IndoorOutdoor Distribution and Risk

Assessment of Volatile Organic Compounds in

the Atmosphere of Industrial and Urban Areas
Laura Massolo,
1
Martina Rehwagen,
2
Andres Porta,
1
Alicia Ronco,
1
Olf Herbarth,
3
Andrea Mueller
2
1
Facultad de Ciencias Exactas, Centro de Investigaciones del Medio AmbienteCIMA,
Universidad Nacional de La Plata (CICPBA-CONICET), 47 y 115; (1900)-La Plata, Argentina
2
UFZ-Helmholtz Centre for Environmental Research, Permoserstrasse 15,
(D-04318)-Leipzig, Germany
3
Faculty of Medicine, Department of Environmental Medicine and Hygiene,
University of Leipzig, Liebigstrae 27, D-04103 Leipzig, Germany
Received 20 January 2009; revised 1 April 2009; accepted 4 April 2009
ABSTRACT: Volatile organic compounds (VOCs), which play an important part indoors and outdoors,
comprise differing compound groups such as n-alkanes, cycloalkanes, aromatic and chlorinated hydro-
carbons and terpenes. In the current study, samples were analyzed from indoor (schools and houses, n 5
92) and outdoor (n 5 33) air in urban, industrial, semirural and residential areas from the region of La Plata
(Argentine) to consider VOC exposure in different types of environments. VOCs were sampled for 1 month
during winter for 3 years, with passive 3M monitors. Samples were extracted with CS
2
and analyzed by
GC/MS detectors. The results show signicant differences in concentration and distribution between
indoor and outdoor samples, depending on the study area. Most VOCs predominantly originated indoors
in urban, semirural and residential areas, whereas an important outdoor inuence in the industrial area
was observed. In all areas alkanes and aromatic compounds dominated, even though a different chemical
distribution was seen. Trafc burden was determined as the major source of outdoor VOC with a ben-
zene/toluene ratio close to 0.5. Indoors, C9C11 alkanes, toluene and xylenes dominated, caused by
human activities. In contrast, in the industrial area higher concentrations of hexane, heptane and benzene
occurred outdoors and affected the indoor air signicantly. The lifetime cancer risk (LCR) associated to
the benzene exposure was calculated for children from the different study areas. For all groups the study
showed a LCR value greater than 1 3 10
26
related to the benzene exposure indoors as well outdoors. A
value two magnitudes higher was detected indoors in the industrial area, what demonstrates the high risk
for children living in this area of La Plata.
#
2009 Wiley Periodicals, Inc. Environ Toxicol 00: 000000, 2009.
Keywords: VOCs; indooroutdoor ratio; urban and industrial burdens; indoor sources; risk assessment
INTRODUCTION
Volatile organic compounds (VOCs), arising from natural
and anthropogenic processes represent an important group
of indoor and outdoor air pollutants, because they are ubiq-
uitous and associated with increased long-term health risks
(WHO, 2004; Brown, 2002). Vehicular and industrial
Correspondence to: Andrea Mueller; e-mail: a.mueller@ufz.de
Contract grant sponsor: International Bureau of the German Federal
Ministry of Education and Research and the Ministry of Science and Tech-
nology of Argentina (MINCyT).
Published online in Wiley InterScience (www.interscience.wiley.com).
DOI 10.1002/tox.20504
C
2009 Wiley Periodicals, Inc.
1
emissions are the major sources of outdoor VOCs. It can be
assumed that 35% of total VOC emissions are due to vehi-
cle exhaust and evaporative losses (Chan et al., 2002;
Khoder, 2007). Petroleum reneries and petrochemical
plants are other contributing sources of VOC emissions,
mainly originating from production processes, storage tanks
and waste areas (Watson et al., 2001; Cetin et al., 2003).
Indoor VOC exposure is thought to be of greater concern
in the community because indoor concentrations of many pol-
lutants are often higher than those typically encountered out-
doors. At the same time, indoor VOC concentration may be
the dominant contributor to personal exposure because most
people spend over 80% of their time indoors, either in the
home or at work place (Guo et al., 2004; Wang et al., 2007).
Measurement of VOCs in the indoor environment has received
substantial research attention for several years because indoor
VOC levels may pose potential health effects to occupants of
dwellings. While some VOCs may be present at concentra-
tions that are not considered acutely harmful to human health
with short-term exposure, long-term exposure may result in
mutagenic and carcinogenic effects (Son et al., 2003).
The occurrence and concentrations of VOCs in residen-
ces can be affected by outdoor atmospheric conditions,
indoor sources, indoor volume, human activities, chemical
reactions, ventilation rates, and seasonal factors (Son et al.,
2003; Schlink et al., 2004).
