Atmospheric Environment 44 (2010) 3529e3537

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Atmospheric Environment
journal homepage: www.elsevier.com/locate/atmosenv

A land use regression model for predicting ambient volatile organic

compound concentrations in Toronto, Canada
Jason G. Su a, Michael Jerrett a, *, Bernardo Beckerman a, Dave Verma b, M. Altaf Arain c,
Pavlos Kanaroglou c, Dave Stieb d, Murray Finkelstein e, Jeffery Brook f
a
Environmental Health Sciences, School of Public Health, University of California, Berkeley, 50 University Hall, Berkeley, CA 94720-7360, USA
b
Department of Family Medicine, McMaster University, Hamilton, ON L8N 3Z5, Canada
c
School of Geography & Earth Sciences, McMaster University, Hamilton, ON L8S 4K1, Canada
d
Environmental Health Directorate, Health Canada, Ottawa, ON K1A 0K9, Canada
e
Department of Family and Community Medicine, University of Toronto, Toronto, ON M5T 3L9, Canada
f
Environmental Services, Environment Canada, 4905 Dufferin St, Toronto, ON M3H 5T4, Canada

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

Article history: More than 25 studies have employed land use regression (LUR) models to estimate nitrogen oxides and
Received 2 December 2009 to a lesser extent particulate matter indicators, but these methods have been less commonly applied to
Received in revised form ambient concentrations of volatile organic compounds (VOCs). Some VOCs have high plausibility as
19 March 2010
sources of health effects and others are specific indicators of motor vehicle exhaust. We used LUR models
Accepted 7 June 2010
to estimate spatial variability of VOCs in Toronto, Canada. Benzene, n-hexane and total hydrocarbons
(THC) were measured from July 25 to August 9, 2006 at 50 locations using the TraceAir organic vapor
Keywords:
monitors. Nitrogen dioxide (NO2) was also sampled to assess its spatial pattern agreement with VOC
Land use regression
Volatile organic compound
exposures. Buffers for land use, population density, traffic density, physical geography, and remote
Nitrogen dioxide sensing measures of greenness and surface brightness were also tested. The remote sensing measures
GIS have the highest correlations with VOCs and NO2 levels (i.e., explains >36% of the variance). Our
Remote sensing regression models explain 66e68% of the variance in the spatial distribution of VOCs, compared to 81%
Air pollution for the NO2 model. The ranks of agreement between various VOCs range from 48 to 63% and increases
Toronto substantially e up to 75% e for the top and bottom quartile groups. Agreements between NO2 and VOCs
are much smaller with an average rank of 36%. Future epidemiologic studies may therefore benefit from
using VOCs as potential toxic agents for traffic-related pollutants.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction between long-term exposure to ambient air pollution and chronic

Exposure to ambient air pollution is associated with both acute
and chronic health effects. The short-term effects reflect the
influence of day-to-day fluctuations in ambient levels of pollution
(Chen et al., 2008), and include daily non-accidental mortality,
cardio-respiratory deaths, hospitalizations, and emergency room
visits (Just et al., 2002; Burnett et al., 2005; Goldberg and Burnett,
2005; Goldberg et al., 2006, 2008; Pattenden et al., 2006). Chronic
health effects include stunted lung development, long-term
cardiovascular and respiratory diseases, and mortality (Gauderman
et al., 2007; Nie et al., 2007; Tonne et al., 2007; Jerrett et al., 2009).
Several studies have been conducted to assess the associations
* Corresponding author. Tel.: þ1 5106423960; fax: þ1 5106425815.
E-mail address: jerrett@berkeley.edu (M. Jerrett).
diseases, with most finding support for the hypothesis of adverse
health effects on various endpoints (Cohen, 2000; Vineis et al,
2004; Pope and Dockery, 2006; Brunekreef, 2007; Chen et al.,
2008). Within the air pollution e health risk literature, the main
pollutants investigated have been criteria air pollutants, such as
fine particulates (particles with an aerodynamic diameter equal to
or less than 2.5 mm), nitrogen dioxide (NO2), carbon monoxide (CO)
and ozone. These criteria pollutants are regulated by standards
such as those in the United States (Code of Federal Regulations,
1998) and Canada (Clean Air Act, 2006) which are based on an
extensive database of health and welfare information. Guidelines
have also been established by the World Health Organization
(WHO, 2005). In addition, monitoring networks are set up in many
locations in an air district or in a country to ascertain whether areas
are in compliance with the standards. For example, the South Coast
Air Quality Management District in southern California has 26 sites

