Aerosol and Air Quality Research, 12: 359370, 2012

Copyright Taiwan Association for Aerosol Research

ISSN: 1680-8584 print / 2071-1409 online
doi: 10.4209/aaqr.2011.07.0105

Carbonaceous and Secondary Inorganic Aerosols during Wintertime Fog and

Haze over Urban Sites in the Indo-Gangetic Plain
Kirpa Ram1,2*, M.M. Sarin1, A.K. Sudheer1, R. Rengarajan1
1
2

Physical Research Laboratory, Ahmedabad-380 009, India

Department of Earth and Planetary Science, Graduate School of Science, The University of Tokyo, Tokyo 113-0033, Japan

ABSTRACT
The chemical composition of total suspended particulate (TSP) matter and secondary aerosol formation have been studied
during wintertime fog and haze events from urban sites (Allahabad and Hisar) in the Indo-Gangetic Plain. The atmospheric
abundances of elemental carbon (EC), organic carbon (OC), water-soluble OC (WSOC) suggest that organic matter is a
major component of TSP, followed by concentrations of sulphate and nitrate under varying meteorological conditions. The
concentrations of EC, OC, and WSOC show a nearly 30% increase during fog and haze events at Allahabad and a marginal
increase at Hisar; whereas inorganic constituents (NH4+, NO3 and SO42) are 23 times higher than those during clear days at
both the locations. The sulphur and nitrogen oxidation ratios (SOR and NOR) also exhibit significant increases suggesting
possible enhancement of secondary formation of SO42 and NO3 during fog and haze events. The significant correlation
between NH4+SO42 (R2 = 0.66, n = 61) and an NH4+/SO42 equivalent ratio 1 during fog-haze conditions suggest nearcomplete neutralization of sulphuric acid by ammonia. In contrast, NH4+/SO42 equivalent ratios are less than 1 during normal
days suggesting an NH3-deficient environment and the possible association of SO42 with mineral dust for neutralization.
Secondary inorganic aerosol formation and their hygroscopic growth can have significant impact on atmospheric chemistry,
air-quality and visibility impairment during fog-haze events over northern India.
Keywords: Elemental carbon; Organic carbon; Secondary inorganic aerosols; Sulphur and nitrogen oxidation ratios; Fog and
haze; Indo-Gangetic Plain.

INTRODUCTION
The Indo-Gangetic Plain (IGP) in northern India, stretching
from north-west to north-east, is a densely populated region
with characteristic emissions from anthropogenic sources.
Among the major sources of aerosol, emissions from
agricultural-waste and biomass burning dominate during the
wintertime (DecFeb) (Venkataraman et al., 2005; Rengarajan
et al., 2007; Gustafsson et al., 2009; Ram et al., 2010a;
Shakya et al., 2010; Rajput et al., 2011; Ram and Sarin,
2011). The transport of mineral aerosol from arid and semiarid regions of western India, during the summer (April
early June), imparts strong temporal variability in the chemical
composition and optical properties of aerosol (Jethva et al.,
2005; Chinnam et al., 2006). In addition, lack of year-round
precipitation further leads to the high aerosol loading over
the entire Gangetic Plain. Measurements of aerosol optical
depth (AOD) and absorption aerosol optical depth (AAOD)

Corresponding author.
E-mail address: ram@eps.s.u-tokyo.ac.jp,
kirpa81@gmail.com

have characterized IGP as a hotspot for anthropogenic aerosol

in south-Asia (Ramanathan et al., 2007).
The enhanced levels of pollutants lead to poor air-quality
and several environmental, health and socio-economical
issues in Asia (Hameed et al, 2002; Lee and Sequeira, 2002;
Husain et al., 2007; Bari et al., 2010; Wan et al., 2010; Ziao
et al., 2010). Among these, fog-haze formation and reduction
in visibility is of major concern (Watson, 2002; Zhang et al.,
2010). The formation of fog and haze is associated with
high aerosol loading from anthropogenic sources as well as
formation of secondary aerosols via gas-to-particle conversion
under favorable meteorological conditions (Reilly et al.,
2001; Husain et al., 2004; Sun et al., 2006; Zhang et al.,
2010; Fang et al., 2011;). Recent studies suggest that a
significant fraction of atmospheric particulate matter (PM)
in the Indo-Gangetic Plain are comprised of carbonaceous
aerosol (~3035% of the PM) and water-soluble inorganic
species (~1020% of the PM) over IGP and other locations
in India (Tare et al., 2006; Rengarajan et al., 2007; Ram et
al., 2010a; Deshmukh et al., 2011; Kothai et al., 2011).
During the wintertime, low ambient temperatures (range:
~1020C, at times dipping as low as 5C) and weak
winds (< 2 m/s) and boundary layer height (~500800 m)
favour stable atmosphere, leading to poor convective