Indoor sources are quite numerous including combustion
products, cooking, construction materials, furnishings,
paints, varnishes and solvents, adhesives and caulks, ofce
equipment and consumer products (Jones, 1999; Watson
et al., 2001; Guo et al., 2003).
Previous studies carried out in La Plata and surrounding
areas showed a higher VOC burden in the area closer to the
industry, with high concentrations of alkanes and aromatic
compounds (Herbarth et al., 1997; Ronco et al., 1998).
Also, high concentrations of benzene, toluene, ethylben-
zene, and xylenes were found in the urban area, indicating
the inuence of trafc sources.
The present study contributes to a more detailed indoor
outdoor characterization over a 3 year period. To consider
the VOC exposure in the different types of environments of
La Plata, measurements of VOC concentrations were car-
ried out indoors and outdoors in area inuenced by indus-
trial emissions, in an urban area inuenced by trafc, as
well as in semirural and residential area as control. The
indooroutdoor ratios were calculated to get an impression
regarding the sources of VOC exposure and the impact of
outdoor-related air pollution on the indoor environment.
METHODS
Sampling Sites
The study region, La Plata and neighboring areas, located
50 km south-eastern of Buenos Aires (Argentine), has a
population around 700 000 inhabitants. Four sampling
zones were considered: industrial (I), urban (U), semirural
(SR), and residential (R) areas (Fig. 1).
The industrial area holds the countrys main oil renery
(total crude oil distillation capacity: 38 000 m
3
/day) located
next to six petrochemical plants producing diverse com-
pounds such as aromatics (benzene, toluene, xylenes),
aliphatic solvents (n-pentane, n-hexane, n-heptane), poly-
propylene, polybutene, maleic anhydride, cyclohexane,
methanol, methyl tertiary butyl ether, and petroleum coke.
This industrial complex is 10 km north-northeastern of
the main urban sector of the city.
The urban area in the city center of La Plata is character-
ized by heavy trafc; the number of vehicles registered is
200 000. The semirural and residential sites, places with
low trafc, were considered as control areas.
Sampling and Analytical Methods
Sampling was carried out indoors and outdoors in winter
time between 2000 and 2002, using passive samplers (3M
OVM 3500, 1986) monitors. A sampling period of 4 weeks
was selected. Choosing this design, the integrative sam-
pling describes a mean load relative to personal exposure.
Using this procedure, it can be assumed that the human ex-
posure is more selectively described compared with a short
time measurement. Indoor samples were collected in kin-
dergartens and in selected homes of children attending
them (n 5 92), whereas outdoor samples were collected in
representative sites of the four sectors (n 5 33) parallel to
the indoor measurement. The outdoor monitors were placed
at rain-protected positions. Indoors, the passive monitors
were placed in the middle of the room at a 1.52 m height
with a minimum distance of 50 cm to the ceiling
(Rehwagen et al., 2003).
The study comprised the analysis of 29 VOCs. Accord-
ing to their structure and composition, they belong to the
following groups: alkanes (hexane, heptane, octane, no-
nane, decane, undecane, dodecane, tridecane); cycloalkanes
(methylcyclopentane, cyclohexane, methylcyclohexane);
aromatic hydrocarbons (benzene, toluene, ethylbenzene,
m1p-xylene, styrene, o-xylene, 4-ethyltoluene, 3-ethylto-
luene, 2-ethyltoluene, naphthalene); chlorinated hydrocar-
bons (chlorbenzene, trichlorethylene, tetrachlorethylene);
terpenes (a-pinene, b-pinene, 2-carene, 3-carene, limo-
nene). After exposure, the VOCs were desorbed from the
adsorption layers (charcoal pads) by means of 1.5 mL of
carbon disulde (with low benzene, from Merck) contain-
ing 1% of methanol. The VOC analysis was performed on a
PerkinElmer gas chromatograph with a masspectrometrical
detector, equipped with an RTX-1 column (60 m 0.32 mm
I.D., 1.0 lm lm thickness; Restek). The oven temperature
was held at 438C for 5 min, and then programmed to 2008C
at a rate of 2.58C min
21
. The injector temperature was held
2 MASSOLO ET AL.
Environmental Toxicology DOI 10.1002/tox
at 2508C as well as the transfer line temperature. An elec-
tron energy of 70 eV was used for ionization. The source
temperature was held at 2008C. A sample volume of 1 lL
was splitless injected. Integrated areas of selected fragment
ions from each of the 29 VOCs were obtained with the soft-
ware Turbomass, Version 4.4 (PerkinElmer) (Rehwagen
et al., 2003; Schlink et al., 2004).
Quantication and Statistical Analysis
A stock solution was prepared diluting original reagents in
highest available purity with methanol (stock solution can
be stored frozen for later use). For calibration, we freshly
prepared a set of ve levels in the range of 0.84 lg/mL by
means of diluting the stock solution with carbon disulde,
which contained an internal standard (benzene d6). For
each component a calibration function was determined
based on the integrated area of the chromatogram. The
VOC masses, adsorbed in a sample, were determined from
the integrated areas by means of the calibration function.
