Microchemical Journal 152 (2020) 104265

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Microchemical Journal
journal homepage: www.elsevier.com/locate/microc

Exploratory analysis of the atmospheric levels of BTEX, criteria air T

pollutants and meteorological parameters in a tropical urban area in
Northeastern Brazil
Lícia P.S. Cruza, , Daniela F. Santosa, Ivanice F. dos Santosb, Ícaro V.S. Gomesa,
⁎

Akácia V.S. Santosa, Keliane S.P.P. Souzaa

a
Analytical Chemistry Department, Chemistry Institute, Federal University of Bahia, Campus Universitário de Ondina, 147, 40170-270 Salvador, Bahia, Brazil
b
Department of Exact Science, State University of Feira de Santana, 44036-900 Bahia, Brazil

ARTICLE INFO ABSTRACT

Keywords: Air pollution is responsible for serious damage to the environment and to the health of the population. The
BTEX objective of this study was to apply chemometric methods to determine and evaluate the relationships between
PCA the atmospheric concentrations of BTEX (benzene, toluene, ethylbenzene and xylene) compounds, criteria air
HCA pollutants and meteorological parameters, as well as to identify the type of emission source associated with these
Criteria air pollutants
pollutants at seven sites in the city of Salvador, Bahia, Brazil during rainy and dry periods. BTEX compounds
Interspecies ratios
were monitored using passive samplers with a solvent desorbable adsorbent (activated charcoal) for 14 days and
Urban air quality
determined by gas chromatography with flame ionization detection. Criteria air pollutants were determined
using automatic continuous analyzers and the meteorological parameters by means of multi-parameters sensors.
The average data obtained were submitted to multivariate analysis, using principal component analysis (PCA)
with varimax rotation and hierarchical cluster analysis (HCA). Some diagnostic ratios between the BTEX species,
besides correlation analysis between the pollutants and meteorological parameters were also used to identify the
origin of the emissions. The sum of average concentrations of BTEX compounds was lower in the dry period
(5.90 ± 3.28 μg m−3) than in the rainy period (7.95 ± 2.95 μg m−3), probably due to higher values of
temperature and solar radiation which favor photochemical reactions in the dry period, thereby increasing the
rate of removal of the BTEX compounds from the atmosphere. The first three principal components together
(PC1, PC2 and PC3) explain 80.1% of the total data variance, with a tendency to separate the samples into two
groups, depending on the seasonal period. According to HCA, four main groups were formed with high degrees
of similarity. Strong correlations were found among BTEX species, and between these compounds with CO, NO,
and NO2, thus indicating a common emission source for these compounds, the vehicular fleet. Toluene/benzene
(T/B), m,p-xylene/benzene (m,p-X/B) and o-xylene/benzene (o-X/B) ratios suggested that vehicular emissions
constituted the main source of BTEX compounds. PCA and HCA results also confirmed these observations.

1. Introduction Urban air pollution has significant regional-scale impacts on human

The atmosphere absorbs a large amount of solid, liquid or gaseous
compounds from both natural and anthropogenic sources. According to
local characteristics, they can be dispersed, transformed or transported
and subsequently deposited by wet or dry processes. The dynamics of
this system depend mainly on atmospheric reactions, removal me-
chanisms, and meteorological and topographic conditions [1].
Urban expansion with the growing fleet of vehicles in circulation,
and the increase of industrial activities in urban areas are associated
with fuel consumption demand, resulting in air quality degradation.
health, ecosystems productivity, and reduced visibility. In addition, it
can promote global-scale changes in climate, ozone depletion and in-
creased oxidative capacity of the atmosphere [2,3].
Several pollutants can be emitted into the atmosphere in urban
areas, such as: particulate matter (PM), classified according to particle
diameter as PM10 (<10 μm), PM2.5 (<2.5 μm) and ultra-fine particles
(<0.1 μm), resulting from incomplete burning of fuels and their ad-
ditives, as well as brake and tyre wear [4]; and gaseous pollutants such
as sulfur dioxide (SO2), from oxidation of sulfur present as impurity in
some fuels; carbon monoxide (CO), produced by partial oxidation of

⁎
Corresponding author.
E-mail address: lila@ufba.br (L.P.S. Cruz).

