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Science of the Total Environment 463464 (2013) 639646

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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 (EPA, 1995). The VOCs that are of scientic interest for indoor and out-
laryngeal cancer, cataract and lung cancer. More specically, indoor door air qualities are specically benzene, toluene, ethyl-benzene and
air pollution causes great concern, since people, especially in urban the xylene isomers (acronym BTEX) (Godoi et al., 2010). These com-
areas, tend to spend approximately 90% of their time indoor buildings. pounds, even in low concentrations, can be readily assimilated by the
Also, the exposure to air pollution present in this kind of environment human body through the air causing health risks when exposure occurs
may be responsible for almost 2 million premature deaths in develop- for a long period of time, especially benzene. This substance is carcino-
ing countries and for some 4% of the global burden of disease (Godoi et genic to humans and probably responsible for countless cases of leuke-
al., 2009; Bruce et al., 2000). In this context, pupils form a group, mia in the world (Buczynska et al., 2009). The BTEX compounds are
which represents particular concern, since they have unique exposure typically found in indoor environments and the sources include com-
and special vulnerabilities to environmental toxicants (Landrigan et bustion by-products, cooking, construction materials, furnishings,
al., 2004). Studies show that the exposure of children to air pollution paints, varnishes and solvents, adhesives and chalk, ofce equipment,
can implicate in asthma and other respiratory symptoms, even in the and consumer products.
case of low exposure (Buonanno et al., 2012; White et al., 2009; In Brazil there are few references about air quality in primary
Hulin et al., 2010; Zakaria et al., 2010; Gl et al., 2011; Kim et al., schools near to petrochemical plants and industrial areas. Thus, in
2011; Zhao, 2006). this study there was interest in analyzing and comparing the air qual-
The Brazilian pupils spend more than 30% of their time at school ity of primary schools located near petrochemical plants and schools
and because of this are important to measure and control the pollution located in the urban area. Also, the possible sources of air pollutants
level in school environments (Avigo et al., 2008). Recently, studies re- were investigated along with the relationship between indoor and
lated to air quality in schools were conducted in France, Belgium, outdoor air qualities. In order to achieve this goal, mass concentra-
India, Portugal and Spain (Rodriguez-Barranco et al., 2008; Pegas et tions, elemental concentration proles and elemental associations of
al., 2011; Stranger et al., 2008; Blondeau et al., 2005; Habil and PM were determined. In addition, SO2, NO2, HAc, HFor, O3 and BTEX
Taneja, 2011). Also, there is evidence that children who study and were monitored in the schools, as well as personal exposure of the
live in industrial areas tend to present increased respiratory symptoms pupils both in the classroom and at home.
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- 2. Methods
leum such as particulate matter, organic and inorganic gases.
It is well-known that one of the major air pollutants is aerosols, also 2.1. Sampling site
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 The sampling was carried out in Curitiba, the capital of Paran
precisely in the fact of how the particles, with their specic sizes and state, in the south of Brazil. Two sampling campaigns were made:
compositions, behave indoor the human body. The process of deposi- the rst one took place in three schools (named, in this article, as
tion in the lungs shows that particles between 0.001 m and 5 m, S1, S2 and S3 schools) during two different periods, representing
when inhaled, may be retained in the lungs, causing serious respiratory spring time (November/December of 2009) and winter time (June
problems. In petrochemical plants the greatest potential source of par- of 2010), during the occurrence of the local thermal inversion phe-
ticulate matter emissions to atmosphere is the unit for regeneration of nomenon. The second campaign was conducted between May and
the catalytic cracking catalyst. The gas exhaust heaters and boilers October of 2011 in four schools (S4, S5, S6 and again S1 schools).
may also contain particles, but in much smaller amounts (Parker, 1977). These schools were chosen based in three basic criteria: local repre-
The most common inorganic gaseous pollutants are ozone (O3), ni- sentatively in relation to pollution sources (vehicles and industries),
trogen dioxide (NO2) and sulfur dioxide (SO2) (WHO, 2000). Ozone electrical support and security against vandalism and theft.