1352-2310/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2010.06.015
3530 J.G. Su et al. / Atmospheric Environment 44 (2010) 3529e3537
for NO2 monitoring, 26 sites for CO and 12 sites for particulate lead.
In Canada, the National Air Pollution Surveillance (NAPS) Network
is managed cooperatively between Environment Canada and the
provinces/territories.
In contrast to criteria air pollutants, much less information is
available on the spatial distribution of ambient concentrations of
volatile organic compounds (VOC). Increasing concentrations
of these compounds in the atmosphere have become a subject of
concern due to their potential effects on human health and the
quality of the environment (Riga-Karandinos and Saitanis, 2005).
These compounds may have significant health risks (WHO, 2000)
and play an important role in atmospheric chemistry as precursors
of secondary pollutants such as ozone (Atkinson, 2000).
One of the important limitations to understanding the potential
health effects of VOCs is a lack of monitoring data to capture the
likely small-area variation within broad geographic coverage over
urban areas. While some monitoring data are available, they are
sparsely distributed (e.g., less than 10 sites for most metropolitan
areas) such that small-area variation of VOCs cannot be adequately
captured in urban areas (Kelly et al., 1994). This hinders efforts to
assess potential health effects and prioritize and evaluate policy
initiatives for reduction of ambient VOC levels. The varied nature
(e.g., chemistry, half-life, and toxicity) and the potential spatial
heterogeneity in distribution and magnitude of concentrations
make monitoring these pollutants routinely a challenging endeavor
(Woodruff et al., 1998). The use of limited central sites as part of
national monitoring networks is likely to be inadequate for repre-
senting small-area variations of these pollutants (Tager et al., 2009).
Vehicular traffic is considered to be responsible for much of the
intra-urban air pollution variability (Briggs et al., 2000; Gilbert
et al., 2005; Hoek et al., 2002; Jerrett et al., 2005). Similar to the
most commonly used traffic marker NO2, VOCs can also vary
spatially across locations (within and across cities) and the
concentrations may vary over time.
Current modeling techniques developed to assess the small-area
variation of intra-urban air pollution for long-term health studies
have been reviewed extensively by Briggs (2005), Jerrett et al.
(2005) and Hoek et al. (2008). Approaches include proximity-
based assessment (e.g., distance to a major road or a hazard loca-
tion), statistical interpolation (e.g. kriging, inverse distance
weighting), land use regression models, line dispersion models,
integrated emission-meteorological models, and hybrid models.
Developments in GIS have contributed to the popularity of land use
regression modeling (LUR). LUR combines monitoring data of air
pollution at a small number of locations and stochastic models are
developed using predictor variables usually obtained through
geographic information systems (GIS) (Jerrett et al., 2005). The
model is then applied to a large number of unsampled locations in
the study area for prediction. Of the more than 25 published studies
using the LUR method (Hoek et al., 2008), only four have investi-
gated VOCs. Carr et al. (2002), Smith et al. (2006), Aguilera et al.
(2008) and Wheeler et al. (2008) applied LUR for modeling
benzene, ethyl-benzene, toluene and xylene. The objective of our
study is to model small-area variation of ambient VOCs in Toronto,
Canada, for subsequent identification of possible health effects in
an ongoing cohort study (Jerrett et al., 2009).
2. Materials and methods
2.1. Study area
Toronto is the provincial capital of Ontario and Canada’s most
populous city with a population of 5.11 million in the greater Tor-
onto area (Statistics Canada, 2006). This study was confined to the
Metro Toronto area (Fig. 1). It is located on the north shore of Lake
Fig. 1. The study region d the City of Toronto.
Ontario (situated at 43 390 N, 79 230 W) with a climate classified as
humid continental, with severe winters and warm summers in the
eastern region of temperate North America (Getis and Getis, 1995;
Arain et al., 2009). Similar to other large cities in North America,
many expressways traverse the Toronto landscape, including some
of the busiest in North America (e.g., Highway 401 has peak flows of
about 400,000 vehicles per day).
2.2. Pollution sampling
VOCs were measured from July 25 through August 9, 2006 at 50
locations. A subset of the 100 locations used to monitor NO2 were