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Ram et al., Aerosol and Air Quality Research, 12: 359370, 2012

mixing and accumulation of pollutants in the lower

atmosphere (Nair et al., 2007; Ram et al., 2010a).
A large variability in aerosol optical properties and
radiative forcing during wintertime haze and fog has been
reported over northern India (Ramachandran et al., 2006;
Tripathi et al., 2006). The aerosol chemical composition
changes through the aqueous phase-reactions on aerosol
surfaces (Sun et al., 2006; Biswas et al., 2008; Jihua et al.,
2009; Tan et al., 2009) and subsequently, it affects aerosol
optical properties during fog-haze conditions. In this
manuscript, we report on the changes in chemical
composition of atmospheric aerosol, secondary species
formation and neutralization processes during fog and haze
events through simultaneous measurements of carbonaceous
species (EC, OC and WSOC) and water-soluble inorganic
ionic constituents (cations: Na+, K+, NH4+, Ca2+ and Mg2+
and anions: Cl, SO42, NO3 and HCO3) from two urban
sites (Allahabad and Hisar) in the IGP. In addition, the
formation of secondary inorganic aerosols (NO3 and SO42)
have been assessed under different meteorological conditions
(clear days, haze and fog events) by sulphur and nitrogen
oxidation ratios (SOR and NOR, respectively).
SAMPLING LOCATIONS, AEROSOL COLLECTION
AND METEOROLOGICAL DETAILS
Ambient aerosol samples were collected at Allahabad and
Hisar during Dec 2004 using a high-volume sampler (model
APM 450, Environtech, India). The sampler does not have
size-selective inlet and thus, all samples correspond to total
suspended particulate (TSP) samples. The sampler was
calibrated before the field campaign and the flow-rate was
found to vary between 0.9 to 1.2 m3/min (average flow rate:
1.0 0.1 m3/min). A total of 42 and 19 samples were
collected from Hisar and Allahabad, respectively. Hisar
aerosol samples include a 31 daytime samples (sampling hrs:
8:00 AM to 7:00 PM, IST, Indian standard time) and 11
nighttime samples (sampling time: 7:30 PM to 7:00 AM,
IST) whereas all the samples (n = 19) were collected on 24
hr basis at Allahabad.
The two sampling sites, Allahabad (25.4N, 81.9E) and
Hisar (29.2N, 79.5E), represent an urban polluted
environment in northern India and their locations are shown
in Fig. 1. As per Census India report in 2011, the populations
of Hisar and Allahabad are 0.3 and 1.2 million, respectively.
Both sites are located in a highly agriculture productive
region of India and high level of pollution is observed from
the burning of cow-dung, agricultural waste and wood-fuel
used for residential heating purposes (Badarinath et al., 2009).
The sampling period (Dec 2004) represents wintertime
weather conditions over northern India and characterized
by calm winds (wind speed < 2 m/s) and low ambient
temperature (range: 525C). In addition, lower boundary
layer height (~500800 m) (Nair et al., 2007) and prevailing
meteorological conditions (lower temperature and calm
winds, and high relative humidity) are conducive to the
accumulation of aerosol and pollutants in the lower
atmosphere over the IGP. The sampling period was also
characterized by a number of fog and haze weather conditions

Fig. 1. Sampling locations of Allahabad and Hisar in the

Indo-Gangetic Plain of northern India during the LandCampaign-II (Dec 2004). The thick haze advecting eastward
and then spreading out over the Bay of Bengal in the Indian
Ocean is seen in the picture. The Moderate Resolution
Imaging Spectroradiometer (MODIS) on NASAs Terra
satellite captured this image of the region on December 17,
2004.
in the Gangetic Plain (Ramachandran et al., 2006; Lal et
al., 2008). Thus, these particulate samples provide an ideal
opportunity to understand the role of primary (derived
from the anthropogenic emissions within the IGP) and
secondary aerosol, and local meteorological conditions in
the modulation of fog-haze formation. The classification of
fog, haze and clear days is based on the visibility, relative
humidity (RH) and the notes in the log book during the
sampling period (Ramachandran et al., 2006; Lal et al.,
2008). When the visibility was in the range of 0.20.5 km,
12 km and ~10 km; the events were defined as fog, haze
and clear days, respectively (Ramachandran et al., 2006).
The diurnal plot of three hourly averaged temperature and
relative humidity data during clear, haze and fog events at
Hisar is shown in Fig. 2. Generally, relative humidity was
less than 70 and 80%, respectively, during clear and haze
days. In contrast, the RH was higher than 90% (especially in
morning hours; see Fig. 2) during foggy days. In addition,
some of the intense fog and haze events (e.g. Fig. 1) in the
IGP region were also captured by the Moderate Resolution
Imaging Spectroradiometer (MODIS) onboard NASAs Terra
satellite (Badarinath et al., 2011). Thus, the classification of
fog, haze and clear days at Hisar and Allahabad (Table 1) is
further substantiated by the earlier published work and the
real time images taken by the MODIS satellite over the IGP
(Ramachandran et al., 2006; Lal et al., 2008; Badarinath et
al., 2011). Based on the meteorological data, field and
satellite observations, 6, 8 and 15 Dec are defined as clear
days, 11, 17, 18 and 27 Dec are hazy and 12, 13, 14 and 22
Dec 2004 as foggy days at Hisar whereas (9, 25 and 27
Dec), (10, 11, 19 and 23 Dec) and (13, 17, 21 and 28 Dec)

