Science of the Total Environment 463464 (2013) 639646

Contents lists available at ScienceDirect

Science of the Total Environment

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

Healthy environment indoor air quality of Brazilian elementary

schools nearby petrochemical industry
Ricardo H.M. Godoi a,, Ana F.L. Godoi a, Srgio J. Gonalves Junior a, Sarah L. Paralovo a,
Guilherme C. Borillo a, Cybelli Gonalves Gregrio Barbosa a, Manoela G. Arantes a, Renata C. Charello a,
Nelson A. Rosrio Filho b, Marco T. Grassi c, Carlos I. Yamamoto d, Sanja Potgieter-Vermaak e,
Giuliana G. Rotondo f, Karolien De Wael f, Rene van Grieken f
a
Department of Environmental Engineering, Federal University of Paran UFPR, Curitiba, PR, Brazil
b
Department of Pediatric, Div. of Allergy & Pneumol, Federal University of Paran Curitiba, PR, Brazil
c
Department of Chemistry, Federal University of Paran, Curitiba, PR, Brazil
d
Department of Chemistry Engineering, Federal University of Paran, Curitiba, PR, Brazil
e
Division of Chemistry and Environmental Science, School of Science and the Environment, Manchester Metropolitan University, Manchester, UK
f
Department of Chemistry, University of Antwerp, Universiteitsplein 1, B-2610 Antwerp, Belgium

H I G H L I G H T S

Pollution in school environment can impact children's health, being critical to evaluate it.
Five schools were selected in Curitiba, Brazil to measure pollutants levels, in 20092011.
Results are interpreted aiming to identify compounds that could affect the scholars' health.

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

Article history: The mitigation of pollution released to the environment originating from the industrial sector has been the aim of
Received 8 March 2013 all policy-makers and its importance is evident if the adverse health effects on the world population are consid-
Received in revised form 10 June 2013 ered. Although this concern is controversial, petroleum renery has been linked to some adverse health effects
Accepted 10 June 2013
for people living nearby. Apart from home, school is the most important indoor environment for children and
Available online 7 July 2013
there is increasing concern about the school environment and its impact on health, also in developing countries
Editor: Pavlos Kassomenos where the prevalence of pollution is higher. As most of the children spend more than 40% of their time in schools,
it is critical to evaluate the pollution level in such environment. In the metropolitan region of Curitiba, South
Keywords: Brazil, ve schools nearby industries and highways with high density trafc, were selected to characterize the
Particle matter aerosol and gaseous compounds indoor and outdoor of the classrooms, during 20092011. Size segregated
Gases aerosol samples were collected for analyses of bulk and single particle elemental proles. They were analyzed
Petrochemical pollution by electron probe X-ray micro-analysis (EPXMA), and by energy-dispersive X-ray uorescence (EDXRF), to
investigate the elemental composition of individual particles and bulk samples. The concentrations of benzene,
toluene, ethylbenzene, and xylene (BTEX); NO2; SO2; acetic acid; and formic acid were assessed indoor and
outdoor using passive diffusion tubes. BTEX were analyzed by GCMS and other collected gasses by ion chroma-
tography. Individual exposition of BTEX was assessed by personal passive diffusion tubes. Results are interpreted
separately and as a whole with the specic aim of identifying compounds that could affect the health of the
scholars. In view of the chemical composition and size distribution of the aerosol particles, local deposition
efciencies in the children's respiratory systems were calculated, revealing the deposition of particles at
extrathoracic, tracheobronchial and pulmonary levels.
2013 Elsevier B.V. All rights reserved.

1. Introduction

Monitoring of air pollution has been framed as a basic requirement

in environmental analysis of indoor and outdoor environments, given
Corresponding author. Tel.: +55 41 3361 3012 its steady increase in recent times. There are evidence indicating that
E-mail address: rhmgodoi@ufpr.br (R.H.M. Godoi). air pollution is associated with low birth weight, increased infant and