Finally, the average concentration of each component over
the sampling interval was calculated according to the
following equation adopted from 3M (1986).
clg=m
3
mt
1
r
1
A 1
where: mabsolute amount of each adsorbed component
on the monitor (in lg), tsampling interval (in min), r
recovery coefcient by incomplete desorption from the
sampler, A includes the diffusion coefcient of the compo-
nent, the diffusion area of the charcoal pad, and the diffu-
sion distance inside the sampler.
The recovery coefcients were determined by direct
injection of a known amount of the standard into a 3M sam-
pler and subsequent extraction with carbon disulde con-
taining 1% methanol. The recovery was between 98 and
102%. The detection limits for the components were esti-
mated as the threefold standard deviation (SD) of ve repli-
cate measurements of monitor blanks. For components with
blank values too low to be registered, it is usual practice to
Fig. 1. Sampling points in La Plata. I, industrial; U, urban; SR, semirural; R, residential.
3 INDOOROUTDOOR DISTRIBUTION AND RISK ASSESSMENT OF VOCs
Environmental Toxicology DOI 10.1002/tox
use the threefold SD of replicate measurements of a low-
level standard solution (Begerow et al., 1999). For the
GCMS system we found detection limits from 0.01 to 0.05
lg/m
3
converted to a sampling interval of 4 weeks.
The nonparametric test (MannWhitney U-Test) was
used for statistical analysis of results, according to the non-
symmetrical distribution of the data (Sokal and Rohlf,
1981; Zar, 1998). Statistical analysis and plots of median
values were prepared using Statistica 6.0. A P-value below
0.05 was regarded to be statistically signicant.
RESULTS AND DISCUSSION
VOC Concentration Outdoors and Indoors
All presented concentrations were calculated as mean, and
median of all samplings carried out in the study areas dur-
ing the sampling period between 2000 and 2002. None sig-
nicant differences were observed during the measurement
period.
Total VOCs
The concentrations of the total VOC content and the con-
centrations per compound groups are given in Table I,
showing the number of measurements, mean, median, and
maximum concentration for outdoors and indoors in the dif-
ferent study areas.
The concentrations of outdoor VOCs in the industrial
area were between three and six times higher than in the
other areas. Signicant differences (P \ 0.05) could be
observed for all compound groups of VOCs, both indoors
and outdoors, between the industrial and the other areas,
with the exception of terpenes.
As different previous studies have already shown, VOC
concentrations are typically higher indoors than outdoors,
due to accumulation by poor ventilation (Adgate et al.,
2004; Schlink et al., 2004). Also in the study presented
here, the median indoor concentration of total VOC was
higher than the outdoor. Similar values indoors were found
for the urban, semirural, and residential areas; the higher
concentrations were detected in the industrial area.
TABLE I. Concentration of VOC groups in lg/m
3
and outdoor/indoor ratio for all studied areas
Outdoor Indoor
Ratio
indoor/outdoor median mean max median mean max
Industrial n 57 n 526
Alkanes 61.70 72.87 160.30 71.56 105.18 476.94 1.16
Cycloalcanes 20.65 21.83 38.11 18.32 21.62 69.18 0.89
Aromatics 49.86 59.84 125.03 55.27 92.72 380.19 1.11
Chlorinated 0.89 1.62 5.03 2.35 2.49 8.00 2.63
Terpenes 0.71 1.17 4.10 6.33 9.30 43.34 8.97**
Sum VOC 129.17 157.34 327.98 180.16 231.32 758.81 1.39
Urban n 5 18 n 524
Alkanes 11.59 14.70 47.17 24.06 51.02 274.40 2.08**
Cycloalcanes 2.99 2.96 4.49 3.98 7.57 56.68 1.33*
Aromatics 21.74 24.50 51.52 28.55 37.57 122.92 1.31
Chlorinated 1.13 1.51 6.23 0.46 1.40 10.98 0.41
Terpenes 0.38 0.85 3.37 4.48 6.59 34.01 11.95**
Sum VOC 37.24 44.51 90.11 70.65 104.15 367.58 1.90**
Semi-rural n 57 n 528
Alkanes 6.75 6.99 12.98 33.07 88.00 540.28 4.90**
Cycloalcanes 1.31 1.40 1.98 4.93 9.10 67.13 3.78**
Aromatics 9.43 9.73 14.77 23.11 44.03 258.40 2.45**
Chlorinated 1.11 3.75 13.83 0.49 1.31 5.58 0.44*
Terpenes 0.29 0.72 3.35 6.49 12.99 60.39 22.06**
Sum VOC 23.46 22.59 41.79 80.23 152.99 659.91 3.42**
Residental n 51 n 514
Alkanes 6.40 53.01 49.53 109.46 8.29
Cycloalcanes 1.20 3.26 5.43 18.48 2.72
Aromatics 8.93 27.03 45.40 205.68 3.03
Chlorinated 5.42 0.37 0.62 2.18 0.07
Terpenes 0.29 7.14 11.48 40.11 24.26
Sum VOC 22.24 81.96 112.46 288.13 3.68
P-value shows signicant difference between indoors and outdoors; * P\0.05, ** P\0.01.
