Atmospheric Environment 44 (2010) 1062e1070

Contents lists available at ScienceDirect

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

Chemical characterization and source apportionment of ne and coarse

particulate matter in Lahore, Pakistan
Elizabeth Stone a, James Schauer a, *, Tauseef A. Quraishi b, Abid Mahmood b
a
b

University of Wisconsin-Madison, Madison, WI, USA

University of Engineering and Technology, Lahore, Pakistan

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 15 April 2009
Received in revised form
28 October 2009
Accepted 12 December 2009

Lahore, Pakistan is an emerging megacity that is heavily polluted with high levels of particle air pollution. In
this study, respirable particulate matter (PM2.5 and PM10) were collected every sixth day in Lahore from 12
January 2007 to 19 January 2008. Ambient aerosol was characterized using well-established chemical
methods for mass, organic carbon (OC), elemental carbon (EC), ionic species (sulfate, nitrate, chloride,
ammonium, sodium, calcium, and potassium), and organic species. The annual average concentration
(
one standard deviation) of PM2.5 was 194
94 mg m3 and PM10 was 336
135 mg m3. Coarse aerosol
(PM102.5) was dominated by crustal sources like dust (74
16%, annual average
one standard deviation),
whereas ne particles were dominated by carbonaceous aerosol (organic matter and elemental carbon,
61
17%). Organic tracer species were used to identify sources of PM2.5 OC and chemical mass balance
(CMB) modeling was used to estimate relative source contributions. On an annual basis, non-catalyzed
motor vehicles accounted for more than half of primary OC (53
19%). Lesser sources included biomass
burning (10
5%) and the combined source of diesel engines and residual fuel oil combustion (6
2%).
Secondary organic aerosol (SOA) was an important contributor to ambient OC, particularly during the
winter when secondary processing of aerosol species during fog episodes was expected. Coal combustion
alone contributed a small percentage of organic aerosol (1.9
0.3%), but showed strong linear correlation
with unidentied sources of OC that contributed more signicantly (27
16%). Brick kilns, where coal and
other low quality fuels are burned together, are suggested as the most probable origins of unapportioned OC.
The chemical proling of emissions from brick kilns and other sources unique to Lahore would contribute to
a better understanding of OC sources in this megacity.
2009 Elsevier Ltd. All rights reserved.

Keywords:
Aerosol
Source apportionment
Pakistan

1. Introduction
One of the many problems aficting the world's largest cities is
particulate matter in the atmosphere. High levels of ambient particulate matter have been linked to increased mortality (Schwartz and
Marcus, 1990; Saldiva et al., 1995) and the inhalation of respirable
particles provides a pathway of human exposure to air toxins (Smith
et al., 1996). The World Health Organization (WHO) estimates that
urban air pollution causes approximately 360,000 premature deaths in
Asia each year. Of particular interest to human health are the particles
that can enter the lung, which have an aerodynamic diameter less than
2.5 or 10 mm (PM2.5 or PM10). These particles are considered to be air
toxins and were the subject of WHO guidelines in 2008 when 24-h
maximum thresholds for ne (PM2.5) and coarse (PM10) particulate
matter were set at 25 and 50 mg m3, respectively (WHO, 2008).

* Corresponding author. Tel.: 1 608 262 4495; fax: 1 608 262 0454.
E-mail address: jjschauer@wisc.edu (J. Schauer).
1352-2310/$ e see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.atmosenv.2009.12.015

Lahore, Pakistan is an emerging megacity aficted with high

levels of particle air pollution well above WHO guidelines. The city
is highly-populated, heavily-industrialized, and located in an arid
region, which gives rise to numerous PM sources including motor
vehicles, industry, power plants, and wind-blown dust. Air quality
issues in Lahore have been exacerbated by the high density of
primary industrial sources, the absence of effective pollution controls
(Biswas et al., 2008), and a lack of mass transportation (Aziz and
Bajwa, 2008). Severe wintertime pollution episodes, sometimes
lasting two weeks, have caused marked reductions in visibility, disrupted transportation, and triggered both injury and death (Hameed
et al., 2000). Previous studies of ambient air quality in Lahore have
documented 24-h maximum wintertime PM2.5 concentrations of
200 mg m3 (Biswas et al., 2008), springtime PM10 concentrations of
460 mg m3 (Zhang et al., 2008a), and total suspended particle
concentrations above 900 mg m3 (Ghauri et al., 2007). The PM
in Lahore has been characterized as containing high levels of toxic
and/or carcinogenic components such as lead (Pb) and polyaromatic
hydrocarbons (PAH) (Smith et al., 1996).