0048-9697/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.scitotenv.2013.06.043
640 R.H.M. Godoi et al. / Science of the Total Environment 463464 (2013) 639646
perinatal mortality, pulmonary tuberculosis, nasopharyngeal and
laryngeal cancer, cataract and lung cancer. More specically, indoor
air pollution causes great concern, since people, especially in urban
areas, tend to spend approximately 90% of their time indoor buildings.
Also, the exposure to air pollution present in this kind of environment
may be responsible for almost 2 million premature deaths in develop-
ing countries and for some 4% of the global burden of disease (Godoi et
al., 2009; Bruce et al., 2000). In this context, pupils form a group,
which represents particular concern, since they have unique exposure
and special vulnerabilities to environmental toxicants (Landrigan et
al., 2004). Studies show that the exposure of children to air pollution
can implicate in asthma and other respiratory symptoms, even in the
case of low exposure (Buonanno et al., 2012; White et al., 2009;
Hulin et al., 2010; Zakaria et al., 2010; Gl et al., 2011; Kim et al.,
2011; Zhao, 2006).
The Brazilian pupils spend more than 30% of their time at school
and because of this are important to measure and control the pollution
level in school environments (Avigo et al., 2008). Recently, studies re-
lated to air quality in schools were conducted in France, Belgium,
India, Portugal and Spain (Rodriguez-Barranco et al., 2008; Pegas et
al., 2011; Stranger et al., 2008; Blondeau et al., 2005; Habil and
Taneja, 2011). Also, there is evidence that children who study and
live in industrial areas tend to present increased respiratory symptoms
when compared to other areas (White et al., 2009; Gl et al., 2011). In
this context, the petrochemical plants are one of the most signicant
industries. Many pollutants can be generated in the rening of petro-
leum such as particulate matter, organic and inorganic gases.
It is well-known that one of the major air pollutants is aerosols, also
known as particulate matter (PM). PM is dispersed in the air and its res-
idence time as a suspended mass varies with size. The problem lies
precisely in the fact of how the particles, with their specic sizes and
compositions, behave indoor the human body. The process of deposi-
tion in the lungs shows that particles between 0.001 m and 5 m,
when inhaled, may be retained in the lungs, causing serious respiratory
problems. In petrochemical plants the greatest potential source of par-
ticulate matter emissions to atmosphere is the unit for regeneration of
the catalytic cracking catalyst. The gas exhaust heaters and boilers
may also contain particles, but in much smaller amounts (Parker, 1977).
The most common inorganic gaseous pollutants are ozone (O3), ni-
trogen dioxide (NO2) and sulfur dioxide (SO2) (WHO, 2000). Ozone
can cause several adverse health effects, mainly among asthmatic indi-
viduals, like alterations of pulmonary function, inammation in respira-
tory system and an estimated 15% increase in daily mortality. There is
also evidence of chronic effects caused by continued exposure to ozone
(WHO, 2000; Godoi et al., 2009). This contaminant is a secondary pol-
lutant in troposphere, being formed through photochemical reaction in-
volving NOx and volatile organic compounds (VOCs).
Exposure to nitrogen dioxide causes acute effects, principally low
respiratory tract infections in children and increased airway respon-
siveness in asthmatics (WHO, 2000). This pollutant is emitted mainly
by combustion processes at high temperatures. The main source of
NO2 to the atmosphere is vehicle trafc, but industrial emissions,
such as from petrochemical plants, can also be considered an impor-
tant source (Wark et al., 1998).
SO2 is emitted by several different sources to the atmosphere, but
the most important ones are combustion processes and industrial
sources. This pollutant is an irritating gas, causing principally irrita-
tion in the superior respiratory tract. The combination of SO2 with
particulate matter can carry this pollutant deeply into the lungs, dam-
aging delicate tissues (Wark et al., 1998; Campos et al., 2006).
Other pollutants of interest are acetaldehyde and formaldehyde,
being listed as possible carcinogenic in humans. These compounds
have as main sources the vehicular emissions and several indoor
components (Godoi et al., 2009).
Among the main pollutants in urban centers are the VOCs, origi-
nated predominantly from motor vehicles and rening of petroleum
(EPA, 1995). The VOCs that are of scientic interest for indoor and out-
door air qualities are specically benzene, toluene, ethyl-benzene and
the xylene isomers (acronym BTEX) (Godoi et al., 2010). These com-
pounds, even in low concentrations, can be readily assimilated by the
human body through the air causing health risks when exposure occurs
for a long period of time, especially benzene. This substance is carcino-
genic to humans and probably responsible for countless cases of leuke-
mia in the world (Buczynska et al., 2009). The BTEX compounds are
typically found in indoor environments and the sources include com-
bustion by-products, cooking, construction materials, furnishings,
paints, varnishes and solvents, adhesives and chalk, ofce equipment,
and consumer products.
In Brazil there are few references about air quality in primary
schools near to petrochemical plants and industrial areas. Thus, in
this study there was interest in analyzing and comparing the air qual-
ity of primary schools located near petrochemical plants and schools
located in the urban area. Also, the possible sources of air pollutants
were investigated along with the relationship between indoor and
outdoor air qualities. In order to achieve this goal, mass concentra-
tions, elemental concentration proles and elemental associations of
PM were determined. In addition, SO2, NO2, HAc, HFor, O3 and BTEX
were monitored in the schools, as well as personal exposure of the
pupils both in the classroom and at home.
2. Methods
2.1. Sampling site
The sampling was carried out in Curitiba, the capital of Paran
state, in the south of Brazil. Two sampling campaigns were made:
the rst one took place in three schools (named, in this article, as
S1, S2 and S3 schools) during two different periods, representing
spring time (November/December of 2009) and winter time (June
of 2010), during the occurrence of the local thermal inversion phe-
nomenon. The second campaign was conducted between May and
October of 2011 in four schools (S4, S5, S6 and again S1 schools).
These schools were chosen based in three basic criteria: local repre-
sentatively in relation to pollution sources (vehicles and industries),
electrical support and security against vandalism and theft.
All sampling points were located on the ground oor; one repre-
sentative outdoor sampling point was chosen as well. All schools
are constructed with plastered or painted concrete and bricks and
the oor material is ceramic cleaned by wet mopping each weekday
before and after school hours. The rooms are naturally ventilated
through open windows and doors, and are equipped with regular
chalkboard, school furniture made of plastic/metal or wood, and
small cupboard in the classroom. Indoor samples were collected at a
height of about 11.5 m above the oor, which is the breathing
zone inside the classroom. The selected place was not allowed to be
closer than 1 m to a wall or a door. Outdoor samples were collected
at heights of 1.52 m above the ground, at a minimum distance of
1 m from the closest building.
The S1 and S2 schools are located in the suburban area and near to
a petrochemical plant, labeled in Fig. 1. The other schools are located
in the urban area of the city and are near to streets and highways
where high volumes of trafc are experienced throughout the year.
Where possible, three classrooms and one outdoor site were cho-
sen at each school as sampling sites. At the same time, two pupils
have been randomly selected in each school to carry personal sam-
plers, which are composed by a necklace with two passive samplers,
one for SO2, NO2, HAc and HFor and another for BTEX. The selected
children carried the personal samplers in all their activities during
this two-week period. The residences of these selected students
have also been sampled to assess the same gaseous pollutants as
those assessed by the personal samplers. It is important to notice
 R.H.M. Godoi et al. / Science of the Total Environment 463464 (2013) 639646
Fig. 1. Map of Curitiba city with the location of Schools 15, with the wind speed direction from petrochemical zone 2011.
Satellite image by GeoEye.