https://doi.org/10.1016/j.microc.2019.104265
Received 28 June 2019; Received in revised form 12 September 2019; Accepted 14 September 2019
Available online 15 October 2019
0026-265X/ © 2019 Elsevier B.V. All rights reserved.
L.P.S. Cruz, et al.
Fig. 1. Sampling sites in the city of Salvador, Bahia, Brazil.
hydrocarbons; nitrogen oxides (NOx = NO + NO2), obtained by in-
ternal combustion in engines, under conditions of high temperatures
and pressures [5,6]; volatile organic compounds (VOCs) constituting an
important group of compounds with boiling point below 250 °C at
ambient atmospheric pressure including aromatics, aliphatics, alde-
hydes, ketones, ethers, carboxylic groups and alcohols [7]; and tropo-
spheric ozone (O3), a secondary pollutant formed through reactions
involving VOCs and NOx, in the presence of sunlight [8]. Various stu-
dies have demonstrated scientific evidence of the relationship between
these air pollutants and the negative impacts on human health [9–11].
It is estimated that approximately 35% of all VOCs emissions into
the atmosphere come from vehicular sources [12]. Among these com-
pounds, the most abundant in urban environments are BTEX com-
pounds (benzene, toluene, ethylbenzene and m,p,o-xylenes). These
compounds have a harmful impact on human health, because they are
toxic [13] and, in the case of benzene, it is classified as carcinogenic to
humans (Group 1) by the International Agency for Research on Cancer
(IARC), associated with myeloid leukemia, besides causing neurolo-
gical, endocrine and immune changes [14,15].
BTEX compounds in the gas phase are degraded mainly by photo-
lysis and/or chemical reactions with reactive species such as hydroxyl
radical – OH (diurnal reactions) and nitrate radical – NO3 (nocturnal
reactions). In these reactions there is the formation of free radicals such
as organic peroxy (RO2) and hydroperoxy (HO2) which favor the
transformation of NO into NO2, contributing to the increase of tropo-
spheric ozone. Therefore, BTEX compounds have a great influence on
atmospheric chemistry, since they are considered important precursors
in forming oxidizing substances such as O3 and peroxyacetyl nitrate
(PAN), as well as secondary organic aerosols (SOA) [16,17].
BTEX emissions in urban areas can be used as indicators of organic
air pollutants from vehicular emissions. Benzene originates pre-
dominantly from these sources and is considered a marker of vehicular
exhaust and evaporative emissions [18]. Particularly, the toluene/
benzene (T/B) ratio is widely used as an indicator of these emission
sources and some studies report T/B values lower than 3 as a char-
acteristic of vehicular emissions in various locations around the world
[19,20]. In addition, other ratios are considered as vehicle emissions
indicators such as m, p-xylene / benzene (m, p-X /B) and o-xylene /
benzene (o-X/B) [19].
Chemometrics is extensively used to perform classification, cali-
bration and exploratory analysis, and can be divided in supervised and
unsupervised methods. Unsupervised statistical methods are used to
study the data structure, to determine similarities between the samples
2
Microchemical Journal 152 (2020) 104265
and to check outliers in the data set. Principal Component Analysis
(PCA) and Hierarchical Cluster Analysis (HCA) are the most widely
used tools to explore similarities and patterns between samples, al-
lowing to obtain a greater amount of information [21,22]. In recent
years, these tools have also been used in atmospheric chemistry to
evaluate air quality by identifying possible relationships between dif-
ferent air pollutants and meteorological parameters as well as to in-
dicate emission sources [12,23–28].
The aim of this study was to apply multivariate techniques to de-
termine and evaluate the relationships between the concentrations of
the BTEX compounds, criteria air pollutants (CO, NO2, NO, NOx, O3 and
PM10) and the values of meteorological parameters (wind speed, re-
lative humidity, precipitation, temperature and solar radiation), as well
as to identify the type of emission source associated with these pollu-
tants, during two different periods of the year (rainy and dry), at seven
sites impacted by the vehicular fleet in the city of Salvador, Bahia, in