E. Stone et al. / Atmospheric Environment 44 (2010) 1062e1070

Reductions in ambient PM and improvements in air quality

in Lahore requires an understanding of the composition of ambient
aerosol and its major sources. This study provides a base line understanding of PM composition and sources of ne and coarse particulate
matter for the year 2007 that can be used to guide emissions reduction
strategies and comparatively to assess future changes in air quality.
These data are crucial in air resources management and are largely
unavailable for rapidly growing megacities, particularly in understudied regions of the world. The analysis of a year-long dataset
provides signicant insight into the factors that drive seasonal variations in particulate matter composition and sources. Results from
this study are compared to earlier studies in Lahore to illustrate this
city's ongoing air quality issues and are evaluated in the context of
megacities worldwide.
2. Methodology
2.1. Sample collection
Particulate matter samples were collected in Lahore, Pakistan on
the campus of the University of Engineering and Technology (UET)
on the roof of the Institute for Environmental Engineering and
Research at a height of 10 m. The medium-volume PM2.5 and PM10
sampling apparatus (URG-3000, Chapel Hill, NC, USA) was made
of Teon-coated aluminum. Air ow through the sampler was
initiated by a vacuum pump and controlled by critical orices. Flow
rates were approximately 16 liters per minute (lpm) through each
of two PM2.5 cyclones and 32 lpm through the PM10 inlet. Flow into
the sampler was split between eight lter holders to a rate of 8 lpm
and was measured before and after sample collection with a calibrated Rotameter. Particulate matter was collected on Teon and
pre-cleaned quartz-ber substrates (47 mm, Pall Life Sciences, East
Hill, NY, USA). All lters and samples were handled using clean
techniques. Samples were collected on sixty-three different days,
at a rate of every sixth day from 12 January 2007 to 19 January
2008. Collection of samples began at 11:00 local time and
continued for 24 h. Field blanks were collected every fth sampling
day. Two samples of motor oil commonly used in Lahore for engine
lubrication and as additives to gasoline for two-stroke engines were
collected following methods described in the Supplemental
Information.
Lahore is located between 31150 and 31450 North latitude and
74 010 and 74 390 East longitude at 217 m above sea level. The Ravi
River ows on the northern side of Lahore and the international
border (with India) is about 15 miles (25 km) to the east of the
sampling site. There is intense agriculture in areas around Lahore,
including on the Indian side of the border, with the main crops being
wheat and rice. After crop harvesting the biomass residues are
sometimes set on re in the elds. The immediate surroundings
of the sampler location can be described as a typical urban area of
Lahore. There are also small metallurgical, chemical and electroplating units dispersed in the area. Nearby is Grand Trunk Road,
a major arterial roadway in the city. Trafc includes animal-driven
carts, diesel-powered buses and trucks, 2-stroke motorcycles,
and three-wheelers (rickshaws) running on a mixture of petroleum
gasoline and motor oil, and motor vehicles that use petroleum
gasoline or compressed natural gas. The sampling location was
approximately 8 km northwest of the Lahore international airport,
2 km north of a railway service station that services diesel locomotives, and 500 m away from a natural gas burning power plant. There
were a number of brick kilns approximately 6 km northeast, which
burned low quality coal, rubber tires, and other combustible materials available at low cost. During the fall and winter season, heaps
of solid waste comprising mostly of fallen leaves, garden cuttings,
plastic bags, and paper are set alight along road sides.