641
642 R.H.M. Godoi et al. / Science of the Total Environment 463464 (2013) 639646
Fig. 2. Concentration average for each element (ng/m3) in 2009.
that the houses of selected pupils were located near to their respec-
tive schools.
2.2. Sampling procedures
For bulk elemental concentration analyses PM was collected on
polycarbonate membranes (nucleopore) by means of impaction. The
sequential sampler was exposed indoors and outdoors for periods of
24 h at a ow rate of 35 L min1. Sampling took place for the ve
school-weekdays consecutively over a period of 2 weeks. For single
particle analysis aerosol particles were sampled on Ag foil using two
stages of a May cascade impactor, with aerodynamic diameter ranges
from 0.5 to 2.5 m and from 2.5 to 4.0 m for stages, at a 20 L min1
sampling ow rate. In this case sampling was conducted during one
day only and the exposure time was 1 h, to ensure that overloading
of the lter does not occur.
Gaseous air pollutants were sampled by means of radial diffusion
passive samplers (Radiello, Fondazione Salvatore Maugeri, Padova,
Italy). This sampler comprises a compound-specic adsorbing car-
tridge, surrounded by a cylindrical microporous diffusive body;
mounted on a supporting plate. The adsorbent for SO2, NO2, HAc and
HFor was triethanolamine and for O3 it was 4,4-dipyridylethylene.
The BTEX compounds adsorb onto thermally desorbable graphitized
carbon. Cartridges were exposed in parallel for 1 week after which
the cartridge was replaced for the second week of sampling. The tem-
perature was recorded every 20 min during the two week sampling
campaign.
2.3. Measurement techniques
Bulk elemental concentrations of the PM were determined by
using XRFS (Epsilon-5 high-energy polarized beam (HE-P) EDXRF).
A Ge (PAN 32) detector with a resolution of 165 eV was used and
allowed analysis from Z = 13. Individual particle analyses were
performed by computer-controlled electron probe X-ray micro analy-
sis (CC-EPXMA). Due to an ultra-thin window detector, elemental
Fig. 3. Concentration average for each element (ng/m3) in 2010.
analysis of low Z (i.e. C, N and O) could be facilitated. Quantitative cal-
culations of particle composition were performed by a newly devel-
oped method based on iterative Monte Carlo simulations (Ro et al.,
2003). Interpretation of data for each individual sample was possible
by using hierarchical cluster analysis with the integrated analysis of
data (IDAS) (Bondarenko et al., 1996). Clusterization of particles
could then be achieved based on elemental associations and average
percentages for each type of particle could be deduced.
SO2, NO2, HAc, and HFor were analyzed by means of ion chromatog-
raphy (dual column Dionex DX-120), after water elution (Stranger et
al., 2008). The ionic species SO2
4 and NO2 were assessed on an AG14
guard column, preceded by an AS14 analytical column (Dionex,
Sunnyvale, CA, USA). For the separation, the eluent was composed of
3.5 mM Na2CO3/1.0 mM NaHCO3 and the ow rate was set at
1.2 mL min1. The separation of acetate (Ac) and formate (For)
was performed with a GA-1 guard column and a custom-made
150 mm Allsep A-2 column (Alltech). The use of an isocratic 1.2 mM
Na2CO3/0.9 mM NaHCO3 buffer solution as eluent at a ow rate of
1 mL min1 allowed a baseline separation between Ac and For
(Stranger et al., 2008). The extracted liquid was analyzed by UVvis
spectrophotometry for the O3 concentrations.
For BTEX, sample extractions were performed by using chemical
desorption with 2 ml of carbon disulde (CS2), during 1 h
(Buczynska et al., 2009). Extracts were analyzed with a Varian gas
chromatograph equipped with a Flame Ionization Detector (FID). An-
alyte separation was achieved with the use of an intermediate polar
phase capillary column, model AT-624 (30 m 0.32 mm 1.8 m).
The carrier gas used was helium and the injection volume was 1 L,
in splitless mode. Each sample was injected tree times.
3. Results and discussion
The bulk elemental concentrations as determined by EDXRF are
summarized in Figs. 2, 3 and 4 for both indoor and outside schools.
Over the three year period the general trend is to nd concentrations
of 1000 ng/m3 and higher for the elements Si, Ca and Al both indoor
 R.H.M. Godoi et al. / Science of the Total Environment 463464 (2013) 639646 643

Fig. 4. Concentration average for each element (ng/m3) in 2011.