Ram et al., Aerosol and Air Quality Research, 12: 359370, 2012

Temperature (C)

30

(a)

Clear
Haze
Fog

25
20

sunrise

15
sunset

10

Relative Humidity (%)

5
100

(b)

80
60
40
20

Clear
Haze
Fog

0
2.5

5.5

8.5

11.5 14.5 17.5 20.5 23.5

Local Time (hrs)

Fig. 2. Three hourly average diurnal plot of (a) temperature

and (b) relative humidity data during clear, haze and fog
events at Hisar.
are classified as clear, hazy and foggy days at Allahabad,
respectively (Table 1).
CHEMICAL ANALYSES OF AEROSOL SAMPLES
AND QUALITY CONTROL
All the filters were wrapped in the Aluminum foil after
sample collection and were packed in zip-lock bags. Samples
were brought to the laboratory and stored in a refrigerator
at ~4C until the analysis. Prior to assessment of total aerosol
mass and chemical analysis, samples were equilibrated in a
laminar flow bench for ~1520 h under constant relative

361

humidity (35 5%) and temperature (22 1C) conditions.

The particulate matter (PM) mass (g/m3) was ascertained
gravimetrically by weighing full-filter before and after the
aerosol sampling, and dividing the aerosol mass (in g) by
the total volume of air sampled (in units of m3). The mass
concentrations of elemental and organic carbon (EC and OC)
in ambient aerosol were assessed on the EC-OC analyzer
(Sunset Laboratory, USA) using thermo-optical transmittance
(TOT) protocol (Rengarajan et al., 2007; Ram et al., 2008).
The transmittance signal measured using a laser source (at
678 nm) was used to define the split-point between EC-OC
and to correct for the pyrolyzed carbon. Also, OC
concentrations were corrected for the carbonate carbon by
acidifying the aerosol sample with 6M HCl in a desiccator
(for ~6 hrs) and re-analyzing the acidified samples on the
EC-OC analyzer. A number of replicate analyses of aerosol
samples (n = 6) provide good reproducibility (reported as
relative percentage deviation; r.p.d.) for OC (~6%), EC (~8%)
and TC (~5%) measurements. In addition, the transmittance
signal at 678 nm of the laser source has been used for the
determination of absorption coefficient (babs) and mass
absorption efficiency (abs) of EC (Ram and Sarin, 2009).
The inorganic constituents, cations (Na+, K+, NH4+, Ca2+
and Mg2+) and anions (Cl, SO42 and NO3) in the waterextract of aerosol samples, were measured using an ion
chromatograph (Dionex-500) whereas water-soluble organic
carbon (WSOC) was analyzed using a total organic carbon
(TOC) analyzer (Shimadzu, TOC-5000A) (Ram and Sarin,
2010). The mass concentration of bicarbonate ion (HCO3)
was measured using a 0.005 M HCl and fixed endpoint
titration method in an auto-titration system. The experimental
details for the measurement of inorganic constituents and
WSOC are described in our recent publication (Ram and
Sarin, 2010). The reproducibility (as r.p.d.) of replicate
analyses of water-extracts for K+, Ca2+, Mg2+, Cl, SO42
and NO3 were better than 3% while it was ~6% for NH4+
analysis (n = 4). All the reported data of carbonaceous species
(EC, OC and WSOC) and inorganic ionic constituents
(cations and anions) are corrected for their respective
procedural blanks (Ram and Sarin, 2010; Ram et al., 2010a).