chosen using a location-allocation approach, which is described
elsewhere (Kanaroglou et al., 2005). Briefly, the location-allocation
algorithm involves a two-step algorithm that: (1) builds a demand
surface of spatial variation (i.e., semi-variances) and (2) solves
a constrained spatial optimization problem to determine locations
for a pre-specified number of samplers. For the 50 VOC sites
assigned, 8, 30 and 35 sites were within 200 m of an expressway,
200 m of a major road and 100 m of a residential area, respectively.
Though the sampling was originally designed to characterize long-
term average concentrations for NO2, we assumed the relative
spatial pattern of a VOC pollutant was likely to be maintained over
time even the levels may go up and down.
We used TraceAir organic vapor monitors (OVMs) to monitor
ambient VOCs (K&M Environmental, Virginia Beach, VA, USA). Two-
sided samplers were deployed in pairs (yielding four observations
per site) at a height of 2.5 m. The deployment of samplers took less
than 72 h. All samplers were removed 14 days after their installa-
tion. We measured benzene, n-hexane, and total hydrocarbons
(THC). Quantification of VOCs using desorption of the charcoal
filters was carried out with a 2 ml extraction volume of carbon
disulphide by constant agitation for several hours at room
temperature. Analytical extracts were not prefiltered. Instrumental
quantification was performed on an HP-6890 Gas Chromatograph
(HewlettePackard Inc., USA) with an SPB-1/60 m/0.32 mm i.d./
1.0 mm film thickness capillary column (Supelco, Bellefonte, PA,
USA). Ogawa samplers, used to measure NO2, were analyzed
according to the manufacturer’s specifications. Quality control and
quality assurance procedures for all laboratory analyses followed
the manufacturer’s specifications. Fig. 1 shows the location of the
50 monitors across the study area.
 J.G. Su et al. / Atmospheric Environment 44 (2010) 3529e3537
2.3. Model variables
The LUR model was developed using the NO2 and VOC
measurements against chosen spatial covariates. Because of the
strong skewness of the distribution of the VOCs, logarithmic
transformation was used to stabilize the variance of the sample
(Bland, 2000). These transformations were reversed to real
concentrations when discussing levels of air pollution and creating
a concentration surface.
The spatial covariates included six categories: highway and
major road lengths and slope gradients, traffic density, land use (e.
g., commercial, industrial, residential, and open), physical charac-
teristics (e.g., elevation, latitude, longitude and distance to coast),
population density and remote sensing derived indices as described
in the following section.
2.3.1. Remote sensing tasseled-cap transformation
Tasseled-cap indices of greenness and surface brightness of the
study area were derived from Landsat Enhanced Thematic Mapper
Plus (ETMþ) data. ETMþ imagery acquired included three visible
(resolution 30 m), three infrared (30 m), two thermal (60 m), and
a panchromatic (15 m) band. The scene for Toronto was at path-18/
row-30 and captured on August 20, 2000. These images were
orthorectified by the United States Geological Survey (USGS) and
projected to Universal Transverse Mercator (UTM) zone 17N coor-
dinate system with a WGS84 datum (World Geodetic System of
1984). The root mean-square error (RMSE) of the rectification was
less than a pixel and the imagery was not atmospherically or
topographically corrected.
The tasseled-cap transformation is an orthogonal trans-
formation of the reflective bands of the TM data (Crist and Cicone,
1984) in which the first component, brightness, is related to the
amplitude of reflectance associated with soils and impervious
surfaces, such as concrete and asphalt. Current LUR models use
road network information as a surrogate for traffic-related pollu-
tion; however, effects from some land uses such as parking lots,
which have similar spectral reflectance to roads, are usually
unavailable. The second component, greenness, is orthogonal to
brightness and is strongly positively related to the amount of green
vegetation and inversely related to the amount of impervious area.
2.3.2. Road network and traffic density
The road network data of Toronto were acquired from Desktop
Mapping Technologies Inc. (Markham, Ontario, Canada) for 2001.
We assumed that roads of steeper slope gradients have higher
emissions because of the acceleration effect. Slope was used in our
modeling process and was defined as angle in degrees. A street was
first converted into raster cells of resolution 5 m and each raster cell
was assigned a slope derived from a digital elevation map (DEM).