and outside the schools investigated. These kinds of elements are indoor environment. The study shows that ACH (the rate at which out-
associated with soil sources and they most commonly originate door air replaces indoor air in given space) is high when the window is
from the resuspension of dust (Godoi et al., 2004). Avigo et al. open and equipment (fans and air conditioned) are on, consequently
(2008) reported similar Ca concentrations at elementary schools in with more circulation of the air there are lowest accumulations of par-
Curitiba, Brazil, and they associated the contribution to the deteriora- ticles inside the classroom. Therefore, the fact of higher indoor concen-
tion of crustal materials. Intermediate concentrations ranging from tration to elements in this present study can be related as accumulation
100 to 1000 ng/m3 were identied for Cl, S, K and Zn. An unusually of the element, indicating it is likely the ventilation indoor the class-
high Cd concentration was registered in 2011 for S5 and S1 schools. rooms are irregular.
To assess the degree of anthropogenic inuence compared to nat- In the suburban area, where the vehicular trafc is not accented,
ural sources, the enrichment factor (EF) was calculated for each ele- the concentration elements showed that the sources are most from
ment according to the following algorithm: Efx = (CnX/Eref)sample/ anthropogenic sources such as complex industrial near to schools. For
(X/Eref)crust, where X is the concentration of the element of interest S1 school the elements in higher concentration were located indoor
and Eref the reference element for normalization. The elemental concen- (I/O > 1) the classroom (Si, K, Ca, Fe, Zn, Al, S and Cl), which means
trations in the crust used in this study were the average continental the accumulation of these particles because the particles can migrate in-
crust data (Mason, 1982). Al was used as reference element assuming door the classroom. Stranger et al. (2008) in a study about indoor air
that its anthropogenic sources to the atmosphere are negligible. Thus, quality at primary school in Antwerp, Belgium, associate the elevated
when EF approaches unity it is regarded as predominantly of natural or- concentration of particulate matter with the presence of carpets and
igin, on the other hand, when the value of EF is much larger than 10, the also determined by the local outdoor air, specic building characteris-
sources are considered to originate mainly from anthropogenic origin tics and indoor activities. So, the microenvironment indoor the schools
(Liu et al., 2003) The value limit of the EF to be considered as arising can be susceptive to be a problem to student health. The EF for S1 school
from natural sources in a sample, according to the literature, is between shows the elements Si, K, Ca, Ti, Fe, Se, Cu, Zn, As, Pb, S and Cl were
4 (Hacisalihoglu et al., 1992) and 5 (Voutsa et al., 2002), this factor is enriched, indicating the anthropogenic sources. Especially, the main el-
greater than 1 to incorporate possible local variations in the composi- ement found in this school was the sulfur. This element is a chemical
tion of chemical elements. For this study, the threshold value was naturally present in the petroleum; however, the percentage varies
considered to be 4, and the sample with values above this will be con- with the source thereof. In the petrochemical plant, the process units re-
sidered as a sample inuenced by anthropogenic sources. quire large amounts of steam at high pressure, loads as well as heat.
The urban area has many sources of particulate matter, most of Thus many types of boilers and heaters are used by reneries and the
which are closely related to anthropogenic actions (humans activity). sulfur oxides are produced during the burning of fuel used to generate
The schools located in the area (S3, S4 and S5) show that the concen- such heat and energy. Also, compounds of sulfur are also produced dur-
tration of elements such as metals (Fe, Al, Zn, and Pb) indicates prob- ing the regeneration of catalyst used in the catalytic cracking process
ably originating from vehicular emissions. The EF for elements in S3 and desulfurization process (Parker, 1977). This can prove that the S1
shows that the same elements in 2009 and 2010 (Si, K, Ca, Fe, Se, school is affected with particle compounds of sulfur.
Cu, Zn, S, Pb, S and Cl) were enriched. This fact proved that there In S2 school, located near to S1 school and the petrochemical plant,
are many kinds of anthropogenic sources near to S3 school. In the the elemental concentration indicated basically the same elements in
case of NS school, the EF reveals that the elements enriched were higher concentrations (Si, K, Ca, Fe, Al, S, Cl) compared with S1 school,
Ni, Zn, S, Cl appeared indoor and K, Ni, Cu, Pb, S and Cl outside, indi- but in another hand it's important to note (see Fig. 3) the abrupt differ-
cating that exists anthropogenic sources around the NS school with ence in indoor concentrations. It was found the enriched elements for
pollution potential. In the S4 school only three elements were Zn, Pb, S and Cl indicating the anthropogenic sources. Unusual, indoor
enriched: Zn, S and Cl (indoor and outside). There are a highway
and a bus stop near to S4 school that probably contribute as sources
near the school. Godoi et al. (2004) associate P, S, and Cl with biomass Table 1
burning aerosol, indicating presence of bioorganic aerosol components. Average concentration (in g m3) of gaseous pollutants in urban and suburban areas.
Probably, the sources in the urban area are from the huge trafc School House Personal exposure
near to S3, S4 and S5. This can be observed for element Fe that in
Indoor Outdoor Indoor
2009 at S3 school resulted in higher than 1000 ng/m3 for concentra-
tion at indoor and outside as in 2010, where the same line for both SO2 Urban 1.83 2.55 1.57 1.20
Suburban 0.90 0.89 1.23 0.85
sides was shown, indicating the xed sources near to school. For the
NO2 Urban 17.64 17.37 19.49 21.02
three schools in the urban area, I/O ratio resulted to the most part Suburban 8.56 8.03 9.00 10.22
of elements a value > 1, which indicates that the indoor is higher HAc Urban 16.41 3.69 6.91 14.05
than outside for elemental concentration. Suburban 28.56 6.36 18.08 23.28
Guo et al. (2008) investigated indooroutdoor concentrations of HFor Urban 4.58 2.88 2.17 3.00
Suburban 4.20 1.35 4.34 6.15
PM in primary school and the impact of air exchange (ACH) on the
644 R.H.M. Godoi et al. / Science of the Total Environment 463464 (2013) 639646