can cause several adverse health effects, mainly among asthmatic indi- All sampling points were located on the ground oor; one repre-
viduals, like alterations of pulmonary function, inammation in respira- sentative outdoor sampling point was chosen as well. All schools
tory system and an estimated 15% increase in daily mortality. There is are constructed with plastered or painted concrete and bricks and
also evidence of chronic effects caused by continued exposure to ozone the oor material is ceramic cleaned by wet mopping each weekday
(WHO, 2000; Godoi et al., 2009). This contaminant is a secondary pol- before and after school hours. The rooms are naturally ventilated
lutant in troposphere, being formed through photochemical reaction in- through open windows and doors, and are equipped with regular
volving NOx and volatile organic compounds (VOCs). chalkboard, school furniture made of plastic/metal or wood, and
Exposure to nitrogen dioxide causes acute effects, principally low small cupboard in the classroom. Indoor samples were collected at a
respiratory tract infections in children and increased airway respon- height of about 11.5 m above the oor, which is the breathing
siveness in asthmatics (WHO, 2000). This pollutant is emitted mainly zone inside the classroom. The selected place was not allowed to be
by combustion processes at high temperatures. The main source of closer than 1 m to a wall or a door. Outdoor samples were collected
NO2 to the atmosphere is vehicle trafc, but industrial emissions, at heights of 1.52 m above the ground, at a minimum distance of
such as from petrochemical plants, can also be considered an impor- 1 m from the closest building.
tant source (Wark et al., 1998). The S1 and S2 schools are located in the suburban area and near to
SO2 is emitted by several different sources to the atmosphere, but a petrochemical plant, labeled in Fig. 1. The other schools are located
the most important ones are combustion processes and industrial in the urban area of the city and are near to streets and highways
sources. This pollutant is an irritating gas, causing principally irrita- where high volumes of trafc are experienced throughout the year.
tion in the superior respiratory tract. The combination of SO2 with Where possible, three classrooms and one outdoor site were cho-
particulate matter can carry this pollutant deeply into the lungs, dam- sen at each school as sampling sites. At the same time, two pupils
aging delicate tissues (Wark et al., 1998; Campos et al., 2006). have been randomly selected in each school to carry personal sam-
Other pollutants of interest are acetaldehyde and formaldehyde, plers, which are composed by a necklace with two passive samplers,
being listed as possible carcinogenic in humans. These compounds one for SO2, NO2, HAc and HFor and another for BTEX. The selected
have as main sources the vehicular emissions and several indoor children carried the personal samplers in all their activities during
components (Godoi et al., 2009). this two-week period. The residences of these selected students
Among the main pollutants in urban centers are the VOCs, origi- have also been sampled to assess the same gaseous pollutants as
nated predominantly from motor vehicles and rening of petroleum 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- analysis of low Z (i.e. C, N and O) could be facilitated. Quantitative cal-
tive schools. culations of particle composition were performed by a newly devel-
oped method based on iterative Monte Carlo simulations (Ro et al.,
2.2. Sampling procedures 2003). Interpretation of data for each individual sample was possible
by using hierarchical cluster analysis with the integrated analysis of
For bulk elemental concentration analyses PM was collected on data (IDAS) (Bondarenko et al., 1996). Clusterization of particles
polycarbonate membranes (nucleopore) by means of impaction. The could then be achieved based on elemental associations and average
sequential sampler was exposed indoors and outdoors for periods of percentages for each type of particle could be deduced.