Median values of each compound was used to calculated the ratio.
4 MASSOLO ET AL.
Environmental Toxicology DOI 10.1002/tox
The main compounds outdoors as well indoors belong to
the group of alkanes and aromatics. A detailed analysis of
these components shows a different spatial distribution
indoors and outdoors, specic to the investigated areas,
which will be examined at length in the following chapters.
The concentration of cycloalkanes in the industrial area
outdoors ranged between 7.9 and 38.1 lg/m
3
, which were
between 5 and 15 times higher than in the other areas due
to emissions of the petrochemical plant producing 85 000
ton/year of cyclohexane (IAPG, 1999). This caused also
signicant higher concentrations of cycloalcanes indoors
(range 6.369.1 lg/m
3
) in the industrial area.
For chlorinated hydrocarbons, signicant differences
occurred only indoors in the industrial area. Chlorinated
hydrocarbons can be contained in cleaning products and
products for disinfection. The concentration of these com-
pounds varied depending on differing human activities
(Tang et al., 2005).
The concentrations of terpenes, which can be emitted
from furniture or other wood products and are contained in
many cleaning and cosmetic products in households, were
generally higher indoors (Gosselin et al., 1984; Hodgson
et al., 2000). The concentrations ranged between 0.6 and 60
lg/m
3
, which were lower than reported by other studies
from European cities (Sareela et al., 2003; Schlink et al.,
2004). No signicant differences between the studied areas
were seen.
Alkanes
Compounds of alkanes are the main group of VOCs out-
doors and indoors. By analyzing the compounds of this
group, different spatial distributions outdoors and indoors
were found. Whereas the exposure of alkanes outdoors was
dominated by C6C8 alkanes (hexane, heptane and octane),
especially in the industrial area, higher concentrations of
C9C13 compounds (nonane to tridecane) appeared indoors
(Fig. 2).
The median outdoor concentrations of hexane, heptane
and octane in sampling places closer to the industrial area
(sum C6C8 ranged between 14.9 and 122.9 lg/m
3
) were
between 7 and 14 times higher than in the other areas
(Table II). These compounds are generated from the petro-
chemical industries located in the region. Because of the
strong outdoor exposure, the indoor concentration of the
C6-C8 alkanes was signicantly higher in the industrial
area (sum ranged between 17.8 and 146.4 lg/m
3
).
In the urban area, a median outdoor concentration of C6-
C8 alkanes of 7.0 lg/m
3
was found, which was two to three
times higher compared with the semirural and residential
areas due to the trafc emissions (Borbon et al., 2003; Na
et al., 2004). Compared with other cities, the mean outdoor
concentration of hexane in the urban area of La Plata (7.4
lg/m
3
) ranged between those levels reported for Helsinki
(4.5 lg/m
3
) (Edwards et al., 2001) and Santiago de Chile
(9.2 lg/m
3
) and Caracas (13.7 lg/m
3
) (Gee and Sollars,
1998).
The median indoor concentration of hexane in the urban,
residential and semirural areas showed similar concentra-
tions near 5 lg/m
3
. Indoor sources of hexane can be a wide
range of household products like cleaners and polishes,
paint, greases and lubricants (Sack et al., 1992).
The concentration of C9C13 alkanes was generally
higher indoors than outdoors in all places, without signi-
cant differences between the investigated areas (Fig. 2),
which indicates mainly indoor sources. These compounds
are associated with human activities indoors like renovation,
painting and cleaning (Lau et al., 1997; Watson et al., 2001).
Aromatic Compounds
Table III shows the concentrations of aromatic compounds
in both outdoor and indoor air for all studied areas.
Fig. 2. Concentrations of alkanes. The sum of C6C8 hex-
ane, heptane, octane) and C9C13 (nonane to tridecane is
plotted I, industrial; U, urban; SR, semirural; R, residential;
A, outdoor; B, indoor.
5 INDOOROUTDOOR DISTRIBUTION AND RISK ASSESSMENT OF VOCs
Environmental Toxicology DOI 10.1002/tox
Benzene, toluene, and xylenes were the predominant aro-
matic compounds in all cases.