concentration for Sb was found and probably can be linked with indoor
source of this element since there was no sign of element concentration
outdoor.
Some studies show that cleaning activities, as operation of oor
polishing machine and wet cleaning by detergents can be one of the
causes of indoor sources (Guo et al., 2008; Morawska et al., 2009).
Once again, high levels of concentration observed within schools
may be associated with the accumulation of the element (both by
the presence of inside sources or by the arrival of particles from the
outside environment).
Low-Z EPMA was performed for fractioned airborne particles.
Some distinctive particle types can be identied according to their
chemical composition. By studying particles on an individual basis
one can determine the size distribution and elemental association
(group or cluster) of these particles, both of which impact on pulmo-
nary deposition and impact. Carbonaceous and soil-derived particles
are compounds characterized by the presence of carbon in its consti-
tution and can be separated into three different groups of species, i.e.
biogenic, soot and organic (Godoi et al., 2004). The particles named
carbon black (or soot) are the varieties of pure carbon particles
(around 70% or more of its carbon composition), forming a colloidal
dispersion of very ne particles (Avigo et al., 2008). Soot comes from
human activity, in particular diesel vehicles and tire wear and brakes
of vehicles in general. The particles of this group were found in all
schools in 2009 and 2010. The percentages of the relative abundance
revealed that the highest values appear for particles in the ne fraction
(0.5 to 2.5 m); the higher value was indoor the School S1 with 34% of
the total of 638 particles (approximately 81% of 638 are in the ne
fraction). The contribution of soot particles is directly linked to
urban areas, primarily by vehicle emissions (Avigo et al., 2008) and
also by small contributions from gas combustion, industrial processes,
dust from paved roads and burned (Gray and Cass, 1998). The aluminosil-
icates (AlSi) are part of the soil or come from human activity and vehicu-
lar trafc, agriculture, incineration, deforestation and desertication. Such
particles consisting mainly of Si are identied as quartz (SiO2). In the sam-
ples, the cluster AlSi appeared in both sampling years (2009 and 2010),
proving to be present in almost all schools. It is worth mentioning the
importance of the characterization that the particle size, as compared
to lung deposition smaller particles are most dangerous because they
can reach the lung alveoli and provide further complications.
Table 1 displays the average concentration values obtained for
SO2, NO2, HAc, and HFor for the urban and the suburban areas, with
the last one comprising the area near the petrochemical plant.
Concerning SO2 pollution, the concentration values obtained were
generally low, in agreement with results reported in the literature
(Kim et al., 2011; Godoi et al., 2009; Stranger et al., 2008; Zhao, 2006).
However, schools located in the urban area in general presented higher
values, which is reected in the values found in Table 1. There was only
one measurement, at one of the schools located in the urban area,
pointing a concentration above the guideline dened by the World
Health Organization (WHO, 2000).
Concerning NO2 pollution, the concentration values obtained were
signicantly higher than the SO2 values, and in general also similar to
the values reported in the literature (Kim et al., 2011; Stranger et al.,
2008; Zhao, 2006; Gl et al., 2011; Zakaria et al., 2010; Hulin et al.,
2010; Hroux et al., 2010). The schools located in more urbanized
areas and near intense vehicular trafc presented levels of NO2 con-
siderably higher than the schools in the industrial (suburban) area,
indicating that the greatest source of NO2 is rather the vehicular traf-
c than the industrial emissions (in this case, the emissions from the
petrochemical plant), in agreement with what was described in the
literature.
In a general form, the schools in the suburban area presented
higher levels of acetic acid pollution. However, it is not possible to
draw any substantial conclusions from this pattern, since the concen-
tration values for acetic acid presented great variation between the
different campaigns, being generally low in the second campaign
and signicantly high in the rst one, for both urban and suburban
areas. In the rst campaign, the concentration values were higher
than the results reported by other studies and presented concerning
peaks of high concentration of the pollutant, when in comparison
with the articles studied (Godoi et al., 2009; Shendell et al., 2004;
Ongwandee et al., 2009; Kinney et al., 2002; Fenech et al., 2010;
Gilbert et al., 2005; Hulin et al., 2010; Marchand et al., 2008). The
I/O ratios obtained in the rst campaign indicated a strong presence of
indoor sources or accumulation of HAc in all the assessed schools.
Regarding formic acid, the pattern was similar to acetic acid. Ac-
cording to Table 1, urban and suburban areas presented similar levels
of formic acid pollution. The concentration values of this pollutant
were in general low, mainly in the second campaign. Besides, the I/O
ratios obtained for the rst campaign suggest that there are important
sources of HFor in the indoor environment or accumulation of this
pollutant in the assessed schools.
Comparing average concentration of formic acid to average con-
centration of acetic acid in each sampling site, it is possible to notice
that the second one is the highest between them in almost all the
sampling sites, with similar behavior for both urban and suburban
areas. The reason for this behavior may be the main outdoor source
of both acids: vehicle emissions (primary acetic and formic acids are
by-products of the incomplete combustion of oxygenated fuels in
engines). While formic acid is a result of predominant release of
formaldehyde from vehicles powered with gasoline with and without
catalytic converters, acetic acid is derived from acetaldehyde emitted
by automobiles powered with pure ethanol or a blend of ethanol/
gasoline. Ethanol is the main fuel used in Brazil's vehicles, which is the
most probable reason why the concentration of acetic acid exceeds
the concentration of formic acid at the assessed schools (Godoi et al.,
2009).

Table 2
Overview of BTEX concentrations in urban and suburban areas in g m3.

School House Personal exposure

Indoor Outdoor Indoor

Benzene Urban 1.5 (0.213.2) 1.4 (0.462.2) 1.5 (0.185.4) 2.3 (0.285.6)
Suburban 1.4 (0.343.3) 1.8 (0.583.0) 2.9 (0.806.2) 2.7 (0.586.0)
Toluene Urban 3.9 (0.378.1) 2.9 (1.164.9) 32 (1.7299) 24 (4.8207)
Suburban 48 (2.0108) 4.2 (2.85.9) 17 (3.583) 15 (4.373)
Ethylbenzene Urban 1.2 (0.163.1) 0.89 (0.191.3) 1.9 (0.524.4) 2.2 (0.155.9)
Suburban 3.9 (0.1920) 0.64 (0.201.6) 0.63 (0.201.6) 0.76 (0.192.5)
m, p-Xylene Urban 2.9 (0.187.0) 2.4 (1.53.7) 3.9 (1.210.3) 5.1 (1.611.7)
Suburban 4.3 (1.89.9) 2.3 (1.33.5) 15 (1.4104) 3.3 (1.36.9)
o-Xylene Urban 0.97 (0.155.2) 0.61 (0.241.6) 1.1 (0.192.4) 2.5 (0.1813.5)
Suburban 1.4 (0.552.8) 0.89 (0.261.3) 7.2 (0.2847) 6.9 (0.2445)

Mean (min. max.).