Table 1. The 24-hr average meteorological data, NO2 and SO2 concentrations during the clear days, haze and fog events at
two sampling sites (Hisar and Allahabad) in northern India.
Species

Hisar#
Clear days
Haze events
Fog events
(11, 17, 18, 27 (12, 13, 14, 22
(6, 8, 15 Dec)
Dec)
Dec)
46.7 9.9
62.3 8.5
61.1 5.7
17.5 0.4
16.7 1.1
17.3 2.1
0.6 0.1
0.5 0.3
0.5 0.2
~10.0
1.02.0
0.20.5
23.3 7.1
31.5 7.6
24.1 4.1

Allahabad
Haze events
Fog events
(10, 11, 19, 23 (13, 17, 21, 28
(9, 25, 27 Dec)
Dec)
Dec)
45.3 1.5
70.3 13.3
56.5 3.4
18.9 2.2
18.9 2.8
19.8 4.0
Clear days

RH (%)$
Temperature (C)$
Wind speed (m/s)$
Visibility range (km)
NO2 (g/m3)##
11.7 2.9
26.8 9.7
17.4 6.2
SO2 (g/m3)##
11.0 1.7
15.6 4.6
17.2 10.9
#
Classification of fog, haze events and clear days as per Ramachandran et al. (2006); Lal et al. (2008).
$
Daily-average data for relative humidity (RH), temperature and wind speed. The fog and haze events persist only for few
hrs (when RH > 80%; see Fig. 1), the 24-hr averaging resulted in lower RH during fog and haze events.
##
Daily-average NO2 and SO2 concentrations at Allahabad is adopted from Kulshreshtha et al. (2009) and those at Hisar
from Lal et al. (2008).

Ram et al., Aerosol and Air Quality Research, 12: 359370, 2012

362

RESULTS AND DISCUSSION

4.5) further attests our inference.

Total Suspended Particulate Matter

The average mass concentrations of total suspended
particulate (TSP), carbonaceous species (OC, EC and WSOC)
and inorganic species during clear days, haze and fog events
are presented in Table 2 and their fractional contribution is
shown in Fig. 3. Among the measured chemical species,
organic matter (OM = 1.6 OC) contributes ~2530% of
the TSP mass whereas the absorbing EC mass is only 2% at
Allahabad and Hisar (Fig. 3). Organic matter often contains
functional groups which comprise of elements such as
oxygen, nitrogen and sulphur and an appropriate conversion
factor is needed to account for these elements. The conversion
factor (i.e. OM/OC ratio) is highly variable (range: 1.42.1)
(Turpin and Lim, 2001) and depends on the sources of
organic aerosol, location and environment (urban, rural or
high-altitude). In this study, we have used a value of 1.6 to
estimate the OM concentration at the urban sites (Rengarajan
et al., 2007; Ram et al., 2010; Turpin and Lim, 2001).
SO42 contributes ~7% to the TSP mass at both sites, followed
by NO3 (8% at Hisar and 4% at Allahabad) and NH4+ (4%
at Hisar and 2.5% at Allahabad). In addition, carbonaceous
and inorganic species together contribute ~60% of the
aerosol mass at Hisar whereas their contribution is ~50% at
Allahabad (Fig. 3). The contribution of unidentified matter
(UM), estimated by taking difference of OM, EC and
inorganic constituents from the TSP, is of the order of 40%
at Hisar and ~50% at Allahabad. The unidentified matter
mainly consists of mineral dust with dominant contribution
from carbonate-rich minerals (such as CaCO3, MgCO3,
dolomite [CaMg(CO3)2]), calcium sulphate (or Gypsum),
and alumino-slilicates (Krueger et al, 2004; Rengarajan et
al, 2007; Zhang et al., 2010). The high-level of Ca2+
concentration in our samples (Table 2) and neutralization
of acidic species by mineral aerosol (Table 3 and section

Mass Concentrations of Carbonaceous and Inorganic

Species
The average mass concentrations of OC and EC are 49.0
14.1 and 6.2 2.0 gC/m3, respectively at Allahabad and
those at Hisar are 30.9 17.9 and 3.8 1.4 gC/m3,
respectively. Although, mass concentrations of OC and EC
are relatively higher at Allahabad; their fractional contribution
is similar at both the urban sites (Fig. 3). In addition, mass
concentrations of OC and EC at Hisar and Allahabad are
also similar with a recent data acquired during the wintertime
from Kanpur, an urban site located at the center of the IGP
(Ram et al., 2010a). However, mass concentrations of OC
and EC at urban sites in the IGP are an order of magnitude
higher compared to those at high-altitude site (Manora Peak)
in the central Himalaya (Ram et al., 2010b). The average
mass concentration of WSOC is 17.7 5.9 and 15.3 7.6
gC/m3 at Allahabad and Hisar, and average WSOC
contributes ~32 and 36% of total OC, respectively.
The mass concentrations of cations follow the trend:
NH4+ > Ca2+ > K+ > Na+ > Mg2+ at Allahabad and Hisar.
Trend for anions is: SO42 >NO3 > HCO3 > Cl for the
samples collected at Allahabad and NO3 > SO42 > HCO3
> Cl at Hisar. The average water-soluble inorganic species
(WSIS: sum of the cations and anions) mass is 61.0 and 45.6
g/m3 at Allahabad and Hisar, and contribute ~20 and 25%
of the TSP mass, respectively. The fractional contribution of
individual cation and anion (to WSIS mass) at both sampling
sites is presented in Fig. 4. Among anions; SO42, NO3
and HCO3 are the major contributor to the WSIS mass
whereas NH4+, Ca2+ and K+ cations contribute significantly
toward the WSIS mass (Fig. 4). The mass concentrations
of NH4+, SO42 and NO3 at Allahabad contribute ~12, 33
and 20% of the WSIS mass, respectively (Fig. 4). The
contribution of SO42 and NO3 is similar (~28 and 29% of