northeastern Brazil, contributing to the assessment of the air quality.
2. Material and methods
2.1. Description of the urban area
Salvador, the capital of Bahia state, is located in a peninsular area of
361 km2 on the northeast coast of Brazil (12°58′16" S and 38°30′39" W).
It has a humid tropical climate and predominant winds in the east
quadrant (SE, E and NE), receiving air masses from the Atlantic Ocean
most of the time and little influence from industrial emissions. The
average annual rainfall is above 1700 mm, with higher precipitation
occurring between the months of April and August (rainy period) and
lower in the months of September to March (dry period) [27]. This city
has around 3.0 million inhabitants and an expressive vehicular fleet
causing constant traffic jams, totaling 996,931 vehicles until May 2019
[29], which corresponds to about one vehicle for every three in-
habitants.
Seven sampling points S1–S7 (Fig. 1) were selected considering
traffic density and proximity to the air quality monitoring network
stations in the city of Salvador. The S1 site is a low traffic region im-
pacted mainly by the flow of light vehicles, S2 and S3 sites are inter-
mediate traffic regions affected mostly by intense flow of public
transport (buses), S4 and S6 sites are high traffic regions impacted by
an intense flow of public transport and light vehicles, and finally the S5
and S7 sites are mainly affected by an intense flow of heavy vehicles.
L.P.S. Cruz, et al.
Table 1
Statistical summary (average, minimum and maximum) of the BTEX concentrations (μg m−3) in the city of Salvador during dry and rainy periods.
BTEX Dry Period
Average ± SD Median Min
Benzene 1.55 ± 0.99 1.27 0.46
Toluene 2.47 ± 1.49 2.52 0.49
Ethylbenzene 0.64 ± 0.25 0.53 0.42
m,p-Xylene 0.72 ± 0.41 0.72 0.34
o-Xylene 0.52 ± 0.14 0.47 0.44
ΣBTEX 5.90 ± 3.28
2.2. Sampling and analytical methods for BTEX determination
BTEX compounds were sampled simultaneously at seven different
urban sites in Salvador for 14 days during two different periods, 2014/
07/14-28 (rainy season) and 2014/11/28–2014/12/12 (dry season),
using Radiello® passive samplers manufactured by Fondazione
Salvatore Maugeri (Padova, Italy). These samplers consist of a cylind-
rical adsorbing cartridge inserted in a cylindrical diffusive body of
microporous polyethylene. The cartridge used was a stainless steel cy-
linder, with 100 mesh grid opening and 5.8 mm diameter, packed with
530 ± 30 mg of 35–50 mesh activated charcoal. Other studies have
also used Radiello® passive samplers (chemically or thermally deso-
rbable) for monitoring air quality [12,24,30,31].
The analytes, chemically desorbed with carbon disulfide (CS2), were
analyzed in a gas chromatograph (7820A GC System, Agilent) equipped
with a flame ionization detector (FID). Chromatographic conditions
used for the quantification of the BTEX compounds were described in a
previous study [32].
2.3. Measurements of criteria air pollutants and meteorological parameters
In the city of Salvador, the Environmental Protection Company
(CETREL) is responsible for the operation of the air quality monitoring
network. Automatic monitoring stations are located in urban areas;
however, BTEX compounds have been not monitored, because the
Brazilian environmental legislation [33], which establishes national air
quality standards in outdoor environments, does not define standards
for these compounds.
On-line automatic analyzers manufactured by Environnement, fre-
quently calibrated, were employed to monitor the following criteria air
pollutants at these stations: nitrogen oxides (NOx = NO + NO2) and O3
were measured by using chemiluminescence method, while CO and
PM10 by infrared and by optical properties, respectively. Meteorological
parameters (wind direction and speed, relative humidity, temperature,
precipitation and solar radiation) were also monitored using Met One's
multiparameter sensors.
The average concentrations of criteria air pollutants and the average
values of meteorological parameters in each sampling period were
provided by CETREL. Information concerning criteria air pollutants
concentrations and values of air temperature, wind speed, relative
humidity (average, and minimum and maximum) during the sampling