The average slope Mi,j of all the road segments (k) within a circular
search distance j (at 50 m intervals) of sampler i for highway or
major road was estimated by:
1Xn
Mi;j ¼ mi;j;k (1)
n Spatial autocorrelation is a measure of spatial similarity and indi-
k¼1
where mi;j;k refers to the mean slope calculated from all the
pixels that make up road segment k. Traffic counts of the
morning and afternoon rush hours, as well as the 24 h average
were obtained from the City of Toronto Information Services for
major roads. Within a circular search distance of j of sampler i,
vehicle density Dvi;j was estimated by summing all (k) the traffic
volumes (Vi,j,k) of a road segment (l) within that search distance
and then dividing by the total number of measured locations Ni,j.
Because some road segments had measurements while others
did not, Ni,j was therefore used to estimate mean traffic volumes
3531
of a road category at sampler i of buffer distance j. The esti-
mation is expressed by:
n 
P 
Vi;j;k  lk
k¼1
Dvi;j ¼ (2)
Ni;j
2.3.3. Land use and population characteristics
Similar to road network data, the land use data for Toronto for
2001 were also acquired from DMTI Spatial. Major land use types
included commercial, residential, industrial, open, and govern-
mental use. The population data were drawn from Statistics Canada
E-Stat (2002) at the enumeration area (EA) level for 2001. EAs are
the smallest of the geostatistical areas used by Statistics Canada
during the census. The total area of a land use type within a circular
buffer was estimated by summing all the areas of that land use type
inside the buffer. Total population inside a buffer was estimated by
summing all the population from every enumeration area that
intersects the buffer based on a proportional algorithm. Population
density was then estimated by dividing the total population inside
that buffer by the circular buffer area.
Additionally, locations of industrial chimneys and railway road
networks provided by DMTI Spatial (Markham, Ontario, Canada)
were identified and used as covariates for our LUR modeling
process.
2.3.4. Model selection and diagnostics
For the model selection process we used a distance decay
regression selection strategy which has been described in detail
elsewhere (Su et al., 2009). Briefly, 30 circular area distances
(buffers) of 50 m intervals were created for each sampling location,
ranging from 0 to 50 m, 0 to 100 m, 0 to 150 m, and up to the final
buffer of 0e1500 m for traffic-related covariates (e.g., road length
and traffic). For population density and land use variables the
maximum buffer distance extended to 3000 m (Jerrett et al., 2005).
Correlations between residuals of a pollutant model and the spatial
covariates of various buffer distances were modeled and then dis-
played in a series of distance decay curves. A spatial covariate with
the highest correlation at an optimized buffer distance was added
to the model if the chosen spatial covariate at that distance was
significant (e.g., p  0.05). The prediction residuals of the bivariate
model were calculated for all the sampling locations, and used to
construct a second series of distance decay curves of correlation.
Guided by the visual distance decay curves, the model was used to
identify the optimized distances of influence for all variables during
the model selection process. Step-by-step, a spatial covariate with
the highest correlation at each search distance was added to the
LUR model based on its significance level (p  0.05). The variable
selection process continued until no further spatial covariate
within a buffer distance could be added to the model (p > 0.05).
In model diagnostics, the variance inflation factor (VIF) was
examined to identify variables that were collinear. Spatial auto-
correlation was evaluated to assess the independence of prediction
residuals using the Moran’s I statistic (Bailey and Gatrell, 1995).
cates whether objects near each other are more or less likely to be
similar. Spatial autocorrelation can result in pseudo-replication and
overestimates the prediction power of a regression model
(Legendre et al., 2002). Additional model diagnostics included
Cook’s distance to examine outliers. Because of the limited sample
sizes, we were concerned not only with the normality of the
response variable, but also with the sensitivity of the model
prediction coefficients. Bootstrapping methods were applied where
with a set of data was randomly resampled (with replacement)
multiple times (as many as 10,000 or more) and statistical
3532 J.G. Su et al. / Atmospheric Environment 44 (2010) 3529e3537

