-
Risk assessment
cence. Associations and indicators are calculated to define possible origins, levels of pollution, natural or an-
thropogenic sources, and ecological and human health risks. High concentrations of As, Ba, Cu, Fe, Mo, Ni, Pb,
Ti, and Zn were found. Main sources of metals were defined as: tire wearing for Zn and Fe; brake wearing for Ba,
Cu, Fe, Pb and Zr; additional industrial sources for Mo, Ni, Pb, and Ti; and other natural sources for As.
Ecological risk was found to be moderate across the city and risk due to Pb concentrations was established for
children.

1. Introduction production. With a contribution of ~9% to the gross domestic product


(GDP) of the country and a GDP per capita only second to Mexico City,
Emissions due to traffic is a recurrent concern for both developed Monterrey is considered the most important industrial region of the
and in-development cities since an increase in population and industrial whole country. The fleet of the city was 1.7 million in 2008 an over 2
activities yields higher traffic and hence higher emissions (Carrera million in 2015, with an estimated 8 million of daily trips (GMM, 2015;
et al., 2015; Xing and Brimblecombe, 2018). Many adverse effects have INEGI, 2016).
been associated with tailpipe emissions and thus, the majority of in- Previous studies have found the city to have high levels of fine or-
ternational regulations point to this specific type of production ganic aerosols in the air, and defined the exhaust from motors as the
(Buzzard et al., 2009; Morin et al., 2016). However, there are other main air pollutant (Carrera et al., 2015; González et al., 2017; Mancilla
discharges from automobiles that may create ecological and human et al., 2016). However, no studies have been carried out in street dusts
health risks that are worth revising. Additional emissions from vehicles across the region. Since street dust has been reported to have enriched
include particles resulting from tires treads and tire dust, brake dust and concentrations of heavy metals compared to soils, and that vehicle
brake pads, and general parts wear. Such particles may become street emissions, aside from tailpipe, may contain high amounts of Zn, Fe, Cu,
dust and join industrial emissions in the area creating a threat once they Pb, among others, an evaluation of the street dust in Monterrey is ne-
are exposed to humans (Adamiec et al., 2016; Apeagyei et al., 2011; cessary to define its metal content, origin, and possible pollution effects
Thorpe and Harrison, 2008). on ecological and human health (Apeagyei et al., 2011; Charlesworth
Monterrey, with dry but extreme temperature conditions, is the et al., 2011). In addition, some metals may be bioavailable in ecosys-
third largest urban center in Mexico with more than 4 million in- tems as toxins, and some of the adverse effects related to exposure and
habitants and 5 million expected for 2030. Its economy is based among inhalation of particulate matter include respiratory illnesses, neurolo-
others, on manufacturing, metallurgy, and food and beverages gical complications, digestive diseases, etc.


Corresponding author.
E-mail addresses: erurrutia@espe.edu.ec (R. Urrutia-Goyes), ornel@itesm.mx (N. Ornelas-Soto).

https://doi.org/10.1016/j.ecoenv.2018.04.054
Received 13 March 2018; Received in revised form 20 April 2018; Accepted 26 April 2018
Available online 21 May 2018
0147-6513/ © 2018 Elsevier Inc. All rights reserved.
R. Urrutia-Goyes et al. Ecotoxicology and Environmental Safety 159 (2018) 198–204

2. Methods

2.1. Study area

Monterrey belongs to the state of Nuevo León, Mexico and is located


~700 km to the north of Mexico City. The city is divided by Santa
Catarina River and comprises several districts into one major urban
zone referred to as Monterrey Metropolitan Area –MMA. Monterrey is
considered a developed industrial city with a mix of commercial streets
and residential areas. Street dust samples were collected from high
traffic roadways across both densely populated areas and peripheral
zones. In total, samples were obtained from 44 locations according to
Fig. 1. Sampling locations in Monterrey, Mexico. Referenced on the field with a
Fig. 1 and analyzed for metal concentrations.
GPS. Greyed-out area denotes densely populated areas.