periods are presented in the Supplementary File (Supplementary
Information, Table S1).
2.4. Statistical analysis
Principal component analysis (PCA) and hierarchical cluster ana-
lysis (HCA) belong to exploratory data analysis. PCA is an important
method in multivariate data analysis and has two main applications:
visualization of multivariate data and data reduction and transforma-
tion. Two- or three-dimensional projection of samples is usually con-
structed using the axes as factors for visual analysis. Each PC is a linear
combination of the original responses and the PCs are orthogonal to
each other. HCA is a method which allows grouping of samples based
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Microchemical Journal 152 (2020) 104265
Rainy Period
Max Average ± SD Median Min Max
2.73 2.05 ± 0.82 1.76 1.06 3.38
4.37 3.18 ± 0.97 3.06 1.70 4.44
1.11 1.00 ± 0.42 0.95 0.46 1.64
1.45 1.04 ± 0.43 0.93 0.52 1.79
0.82 0.68 ± 0.31 0.49 0.45 1.13
7.95 ± 2.95
on their similarities or differences. The HCA result is usually presented
in a dendrogram, a tree-like graph that shows the organization of
samples and their relationships [21,22].
The correlations between the average concentrations of the mea-
sured BTEX compounds and data provided by the air quality monitoring
network of the city of Salvador (mean concentrations of the criteria air
pollutants and mean values of meteorological parameters) were eval-
uated in seven sampled points. The data were submitted to multivariate
analysis, applying PCA with Varimax rotation and HCA, using the
Statistica software 7.0 [34] with data pre-processed by autoscaling. The
letters R and D were used to define the rainy and dry periods, respec-
tively. Pearson's correlation coefficients were also used to quantify as-
sociations between two variables.
3. Results and discussion
3.1. Concentrations of the BTEX compounds
A statistical summary of BTEX concentrations measured in the city
of Salvador during dry and rainy periods is presented in Table 1. The
results presented herein demonstrate that toluene had the highest
concentration, followed by benzene, m,p-xylene, ethylbenzene and o-
xylene compounds in both periods.These observations are consistent
with previous studies where toluene was the most abundant pollutant
among BTEX compounds in the atmosphere of urban areas [24,35–38].
The main process of degradation of BTEX compounds in the atmo-
sphere is through photochemical reactions with OH radicals. Benzene,
toluene and ethylbenzene have atmospheric lifetimes of 9.4, 1.9 and 1.6
days, respectively, assuming [OH] = 106 molecules cm−3. Benzene is
the most stable species in the atmosphere because it has a longer at-
mospheric lifetime and therefore a lower reactivity, followed by to-
luene. Xylenes are considered the most reactive species and generally
remain in the atmosphere for a short time, having atmospheric lifetimes
of 20.3 h (o-xylene), 19.4 h (p-xylene) and 11.8 h (m-xylene) [1,39].
Benzene and toluene with lower reactivities remain in the atmo-
sphere longer and can be transported over long distances, up to tens of
kilometers without degradation. Thus, these compounds can also have
been from other regions and transported to the sampling sites, resulting
in higher concentrations. Studies indicate strong evidence that toluene
is also emitted by plants [40–42], which may also justify the higher
concentrations found for this compound when compared to the con-
centrations of the other compounds in the city of Salvador, because the
toluene, besides being emitted from the vehicular fleet, can also have
been emitted from biogenic sources from neighbouring regions and
transported to the sampling sites. The low concentrations of the xylenes
can be attributed to the higher reactivity of these compounds in the
atmosphere.
As shown in Table 1, benzene levels were 0.46–2.73 and
1.06–3.38 μg m−3; toluene levels were 0.49–4.37 and
1.70–4.44 μg m−3; ethylbenzene levels were 0.42–1.11 and
0.46–1.64 μg m−3; m,p-xylene levels were 0.34–1.45 and
0.52–1.79 μg m−3; and o-xylene levels were 0.44–0.82 and
0.45–1.13 μg m−3, in the city of Salvador in the dry and rainy periods,
respectively. For benzene, which is carcinogenic to humans, the
L.P.S. Cruz, et al. Microchemical Journal 152 (2020) 104265