Table 1
Descriptive statistics of selected VOCs and NO2.

N Mean Median Minimum Maximum Percentiles

25 50 75
Benzene (mg m3) 45 0.68 0.62 0.44 1.28 0.54 0.62 0.74
n-Hexane (mg m3) 45 1.15 1.02 0.74 3.30 0.88 1.02 1.19
Total hydrocarbon (mg m3) 45 29.45 25.62 17.13 77.55 22.57 25.62 30.96
Nitrogen dioxide (ppb) 45 10.35 10.05 4.94 19.31 7.11 10.05 12.88

conclusions (e.g. mean or standard deviation) were drawn from this
data collection. Each time, 95% of the data were randomly selected
to build a multiple linear regression model and corresponding
regression coefficients were recorded. The sampling distribution
from a non-parametric (i.e., not assuming a normal distribution)
bootstrap for each spatial covariate was drawn to identify any
normality of its coefficient distribution. In total, 18 bootstrap
models were used to check parameters normality of distribution.
We also identified the degree of agreement between VOCs’
ranks, and between NO2 and VOCs. In doing so, the ambient
concentrations of a pollutant in a sampling network were sorted
and then classified into four equal categories. The correlation
coefficient between the sorted and the pollutant being compared
was calculated for each category. The degree of agreement gives us
a means of how well two pollutants are spatially related.
concentrations. Steeper slope gradients were associated with
higher benzene emissions and concentrations on highways. The
slope gradients of the road network explained 25% and 16% of the
variances for expressway NO2 and benzene emissions, respectively.
3.2. VOC modeling results
The modeling results for the VOCs are listed in Table 2 and Fig. 4.
The models have R2 ranging from 0.66 to 0.68. For the three VOC
models and NO2, each individual variable has a significant t score
and acceptable collinearity, as demonstrated by the VIF. All of the
coefficients have the expected signs. For benzene, the major

3. Results

Among the 50 VOC sampling sites, five were excluded from the
analysis because of damaged samplers (4) or extreme values
detected (1) (see below for explanation). The mean concentrations
of benzene, n-hexane and THC at the remaining 45 locations were
0.68, 1.15 and 29.45 mg m3, respectively, and measured NO2
concentration was 10.34 ppb (Table 1). The modeling results and
diagnostics are described in detail below.