24 h at a ow rate of 35 L min1. Sampling took place for the ve SO2, NO2, HAc, and HFor were analyzed by means of ion chromatog-
school-weekdays consecutively over a period of 2 weeks. For single raphy (dual column Dionex DX-120), after water elution (Stranger et
particle analysis aerosol particles were sampled on Ag foil using two al., 2008). The ionic species SO2
4 and NO2 were assessed on an AG14
stages of a May cascade impactor, with aerodynamic diameter ranges guard column, preceded by an AS14 analytical column (Dionex,
from 0.5 to 2.5 m and from 2.5 to 4.0 m for stages, at a 20 L min1 Sunnyvale, CA, USA). For the separation, the eluent was composed of
sampling ow rate. In this case sampling was conducted during one 3.5 mM Na2CO3/1.0 mM NaHCO3 and the ow rate was set at
day only and the exposure time was 1 h, to ensure that overloading 1.2 mL min1. The separation of acetate (Ac) and formate (For)
of the lter does not occur. was performed with a GA-1 guard column and a custom-made
Gaseous air pollutants were sampled by means of radial diffusion 150 mm Allsep A-2 column (Alltech). The use of an isocratic 1.2 mM
passive samplers (Radiello, Fondazione Salvatore Maugeri, Padova, Na2CO3/0.9 mM NaHCO3 buffer solution as eluent at a ow rate of
Italy). This sampler comprises a compound-specic adsorbing car- 1 mL min1 allowed a baseline separation between Ac and For
tridge, surrounded by a cylindrical microporous diffusive body; (Stranger et al., 2008). The extracted liquid was analyzed by UVvis
mounted on a supporting plate. The adsorbent for SO2, NO2, HAc and spectrophotometry for the O3 concentrations.
HFor was triethanolamine and for O3 it was 4,4-dipyridylethylene. For BTEX, sample extractions were performed by using chemical
The BTEX compounds adsorb onto thermally desorbable graphitized desorption with 2 ml of carbon disulde (CS2), during 1 h
carbon. Cartridges were exposed in parallel for 1 week after which (Buczynska et al., 2009). Extracts were analyzed with a Varian gas
the cartridge was replaced for the second week of sampling. The tem- chromatograph equipped with a Flame Ionization Detector (FID). An-
perature was recorded every 20 min during the two week sampling alyte separation was achieved with the use of an intermediate polar
campaign. 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,
2.3. Measurement techniques in splitless mode. Each sample was injected tree times.

Bulk elemental concentrations of the PM were determined by 3. Results and discussion


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 The bulk elemental concentrations as determined by EDXRF are
allowed analysis from Z = 13. Individual particle analyses were summarized in Figs. 2, 3 and 4 for both indoor and outside schools.
performed by computer-controlled electron probe X-ray micro analy- Over the three year period the general trend is to nd concentrations
sis (CC-EPXMA). Due to an ultra-thin window detector, elemental of 1000 ng/m3 and higher for the elements Si, Ca and Al both indoor

Fig. 3. Concentration average for each element (ng/m3) in 2010.


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 pointing a concentration above the guideline dened by the World
source of this element since there was no sign of element concentration Health Organization (WHO, 2000).
outdoor. Concerning NO2 pollution, the concentration values obtained were
Some studies show that cleaning activities, as operation of oor signicantly higher than the SO2 values, and in general also similar to
polishing machine and wet cleaning by detergents can be one of the the values reported in the literature (Kim et al., 2011; Stranger et al.,
causes of indoor sources (Guo et al., 2008; Morawska et al., 2009). 2008; Zhao, 2006; Gl et al., 2011; Zakaria et al., 2010; Hulin et al.,
Once again, high levels of concentration observed within schools 2010; Hroux et al., 2010). The schools located in more urbanized
may be associated with the accumulation of the element (both by areas and near intense vehicular trafc presented levels of NO2 con-
the presence of inside sources or by the arrival of particles from the siderably higher than the schools in the industrial (suburban) area,
outside environment). indicating that the greatest source of NO2 is rather the vehicular traf-
Low-Z EPMA was performed for fractioned airborne particles. c than the industrial emissions (in this case, the emissions from the
Some distinctive particle types can be identied according to their petrochemical plant), in agreement with what was described in the
chemical composition. By studying particles on an individual basis literature.