Table 2 bathed by the All Saints Bay and the Atlantic Ocean (Fig. 1), thereby
Loadings of 16 variables on the first three principal components. making relative humidity values are high throughout the year. More-
PC1 PC2 PC3 over, according to data obtained from the air quality monitoring net-
work, the wind speed values had little variation in both sampled per-
Benzene 0.175 0.120 0.887 iods, with a small increase during the dry period (Table S1).
Toluene 0.182 0.135 0.832
However, average solar radiation values of 1107 KJ m−2 and
Ethylbenzene 0.047 0.392 0.827
m,p-Xylene 0.280 0.177 0.932
2216 KJ m−2 in the rainy and dry periods, respectively, indicate that
o-Xylene 0.135 0.205 0.846 there was a significant variation in this parameter, with an increase of
CO 0.757 −0.139 0.365 more than 100% in the dry period. Therefore, the trend of decreasing
O3 −0.759 0.362 0.269 BTEX concentrations observed in the urban areas of the city of Salvador
PM10 0.354 0.138 0.627
during the dry period is probably related to the increase of BTEX de-
NO 0.831 0.057 0.388
NOx 0.877 0.142 0.356 gradation through photochemical reactions, increasing the removal rate
NO2 0.769 0.384 0.139 of these compounds from the atmosphere, and thus reducing BTEX
Wind Speed −0.277 −0.081 0.107 concentrations in this period. These observations are also confirmed by
Temperature −0.119 −0.848 −0.406
other studies [35,36].
Humidity −0.174 0.946 −0.021
Preciptation 0.114 0.936 0.239
Furthermore, although average temperatures in this city are high in
Radiation −0.082 −0.957 −0.175 both periods (24 °C and 27 °C in the rainy and dry periods, respec-
Variance% 45.8 21.5 12.8 tively), the maximum temperature values can reach 32 °C in the dry
Cumulative variance % 67.3 80.1 period (Table S1), favoring photochemical reactions [54–56].
Eigenvalue 7.32 3.44 2.05