Concerning the outdoor concentrations of benzene, tolu-
ene and xylenes (BTX), the industrial area exhibits signi-
cantly higher concentrations (mean BTX 53.3 lg/m
3
) than
the other areas (Table III) due to industrial emissions, con-
sidering that the regional petrochemical plants produce 250
000 ton/year of BTX (IAPG, 1999).
The urban area showed outdoor levels of BTX (mean
20.2 lg/m
3
) two times higher than the control sectors,
which is related with more intensive trafc in the city.
In previous studies a mean concentration level of BTX
outdoors of 37.3 lg/m
3
was found in the industrial area and
54.6 lg/m
3
in the urban area (Ronco et al., 1998). The
results reported here show that the levels have increased in
the industrial and decreased in the urban area. This last
result can be caused by a change in the use of car fuels to
more gas (methane).
The analysis of the benzene/toluene ratio shows for the
urban, semirural and residential sectors values of 0.47,
0.56, and 0.55, respectively. According to other studies a
value near 0.5 indicates vehicular exhaust as the dominant
source for aromatic VOCs (Fernandes et al., 2002; Zou
et al., 2003). The higher ratio obtained for the industrial
area (0.71) points out the presence of additional sources of
these compounds, such as the petrochemical industry.
TABLE II. Concentrations of alkanes in lg/m
3
and indoor/outdoor ratio for all studied areas
Outdoor Indoor
Ratio
indoor/outdoor median mean max median mean max
Industrial n 57 n 526
Hexane 26.52 35.28 81.65 26.11 36.43 110.61 0.98
Heptane 11.87 13.87 29.38 11.16 13.64 39.35 0.94
Octane 5.86 6.87 12.13 5.89 6.77 19.09 1.01
Nonane 4.18 5.03 8.45 7.06 9.57 33.43 1.69
Decane 4.12 6.00 15.36 7.04 12.78 81.42 1.71
Undecane 2.10 3.30 8.50 4.19 12.17 83.20 1.99
Dodecane 0.98 1.50 3.18 2.62 8.11 90.03 2.67
Tridecane 0.74 1.03 1.88 1.18 5.71 58.44 1.60
Urban n 5 18 n 524
Hexane 4.64 7.41 39.86 4.87 7.05 27.59 1.05
Heptane 1.69 1.62 2.23 1.94 3.22 15.97 1.15
Octane 0.64 0.69 2.32 1.01 1.99 17.66 1.57*
Nonane 1.17 1.18 2.68 3.08 12.34 87.29 2.62**
Decane 1.58 1.99 5.90 4.62 15.19 90.71 2.92**
Undecane 0.88 1.09 4.02 2.53 8.24 76.94 2.90**
Dodecane 0.37 0.38 0.60 0.93 2.22 20.10 2.55**
Tridecane 0.35 0.33 0.58 0.57 0.78 2.74 1.65**
Semi-rural n 57 n 523
Hexane 2.26 2.10 3.31 5.49 17.41 123.93 2.43**
Heptane 0.76 0.71 1.19 1.96 2.59 8.16 2.58**
Octane 0.32 0.34 0.45 1.45 1.92 6.57 4.54**
Nonane 0.74 0.83 1.25 3.13 10.71 84.92 4.20**
Decane 1.30 1.38 2.73 7.28 19.42 133.31 5.60**
Undecane 0.67 1.18 4.55 5.74 24.13 228.15 8.57**
Dodecane 0.21 0.22 0.45 2.41 6.53 39.07 11.50**
Tridecane 0.19 0.22 0.54 1.03 2.85 12.84 5.41**
Residential n 51 n 514
Hexane 2.98 4.70 12.78 41.40 1.58
Heptane 0.97 1.47 2.61 11.34 1.52
Octane 0.32 0.85 1.84 5.52 2.66
Nonane 0.70 5.18 8.56 25.29 7.41
Decane 0.81 7.74 11.54 38.25 9.53
Undecane 0.45 6.07 9.00 35.31 13.56
Dodecane 0.17 1.36 2.29 6.54 8.20
Tridecane 0.01 0.58 0.91 4.74 110.28
P-value shows signicant difference between indoors and outdoors; * P\0.05. ** P\0.01.
Median values of each compound was used to calculated the ratio.
6 MASSOLO ET AL.
Environmental Toxicology DOI 10.1002/tox
Benzene has raised the focus of interest because of its
known genotoxicity and carcinogenicity even at typical am-
bient concentrations (class I, IARC, 1995). The mean out-
door concentration in the industrial area (16.1 lg/m
3
) was
signicantly higher than in the other areas, due to the indus-
trial emission.