Sample size (n): outdoor: 13, school: 30, house: 20 and personal: 21.
 R.H.M. Godoi et al. / Science of the Total Environment 463464 (2013) 639646
Unfortunately, due to the lack of data to increase the reliability of the
results, the concentration values obtained for ozone can only show that
the levels of this pollutant are not signicantly higher than the results
reported by other studies.
Table 2 presents an overview of the results for BTEX. All compounds
(benzene, toluene, ethyl-benzene, m-, p-xylene and o-xylene) were
detected in 100% of the sampling locations.
Toluene was the most abundant compound in 85.7% of the samples,
followed by m-, p-xylene in 10.7% of the samples. This scenario was also
found in several national and international studies (Stranger et al.,
2007; Godoi et al., 2009; Eplugues et al., 2010; Geiss et al., 2011). For
benzene, 7.0% of the samples exceeded the European limit in environ-
ment of 5 g m3. This low percentage was nominated by Stranger et
al. (2008), relative to schools in Belgium, and by Esplugues et al.
(2010), for homes located in Spain.
In urban and suburban schools, indoor and outdoor concentra-
tions of BTEX did not indicate signicant differences (I/O ratios nearly
1) showing that the outdoor environment denes the indoor air qual-
ity. The exception was toluene in the suburban schools. The I/O ratios
for suburban schools indicated values from 6.4 to 23.2 for toluene,
representing a possible indoor source and/or this pollutant accumu-
lates indoor the classrooms mainly because of the high density of
the substances (Godoi et al., 2010) and the adverse ventilation condi-
tions indoor the classrooms. Geiss et al. (2011), in Europe, and Guo et
al. (2002), in Hong Kong, found I/O ratios near 1, for all BTEX, inclu-
sive for toluene.
In outdoor of these schools null and weak correlation (R =
0.0170.990) was observed, which can indicate a somatic effect be-
tween two emissions sources: vehicular trafc and petrochemical
plant. In addition it is important to understand that petrochemical
plants can be considered an important punctual source of each BTEX
compound, mainly because they are present in countless rening oper-
ations, in more proportions in the separation of these compounds (EPA,
1995). This scenario also was found in Taiwan by Hsieh et al. (2005) in
schools near a petrochemical plant, but the BTEX concentrations were
in several higher than the results present in this research.
In outdoor schools located in urban areas the strong correlations
(R = 0.7000.972) support that the main BTEX source is the trafc
emissions. Buczynska et al. (2009) also reported trafc emissions
like main source of BTEX in urban areas of Antwerp, Belgium, sup-
ported by high correlation between the compounds. Godoi et al.
(2009), Stranger et al. (2008) and Hsieh et al. (2005) also reported
this correlation level. Additionally, in agreement with this study, the
two last authors reported that there were not indoor benzene source,
but for the other compounds there is a high probability of an indoor
source.
Stevenson et al. (1997), Brocco et al. (1997) and Guicherit (1997),
cited by Godoi et al. (2010), proposed that the ratios lower than 2.7,
1.8 and 0.9 for toluene/benzene, m, p-xylene/benzene and o-xylene/
benzene, respectively, are indicative that the main source of BTEX
comes from fossil fuel burning. In this way, in urban areas the outdoor
concentrations presented ratios lower than the exposed (2.3, 1.9 and
0.4) conrming the vehicular emissions like a BTEX source. In subur-
ban areas the ratios did not indicated this source (4.2, 1.7 and 0.5)
strengthening the assumption that there are several sources of
these gaseous compounds.
Indoor school concentrations of BTEX in urban areas, showed a
strong linear correlation (R = 0.6920.942) and for suburban areas
a weak correlation. No linear correlation could be established for
indoor and outdoor school concentrations and inside homes.
In both areas, high concentrations of benzene, toluene and xylenes
were reported in some residences, in some cases exceeding the Euro-
pean limit of benzene (5 g m3) and the WHO (2010) guidelines for
toluene (260 g m3). Guo et al. (2002) reported similar results for
homes located in Hong Kong and Esplugues et al. (2010), in Spain,
found high concentrations only for toluene. These results reect the
645
personal exposure of the children which also presents high concen-
trations of benzene and toluene. In a general analysis, the children
that live and study in suburban areas are more exposed of all BTEX
compounds than the children of urban areas. However, in both
areas, the concentrations reported in this research can cause several
chronic diseases, especially benzene that is a known carcinogenic
compound and there are no recommended concentrations as safe
for this substance (WHO, 2010).
4. Conclusion
The schools in urban area revealed high exposure to particulate mat-
ter from the highways of motor vehicles indicating the anthropogenic
sources near to schools. For suburban area, the analysis indicated the
proximity with anthropogenic sources, especially the industrial plants
around. So, one can conjecture that these aerosols may be a cause of
the sources/potentiating respiratory disease in some students of the