1063

2.2. Chemical analysis

Particulate mass was measured gravimetrically using a highprecision microbalance (Mettler Toledo, USA) and taking the difference of the pre- and post-sampling lter weights. Elemental and
organic carbon (EC and OC) were measured on-lter using a thermaloptical analyzer (Sunset Laboratories, USA) following the ACE-Asia
base case protocol (Schauer et al., 2003). Water-soluble ions (sulfate,
nitrate, chloride, ammonium, sodium, calcium, and potassium)
were measured in water-extracts of individual Teon lters using
ion-exchange chromatography (Dionex Corporation, USA). Organic
species were measured in monthly composite samples that consisted
of equal quartz-ber lter portions from 4 to 6 samples per month.
Filters were pre-spiked with isotopically-labeled standard solutions to
aid in quantication then extracted by dichloromethane and methanol using Soxhlets, followed by rotary evaporation and reduction in
volume under puried nitrogen. Extracts were analyzed twice by GC
(6890)-MS(5973) (Agilent Technologies, with DB-5 capillary column)
after derivitization of carboxylic acids with diazomethane and after
silylation of hydroxyl groups (Nolte et al., 2002). Additional details
about the GCMS analysis are described in detail elsewhere (Stone
et al., 2008). The following molecular markers were observed: levoglucosan, 17-a(H)-21-b(H)-hopane, 17-b(H)-21-a(H)-norhopane, 17-a
(H)-22,29,30-trisnorhopane, abb-20(S&R)-C29-sitostane, benzo(b)uoranthene, benzo(k)uoranthene, benzo(e)pyrene, indeno(1,2,3-cd)
pyrene, benzo(ghi)perylene, picene, and C31eC33 n-alkanes. Motor
oil samples were diluted in dichloromethane to concentrations of
0.2e0.4% by weight and were analyzed analogously to particulate
matter samples for quantication of organic species. All measurements were eld blank subtracted and uncertainties were propagated
from the standard deviation of eld blanks and a percentage of the
measurement.
2.3. Source apportionment
Source contributions to OC were estimated using the United
States Environmental Protection Agency's Chemical Mass Balance
model (EPA CMB v8.2) which solved the effective-variance leastsquares solution to a linear combination of PM sources and their
relative contributions to aerosol species (Watson et al., 1984). The
model assumed that the input source proles were representative
of sources in Lahore. Source proles were selected from the literature based on a previous CMB study of PM10 in Lahore; they
included non-catalyzed gasoline vehicles (Schauer et al., 2002),
diesel engines (Lough et al., 2007), coal soot from low temperature
combustion representative of kilns or small industries (Zhang et al.,
2008b), vegetative detritus (Rogge et al., 1993a), and open burning
of biomass (Lee et al., 2005). The source prole for diesel was found
to be co-linear with that of fuel oil (Rogge et al., 1997), which was
expected to be an important source based on the presence of Ni and
V (Pakkanen et al., 2001). Consequently diesel and residual oil
combustion were lumped together in source apportionment as one
source. Contributions to OC from natural gas (Rogge et al., 1993b)
were not statistically signicant.
Molecular marker compounds were selected as tting species
and assumed to be atmospherically stable during transport
from source to receptor (Schauer et al., 1996). Model results were
considered acceptable if R2 > 0.80, c2 < 7, and if calculated species
concentrations agreed within 25% of the measured value. The
criteria used to evaluate CMB results were based upon the software
manual (EPA, 2004) and prior publications (Sheesley et al., 2007;
Zhang et al., 2008a). For July and August samples, calculated OC
exceeded measured OC by 2% and 10%, respectively. For these two
months other sources were not statistically signicant and percent
contributions to OC were normalized to the calculated value.

1064

E. Stone et al. / Atmospheric Environment 44 (2010) 1062e1070

Vegetative detritus contributions were not apportioned during the

month of November because n-alkanes did not demonstrate an
odd-carbon preference indicative of modern plant material.
3. Results and discussion
3.1. Particulate mass and composition
Ambient concentrations of PM2.5 and PM10 in Lahore were among
the highest ever documented in the world. Monthly-average ne
(PM2.5) and coarse (PM102.5) particle mass and bulk composition are
shown in Fig. 1 and are summarized in Table 1. Monthly PM2.5
concentrations averaged 200
80 mg m3 (
one standard deviation)
and PM10 concentrations averaged 340
100 mg m3. Daily PM2.5
concentrations were in excess of the WHO guideline value (of
25 mg m3) every sampling day (n 63); in fact, they were in excess of
100 mg m3 on 84% of days. Likewise, PM10 concentrations were in
excess of the WHO guideline value (of 50 mg m3) every sampling day
and were greater than 200 mg m3 on 84% of days. The highest PM2.5
concentration observed was 410 mg m3 and occurred on 14
November 2007, while the maximum PM10 concentration of
650 mg m3 occurred on 9 October 2007. PM levels in Lahore were on
the same order of magnitude as previous studies in this megacity
(Husain et al., 2007; Biswas et al., 2008; Zhang et al., 2008a) and other
urban locations in Pakistan (Ghauri et al., 2007), but were signicantly
higher than in less-populated Asian locations (Hopke et al., 2008).

Concentration (g m-3)

400

Carbonaceous aerosol, dened as OC and EC, was the dominant

component of PM2.5, accounting for 37
8% of ne particle mass
but was not a major component of coarse PM, contributing only
5
2% of mass. Monthly-average PM2.5 OC concentrations ranged
from a low of 26 mg m3 in July to a high of 152 mg m3 in November,
while EC followed an analogous trend and ranged from 4.5 to
21 mg m3. EC accounted for an average of 1.4% of coarse PM, which
probably derived from tire wear, emissions from inefcient
combustion including brick kilns, and atmospheric coagulation of
soot particles with coarse PM (Chuang et al., 2003).
A previous study in Lahore documented average EC concentrations of 22 mg m3 during November to January 2006 (Husain et al.,
2007). The ratio of OC to EC increased during 2007 from 4.1 in lateJanuary to 9.1 in December, a trend similar to previous observations
in Hong Kong (Zheng et al., 2006). The water-soluble fraction of OC
averaged 19
9% and ranged from a low of 10% during the summer
monsoon to 41% in October as shown in Fig. 2.
The amount of dust in ne and coarse PM was estimated as the
sum of crustal elements in their oxide form: Al2O3, SiO2, TiO2, K2O,
CaO, MnO2, and Fe2O3, where Si concentrations were estimated
from Al:Si ratios (Seinfeld and Pandis, 1998) and crustal-potassium
represented the non-water-soluble fraction. Ambient concentrations of metal oxides are shown in Supplemental Table S1 and
additional details can be found in von Schneidemesser et al. (in
press). By this calculation, dust accounted for an average of
74
16% of coarse PM and 14
6% of PM2.5. For the month of May,