3.1. Spatial covariates and distance decay curves

The remote sensing greenness index (Fig. 2a, top), derived from
the tasseled-cap transformation, was found to have a higher
proportion of vegetative cover on the northeast corner of the city
and along the two rivers flowing northeast toward Lake Ontario in
the southeast study area. By contrast, surface brightness (Fig. 2b,
bottom) was found to be relatively high on the west side of the city,
inversely related to the greenness. The distance decay curves
illustrated in Fig. 3 (variables shown were either selected in the
final models or among the highest correlations with VOCs) show
that in most of the situations, both greenness and surface bright-
ness could be used as effective predictors of VOC concentrations;
especially for greenness, the index alone could explain 25e40% of
the VOC variance. Because surface brightness is directly associated
with traffic-related land use, the distance decay curve showed
dramatic change (both increase and decrease) compared to the
greenness index as buffer distance increased. Buffer distances
600e1000 m had the highest correlations for surface brightness
(highest R ¼ 0.50) compared to the 500e1300 m buffer distances
for greenness (highest R ¼ 0.68). Residential land use had overall
high negative correlations with the VOCs, and these high correla-
tions were observed starting from buffer distance 500 m (highest
R ¼ 0.55), except for benzene with a distance of 1100 m (highest
R ¼ 0.5). Industrial land use was also a major predictor of VOC
pollution for the city (highest R ¼ 0.65). The high correlations were
observed for buffer distances from 700 to 1500 m. Latitude, longi- Fig. 2. Greenness (a) and surface brightness (b) indices derived from tasseled-cap
tude and elevation were also significantly correlated with VOC transformation of Landsat Enhanced Thematic Mapper Plus (ETMþ) data.
 J.G. Su et al. / Atmospheric Environment 44 (2010) 3529e3537 3533

Fig. 3. Initial correlation matrix between log-transformed VOCs and some chosen spatial covariates.

contributors include traffic (road network as surrogates) and
industrial land use. Though smaller in variance explained, this is
still comparable to NO2, which has an R2 of 0.81. n-Hexane and THC,
by contrast, were found to be associated with industrial land use
with the addition of the influences of surface brightness and
commercial land use, indicators of traffic-related pollution. Because
both traffic and industrial land use had significantly high contri-
butions (R2 > 0.25 in bivariate models) to benzene concentrations
but at the same time maintained distinctive spatial patterns, we
also modeled benzene without industrial (i.e., road network model)
and without traffic influence (i.e., land use model), separately.
Fig. 5aec display the predicted benzene concentration surfaces of
the land use model (5a), road network model (5b) and the opti-
mized model with both land use and traffic variables considered
(5c).
3.3. Model diagnostics
Outlier analysis found that the z-scores for both benzene and n-
hexane at a southwest sampling site were greater than 6 units (6.22
and 6.13 for benzene and n-hexane, respectively) and the proba-
bility of those two scenarios were near 0. Land use and aerial
3534 J.G. Su et al. / Atmospheric Environment 44 (2010) 3529e3537

Table 2
The LUR modeling results of selected VOCs and NO2 based on 45 sampling sites.

VOCa Benzeneb n-Hexaneb THCb NO2

Intercept 36.912725 1.827158 2.017391 9.436702
Road network Expressway (m) 0.000160 (100)c 0.000059 (350)
Major road (m) 0.001419 (50) 0.001034 (50)
Local road (m) 0.001157 (50)
Rail (m) 0.000029 (1100)

Land use Commercial (ha) 0.001238 (2900) 0.002483 (3000)

Industrial (ha) 0.001413 (1200) 0.082402 (100) 0.170179 (100)
Residential (ha)
Open (ha) 0.818055 (50) 0.590493 (50)
0.001086 (1200)
# Chimney (count) 0.061389 (2050) 0.074200 (1850)

Population Density (pop ha1) 0.003088 (1150)

Tasseled-cap transformation Greenness

Soil brightness 0.011239 (1650) 0.007636 (1650) 0.007222 (3000)

Physical geography X coordinate 0.000014

R2 0.67 0.68 0.66 0.81

Moran’s I (p value) 0.043 (0.37) 0.077 (0.19) 0.053 (0.32) 0.047 (0.35)
Average VIF 1.27 1.23 1.1 1.20
Maximum cook’s distance 0.38 0.31 0.25 0.35
a
All the measured VOCs were log-transformed to satisfy the normality requirement of the models.
b
Sampler 1016 was excluded in modeling process because of the extreme values.
c
Parenthetic values are buffer distances in meter from the central sampler of interest in meter.