2.2. Sampling

In order to analyze the concentration of metals in street dust and Street dust samples were collected in August 2017. The sampling
soil, techniques such as inductively coupled mass spectrometry, X-ray process was completed throughout the day (20–30 °C), within one week
fluorescence (XRF), and atomic absorption have been used (OSHA, after several without any rain during the dry season. Specific locations
2014; USEPA, 2014). The advantages of using a portable XRF device can be seen in Fig. 1. Two plastic brushes (with thick and thin bristles
include multi-element analysis, immediate results, simple sample pre- respectively) were used to sweep street dust up onto a flat piece of
paration, and the ability to take non-destructive measurements in the paper and then placed into a zip locked plastic bag. Water and a cloth
field. The technique is based on the release of energy produced by the were used to clean tools after sampling to avoid cross contamination.
interaction between electrons and a radiation applied to the atoms of Each sample represents 400–800 g of dust from an area of approxi-
the sample. Such energy is detected and matched to signature spec- mately one square meter on road shoulders, at a distance of few cen-
trums that are element-dependent (USEPA, 2015; Weindorf et al., timeters away from the curb or gutter. Subsequently, samples were
2014). disaggregated, air-dried and stored in the laboratory at room tem-
The aim of this study is to characterize street dust from an over- perature.
populated city in Mexico by using portable XRF to assess any associa-
tion to natural or anthropogenic sources such as traffic or industry 2.3. Analysis
emissions, and to find any possible risks posed to the environment and
human health. To the best of our knowledge, the present study would Any vegetation and gravel-sized particles were removed from every
be first of its kind to intertwine sources, sinks, and repercussions in a street dust sample collected. Plastic bags were then poured out onto a
city from Mexico. This work can serve as a multidisciplinary example of 250 µm sieve. Samples were sieved and the resulting subsamples were
the sources and effects of pollution present in highly populated and placed into plastic bags (100 µm thickness) before homogenizing by
industrialized cities across the globe. mixing and rotating at 45 degrees. Shaking of the subsamples was
avoided since it produces stratification. The subsample in the bag was
then flattened to form a uniform layer of approx. 3 cm thickness. Loss of

Fig. 2. Box plots of (standardized) concentrations (in mg/kg) of the elements present in street dust in Monterrey.

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R. Urrutia-Goyes et al. Ecotoxicology and Environmental Safety 159 (2018) 198–204

Fig. 3. Spatial distribution and concentration (in mg/kg) of the elements present in street dust samples from Monterrey. Circles represent sampling locations.

material due to sieving was insignificant (Gerlach et al., 2002; Hall Tennessee, Knoxville, USA; XLSTAT 2017 from Addinsoft, Paris, France;
et al., 2014; Urrutia-Goyes et al., 2018, 2017). and The Unscrambler 10.1 from CAMO, Oslo, Norway. Among the
An Olympus Delta Premium 6000 PXRF analysis device was used to process run by these packages are descriptive statistics, principal
quantify the presence of metals. After factory- and laboratory-calibra- component analysis (PCA), cluster analysis (CA), spatial interpolation,
tion, the measurement window of the device was placed on top of the and human health risk assessment representation.
subsample and readings were taken for 90 s in soil mode to reach the
detection limits defined by the manufacturer. Certified Reference 2.5. Pollution Indicators
Materials (CRMs) NIST-2710a and NIST-2711a (from NIST®), and CRM-
023 and CRM-025 (from AccuStandards®) were used to evaluate the Pollution indicators Enrichment Factor (EF) and Geoaccumulation
accuracy of the measurements in addition to a blank sample that Index (Igeo) were calculated for the samples taken across the city. EF for
comprises silica sand (USEPA, 2007). After multiple readings and al- elements present in street dust samples was calculated using Mn as a
though results are element dependent, the calculated relative standard reference element since it showed low variability. EF and Igeo were
deviation values ranged from 1% to 21% and mean recoveries ranged calculated according to Eq. (1) and Eq. (2), where C and B are the
from 92% to 113%. Overall, the device was considered appropriate to concentrations of the studied element n and the reference element ref,
perform the required analysis. in the sample and in the background, respectively. Background values
for the studied elements were obtained from official local sources or
2.4. Statistics and spatial representation from reported concentrations in the earth's crust (Bourliva et al., 2016;
Muller, 1969; Rudnick and Gao, 2003; SGM, 2000).
Elemental concentrations were analyzed by descriptive statistics
and plotted. Correlations were assessed between variables. Data sets 2.6. Ecological and human health risk assessment
were also evaluated by principal component analysis (PCA) and cluster
analysis (CA) to define any relationship between variables from street Potential Ecological Risk Index (RI), Hazard Quotient (HR) and
dust samples. Spatial representation and statistical analyses were per- Cancer Risk (CR) were calculated for the city. RI was calculated ac-
formed by using software packages SADA 5.0 from The University of cording to Eq. (3), where Tri is the toxic response factor. HQ and CR