PM2.5

300

200

100

0
late-Jan Feb

Concentration (g m-3)

400

Mar

Apr

May

Jun

Jul

Aug

PM10-2.5

Sep

Oct

Nov

Dec early-Jan

Nov

Dec early-Jan

Organic Carbon
Elemental Carbon
Dust
Chloride
Sulfate
Nitrate
Ammonium
Other Mass

300

200

100

0
late-Jan Feb

Mar

Apr

May

Jun

Jul

Aug

Sep

Oct

Fig. 1. Chemical composition of ambient ne (PM2.5) and coarse (PM10e2.5) particulate matter in Lahore on a monthly basis in 2007e2008. Other mass includes elements associated
with organic carbon (hydrogen, oxygen, nitrogen, etc.), toxic metals, and species that were not measured.

E. Stone et al. / Atmospheric Environment 44 (2010) 1062e1070

1065

Table 1
Measured components of ne (PM2.5) and coarse (PM10e2.5) particulate matter in Lahore, Pakistan. Dust was estimated based on concentrations crustal metals in oxide form
and inorganic ions represent water-soluble fraction.
Date

Mass mg m3

Organic
Carbon mg C m3

Elemental
carbon mg C m3

PM2.5
Jan-07
Feb-07
Mar-07
Apr-07
May-07
Jun-07
Jul-07
Aug-07
Sep-07
Oct-07
Nov-07
Dec-07
Jan-08

294.9
204.5
177.1
189.1
138.0
117.5
96.1
113.5
135.2
268.1
343.3
258.6
215.0

76.5
63.9
44.6
46.2
40.7
26.1
31.5
31.7
41.9
70.4
152.0
125.6
85.7

18.5
14.5
11.1
12.6
6.6
4.5
5.2
5.3
5.6
13.1
21.0
13.8
14.0

PM10e2.5
Jan-07
Feb-07
Mar-07
Apr-07
May-07
Jun-07
Jul-07
Aug-07
Sep-07
Oct-07
Nov-07
Dec-07
Jan-08

148.3
144.7
135.4
182.0
173.6
158.6
99.8
99.9
115.8
172.8
180.1
150.7
81.2

9.1
8.2
6.7
7.0
8.3
3.3
1.4
4.4
4.7
6.4
1.9
3.1
4.7

1.5
3.4
1.5
4.8
0.2
0.0
0.1
0.8
1.6
2.2
6.1
6.0
0.0

Dust mg m3

Sulfate mg m3

Nitrate mg m3

Chloride mg m3

Ammonium
mg m3

13.2
15.3
16.3
20.5
29.0
31.5
19.8
16.5
16.0
36.1
47.0
24.1
27.1

16.6
8.9
7.8
6.4
6.8
6.9
10.3
8.0
14.0
11.8
22.4
8.8
7.3

16.2
6.7
4.7
3.3
3.0
2.6
1.3
1.7
3.1
7.6
15.9
11.3
7.8

14.6
5.1
4.4
5.5
2.5
3.4
0.3
2.1
1.5
7.4
8.1
10.5
7.4

9.3
6.1
3.8
2.1
1.5
1.3
3.6
2.7
4.9
1.7
5.5
2.1
2.8

85.3
91.4
78.6
82.4
179.3
141.1
68.9
73.4
100.6
145.6
135.1
108.5
71.0

0.6
1.3
0.8
1.3
1.9
1.4
1.3
1.2
1.4
2.2
4.3
3.0
0.6

1.4
1.0
1.3
1.5
2.3
2.1
2.9
2.2
3.8
3.5
5.5
2.7
1.1

0.6
0.9
0.5
0.7
0.7
0.8
0.4
0.7
0.7
1.5
3.4
3.8
0.7

bd
bd
bd
bd
bd
bd
bd
bd
bd
bd
bd
bd
bd

bd Below detection.