3.2. Multivariate analysis

concentrations found in this city are below ambient air quality and
cleaner air for Europe limit of 5 μg m−3 [43]. However, the maximum
concentrations of benzene in both periods exceed a more restricted
value (2.30 μg m−3) according to Ambient Air Quality Criteria (AAQCs)
developed by the Ontario Ministry of the Environment (OME) [44].
The concentrations of BTEX compounds found in this study are
lower when compared to other studies carried out elsewhere in the
world (India, China, Greece, Thailand) [37,45–47], but are comparable
to studies conducted in other Brazilian cities in recent years
[25,41,48–50]. The justification for this fact should be associated with
the regulations on vehicle emissions adopted in Brazil through the
Program for Control of Air Pollution by Motor Vehicles (PROCONVE)
and other specific environmental laws, emission control technologies,
use of alternative fuels and improvements in fuel quality [51]. In ad-
dition, the city of Salvador has a privileged geographical position be-
cause it is located on the Atlantic Ocean coast, allowing the penetration
of trade winds from east to the interior of the city, favoring a good
dispersion of the air pollutants.
The distribution of BTEX fractions in the atmosphere was similar
during the two sampling periods, being 26%, 42%, 11% and 21% in the
dry period, and 25%, 40%, 13% and 24% in the rainy season, con-
sidering the compounds benzene, toluene, ethylbenzene and sum of
xylenes, respectively. Similar results were obtained in the city of Rio de
Janeiro, in southeastern Brazil, with values of 11% for benzene and
ethylbenzene, 48% for toluene and 21% for xylenes [25]. Different fuels
are commonly used in Brazil, such as: diesel with 10% biodiesel, hy-
drated ethanol, compressed natural gas and gasohol – gasoline blends
with 25–27% v/v of anhydrous ethyl alcohol as antiknock additive,
containing a maximum of 1.0% v/v of benzene and 35% v/v of aro-
matic hydrocarbons [27,52]. Such similarities in these two Brazilian
cities are possibly related to the type of emission source of these pol-
lutants, predominantly from light vehicles fleet (‘‘flex-fuel’’ vehicles)
that use mainly gasohol in addition to hydrated ethanol.
Table 1 also shows that the sum of the average concentrations of
BTEX compounds determined in the dry period (5.90 ± 3.28 μg m−3)
is lower than in the rainy period (7.95 ± 2.95 μg m−3). In cities with
temperate climate, variations in BTEX concentrations can also be at-
tributed to increased emissions during the winter due to combustion
processes for indoor heating. However, in cities with tropical climate
such as Salvador, indoor heating is not required, and the evaluation of
meteorological parameters helps to better understand the seasonal
variations, since these have influence on the BTEX compounds con-
centrations in urban areas, at different times of the year [53,54].
The city of Salvador is surrounded by a great water volume, as it is
In order to carry out the exploratory analysis, a data matrix was
generated (14 × 16) in which results of of sampling at the seven sites in
the rainy (RS1–RS7) and dry (DS1–DS2) periods were arranged in lines,
while the informations about BTEX variables (benzene, toluene, ethyl-
benzene, m,p-xylene and o-xylene), criteria air pollutants (NO, NO2,
NOx, CO, O3 and PM10) and meteorological parameters (wind speed,
temperature, relative humidity, precipitation and solar radiation) were
disposed in columns. Autoscaling was chosen as pre-processing due to
the different orders of magnitude of these variables. The PCA was
performed with Varimax rotation, because it allowed a better data in-
terpretation.
The first three principal components (PC1, PC2 and PC3) were se-
lected for data characterization, as they presented eigenvalues greater
than 1 and together explain 80.1% of total data variance, as shown in
Table 2. PC1 and PC2 can explain 67.3% of the data variance, i. e., more
than half of the variance is described.
PC1 has accumulated 45.8% of the data variance. The variables that
most contributed to data characterization were the criteria air pollu-
tants (NO, NOx, NO2, O3 and CO), because these are the variables
which had the largest absolute loadings for this PC (Table 2 and Fig. 2).
Nitrogen oxides and CO are negatively correlated with O3, meaning the
higher the ozone concentrations, the lower the nitrogen oxides and CO
concentrations. This was expected as these pollutants are precursors of
tropospheric ozone formation [8,25].
On the other hand, PC2 has accumulated 21.5% of the data variance
and presented only the influence of meteorological parameters – tem-
perature, solar radiation, relative humidity and precipitation – since
they are the variables with the highest absolute weights on this PC,
according to Table 2. The following correlations were verified: i) tem-
perature and solar radiation had positive correlation; ii) relative hu-
midity and precipitation had positive correlation; iii) temperature/solar
radiation and relative humidity/precipitation had negative correlation
(Table 2 and Fig. 2). Additionally, the wind speed had a low influence
on this PC, because it showed an absolute weight close to zero. The
direct relationship between temperature and solar radiation was due to
the fact that solar radiation is one of the factors influencing the tem-
perature of a site, so that the higher solar radiation intensity, the higher
the temperature. Moreover, relative humidity is related to the amount
of water in the atmosphere, which explains the direct relationship be-
tween precipitation and relative humidity.
It is also possible to observe in PC2 that BTEX compounds and
criteria air pollutants (NO, NOx, NO2, PM10 and CO) presented negative
correlations between temperature and solar radiation, whereas positive
correlations between relative humidity and precipitation were verified