Outdoor sources of benzene in urban, semirural and resi-
dential areas are vehicular emissions (Watson et al., 2001;
Na et al., 2004). The mean concentration in these areas
ranged between 3.1 and 1.5 lg/m
3
, and are higher than in
some European cities like Helsinki (Edwards et al., 2001),
Munich and Leipzig (Schlink et al., 2004), but are lower
TABLE III. Concentrations of aromatic compounds in lg/m
3
and indoor/outdoor ratio
Outdoor Indoor
Ratio
indoor/outdoor median mean max median mean max
Industry n 57 n 526
Benzene 13.42 16.10 37.21 18.00 19.07 59.54 1.34
Toluene 18.90 21.69 54.49 20.81 35.56 219.44 1.10
Ethylbenzene 1.80 2.12 3.46 2.13 4.21 18.79 1.18
m1p-Xylene 10.91 12.85 24.71 10.16 17.16 69.63 0.93
Styrene 0.13 0.15 0.38 0.25 0.30 0.85 1.89
o-Xylene 2.30 2.71 4.40 3.04 4.88 17.13 1.32
4-Ethyltoluene 1.90 2.26 4.12 2.03 5.38 55.17 1.07
3-Ethyltoluene 0.77 0.94 1.70 0.81 2.29 26.09 1.05
2-Ethyltoluene 0.74 0.86 1.58 0.85 2.33 29.36 1.15
Naphthalene 0.13 0.14 0.22 0.58 1.53 12.80 4.44**
Urban n 5 18 n 524
Benzene 3.06 3.15 5.63 3.20 3.58 12.74 1.04
Toluene 6.53 8.82 30.09 11.70 15.12 89.00 1.79*
Ethylbenzene 1.01 1.15 2.29 1.27 1.35 2.85 1.26
m1p-Xylene 6.35 6.94 15.01 6.33 6.54 18.75 1.00
Styrene 0.12 0.17 0.46 0.20 0.25 0.74 1.70
o-Xylene 1.13 1.27 2.48 1.42 1.55 4.76 1.25
4-Ethyltoluene 1.51 1.44 3.06 1.38 2.74 28.24 0.92
3-Ethyltoluene 0.58 0.60 1.34 0.58 1.13 11.72 1.01
2-Ethyltoluene 0.56 0.55 1.02 0.75 1.27 11.62 1.35
Naphthalene 0.12 0.42 5.55 0.23 4.03 77.51 1.94**
Semi-Rural n 57 n 523
Benzene 1.71 1.64 1.80 3.14 4.69 13.17 1.84**
Toluene 3.04 3.78 6.26 9.44 17.92 87.83 3.11**
Ethylbenzene 0.41 0.43 0.63 0.97 2.57 25.26 2.33**
m1p-Xylene 2.22 2.18 4.25 3.82 9.77 97.16 1.72
Styrene 0.07 0.07 0.09 0.18 0.31 1.09 2.51**
o-Xylene 0.45 0.45 0.73 0.97 2.77 25.63 2.16**
4-Ethyltoluene 0.57 0.64 1.34 1.16 2.92 13.43 2.04*
3-Ethyltoluene 0.22 0.26 0.63 0.49 1.19 4.91 2.25*
2-Ethyltoluene 0.20 0.21 0.50 0.52 1.16 5.63 2.59*
Naphthalene 0.05 0.05 0.08 0.26 0.71 7.14 5.21**
Residential n 51 n 514
Benzene 1.52 3.10 3.69 10.05 2.04
Toluene 2.76 9.51 15.16 40.81 3.45
Ethylbenzene 0.66 1.66 3.60 23.99 2.53
m1p-Xylene 2.50 4.44 13.82 104.70 1.78
Styrene 0.01 0.16 0.25 0.92 10.58
o-Xylene 0.73 1.43 3.55 24.58 1.97
4-Ethyltoluene 0.39 1.50 2.26 7.82 3.87
3-Ethyltoluene 0.14 0.58 0.97 3.80 4.12
2-Ethyltoluene 0.17 0.79 1.02 2.78 4.77
Naphthalene 0.06 0.31 1.08 7.33 4.86
P-value shows signicant difference between indoors and outdoors; * P\0.05. ** P\0.01.
Median values of each compound was used to calculated the ratio.
7 INDOOROUTDOOR DISTRIBUTION AND RISK ASSESSMENT OF VOCs
Environmental Toxicology DOI 10.1002/tox
than other highly polluted cities like Athens (Chatzis et al.,
2005), Caracas and Santigo de Chile (Gee and Sollars,
1998), and Seoul (Son et al., 2003).
According to a European Union directive (December
2000) the benzene concentrations in ambient air should not
exceed 5 lg/m
3
as a running annual average with a long-
term target of less than 1 lg/m
3
(OJ, L 313, 2000).