photographs around the sampler were examined, and there was no distance (0.25e0.38) and leverage statistics confirmed the absence
apparent reason for the elevated benzene level. That sampler was of significant outliers (Table 2) after removing sampler 1016.
thus excluded for modeling VOCs and NO2 as it either represents Additionally, Moran’s I values for benzene, n-hexane and THC are
a highly local source or a sampling error. Examination of Cook’s 0.043 (p ¼ 0.37), 0.077 (p ¼ 0.19) and 0.053 (p ¼ 0.32),

Fig. 4. Logarithmic-observed mean NO2 and VOCs on predicted values.

 J.G. Su et al. / Atmospheric Environment 44 (2010) 3529e3537
Fig. 5. Modeled benzene concentration surfaces through (a) land use variables, (b) road
network variables and (c) both land use and industrial variables (i.e., final model surface).
respectively. Spatial autocorrelation is therefore insignificant in
every model when using a first order queen adjacency matrix. This
suggests that the models developed conform to the independence
assumption when nearest neighbor adjacency is assumed, and
fixed predictors were included to account for the autocorrelation.
Because of the collinearity, greenness or surface brightness were
not always in the final optimized VOC models.
3535
The bootstrap results (in total 18 bootstrap models applied) for
benzene, n-hexane and THC models (distributions not shown)
demonstrated stability of the choice of samples. No bimodal shape
was presented and the majority of the parameters (intercept and
covariates) were normally distributed. The buffer distance of 250 m
around expressways had a very narrow distribution (i.e., small
standard deviation) and that indicates the similarity of expressway
distribution within that buffer distance for all the samplers. The
level of agreement between the ranks of the VOCs was 48 to 63% for
all the four categories with an average of 53%. The level of agree-
ment increased substantially for those top and bottom quartile
groups up to 75%. By contrast, the level of agreement between NO2
and VOCs was smaller with an average of 36%.
4. Discussion and conclusion
In this study, we used a distance decay variable selection
strategy to develop predictive land use regression models for
benzene, n-hexane, THC and NO2 in the City of Toronto. These
models explained 66e81% of the variability in the VOC concen-
trations. The predictive power for benzene is comparable to those
of Carr et al. (2002), Aguilera et al. (2008) and Wheeler et al. (2008),
who found that 73e80% of the variance could be explained. Our
LUR models also found that n-hexane and THC could be effectively
predicted.
The measured benzene concentrations in our study ranged from
0.44 to 1.28 mg m3 with a mean value 0.68 mg m3, ten times lower
than typically identified (Adgate et al., 2004; Rappaport and
Kupper, 2004; Weisel et al., 2005; Sexton et al., 2007). However,
the values are similar to those reported by Beckerman et al. (2008)
in the same city, Wheeler et al. (2008) in Windsor, Ontario, and
Mukerjee et al. (2009) in Detroit.
Recent evidence suggests that humans metabolize benzene
more efficiently at environmental air concentrations less than
1 ppm. Rappaport et al. (2009) found strong statistical evidence
favoring two metabolic pathways, with respective affinities
(benzene air concentrations) of 0.301 ppm for the low-affinity
pathway and 0.594 ppm for the high-affinity pathway. They iden-
tified that 73% of the ambient benzene dose would be metabolized
via the high-affinity pathway. Based on this biologic model, the low
concentrations of benzene found in our study might still have
adverse health effects.
Comparing the prediction variables used in a model, n-hexane
and THC were largely predicted by land use characteristics (e.g.,
industrial land use). This demonstrates that these two pollutants
are mainly from non-road sources (e.g., distance > 1000 m). By
contrast, both benzene and NO2 LUR models contained expressway
and major road at smaller buffer distances (350 m) in their
models. Emissions/formations of these two pollutants from
expressway and major road were high near roadways but
decreased significantly outwards. Comparing the optimized buffer
distances between the same variable for the benzene and NO2
models, however, we found that buffer distances were compara-
tively larger for NO2. This is probably because benzene is a near
source primary emission from the tailpipe but NO2 forms as