the amount of dust estimated exceeded coarse PM mass by 3%,

which indicated that this estimation method was not optimized for
Lahore. The contribution of dust to PM followed an annual trend in
which maximum concentrations occurred in the spring dust season
and the dry winter season.
Inorganic ions that were signicant components of PM2.5
included sulfate (6
2%), nitrate (3
1%), chloride (3
1%), and
ammonium (2
1%). Sodium and potassium contributed to <1% of
ne particle mass. These ions were not signicant contributors to
coarse PM, constituting <4% of mass. Sulfate, nitrate, and ammonium
were considered to be secondary inorganic species that were formed
in the atmosphere from gas-phase precursors. Very high chloride
levels of 5e15 mg m3 were observed, which were associated with
metal industry sources in a preceding study (Quraishi et al., 2009).
The difference between measured components and total mass
corresponded to 35
9% of PM2.5 and 17
14% of coarse PM.
Unmeasured components include the auxiliary elements associated
with OC that make up organic matter (OM) including oxygen,
nitrogen, hydrogen, and others, which were estimated to equal 80%
of OC mass in a earlier study in Lahore (Zhang et al., 2008a). By
applying this same ratio, auxiliary elements accounted for 81%
and 34% of unidentied PM2.5 and coarse mass, respectively. The
remaining mass was expected to represent particle-phase water,
additional components of dust and/or soil, and other metal species.
3.2. Organic species and source identication
The relative importance of OC to PM2.5 warranted further investigation of this aerosol component. To this end, organic molecular
markers were measured in monthly composite samples of PM2.5.
While molecular markers make up a small fraction of total aerosol
mass in Lahore, they contain valuable information about the presence
of aerosol sources and can be used quantitatively to assess relative

source contributions (Zhang et al., 2008a). Ambient concentrations of

several molecular markers observed in Lahore are shown in Fig. 2 and
are summarized in Table S2 in the Supplemental Information.
Polyaromatic hydrocarbons (PAH) were indicative of combustion
sources and ve PAH isomers with molecular weights (MW) of
252 amu are shown in Fig. 2. These compounds were present at
an average concentration of 370
50 ng mg1 OC1 (
one standard
deviation) and followed the same temporal trend as PM2.5 and OC.
Many PAH are known or believed to be carcinogenic and high
concentrations are considered to be a threat to human health. In
Lahore, monthly-average concentrations of benzo(a)pyrene ranged
from 2 to 13 ng m3 and averaged 5.3 ng m3, which were comparable to previous levels observed in Lahore (Smith et al., 1995). PAH
levels were elevated in comparison to other Asian locations like
Mumbai (2.0 ng m3) (Kulkarni and Venkataraman, 2000) and Hong
Kong (0.75e1.0 ng m3) (Zheng et al., 2006) and were an order of
magnitude greater than levels observed in downtown Los Angeles
(0.18e0.44 ng m3) (Schauer et al., 1996).
Picene is a PAH with a MW of 278 amu that is produced
specically by burning of coal (Oros and Simoneit, 2000) and was
found at a concentration of 0.57
0.11 mg mg1 OC1 in coal soot
generated by a residential stove (Zhang et al., 2008b). In Lahore,
picene was observed at monthly-average concentrations ranging
from 0.6 to 2.4 ng m3. These levels were comparable to spring
and wintertime concentrations of 1.3e1.5 ng m3 observed in
neighboring Delhi, India (Chowdhury et al., 2007). The seasonal
trend of picene in Lahore suggested that coal combustion contributed to ambient PM2.5 throughout the year, while and maximum
contributions occurred during November and December.
Levoglucosan is a well-established marker for biomass combustion
as it is the major product of cellulose pyrolysis (Simoneit et al., 1999);
it occurs at concentration ranges of 95
40 mg mg1 OC1 in opentype biomass burning (Lee et al., 2005). Concentrations of this marker

1066

E. Stone et al. / Atmospheric Environment 44 (2010) 1062e1070

60

200

PAH (MW 252)

EC
non-WSOC
WSOC

150

Concentration (ng m-3)

Concentration (g m-3)

Carbonaceous Aerosol

100

50

50

Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(j)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene

40
30
20
10
0

3.0

3.0

Picene

2.5

Concentration (ng m-3)

2.0
1.5
1.0

2.5
2.0
1.5
1.0
0.5
0.0
500

150

100

50

n-Alkanes

Heptacosane
Octacosane
Nonacosane
Triacontane
Hentriacontane
Dotriacontane
Tritriacontane

400
300

*see text for details

17(H)-22,29,30-Trisnorhopane
17(H)-21(H)-30-Norhopane
17(H)-21(H)-Hopane

Concentration (ng m-3)

200
100

Sep
Oct

Jul
Aug

Jun

early-Jan

Nov
Dec

Sep
Oct

Aug

Jun
Jul

Apr
May

Feb
Mar

late-Jan

Apr
May

late-Jan

Concentration (ng m-3)

Hopanes

early-Jan

0.0
200

Nov
Dec

0.5

Feb
Mar

Concentration (g m-3)

Levoglucosan

Fig. 2. Concentrations of carbonaceous aerosol components and organic species in Lahore by month.