Table 2. Mass concentrations ( 1) of carbonaceous (OC, EC and WSOC) and selected inorganic species (in the units of
g/m3) during the clear days, haze and fog events at two sampling sites in northern India. Aerosol absorption coefficient (babs;
unit: M/m) and mass absorption efficiency (abs; unit: m2/g) of EC, at 678 nm, is also given. The scattering coefficient (bscat; at
678 nm) is estimated using an average mass scattering efficiency of 3.0 m2/g (Ram et al., 2012).
Species
TSP
OC
EC
WSOC
Na+
K+
Ca+2
Mg+2
NH4+
Cl
NO3
SO42
babs
abs
bscat

Clear
147 21
31.5 9.7
3.5 1.0
9.4 3.9
0.7 0.1
2.5 0.7
3.4 0.4
0.3 0.1
3.2 2.6
0.4 0.4
9.9 5.3
7.0 2.9
39.4 6.7
12.2 1.0
441 63

Hisar
Haze
199 19
34.9 12.8
4.0 1.4
11.3 3.7
0.8 0.2
2.6 0.6
4.4 0.8
0.4 0.1
6.8 1.9
0.4 0.1
16.7 4.2
12.7 1.8
40.0 15.7
11.2 3.1
597 57

Fog
162 29
31.6 8.8
4.1 1.3
11.8 2.1
0.7 0.1
2.7 0.7
2.7 1.0
0.3 0.1
9.7 3.8
0.4 0.1
17.1 5.6
17.3 6.1
49.3 6.2
12.0 2.8
486 87

Clear
212 45
33.8 9.5
5.0 2.1
12.5 4.8
0.4 0.1
1.8 0.4
5.8 1.2
0.5 0.1
2.9 1.1
0.1 0.1
5.5 1.9
10.8 2.8
56.4 14.2
11.9 3.0
636 135

Allahabad
Haze
247 42
45.1 8.5
6.4 2.5
19.0 5.4
0.8 0.2
2.5 0.4
5.2 2.2
0.6 0.1
7.3 2.3
0.1 0.1
9.9 3.7
18.6 2.6
72.9 25.5
12.0 3.0
741 126

Fog
302 95
60.1 12.7
6.9 2.6
21.3 1.7
0.8 0.1
2.9 0.5
6.2 2.4
0.6 0.1
8.5 2.8
0.3 0.2
12.4 6.0
23.6 8.6
71.9 10.6
11.4 4.1
906 285

Ram et al., Aerosol and Air Quality Research, 12: 359370, 2012

Fig. 3. TSP mass closure at urban Hisar and Allahabad for

the samples collected during Dec 2004. OM refers to the
organic matter (= 1.6 OC), WSIS# (sum of inorganic
species excluding SO42, NO3 and NH4+) and unidentified
matter (UM) is defined as TSP OM EC WSIS#.
the WSIS mass) and ~14% from NH4+ at Hisar (Fig. 4).
Thus, secondary inorganic aerosol (SIA: NH4+, SO42 and
NO3) contribute ~65 and 70% of the WSIS mass at
Allahabad and Hisar, respectively.
Chemical and Absorption Properties of Aerosol during
Clear Days, Haze and Fog Events
In general, total suspended particulate (TSP) and
concentrations of selected chemical species (EC, OC, WSOC,
NH4+, SO42 and NO3) increases during haze and fog
events. Although, fog and haze events persist only for few
hrs (when RH > 80%; see Fig. 1), the increase in daily mass