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3. Results and discussion

3.1. Total elemental concentrations

Street dust samples were analyzed and the following elements


showed concentrations above the limit of detection of the portable
XRF device: As, Ba, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Ti, Zn, and Zr.
Boxplots of the elemental concentrations can be seen in Fig. 2, after
standardizing in order to fit every plot under one scale for compar-
ison purposes. See Table S3 for a summary of descriptive statistics for
the elements found across the city. Mean values for As, Ba, Cu, Fe,
Mo, Ni, Pb, and Zn were above soil background values reported of-
ficially for Monterrey by local authorities (SGM, 2000), while Cr and
Zr showed values slightly below. Ti is the only element lacking a
previously reported soil background value and hence such compar-
ison is not possible. This provides a first indication of enrichment due
to either natural or anthropogenic sources. From Fig. 2, it can be
noted that most of the elements showed a log-normal tendency and a
positive skewness, which is typical for environmental variables. Also
elements Ba, Pb, Zn, and Zr showed the greatest range in con-
centrations suggesting a more heterogeneous distributions whereas
Cu, Fe, Ni, Mn, and Mo showed the shortest range in concentrations
suggesting a more homogeneous distribution. Among the elements
that showed distinctly high concentrations, Ba, Cu, Fe, Ti, and Zr,
can be related to their presence in tire breaks, as well as Mo, Sn, V,
Sr, and Pb in smaller quantities (Apeagyei et al., 2011). Thus some
influence of traffic in the composition of local road dust could be
suggested. Likewise, high concentrations of Zn might be related to
tire wearing besides (in smaller quantities) Fe, Ti, and Cr (Apeagyei
et al., 2011). Finally, in the case of Zn, measured concentrations
Fig. 4. a) PCA score plot of elemental concentrations of the first two principal showed values above soil thresholds recommended by local agencies
components and b) dendrogram for clustering of street samples from (SEMARNAT, 2006); and Ti showed up as the element with the most
Monterrey. notorious high concentration in spite of lacking a reported soil
background value for comparison.
A spatial representation of the most important detected elements
were calculated according to Eq. (4) and Eq. (5), based on their cor- can be seen in Fig. 3. High concentrations of metals in street dust can be
responding chronic daily intake (CDI), reference dose (RfD), and slope problematic since such elements do not degrade and their concentration
factor (SP) for three different exposure pathways, namely ingestion, can only increase with time or their subsistence can change from one
inhalation, and dermal contact. CDI values were calculated according to media to another i.e. rain water can wash street dust to some degree
Eqs. 6, 7 and 8 and to defined parameters (see Table S1). RfD and SP and particles might be transported to nearby water streams (Marrugo-
values are element dependent (see Table S2) (De Miguel et al., 2007; Negrete et al., 2017). As can be noted, some higher-than-average con-
Ferreira-Baptista and De Miguel, 2005; Hakanson, 1980; USEPA, 2002, centrations were measured for As, Ba, Cr, Ni, Pb, and Zn in the central
1989). and central-eastern areas of the city. Similarly, Ti shows anomalous
high concentrations across the entire central-southern area of the city.
(Cn/ Cref ) sample
EF = Additional relationships and the nature of these metals are discussed
(Bn / Bref )background (1) below.