were the highest of any observed organic species, and ranged from
0.16 to 2.6 mg m3. The lowest levoglucosan concentrations occurred
during the summer monsoon season and were ve times greater in
January, November, and December compared to other months. While
cow dung is used as a cooking fuel in the region, its primary molecular
markersdcoprostanol and cholestanol (Sheesley et al., 2003)dwere
not observed in Lahore aerosol samples, indicating that this source
was not a major contributor to aerosol in the urban area during this
study.
Hopanes are biomarkers that are formed geologically over
millions of years and are present in emissions from fossil fuel
combustion and related sources (Simoneit, 1986): coal combustion
(Oros and Simoneit, 2000), motor vehicles (Lough et al., 2007), and
fuel oil combustion (Rogge et al., 1997). A homologous series of
hopanes, including 17a(H)-22,29,30-trisnorhopane, 17b(H)-21a(H)30-Norhopane, and 17a(H)-21b(H)-hopane, is shown in Fig. 2. The
sum of these three compounds ranged from a low of 44 ng m3 in July
to a high of 110 ng m3 in November with consistent relative ratios
throughout the year. The levels of hopanes in Lahore were among the
highest in the world and were much greater than those observed in
major cities in the United States and in Beijing, China, as previously
noted by Zhang et al. (2008a).

Concentrations of C27e33 n-alkanes are shown in Fig. 2. The range

of individual species concentrations in most months ranged from 6.4
to 68 ng m3 and demonstrated an odd-numbered carbon preference
with a maximum at C29, indicative of modern plant wax contributions
to ambient OC. Drastic differences were observed in the month of
November when concentrations were elevated to 400e1100 ng m3
for these compounds and no odd or even preference was observed,
suggesting fossil fuel sources were their dominant source.

3.3. Source apportionment of primary organic carbon

Primary source contributions to ambient PM2.5 OC calculated by
the CMB model are shown in Fig. 3 and are summarized in Table 2.
Input sources were based upon observed molecular markers discussed in the previous section and included non-catalyzed gasoline
vehicles, diesel and residual oil combustion, coal soot, biomass
burning, and vegetative detritus. The amount of OC apportioned to
these sources ranged from 62 to 100% of the measured value, and
the remainder was attributed to other sources that represented
unknown primary sources and secondary organic aerosol (SOA) that
were not included in the model (discussed in the following section).

E. Stone et al. / Atmospheric Environment 44 (2010) 1062e1070

160
140

Source Contribution (gC m-3)

1067

120
100

non-Catalyzed Gasoline Vehicles

Diesel and Residual Oil Combustion
Coal Soot
Biomass Burning
Vegetative Detritus
Other Sources

80
60
40
20

100

Source Contribution (% OC)

80

late-Jan Feb

Mar

Apr

May

Jun

Jul

Aug

Sep

Oct

Nov

Dec early-Jan

late-Jan Feb

Mar

Apr

May

Jun

Jul

Aug

Sep

Oct

Nov

Dec early-Jan

60

40

20

Fig. 3. Source contributions to ambient PM2.5 organic carbon (OC) estimated using chemical mass balance (CMB) modeling on (a) absolute and (b) percent scales. Other sources are
the sum of secondary sources and unidentied sources.

The largest single contributor to ambient PM2.5 OC was noncatalyzed gasoline vehicles whose monthly-average contribution
ranged from 20
3 to 51
8 mg m3 (
standard error) and
contributed 29e86% of the observed OC (average
one standard
deviation of 53
19%). The maximum contributions from noncatalyzed gasoline vehicles occurred in winter months whereas the
relative contributions from this source peaked during the summer.
The magnitude of contributions from this source is similar to those
observed previously in Lahore (Zhang et al., 2008a). However,
concentrations were signicantly higher than observed in other
large metropolitan areas like Los Angeles, CA where the annual
average contribution of catalyzed and non-catalyzed gasoline vehicles to ne OC was 1.6
0.2 mg m3 (Schauer et al., 1996) and Hong
Kong where seasonal average contributions from gasoline exhaust
ranged from 0.8
0.4 mg m3 to 1.4
0.4 mg m3 at a roadside site in
2000e01 (Zheng et al., 2006). The impact of diesel and residual
oil combustion was small in comparison to non-catalyzed gasoline
vehicles, but contributed an average of 3.8
1.9 mg m3 or 6.3% of
PM2.5 OC. Diesel contributions in Lahore were similar to Los Angeles
where annual average contributions were 2.7
0.3 mg m3 (Schauer
et al., 1996). In Lahore, coal soot contributed an average
1.2
0.8 mg m3 or 2% of OC on a monthly basis. Like motor vehicles,
diesel and residual oil and coal soot were relatively consistent
in Lahore over the course of the annum, indicating the year-round
importance of these combustion sources.