4
L.P.S. Cruz, et al.
Fig. 2. Plot of loadings (PC1 versus PC2) of the 16 variables.
(Fig. 2). The increase in temperature and solar radiation favor photo-
chemical reactions, mainly involving hydroxyl radical, resulting in in-
creased degradation of BTEX, nitrogenous compounds and CO in the
atmosphere, leading consequently to a decrease in their concentrations
and an increase of tropospheric ozone concentration, which is one of
the pollution problems in urban areas [36,55,56].
Regarding PC3, 12.8% of data variance was accumulated. It was
observed the BTEX compounds (benzene, toluene, ethylbenzene, m,p-
xylene and o-xylene) were the variables that most contributed to the
discrimination of the sample set, because they had the highest absolute
weights on this PC. These compounds were positively correlated
(Table 2), thereby indicating a common source for these compounds,
predominantly the vehicle fleet of the city of Salvador.
The graph of scores referring to the first two main components (PC1
and PC2) is shown in Fig 3. According to this figure and in relation to
PC2, it was possible to observe a tendency towards separation of the
samples into two groups, depending on the seasonal period. Samples
collected during rainy period (RS1–RS7) were displaced to the region of
positive scores, while those collected during the dry period (DS1–DS7)
were displaced to the region of negative scores.
A comparison between the graph scores (Fig 3) and the loading
graph (Fig. 2) shows that samples from the rainy period presented
higher values both for precipitation and relative humidity, whereas
samples from the dry period demonstrated higher values of temperature
and solar radiation. These four variables were those which most con-
tributed to the discrimination of samples in PC2, corresponding to
average values for temperature and solar radiation of 24 °C and
1107 W m−2, 27 °C and 2216 W m−2; and for precipitation and relative
humidity of 119 mm and 76%, 35 mm and 70% in the rainy and dry
periods, respectively. Besides, it can also be noted in PC2 that the BTEX
compounds exhibited higher average concentrations during the rainy
period than the dry period, as it is also shown in Table 1.
A very similar behaviour of the variables under study could also be
verified through the application of HCA. The grouping of data was
performed acoording to the Ward method, and the metric used to cal-
culate the degree of similarity was 1-Pearson's r distance. The result is
presented in the form of a horizontal dendrogram, where the vertical
5
Microchemical Journal 152 (2020) 104265
lines, or the y-axis, represent the groups united in descending order of
similarity, and the position of the line on the x-axis indicates the dis-
tances between the groups that were formed. Thus, the dendrogram
should be read from top to bottom (Fig. 4).
According to the dendrogram data (Fig. 4), it was possible to ob-
serve at a distance of 1.5 there was formation of 4 main groups. The
first group was formed by BTEX and PM10. The PM10 constituted an
isolated subgroup, while BTEX compounds represented the variables
which presented well established linear correlations (high degrees of
similarity), since they had the shortest 1-Pearson's r distance, signaling
that they came from the same emission source. The second large group
was formed by criteria air pollutants (CO, NO, NOx and NO2) also with
a high degree of similarity. These compounds are the precursors of
tropospheric ozone formation and are also directly related to vehicular
emissions in urban areas. There was also formation of a third group
consisting of ozone, relative humidity and precipitation, including a
subgroup due to the high similarity between relative humidity and
precipitation. Wind velocity, temperature and solar radiation re-
presented the fourth group, where temperature and solar radiation
were considered as a subgroup due to the high similarity of these me-
teorological parameters, corroborating with the data observed in the
PCs.
3.3. Pearson’ correlation of BTEX, criteria air pollutants and meteorological
parameters
A linear correlation matrix (Pearson) between data generated by
BTEX compounds, six criteria air pollutants and five meteorological
parameters is shown in Table 3. Results from the correlation analysis
show that BTEX compounds presented positive correlations ranging
from strong to very strong, thereby reaffirming that these compounds
probably come from the same source. In addition, BTEX compounds
were exposed to the same influence of meteorological parameters
during the sampling periods. They showed negative correlations with
temperature and solar radiation, indicating that these meteorological
parameters affect photochemical reactions involving these compounds
and contribute to reduce their concentrations in the atmosphere,
L.P.S. Cruz, et al. Microchemical Journal 152 (2020) 104265

Fig. 3. Plot of scores (PC1 versus PC2) for sampling sites of the city of Salvador during the rainy (RSx) and dry (DSx) periods.

Fig. 4. Dendrograms for BTEX compounds, six criteria air pollutants and five meteorological parameters obtained during rainy and dry periods in the city of
Salvador.

corroborating the data obtained in the PCs.
Nitrogen compounds (NO, NO2 and NOx), mainly from vehicular
emissions in urban areas, showed strong positive correlations with
BTEX compounds, suggesting these compounds were probably emitted
from the same source and presented similarities in the degradation
process in the atmosphere, again in accordance with data obtained in
the PCs.
Carbon monoxide (CO) is generated by incomplete combustion
processes of nearby vehicle engines and it has been used as an indicator
for vehicular emissions in urban areas [57]. Thus, as can be seen in
Table 3, CO presents a linear correlation ranging from strong to very
strong with BTEX compounds, hence confirming a common source for
these compounds in urban areas of the city of Salvador, predominantly
the vehicular fleet.
3.4. Ratios between BTEX compounds
The ratios of toluene/benzene (T/B), (m,p)-xylene/benzene (m,p-X/
B) and o-xylene/benzene (o-X/B) are commonly used for the determi-
nation and evaluation of the type of emission source associated with