a secondary reaction. In addition, industrial land use has significant
influence on benzene concentrations but not on NO2, thus the lack
of the industrial land use variable in the NO2 model. NO2 could be
treated as traffic-related air pollution. The distance decay curves
used in our models provide a visual display of correlations and
facilitate the easy selection of a prediction variable and its opti-
mized buffer distance.
In most LUR models, road networks are used as a surrogate for
road traffic emissions and open land use for places without such
emissions. Our research also found that remote sensing derived
3536 J.G. Su et al. / Atmospheric Environment 44 (2010) 3529e3537
data such as vegetation greenness and surface brightness could be
useful surrogates of these features to improve the estimation of
spatial variability in ambient VOC concentrations. The surface
brightness was comparable to and in some situations more effec-
tive than road networks in explaining the variance of VOCs
(R ¼ 0.25e0.52). Correlations with greenness were much higher
than with open land use in all the scenarios (R from 0.55 to
0.70). Unlike road networks and open land use whose within
feature variations are rather limited, vegetation greenness and
surface brightness can change values from one pixel to another
(remote sensing data are raster-based). For example, higher
greenness is associated with more vegetation, less traffic influ-
ences, better cleansing of air, and lower pollutant concentrations.
Though remote sensing data may introduce new forms of error,
such as the identification of pedestrianized areas and school play-
grounds as high traffic, surface brightness could also be used to
identify both road network and other bare ground having high
volumes of traffic such as open space parking lots. In areas with
well-mapped land use and traffic, the marginal value of remote
sensing data appears limited. However, in locations where other
spatial covariates are not readily available such as certain land use
data, Landsat ETMþ data might provide effective surrogate
measures. Many of the world’s large cities are in poorer countries
with less developed geospatial infrastructure, making this method
for deriving land cover information potentially useful. The advan-
tage of using ETMþ data for LUR is its global coverage and free
access (http://landsat.gsfc.nasa.gov/). The other advantage is the
comparability between places with regard to land use classification.
The model we developed here provides a relatively easy and
feasible way to improve exposure analysis where highly resolved
traffic, road and land use data are unavailable.
The slope gradients of the road network in our paper explained
25% and 16% of the variances for expressway NO2 and benzene
emissions, respectively. Because slope gradient is a proxy for hard
acceleration driving patterns, it may supply a useful approximation
for elevated emissions in some study areas.
Attempts were also made to model toluene, ethyl-benzene,
xylenes (TEX); however, principle component analysis on BTEX
(benzene, toluene, ethyl-benzene, m,p-xylene and o-xylene) iden-
tified two distinct components: benzene and TEX. TEX had a much
stronger influence from industrial sources than did benzene. Future
efforts need to optimize placement of monitors designed specifi-
cally for TEX and investigate further the relationship between
benzene and TEX.
Our research found a much higher degree of agreement
between different VOCs compared to that observed between VOCs
and NO2. This demonstrates that the spatial patterns of VOCs are
different from NO2, probably because they have different emission
sources, chemical characteristics and, atmospheric trans-
formations. Because of VOCs’ high vapor pressure, they can easily
evaporate at average temperatures and enter the atmosphere from
fuels, solvents, coatings, feedstocks and refrigerants. By contrast,
NO2 arises via the oxidation of nitric oxide (NO) by oxygen in air. It
depends on, among other things, the richness of NO in the atmo-
sphere. In addition, industrial land use and other point and areal
sources have higher contributions to VOC concentrations while NO2
mainly comes from traffic-related road networks. Future epidemi-
ologic studies may benefit from using VOCs as a more specific
marker of traffic or industry that may directly exert health effects.
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