Due to the motor vehicle inuence on organic aerosol in Lahore,

the accuracy of the motor vehicle contribution estimate was further
investigated by the analysis of Pakistani motor oil. Since two-stroke
engines burn a combination of motor oil and gasoline, there
was expected to be a large potential for motor oil to contribute to
ambient OC in Lahore. The chemical signatures observed in Pakistani motor oil samples were similar to those previously documented in a study in the United States (Zielinska et al., 2008) as
further described in the Supplemental Information. This indicated
that motor vehicle emissions in Lahore could be adequately
modeled using American source proles and the motor vehicle
emissions from two-stroke engines in Lahore were expected to be
grouped with the source category of non-catalyzed vehicles.
Biomass burning was the second-largest known contributor
to PM2.5 OC after non-catalyzed gasoline motor vehicles. Biomass
contributions to OC were highly variable with season and ranged
from a low of 1.5
0.7 mg m3 (5% of OC) in July to a maximum of
22.6
10.7 mg m3 (15% of OC) in November. The greatest relative
contribution of biomass burning occurred in late-January 2007 at
22%. The estimates of biomass burning were based upon a prole for
open-type burning (Lee et al., 2005), which has been demonstrated
to be a high-end estimate of biomass contributions compared to
other proles for replace or wood stove combustion (Sheesley
et al., 2007). Seasonal trends are consistent with crop residue
burning in agricultural areas and yard waste burning in urban areas.

1068

E. Stone et al. / Atmospheric Environment 44 (2010) 1062e1070

Table 2
Source contributions to organic carbon in ne particulate matter and uncertainties (unc). Statistically signicant source contributions are shown in bold.
Date

Non-catalyzed
gasoline vehicles

Diesel and residual

oil combustion

Coal soot

mg C m3

unc

mg C m3

unc

mg C m3

unc

Jan-07
Feb-07
Mar-07
Apr-07
May-07
Jun-07
Jul-07
Aug-07
Sep-07
Oct-07
Nov-07
Dec-07
Jan-08

22.4
23.8
19.9
24.8
21.3
19.6
27.5
28.9
26.2
32.6
51.3
47.2
35.6

3.5
3.7
3.1
3.7
3.2
3.0
4.0
4.1
3.9
4.9
7.8
7.2
5.5

6.5
5.2
4.1
4.6
2.3
1.5
1.8
1.8
1.9
4.6
7.0
4.4
4.8

0.7
0.5
0.4
0.4
0.2
0.2
0.2
0.2
0.2
0.5
0.8
0.6
0.5

1.8
1.3
0.9
1.0
0.7
0.6
0.6
0.6
0.5
1.1
2.7
2.7
1.7

0.3
0.2
0.2
0.2
0.2
0.1
0.2
0.2
0.2
0.2
0.5
0.5
0.3

Vegetative detritus

Biomass burning

mg C m3

unc

mg C m3

unc

mg C m3

unc

0.3
0.2
0.2
0.3
0.2
0.1
0.1
0.2
0.2
0.3

16.8
6.1
2.9
3.0
3.0
2.1
1.5
2.4
4.7
8.1
22.6
15.1
12.9

7.7
3.0
1.4
1.4
1.5
1.0
0.7
1.1
2.3
3.9
10.7
7.3
6.2

27.7
26.5
16.0
11.3
12.5
1.5
0.0
0.0
7.7
22.7
68.4
54.6
29.5

8.7
5.1
3.6
4.2
3.7
3.2
4.1
4.4
4.7
6.5
13.7
10.7
8.8

1.3
0.9
0.8
1.4
0.9
0.7
0.7
1.1
0.8
1.2
nq
1.6
1.2

0.3
0.3

Other sources

R2

c2

0.88
0.86
0.85
0.86
0.86
0.85
0.83
0.84
0.81
0.85
0.89
0.86
0.85

3.9
4.3
4.8
4.8
4.7
5.1
5.9
5.3
6.3
5.0
3.8
4.2
4.7

nq Not quantied, see text for details.

The seasonal variation in biomass burning is similar to that observed

in Godavari, Nepal (Stone et al., in press), suggesting this source
follows region-wide trends. Vegetative detritus was a very small
contributor to ambient OC at an average of 2.0
0.6%.
3.4. Secondary organic carbon and unidentied sources
The CMB model apportioned OC to well-dened primary sources
and unapportioned OC is related to SOA and uncharacterized

primary sources. Secondary contributions to OC were estimated as

the water-soluble OC that was not associated with biomass burning
emissions. Open-type biomass burning was found to be 71% watersoluble (Sannigrahi et al., 2006) and was considered to be the
predominant source of primary water-soluble OC and all of SOA was
assumed to be water-soluble. This type of calculation was determined to give a reasonable estimate of SOA at a suburban site in
Mexico City and was validated by co-located measurements (Stone
et al., 2008). The uncertainty in this estimation was propagated from

60

PM2.5 Secondary Organic Aerosol

-3

Contribution to OC (gC m )

50

40

30

20

10

0
late-Jan Feb

Mar

Apr

May

Jun

Jul

Aug

Sep

Oct

Nov

Dec early-Jan

Jun

Jul

Aug

Sep

Oct

Nov

Dec early-Jan

70

PM2.5 Unidentified Sources

-3

Contribution to OC (gC m )

60

50

40

30

20

10

0
late-Jan Feb

Mar

Apr

May

Fig. 4. (a) Estimates of SOA contributions to PM2.5 organic carbon (OC) in Lahore. (b) PM2.5 OC that was not apportioned to primary sources by the CMB model and not accounted for
by SOA.