schools.
Better assessment of the reasons that contributed to the results
obtained in the present research is necessary, along with a verica-
tion of the potential sources of pollutants indoor the school environ-
ment for acetic and formic acids and the relationship between the
distance of the classrooms to the highways and pollutant concentra-
tion. This information would be of great importance for better under-
standing of the scenario in the study. Regarding the inorganic gaseous
pollutants, it seems reasonable to say that the presence of the petro-
chemical plant is not a determinant factor referring to their atmo-
spheric concentration. The concentration values found for SO2 were
in general low and similar among all the schools assessed, in both
urban and suburban areas, indicating that the vehicular trafc and
the petrochemical plant present approximately the same potential
for SO2 emission. Analyzing NO2 concentrations, however, it is possi-
ble to note that the suburban areas presented substantially higher
concentration of this pollutant when in comparison to the schools
at the urban area. This is in agreement with the information provided
by the scientic literature that the vehicular emissions are the most
important source of NO2 in the atmosphere.
Two main sources of BTEX were identied in this study: trafc
(urban areas) and petrochemical industry (suburban areas) emissions.
These outdoor sources have a high inuence in houses and schools in-
door air quality. However in the suburban areas there is a somatic effect
of the two sources exposing the children that live and study in these
areas of high concentrations of BTEX. Toluene presented the higher con-
centrations in some schools and homes reecting the children's person-
al exposure and 7% of the samples of benzene exceeded the European
limit of 5 g m3.
Acknowledgments
We would like to thank Araucaria Foundation and the National
Council for Scientic and Technological Development (CNPq) who
supported the funding and promoted the development of this study.
References
Avigo D, Godoi AFL, Janissek PR, Makarovska Y, Krata A, Potgieter-Vermaak S, et al.
Particulate matter analysis at elementary schools in Curitiba, Brazil. Anal Bioanal
Chem 2008;391:145968.
Blondeau P, Iordache V, Poupard O, Genin D, Allard F. Relationship between outdoor
and indoor air quality in eight French schools. Indoor Air 2005;15:212.
Bondarenko L, Treiger B, Van Grieken R, Van Eespen PI. A Windows based software
package for cluster analysis. Spectrochim Acta 1996;51:41356.
Brocco D, Fratarcangeli R, Lepore L, Petricca M, Venrrone I. Determination of aromatic
hydrocarbons in urban air of Rome. Atmos Environ 1997;31:5516.
Bruce N, Perez-Padilla R, Albalak R. Indoor air pollution in developing countries: a
major environmental and public health challenge. Bull World Health Organ
2000;78(9):107892.
646 R.H.M. Godoi et al. / Science of the Total Environment 463464 (2013) 639646
Buczynska AJ, Krata A, Stranger M, Godoi AFL, Kontozova-Deutsch V, Bencs L, et al.
Atmospheric BTEX-concentrations in an area with intensive street trafc. Atmos
Environ 2009;43:3118.
Buonanno G, Marini S, Morawska L, Fuoco FC. Individual dose and exposure of Italian
children to ultrane particles. Sci Total Environ 2012;438:2717.
Campos VP, Cruz LPS, Alves EM, Santos TS, Silva AD, dos Santos ACC, et al.
Monitoramento Atmosfrico Passivo de SO2, NO2 e O3 em reas Urbanas e de
Inuncia Industrial como Prtica de Qumica Ambiental para Alunos de Graduao.
Qum Nova 2006;29(4):8725.
EPA. Prole of the petroleum rening industry. Washington, D.C.: Ofce of Compliance;
1995.
Esplugues A, Ballester F, Estarlich M, Llop S, Fuentes-Leonarte V, Mantilla E, et al. Indoor
and outdoor air concentrations of BTEX and determinants in a cohort of one-year
old children in Valencia, Spain. Sci Total Environ 2010;409:639.
Fenech A, Strlic M, Cigic IK, Levart A, Gibson LT, Bruin G, et al. Volatile aldehydes in
libraries and archives. Atmos Environ 2010;44:206773.
Geiss O, Giannopoulos G, Tirendi S, Barrero-Moreno J, Larsen BR, Kotzias D. The AIRMEX
study VOC measurements in public buildings and schools/kindergartens in eleven
European cities: statistical analysis of the data. Atmos Environ 2011;45:367684.
Gilbert NL, Guaya M, Millera JD, Judeka S, Chanc CC, Dales RE. Levels and determinants
of formaldehyde, acetaldehyde, and acrolein in residential indoor air in Prince
Edward Island, Canada. Environ Res 2005;99:117.
Godoi RHM, Godoi AFL, Worobiec A, Andrade SJ, Hoog J, Silva MRS, et al. Characterisa-
tion of sugar cane combustion particles in the Araraquara Region, Southeast Brazil.
Microchim Acta 2004;145:536.
Godoi RHM, Avigo Jr D, Campos VP, Tavares TM, de Marchi MRR, Van Grieken R, et al.
Indoor air quality assessment of elementary schools in Curitiba, Brazil. Water Air
Soil Pollut Focus 2009. http://dx.doi.org/10.1007/s11267-009-9220-3.
Godoi AFL, Godoi RHM, Azevedo R, Maranho LT. Pollution and density of vegetation:
BTEX in some public areas of Curitiba PR, Brazil. Quim Nova 2010;33(4):82733.
Gray HA, Cass GR. Source contributions to atmospheric ne carbon particle concentra-
tions. Atmos Environ 1998;32(22):380525.
Guicherit R. Trafc as a source of volatile hydrocarbons in ambient air. Sci Total Environ