Cn ⎞ 3.2. Correlations and PCA/CA


Igeo = log 2 ⎛⎜ ⎟

⎝ ×Bn ⎠
1.5 (2)
Pearson correlation coefficients for the analyzed elements were
7 C calculated (see Table S4). Some positive and relatively strong cor-
RI = ∑i =1 Tri ⎛ n ⎞
⎜ ⎟

⎝ Bn ⎠ (3) relations (p < 0.05) were found among Ba, Fe, Mn and Zr; Cr, Fe,
and Zr; Fe and Zn; Fe and Zr; Ni and Mn; As and Pb; Ba and Mn;
HQ = CDI /RfD (4)
suggesting similar sources for their release. On the other hand, weak
CR = CDI × SF (5) relationships were found for Ti and the rest of the elements showing
origins more unique for this element. Detailed analysis based on PCA
Ring × EF × ED and CA might help with the identification of shared sources and is
CDIing = Cexp × × 10−6
BW × AT (6) hence necessary.
Rinh × EF × ED Two principal components explained more than 90% of the total
CDIinh = Cexp × variance. Principal component 1 explained 85% of the total variance
PEF × BW × AT (7)
and confirms that Ti and Zn have a distinct source of release (see
SA × SAF × ABS × EF × ED Fig. 4.a). On the other hand, Ba, Cr, Cu Pb, Ni, and Zr appear to a
CDIdermal = Cexp × × 10−6
BW × AT (8) have a common origin. Additionally, hierarchical cluster analysis

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Fig. 5. Boxplots of EF and Igeo indicators for the studied elements in street dust in Monterrey.

was applied to the data set in order to identify similar groups ac- pads wearing. Chemical elements, such as As, Cr, Ni, and Pb could
cording to concentrations. Fig. 4.b shows a dendrogram where three have different industrial sources since they also show high con-
main clusters can be recognized. Again, Ti seems to have an in- centrations.
dependent source since it shows the greatest dissimilarity, whereas
Ba, Cu, Pb, and Zr appear in a different cluster confirming their 3.3. Pollution Indicators
shared origin from braking pads.
Correlation analysis, PCA and CA have led to the conclusion that In order to prove that anomalous concentrations occur due to nat-
elements with similar sources can be grouped as follows: Ti as an ural or anthropogenic sources, pollution indicators EF and Igeo were
independent element possibly from wearing of brake pads and in- calculated. Enrichment factors greater than 10 and geoacummulation
dustry releasing; Zn and Fe released from tire wear dust and heavy indicator values greater than 1 suggest anthropogenic sources. Fig. 5
traffic across the city; and Ba, Cu, Fe, Pb, and Zr released from brake shows box plots for EF and Igeo calculated for every element considered

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3.4. Ecological and health risk

Potential Ecological Risk Index (RI) allows to evaluate the potential


adverse ecological effects of trace metals in soils. Calculated values
above 150 define a moderate risk, above 300 a considerable risk, and
above 600 a high ecological risk. The toxic response factor (Tri) is de-
fined as a 10, 2, 30, 5, 1, 5, and 5 for As, Cr, Cd, Cu, Zn, Pb, and Ni.
Since Cd concentrations were under the detection limits of the tech-
nique, they are not included in the analysis. The calculated global RI for
the city was 158.44 (by using mean values), which defines a moderate
ecological risk. However, a point by point analysis can also be held to
determine the risk spatially. Fig. 6.a shows RI values across the city of
Monterrey. Although there are no zones that show an RI value greater
than 300, the area showing a moderate ecological risk is widespread
and three different hot spots for higher risk are defined. Southern,
central and central-eastern regions of the city need precautions re-
garding heavy metal concentrations producing ecological risks. It is
worth noting that the central and central-eastern hotspots are close to
‘Niños Héroes Park’ and ‘La Pastora’, respectively. Both are public areas
in the city where people gather for leisure and a significant number of
plant and animal species can be found.
Table 1 shows health risks calculated for population of the city. The
corresponding contribution for each exposure pathway is included for
Hazard Quotient (HQ) values. It can be readily noted that values re-
garding ingestion are the greatest and hence such exposure pathway is
the main concern. Although all the HQ values are smaller than one, the
total HQ value is slightly below one. Likewise, in the case of Pb, HQ
values for children are fairly close to such limit and awareness must be
raised among local authorities to maintain a proper monitoring of these
indicators. As can be seen in Fig. 6.b-c, HQ values for Pb for adults show
areas of concern with values reaching the unity, but the equivalent re-
presentation for children, shows some hotspots with HQ values already
greater than one and hence posing a non-carcinogenic risk. The two
hotspots in the central and central-eastern areas are located either in
industrialized or heavy-traffic zones, and are very close to public spaces
where children can be greatly exposed. On the other hand, Cancer Risk
(CR) values was in the tolerable zone for As (CR=2.50E-05) while the
rest of the elements did not produce any carcinogenic risks to report.