E. Stone et al. / Atmospheric Environment 44 (2010) 1062e1070

the uncertainty of the water-soluble OC measurement and 71% of the

uncertainty of the biomass burning contribution.
SOA contributions to PM2.5 OC in Lahore and their associated
uncertainties are shown in Fig. 4a. This estimate suggested that on
an annual average basis, secondary sources contributed to 11
8%
of organic aerosol in Lahore, such that the vast majority was fresh
aerosol from primary sources. The estimated concentrations of SOA
ranged from summertime lows of 1e4 mg m3 (5e11% of OC) to
wintertime highs reaching 23e27 mg m3 in October and November
(32% and 18%, respectively). The annual trend in SOA suggested that
peak concentrations occurred in wintertime, specically October to
early-January. This trend is somewhat contrary to SOA observed in
the Midwestern United States, which is greatest in the summertime
(Lewandowski et al., 2008), but is consistent with trends in
secondary sulfate formation in Lahore that has been observed to be
enhanced by wintertime fog episodes (Hameed et al., 2000; Rattigan et al., 2002; Biswas et al., 2008).
Unidentied source contributions are shown in Fig. 4b and were
estimated as the difference between other sources from the CMB
model and estimated SOA. The uncertainty of unidentied sources
was propagated from the uncertainty of other sources and SOA.
These unidentied sources were not found to be statistically significant during JuneeOctober but were important contributors to PM2.5
OC from November to May, accounting for 15e35% of the measured
concentration. The annual trend in unidentied sources follows that
of total PM2.5 and consequently most other aerosol components.
The seasonal trend revealed that unidentied sources peaked in the
wintertime and suggested wintertime combustion-related sources.
A major contributor to the unidentied source category was
expected to be brick kilns in Lahore. Previous studies in Lahore have
suggested the brick kilns are an important source of PAH (Smith
et al., 1996) and sulfur (Biswas et al., 2008) to the atmosphere, also
making them likely contributors to organic aerosol. Kilns are known
to burn low quality coal, biomass, and other materials like rubber
tires. Source proles for Lahore brick kilns were not available at the
time of this study, nor was there detailed information on the relative
amounts of different fuels burned. The co-combustion of coal with
these other fuels, however, provides a method of assessing how
these kilns may have contributed to OC. To this end, we compare the
contributions of coal combustion to OC with estimates of unidentied sources. A relatively strong linear correlation (R2 0.90)
between the two is shown in Supplemental Figure S1. This nding
supports the hypothesis that much of OC from unidentied sources
came from sources burning coal, such as brick kilns.
4. Conclusions
Ambient concentrations of PM2.5 and PM10 were very high in
Lahore at levels comparable to other Asian megacities. The magnitude of particulate air pollution in this megacity likely has a significant impact on the surrounding region. Carbonaceous components
were a major contributor to ambient PM2.5: OC accounted for 31% of
PM2.5, while organic matter (OC plus oxygen, hydrogen, and other
associated elements) was estimated to account for a total of 56% of
PM2.5. The sources contributing to ambient OC were estimated
using CMB modeling, which revealed that the most dominant
contributor to ambient OC was non-catalyzed motor vehicles, with
an annual average contribution of 29
10 mg m3. Other important
contributors included diesel engines, residual fuel oil combustion,
and biomass burning. While motor vehicle contributions were
relatively consistent over the course of the year-long study, biomass
and coal sources demonstrated seasonal variability and peaked in
the wintertime. SOA contributions also peaked in the wintertime
and were potentially enhanced by fog processing. Coal contributions were strongly-correlated with unidentied sources of OC; this

1069

suggested that uncharacterized sources included the co-combustion of coal along with other materials and pointed to brick kilns as
a probable source. The further characterization of emissions from
brick kilns and other industrial point sources in Lahore presents an
opportunity to improve upon source apportionment. Coarse-mode
particulate matter (PM10e2.5) was largely attributed to crustal
sources, like dust, which presents difculty from an air quality
management perspective. Sources of PM2.5, particularly the
anthropogenic sources implicated in this study, present a better
opportunity for reducing emissions.
Acknowledgements
We thank the Government of Pakistan, the Pakistani Higher
Education Commission, and the United States Agency for International Development (US-AID) for funding this research. We also
thank Jeff DeMinter, Brandon Shelton, Christopher Worley, Marya
Orf, Todd Jasienski, Erika von Schneidemesser, and Dr. Martin
Shafer for their assistance with chemical and/or data analysis.
Appendix. Supplementary material
Supplementary data associated with this article can be found in
the online version at doi:10.1016/j.atmosenv.2009.12.015.
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