363

concentrations of chemical species were significant at both

sites. The average ratios of mass concentrations of selected
chemical constituents during fog and haze events, with
respect to those during clear days, at Allahabad and Hisar
are shown in Fig. 5. The average TSP mass increases by
~2550% during haze-fog events at Hisar and Allahabad.
The mass concentrations of OC, EC and WSOC also exhibit
an increase of ~30% (Fig. 5). However, their fractional
contribution (to TSP) increases only 5% during foggy days.
The OC/EC and WSOC/OC ratios are also similar during
clear days, haze and fog events at both the sampling sites
(Table 3).
Secondary organic carbon (SOC), estimated using the
EC tracer method, contributes ~30% of total OC at urban
sites in the Gangetic Plain during wintertime (Ram and
Sarin, 2010). The EC tracer approach provides an easier
and convenient method to estimate SOC concentration.
However, the estimated SOC concentration can be associated
with some degree of uncertainty due to varying nature and
source strength of primary emissions (biomass vs. fossil
fuel emissions) and changes in the primary OC/EC ratio.
Biomass burning emissions dominate in the IGP during
winter months (Rengarajan et al., 2007; Gustafsson et al.,
2010; Ram and Sarin 2010; Ram et al., 2012). Therefore,
primary OC/EC ratio from biomass burning emission sources
is reasonably constant so that the estimation of SOC is quite
reliable in the present study. In addition, mass concentrations
of K+, a tracer of biomass burning emissions, shows an
increase (~3560%; Table 2) at Allahabad suggesting that
strength of biomass burning emissions was higher during
haze and fog events. In addition, absorption coefficient
(babs) also exhibits an increase by ~2530% during haze
and fog events (Table 2). Since, mass absorption efficiency
(abs) remains similar during haze and fog events; the
increase in absorption coefficient is attributed to the
increase in EC mass concentration.
The mass concentrations of secondary inorganic aerosol
(SIA: NH4+, SO42 and NO3) show a factor of 23 increase
during haze and fog events (Table 2, Fig. 5). Among
secondary inorganic aerosol; NH4+ shows the maximum
increase followed by SO42 and NO3 at both sites (Fig. 5).
The fractional contribution of EC, OM and secondary
inorganic aerosol during clear days, haze and fog events
are presented in Fig. 6. It is observed that the contribution

Table 3. Ratios of selected chemical species during clear days, haze and fog events at Hisar and Allahabad.
Species

Clear
OC/EC
8.9 0.5
WSOC/OC
0.29 0.05
WIOC/EC
6.3 0.6
NH4+/SO42 (equivalent)
0.9 0.6
NO3/Ca2+ (molar)
1.5 0.7
SO42/Ca2+ (molar)
0.8 0.3
0.48 0.32
NF (NH4+)#
NF (Ca2+)#
0.72 0.49
NF (Mg2+)#
0.10 0.07
#
NF stands for neutralization factor.

Hisar
Haze
8.6 0.4
0.33 0.03
5.8 0.5
1.4 0.2
2.2 0.7
1.1 0.3
0.70 0.08
0.41 0.06
0.07 0.01

Fog
7.7 0.9
0.38 0.05
4.8 0.7
1.5 0.2
3.6 1.4
2.1 0.8
0.82 0.12
0.23 0.14
0.04 0.02

Clear
7.2 2.2
0.36 0.10
4.4 0.6
0.7 0.1
0.6 0.1
0.8 0.4
0.50 0.14
0.94 0.24
0.14 0.03

Allahabad
Haze
7.7 2.5
0.42 0.07
4.5 1.4
1.05 0.2
1.3 0.2
1.8 1.0
0.74 0.21
0.47 0.20
0.09 0.02

Fog
9.2 1.9
0.37 0.08
5.8 1.6
1.0 0.1
1.3 0.5
1.9 1.1
0.70 0.18
0.49 0.25
0.08 0.03

364

Ram et al., Aerosol and Air Quality Research, 12: 359370, 2012

Fig. 4. Mass closure of water-soluble inorganic species

(WSIS) at Hisar and Allahabad.
of SIA increases from 12.5% (during clear days) to 23%
(during fog events) at Hisar and 9.4 to 16% at Allahabad.
The increase in mass concentrations of NH4+, SO42 and
NO3 can not be attributed to the simultaneous increase in
aerosol loading as their fractional contribution is also higher
during haze and fog events (Fig. 6). In addition, fractional

contribution of UM during fog events decreases to 30% at

Hisar and 40% at Allahabad. Furthermore, SO42/Ca2+ and
NO3/Ca2+ molar ratios are also higher during haze and fog
events (Table 3). The mass concentration of Ca2+ is similar
during clear days, haze and fog events at both sites (Table
2). Thus, the increase in mass concentrations of SO42 and
NO3 can be attributed to secondary formation from their
respective precursor gases.
Aerosol absorption coefficient (babs), measured at 678
nm, varies from 24.9 to 54.6 M/m (1 M/m = 106 1/m) at
Hisar with an average of 39.9 9.1 M/m during Dec 2004.
Similarly, babs ranges from 36.8 to 109.4 M/m (av.: 66.1
17.2 M/m) at Allahabad. Furthermore, absorption coefficient
is relatively higher during fog and haze events at both urban
sites (Table 2). In contrast, average mass absorption
efficiency (abs) of EC at both urban sites (11.1 2.6 m2/g
at Allahabad and 11.3 2.2 m2/g at Hisar) are similar
during clear, fog and haze events (Table 2). Thus,
relatively higher babs at Allahabad are attributed to the
higher EC mass concentrations. The abs values, obtained
in the present study, are relatively higher compared to
those reported over Chinese regions; for example 7.7 m2/g
(in PM2.5 samples collected at urban Guangzhou) (Andreae
et al., 2008), 9.3 1.4 m2/g (for PM1.0) at urban Xinken
(Cheng et al, 2008) and 8.45 1.7 m2/g for aerosol over
Bejing during wintertime (Cheng et al, 2011). There is a
lack of scattering coefficient (bscat) measurements over
northern India. However, more recently, Ram et al. (2012)
have reported an average mass scattering efficiency of 3.0
0.9 m2/g for PM10 samples collected during OctNov
2008 at Kanpur. Assuming this value applicable for TSP
samples also, scattering coefficient (at 678 nm wavelength)
ranges from 450 to 1600 M/m (at Allahabad) and 201 to 885
M/m (at Hisar) during the observation period. The average