4. Conclusion

In this study, dust samples from the streets of an overpopulated city


were analyzed for heavy metals. Elemental characterization has shown
high concentrations of As, Ba, Cu, Fe, Mo, Ni, Pb, Ti, and Zn.
Correlation analysis, PCA, CA, and pollution indicators EF and Igeo have
led to the conclusions that Zn and Fe concentrations are related to tire
wearing; Ba, Cu, Fe, Pb and Zr relate to brake pads wearing; Mo, Ni, Pb,
and Ti show additional undefined anthropogenic sources, possibly re-
Fig. 6. Spatial distribution across Monterrey of a) potential ecological risk
lated to industrial emissions; and As suggests and undefined natural
index (RI); and non-carcinogenic risk index HQ due to Pb presence in street dust
for b) adults and c) children.
source. Ecological risk in the city was found to be moderate with three
hot spots of higher risk defined across the region. Finally, four hot spots
of non-carcinogenic risk due to Pb was found for children. Monterrey is
a highly populated city and although high traffic can be found all
in this study, excluding Ti since no background values have been re- across, the location of such hotspots are close to public places and hence
ported yet. Significant, very high, or extremely high enrichment can immediate action should be taken in order to alleviate the risks posed
readily be seen for Ba, Cu, Mo, Ni, Pb and Zn. Results in this study show both to the environment and the population.
that anthropogenic activities are the main reason for the presence of This study has identified and documented pollution and ecological
these metals. Additionally, pollution categories moderate, moderate to and human health risks due to the presence of metals in street dust in
heavy, and heavy are reported for the same elements, confirming the Monterrey, Mexico. Efforts must be undertaken by the authorities in
last statements. This way, it has been confirmed that high traffic and order to apply policies regarding monitoring of indicators seeking the
industrial activities are responsible for releasing and depositing high health of the whole population and the environment. Similar studies
quantities of metals in the city producing high levels of pollution. can be carried out in cities with an excessive automobile traffic.
However, some elements such as Mo, Ni, and Pb suggest additional Suggested further research include the definition of background values
unidentified industrial origins; and other elements such as As and Zr for Ti, and temporal studies that allow to define the change in con-
suggest unidentified natural origins. centration of the elements, possible migrations, and effects in other
media.

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Table 1
Health risks for adults and children due to exposure to the studied elements in street dust in Monterrey.
Element Concentration Ingestion Inhalation Dermal Total

Hazard (Adult) Hazard (Child) Hazard (Adult) Hazard (Adult) Hazard (Adult)

As 10.11 4.60E- 02 4.30E- 01 7.10E- 06 6.00E- 03 5.20E- 02


Ba 265.51 5.20E- 03 4.80E- 02 3.70E- 04 3.90E- 03 9.50E- 03
Cr 101.47 4.60E- 02 4.30E- 01 7.20E- 04 1.20E- 01 1.70E- 01
Cu 167.03 5.70E- 03 5.30E- 02 8.80E- 07 1.00E- 03 6.70E- 03
Mn 398.46 1.20E- 02 1.10E- 01 5.60E- 03 1.60E- 02 3.30E- 02
Mo 6.27 1.70E- 03 1.60E- 02 2.50E- 07 2.40E- 04 2.00E- 03
Ni 52.84 3.60E- 03 3.40E- 02 4.10E- 04 7.10E- 04 4.70E- 03
Pb 226.85 8.90E- 02 8.30E- 01 1.30E- 05 3.10E- 02 1.20E- 01
Zn 649.41 3.00E- 03 2.80E- 02 4.40E- 07 7.90E- 04 3.80E- 03
Total 2.50E- 01 2.40E+ 00 3.80E- 01 2.10E- 01 8.50E- 01

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