6
L.P.S. Cruz, et al. Microchemical Journal 152 (2020) 104265

Table 3
Linear correlation matrix for BTEX compounds, six criteria air pollutants and five meteorological parameters.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

1-B 1
2-T 0.98 1
3-E 0.85 0.79 1
4-m,p-X 0.89 0.95 0.82 1
5-o-X 0.80 0.84 0.98 0.86 1
6-CO 0.67 0.75 0.69 0.85 0.69 1
7-O3 0.02 0.48 0.34 0.51 0.45 −0.43 1
8-PM10 0.51 0.51 0.51 0.73 0.65 0.48 −0.01 1
9-NO 0.5 0.56 0.66 0.63 0.58 0.81 −0.43 0.65 1
10-NOx 0.60 0.59 0.5 0.61 0.64 0.8 −0.44 0.62 0.98 1
11-NO2 0.58 0.60 0.62 0.67 0.56 0.74 −0.31 0.32 0.62 0.76 1
12-WS −0.18 -0.16 −0.12 −0.22 −0.15 −0.29 0.11 −0.23 −0.32 −0.32 −0.24 1
13-T −0.62 −0.61 −0.67 −0.77 −0.69 −0.18 −0.33 −0.41 −0.34 −0.39 −0.45 0.54 1
14-RH 0.07 0.05 0.36 0.08 0.17 −0.29 0.4 0.04 −0.11 −0.04 0.19 0.14 −0.75 1
15-PPT 0.70 0.75 0.50 0.68 0.72 −0.04 0.4 0.3 0.13 0.2 0.37 −0.05 −0.86 0.87 1
16-SR −0.48 −0.52 −0.57 −0.65 −0.60 −0.01 −0.32 −0.36 −0.22 −0.28 −0.38 0.15 0.89 −0.87 −0.98 1

WS: wind speed; T: temperature; RH: relative humidity; PPT: precipitation; SR: solar radiation; in bold: significant correlation (r > | 0.50 |); strong correlation
(0.60 ≤ | r | < 0.80); very strong correlation (0.80 ≤ | r | < 1.0).

Fig. 5. Concentrations ratios of toluene/benzene (T/B) versus m,p-xylene/benzene (m,p-X/B) and versus o-xylene/benzene (o-X/B).

these pollutants [58]. Fig. 5 shows these ratios obtained for each
sampling point in the rainy and dry period. The ratios of T/B < 2.7, m,
p-X/B < 1.8 and o-X/B < 0.9 are indicative of vehicular emissions
sources [20,58] and were the rations adopted in this study. All data
achieved were below these limit values, which confirms that BTEX
compounds were emitted from the same source, predominantly vehi-
cular emissions.
The ratios between toluene and benzene (T/B) found in the city of
Salvador were similar to those found in other cities, such as: Cairo
(1.29–2.45), Gdansk (1.43) and Caracas (2.04) [20,56,59], indicating
that the main source of benzene and toluene in these cities was the
vehicular fleet. Possible differences in these ratios may reflect the dif-
ferences between type and age of vehicles, composition, type and
quality of the fuels, influence of meteorological parameters, industrial
activities and gas stations near monitoring areas [54,60].
The ratios between m,p-xylene and ethylbenzene (m, p-X/ E) are
used to investigate the degree of photochemical reactivity of these
compounds in the atmosphere, because the photochemical reactivity of
the m,p-xylene is larger than of ethylbenzene [39,58]. The m,p-X/E
ratios have a tendency to increase with increased temperature and solar
radiation due to enhanced photochemical activity [53]. In this study, it
was observed that during dry period, in some sites, there was an in-
crease in the m,p-X/E ratios (Table 4), contributing to the formation of
tropospheric ozone. The m, p-X/E ratios showed in general low varia-
bility between the different sites for each sampling period, indicating
the existence of a common emission source throughout the region,
which is also reinforced by the strong correlation between these com-
pounds, as demonstrated by the Pearson correlation (Table 3).
4. Conclusions
In this study, concentrations of BTEX compounds were measured for
the first time in the city of Salvador. The relationships between the
concentrations of these compounds, criteria air pollutants and me-
teorological parameters were determined in two different periods
(rainy and dry) using PCA and HCA analyses.

7
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