Fig. 5. The mass ratios of selected aerosol constituents, with respect to clear days, during fog and haze events: (a) and (b)
at Hisar; (c) and (d) at Allahabad.

Ram et al., Aerosol and Air Quality Research, 12: 359370, 2012

Fig. 6. Aerosol chemical composition during fog, haze

events and clear days at two urban locations in the IGP.
Abbreviations are same as referred in Fig. 3.
absorption and scattering coefficients are summarized in
Table 2 and both optical parameters are relatively higher
during fog and haze events at Hisar and Allahabad.
Sulphur and Nitrogen Oxidation Ratios (SOR and NOR)
The 24-hr average meteorological data including ambient
temperature, relative humidity (RH) and wind speed during
clear days, haze and fog events at both the sampling sites are
presented in Table 1. Although, only NO2 data is available
at Hisar; concentration of SO2 and NO2 gases are available
at Allahabad. Kulshrestha et al. (2009) have reported that
daily-average concentrations of SO2 and NO2 varied from
5 to 43 g/m3 and 2 to 45 g/m3, respectively during the
sampling period at Allahabad. The average concentration of
SO2 at Allahabad during clear days, haze and fog, events
are: 11.0 1.7, 15.6 4.6 and 17.2 10.9 g/m3 whereas
that of NO2 are: 11.7 2.9, 26.8 9.7, and 17.4 6.2 g/m3.
It is observed that concentration of precursor gases as well
as those of SO42 and NO3 increases significantly during
haze and fog events. Relative humidity is relatively higher
during haze and fog events at Allahabad (Fig. 1). Thus, it
is evident that higher RH and concentrations of precursor
gases during haze and fog events led to enhanced formation
of SO42 and NO3 aerosols.
The acidic species, SO42 and NO3, are generally produced
by the oxidation of their precursor gases (SO2 and NOx,
respectively) in the atmosphere under the favorable
atmospheric conditions via homogeneous and heterogeneous
oxidation processes. Homogeneous oxidation processes
involves the gas-phase reaction of SO2 with OH radicals
and is a temperature dependent process. On the other hand,
heterogeneous oxidation reaction of SO2 can take place on
dust aerosol surfaces (Bauer et al., 2004; Krueger et al.,
2004), aqueous transformation though catalytic oxidation
(via H2O2/O3 oxidation in the presence of Mn2+ and Fe3+)
(Martin and Good, 1991; Seinfeld and Pandis, 1998; Tursic
et al., 2004) and in-cloud scavenging processes (Warneck,
1999). It has been found that gas phase oxidation is more
important prior to fog formation and heterogeneous oxidation
take over after fog formation (Rattigan et al., 2001a, b).
Thus, the conversion of SO2 to sulfate depends on the