The indoor concentrations of aromatic compounds were
signicantly higher in the industrial area resulting from the
outdoor exposure, especially the concentration of the carci-
nogenic compound benzene, which was six times higher
than in the other areas (Table III). A median concentration
of 18.0 lg/m
3
indoors presents a signicant health hazard
for these inhabitants. According to the WHO (2000), an ex-
posure to 1 lg/m
3
produces a lifetime risk of 4 3 10
26
for
leukemia.
In the other areas, sources for indoor exposure of ben-
zene can be inuenced by trafc outside, but also by human
activities like smoking. The urban, semirural and residential
areas have close median indoor values of benzene, whereas
the semirural sector exhibits a higher standard deviation,
probably due to the use of kerosene for heating in many
houses in this area (Table III) (Pandit et al., 2001).
Indoor sources of toluene, the aromatic compound with
the highest concentration, can be products for cleaning and
renovation, solvents, and newspapers (Watson et al., 2001).
A similar value was observed in the urban and control
areas, mainly due to human activities. However, the higher
concentration of toluene outdoors in the industrial area led
to a doubling of the toluene level indoors in this region.
Similar results were observed for xylenes.
Table III also demonstrates higher levels indoors for
naphthalene, as well a carcinogenic compound (IARC,
2002). Naphthalene exposure outdoors is associated with
vehicle emission. However, a signicantly higher concen-
tration indoors indicates a stronger indoor source for this
substance. Naphthalene can be used as a household insecti-
cide (Zou el al., 2003) and can be contained in paints, dyes
and resins. Crystalline naphthalene is also used as a moth
repellent and as a solid block deodorizer for toilettes
(ATSDR, 1995). Additionally, naphthalene indoors can
originate from attached garages and the use of a gas stove.
Both are very common in La Plata. Nevertheless, the main
indoor source for naphthalene is smoking (Edwards et al.,
2005).
IndoorOutdoor Ratios
Since most people spend over 80% of their time indoors
(Schlink et al., 2004; Wang et al., 2007), indoor VOCs are
thought to be of greater concern because the indoor concen-
trations of these compounds are often higher than those typ-
ically encountered outdoors. The indoor/outdoor ratio is
generally used to infer penetration to indoor environments
and indoor sources (Tang et al., 2005). An I/O ratio lower
and close to one indicates more outdoor sources (Edwards
et al., 2001). A mixture of indoor and outdoor sources can
be assumed for a ratio between one and four without signi-
cant differences between indoors and outdoors. Signicant
differences between indoor and outdoor concentrations
indicate mainly indoor sources for the VOC compounds. A
more detailed analysis of the indoor/outdoor ratio indicates
a different distribution for all VOC families and their
compounds, dependently from the investigated area. The
median concentration of each compound was taken into
account to calculate the I/O ratios (Tables I, II, and III).
In the industrial area a ratio close to one for most of the
compounds indicates a strong impact of the industrial emis-
sions outdoors on the VOC concentration indoors. Only for
the group of terpenes and for naphthalene signicant higher
levels were found indoors. Also for the compounds related
to renovation activities like the C9C13 alkanes, no signi-
cant differences between indoors and outdoors were
observed in the industrial area. In addition, in this region,
social aspects and lifestyle quality are related to this nd-
ing. Mainly poor people are living in this area in simply
constructed houses, where the outdoor emissions can easily
permeate.
In the urban area signicant higher levels indoors were
found for the alkanes, but only for the group of C9C13
compounds, the cycloalkanes and terpenes. All of these
substances are associated with human activities, showing a
better living standard of the population in this region. No
differences occurred for the aromatic compounds associ-
ated with trafc like benzene, toluene and octane, indicat-
ing the inuence of vehicle exhaust on the VOC exposure
indoors, too (Chan et al., 2002; Rehwagen et al., 2003; Son
et al., 2003).
In the control regions without industrial or trafc emis-
sions, human activities are the exclusive sources for indoor
VOC exposure. For all investigated compounds, with
exception of chlorinated hydrocarbons, the concentrations
were signicantly higher indoors. Sources of chlorinated
hydrocarbons are probably mostly outdoors.
A very high indoor/outdoor ratio were found for ter-
penes, indicating a clear indoor source for these chemicals,
such as room deodorizers, furniture polishes, household
cleaners, fragrances, pharmaceutical products, wood and
wood-based materials (Hodgson et al., 2002; Saarela et al.,
2003).
Life Time Cancer Risk
Calculation of cancer risk requires the carcinogenic potency
of the specic compound and the mean exposure of the tar-
get group. The lifetime cancer risk (LCR) associated to
benzene in the different study areas was calculated by mul-
tiplication of the chronic daily intake (CDI) by the IRIS
8 MASSOLO ET AL.
Environmental Toxicology DOI 10.1002/tox
system potency factor (IRISIntegrated Risk Information
System) for benzene (IPCS, 2000; Hoddinott and Lee,
2000; Muller at al., 2003; Guo et al., 2004).