one can determine the size distribution and elemental association In a general form, the schools in the suburban area presented
(group or cluster) of these particles, both of which impact on pulmo- higher levels of acetic acid pollution. However, it is not possible to
nary deposition and impact. Carbonaceous and soil-derived particles draw any substantial conclusions from this pattern, since the concen-
are compounds characterized by the presence of carbon in its consti- tration values for acetic acid presented great variation between the
tution and can be separated into three different groups of species, i.e. different campaigns, being generally low in the second campaign
biogenic, soot and organic (Godoi et al., 2004). The particles named and signicantly high in the rst one, for both urban and suburban
carbon black (or soot) are the varieties of pure carbon particles areas. In the rst campaign, the concentration values were higher
(around 70% or more of its carbon composition), forming a colloidal than the results reported by other studies and presented concerning
dispersion of very ne particles (Avigo et al., 2008). Soot comes from peaks of high concentration of the pollutant, when in comparison
human activity, in particular diesel vehicles and tire wear and brakes with the articles studied (Godoi et al., 2009; Shendell et al., 2004;
of vehicles in general. The particles of this group were found in all Ongwandee et al., 2009; Kinney et al., 2002; Fenech et al., 2010;
schools in 2009 and 2010. The percentages of the relative abundance Gilbert et al., 2005; Hulin et al., 2010; Marchand et al., 2008). The
revealed that the highest values appear for particles in the ne fraction I/O ratios obtained in the rst campaign indicated a strong presence of
(0.5 to 2.5 m); the higher value was indoor the School S1 with 34% of indoor sources or accumulation of HAc in all the assessed schools.
the total of 638 particles (approximately 81% of 638 are in the ne Regarding formic acid, the pattern was similar to acetic acid. Ac-
fraction). The contribution of soot particles is directly linked to cording to Table 1, urban and suburban areas presented similar levels
urban areas, primarily by vehicle emissions (Avigo et al., 2008) and of formic acid pollution. The concentration values of this pollutant
also by small contributions from gas combustion, industrial processes, were in general low, mainly in the second campaign. Besides, the I/O
dust from paved roads and burned (Gray and Cass, 1998). The aluminosil- ratios obtained for the rst campaign suggest that there are important
icates (AlSi) are part of the soil or come from human activity and vehicu- sources of HFor in the indoor environment or accumulation of this
lar trafc, agriculture, incineration, deforestation and desertication. Such pollutant in the assessed schools.
particles consisting mainly of Si are identied as quartz (SiO2). In the sam- Comparing average concentration of formic acid to average con-
ples, the cluster AlSi appeared in both sampling years (2009 and 2010), centration of acetic acid in each sampling site, it is possible to notice
proving to be present in almost all schools. It is worth mentioning the that the second one is the highest between them in almost all the
importance of the characterization that the particle size, as compared sampling sites, with similar behavior for both urban and suburban
to lung deposition smaller particles are most dangerous because they areas. The reason for this behavior may be the main outdoor source
can reach the lung alveoli and provide further complications. of both acids: vehicle emissions (primary acetic and formic acids are
Table 1 displays the average concentration values obtained for by-products of the incomplete combustion of oxygenated fuels in
SO2, NO2, HAc, and HFor for the urban and the suburban areas, with engines). While formic acid is a result of predominant release of
the last one comprising the area near the petrochemical plant. formaldehyde from vehicles powered with gasoline with and without
Concerning SO2 pollution, the concentration values obtained were catalytic converters, acetic acid is derived from acetaldehyde emitted
generally low, in agreement with results reported in the literature by automobiles powered with pure ethanol or a blend of ethanol/
(Kim et al., 2011; Godoi et al., 2009; Stranger et al., 2008; Zhao, 2006). gasoline. Ethanol is the main fuel used in Brazil's vehicles, which is the
However, schools located in the urban area in general presented higher most probable reason why the concentration of acetic acid exceeds
values, which is reected in the values found in Table 1. There was only the concentration of formic acid at the assessed schools (Godoi et al.,
one measurement, at one of the schools located in the urban area, 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 645

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