1997;205:20113.
Gl H, Gaga EO, Derolu T, zden O, Ayvaz O, zel S, et al. Respiratory health symp-
toms among students exposed to different levels of air pollution in a Turkish city.
Int J Environ Res Public Health 2011;8:111025.
Guo H, Lee SC, Li WM, Cao JJ. Source characterization of BTEX in indoor microenviron-
ments in Hong Kong. Atmos Environ 2002;37:7382.
Guo H, Morawksa L, He C, Gilbert D. Impact of ventilation scenario on air exchange
rates and on indoor particle number concentrations in an air-conditioned class-
room. Atmos Environ 2008;42:75768.
Habil M, Taneja A. Children's exposure to indoor particulate matter in naturally venti-
lated schools in India. Indoor Built Environ 2011;20:43048.
Hacisalihoglu G, ELiyakurt F, Olmez I, Balkas TI, Tuncel G. Chemical composition of
particles in the Black Sea atmosphere. Atmos Environ 1992;17:320718.
Hroux ME, Clark N, Van Ryswyk K, Mallick R, Gilbert NL, Harrison I, et al. Predictors of
indoor air concentrations in smoking and non-smoking residences. Int J Environ
Res Public Health 2010;7:308099.
Hsieh L, Yang H, Chen H. Ambient BTEX and MTBE in the neighborhoods of different
industrial parks in Southern Taiwan. J Hazard Mater 2005;128:10615.
Hulin M, Caillaud D, Annesi-Maesano I. Indoor air pollution and childhood asthma:
variations between urban and rural areas. Indoor Air 2010;20:50214.
Kim JL, Elfman L, Wieslander G, Ferm M, Torn K, Norbck D. Respiratory health among
Korean pupils in relation to home, school and outdoor environment. J Korean Med
Sci 2011;26:16673.
Kinney PL, Chillrud SN, Ramstrom S, Ross J, Spengler JD. Exposures to multiple air
toxics in New York city. Environ Health Perspect 2002;110(4):53946.
Landrigan PJ, Kimmel CA, Correa A, Eskenazi B. Children's health and the environment:
public health issues and challenges for risk assessment. Environ Health Perspect
2004;12(2):25765.
Liu QT, Diamond ME, Gingrich SE, Ondov JM, Maciejczyk P, Gary AS. Accumulation of
metals, trace elements and semi-volatile organic compounds on exterior window
surfaces in Baltimore. Environmental Pollution 2003;122:5161.
Marchand C, Le Calv S, Mirabel P, Glasser N, Casset A, Schneider N, et al. Concentra-
tions and determinants of gaseous aldehydes in 162 homes in Strasbourg (France).
Atmos Environ 2008;42:50516.
Mason B. Principles of geochemistry. New York: Wiley; 1966.
Morawska L, He C, Johnson G, Guo H, Uhde E, Ayoko G. Ultrane particles in indoor air
of a school: possible role of secondary organic aerosols. Sci Total Environ 2009;43:
91039.
Ongwandee M, Moonrinta R, Panyametheekul S, Tangbanluekal C, Morrison G. Concen-
trations and strengths of formaldehyde and acetaldehyde in ofce buildings in
Bangkok Thailand. Indoor Built Environ 2009;18(6):56975.
Parker A. Industrial air pollution handbook. London: McGraw-Hill Book Company;
1977.
Pegas PN, Alves CA, Evtygina MG, Nunes T, Cerqueira M, Franchi M, et al. Indoor air
quality in elementary schools of Lisbon in spring. Environ Geochem Health
2011;33:45568.
Ro CU, Osan J, Van Grieken R. A Monte Carlo program for quantitative electron-induced
X-ray analysis of individual particles. Anal Chem 2003;15:8519.
Rodriguez-Barranco M, Gonzalez-Alzaga B, Daponte A, Lacasaa M. Personal exposure
to BTEX in children of a Spanish area with high industrial activity. Epidemiol
2008;19(6):S141.
Shendell DG, Winer AM, Stock TH, Zhang L, Zhang J, Maberti S, et al. Air concentrations
of VOCs in portable and traditional classrooms: results of a pilot study in Los
Angeles County. J Expo Anal Environ Epidemiol 2004;14:4459.
Stevenson KJ, Stacey B, Willis PG. Air quality at Heathrow Airport annual report for
1996. AEA Technology; 1997.
Stranger M, Potgieter-Vermaak SS, Van Grieken R. Comparative overview of indoor air
quality in Antwerp, Belgium. Environ Int 2007;33:78997.
Stranger M, Potgieter-Vermaak SS, Van Grieken R. Characterization of indoor air quality
in primary schools in Antwerp. Indoor Air 2008;18:45463.
Voutsa D, Samara C, Kouimtzis Th, Ochsenkuhn K. Elemental composition of airborne
particulate matter in the multi-impacted urban area of Thessaloniki, Greece.
Atmos Environ 2002;36:445362.
Wark K, Warner CF, Wayne TD. Air pollution: it's origin and control. 3 ed. Addison-
Wesley Longman, Inc.; 1998
White N, WaterNaude J, van der Walt A, Ravenscroft G, Roberts W, Ehrlich R. Mete-
orologically estimated exposure but not distance predicts asthma symptoms in
schoolchildren in the environs of a petrochemical renery: a cross-sectional study.
Environ Health 2009;8:45.
WHO. Air quality guidelines for Europe. WHO regional publications. European series,
2nd ed.Copenhagen: World Health Organization; 2000.
WHO. Air guidelines for indoor air quality: selected pollutants. Copenhagen, Denmark:
WHO World Health Organization Regional Ofce for Europe; 2010.
Zakaria J, Lye MS, Hashim JH, Hashim Z. Allergy to air pollution and frequency of
asthmatic attacks among asthmatic primary school children. Am Eurasian J Toxicol
Sci 2010;2:8392.
Zhao, Z. Indoor and outdoor air pollution in relation to allergy and asthma in Taiyuan,
China. Acta Universitatis Upsaliensis Uppsala: Digital Comprehensive Summaries
of Uppsala Dissertations from the Faculty of Medicine 196., 2006.