According to Guo et al.(2004) the CDI in mg/(kg x day)
was calculated with the following equation:
CDI
CC 3 IR 3 ED 3 EF 3 LE
BW 3 ATL 3 NY
2
where CC is the contaminant concentration (mg/m
3
), IR the
inhalation rate (m
3
/h), ED the exposure duration (h/week),
EF the exposure frequency (weeks/year), LE the length of
exposure (years), BW the body weight (kg), ATL the average
lifetime (period over which exposure is averaged, 70 years
were used), NY the number of days per year (365 days).
LCR was calculated for the exposure to benzene in
indoor and outdoor environments for the children of the
study group living in the different study areas (Table IV).
The average age of the study group was 6 years (value for
LE) because these children were living in the study areas all
this time. For the calculations we assumed an average body
weight (BW) of 20 kg and an average inhalation rate (IR) of
5 m
3
of air per day (Guo et al., 2004; Hoddinott and Lee,
2000). An annual average (ED) of 20 h per day in indoor
environments and 4 h per day outdoors and an exposure fre-
quency (EF) of 52 weeks per/year was guessed. The absorp-
tion factor of the VOCs for human was supposed to be 90%.
For the calculations the median concentrations of benzene
were exerted and according to USEPA (1998) a potency
factor for benzene of 0.029 (mg/(kg 3day))
21
was used.
The results showed a LCR one order of magnitude
higher for children from industrial area in indoor and out-
door environments than the other areas due to the high ben-
zene concentration in this area. The LCR from outdoor in
the urban area is two times higher compared with semirural
and residential sites results from the benzene emission by
trafc. Because people spend more time indoor, the LCR is
one order of magnitude higher for indoor environment than
outdoor in all cases, the higher value is observed in the
industrial area. The others areas showed similar values of
LCR indoors (Table IV).
The World Health Organization (WHO) considered as
acceptable a LCR under the range between 1 3 10
25
and 1 3 10
26
whereas the USEPA recommended a LCR
under 1 3 10
26
(Miller et al., 1999; IPCS, 2000). For all
children groups, this study showed that the benzene expo-
sure in the investigated areas may lead to LCR in excess of
1 3 10
26
for indoor and outdoor. Especially, for the indoor
environment the LCR exceeded this acceptable value by
one magnitude, in case for children living in the industrial
area by two magnitudes.
CONCLUSIONS
The analysis of a three-year VOC dataset has provided
interesting insights on the characterization of VOCs in
indoor and outdoor air in the region of La Plata. Ambient
air in the vicinity of the industrial site is signicantly differ-
ent than the air quality found in the urban, semirural and
residential areas of La Plata. Whereas trafc was identied
as the main source of outdoor VOC exposure in the urban,
semirural and residential areas, in the industrial area, out-
door as well indoor air is strongly affected by emissions of
the petrochemical industry.
Total VOCs in the urban, residential and semirural areas
are equivalent to those reported for other major cities
worldwide, indicating comparable burdens, although none-
quivalent distribution patterns could be a result of different
lifestyles and habits.
Indoor/outdoor ratios suggest higher indoor burdens in
all places and demonstrate an exceptional importance of
indoor exposure. C9C13 alkanes and terpenes, which are
associated with human activities, are especially responsible
for a high indoor VOC concentration.
The high outdoor VOC content in the industrial area, to-
gether with the lifestyle quality, affected very strongly the
indoor exposure for these inhabitants. In particular, besides
other compounds like hexane and heptane, the higher con-
centration of the carcinogenic compound benzene, outdoors
as well indoors, documents a high risk for human health in
the industrial area.
For all children groups this study showed a LCR associ-
ated to benzene exposure indoors and outdoors greater than
the acceptable levels, the highest values appeared in the
industrial area. For outdoor exposure, the urban area
showed a LCR higher than residential and semirural areas.
The health risks from benzene exposure may be minimized
increasing the controls to reduce the industrial emissions as
well as trafc pollution, taking also into consideration a
low VOC indoor emission.
Further research will be taking into account to evaluate
the environmental impact of VOCs and the assessment of
effects of the different volatile compounds on human
health.
The authors would also like to thank Brigitte Winkler for her
excellent assistance in the chemical analyses.
TABLE IV. Childrens lifetime cancer risk (LCR) for
benzene exposure indoors and outdoors in the
different study areas
Outdoor LCR Indoor LCR
Industry 2,99E-05 2,01E-04
Urban 6,83E-06 3,57E-05
Semi-rural 3,81E-06 3,50E-05
Residential 3,39E-06 3,46E-05
9 INDOOROUTDOOR DISTRIBUTION AND RISK ASSESSMENT OF VOCs
Environmental Toxicology DOI 10.1002/tox
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