365

concentrations of precursor gases and oxidants, cloud cover,

availability of surface area and meteorological conditions
such as temperature and relative humidity (Liang and
Jacobson, 1999; Rattigan et al., 2001a, b). For example,
Rattigan et al. (2001b) investigated SO2 oxidation in clouds
as a function of droplet size, and found that SO2 oxidation
was dominated by hydrogen peroxide when the pH of the
cloud water was lower (in the range of 2.8 to 4.7).
Model simulations suggest that aqueous phase reactions
contribute ~two-thirds of the total sulfate production in the
troposphere (Warneck, 1999; Unger et al, 2006). Since,
ambient temperature is similar during clear days, haze and
fog events (Table 1); the higher sulfate formation during
haze and fog events can not be fully explained only by the
homogeneous gas-phase oxidation of sulphur dioxide. Tursic
et al. (2004) concluded that heterogeneous reactions under
haze conditions can contribute significantly to formation of
secondary sulfate aerosol. Recent studies have reported
that PM1.0 and PM2.5 contribute ~6580% of the PM10
mass at Kanpur, an urban site in the Gangetic Plain (Tare
et al., 2006; Ram and Sarin, 2011). Thus, conversion of
SO2, through heterogeneous reactions (either on surface or
aqueous phase) is expected to be higher under favorable
meteorological conditions (lower ambient temperature and
wind speed, high RH and SO2) and in the presence of
higher particle concentration. However, this proposition
and heterogeneous reactions needs a detailed investigation
in the IGP.
The secondary NO3 formation depends on the
concentrations of NOx and NH3, ambient temperature, RH,
OH radical (in daytime) and the photochemical activity. In
addition; nighttime secondary NO3 formation involves the
hydrolysis of dinitrogen-pentaoxide (N2O5) through the
heterogeneous reaction on aerosol surfaces and higher
relative humidity enhances the heterogeneous hydrolysis
of N2O5 (Ravishankara et al., 1997; Jacob, 2000; Pathak et
al., 2009). Brown et al. (2004) have suggested that the
conversion efficiency of NOx to HNO3 during nighttime
can be equivalent to the daytime photochemical conversion.
Moreover, Vrekoussis et al. (2006) have found that ~55
65% of the total production of nighttime HNO3 and NO3
were through the heterogeneous reactions of NO3 radical
in an anthropogenically-influenced eastern Mediterranean
marine boundary layer. The higher abundances of NOx and
high RH may facilitate the secondary NO3 NO3 formation
during the wintertime in the polluted atmosphere of the IGP
(Ram and Sarin, 2011). The presence of particulate nitrate is
a temperature dependent equilibrium between ammonia
and HNO3 with lower ambient temperature favouring the
existence of ammonium nitrate (NH4NO3) (Seinfeld and
Pandis, 1998). Furthermore, this equilibrium also depends on
concentration of sulfuric acid as NH4NO3 formation follows
ammonium sulfate and ammonium bisulfate (see section 4.5).
In order to understand the oxidation of SO2 and NO2
precursor gases, we have investigated the efficiency of
oxidation of SO2 to SO42 and NO2 to NO3 during clear
days, haze and fog events at Allahabad. The sulphur and
nitrogen oxidation ratios (SOR and NOR) were calculated
using the following equations (Wang et al., 2006; Tan et

Ram et al., Aerosol and Air Quality Research, 12: 359370, 2012

366

al., 2009):
SOR [ SO4 2 ] / {[ SO4 2 [ SO2 ]}

(1)

NOR [ NO3 ] / {[ NO3 [ NO2 ]}

(2)

where daily-average concentrations of all the chemical

species are reported in molar units. The sulphate
concentration represents non-sea salt (nss)-SO42 (where
nss-SO42 = [SO42] 0.2514 [Na+]) concentration and is
corrected for the contribution from sea-salt (Ram et al.,
2010). However, the contribution of sea-salt SO42 is very
low (~0.10.2 g/m3) and contributes only 1% to total SO42
in our samples. The average SOR and NOR, at Allahabad,
during clear days, haze, and fog events are presented in
Table 4. The SOR and NOR show an increase during haze
and fog events (with the highest values during fog events)
and thus, suggesting higher oxidation of SO2 and NO2
during haze and fog events. The average SOR, at Allahabad,
during clear, haze and fog events are 0.39 0.05, 0.45
0.12 and 0.52 0.15, respectively. Similarly, the average
NOR, at Allahabad, during haze and fog events are 0.20
0.04 and 0.33 0.11 whereas those at Hisar are 0.30 0.04
and 0.39 0.08, respectively. The NOR values are 0.25
0.08 and 0.23 0.15 during clear days at Allahabad and
Hisar, respectively. These values are compared with those
over the Chinese region (Table 4). It is noteworthy that total
aerosol mass as well as concentrations of SO42 and NO3
is similar over urban sites in India and China but
concentrations of SO2 and NO2 are factor of 34 times
higher over China (Wang et al., 2006; Rengarajan et al.,
2007; Jihua et al., 2009; Tan et al., 2009). However, NOR
and SOR over Chinese regions, during clear days, are
much lower (except at Beijing) than those at Allahabad
and Hisar. Thus, the oxidation efficiency of SO2 to SO42
and NO2 to NO3 aerosol are relatively higher over Indian
regions. The diurnal variability of O3 concentration were
relatively higher (by ~11 ppbv) during the haze condition
(compared to clear days) (Lal et al., 2008). This observation
suggests an increase in photochemical activity with
simultaneous increase in OH production and thus, results in
the lower concentrations of non-methane hydrocarbons and
NOx species (Lal et al., 2008). These differences in oxidation
efficiency could arise due to the meteorology, photochemical
activity, and the levels of OH radical which are expected to
be higher in India than China due to the meridional variations
in solar flux (Volz et al., 1981; Lal et al., 2008).

Ion-charge Balance and Neutralization of Acidic Species

The ratio of equivalent concentrations of cations (+: sum
of cations) and anions (: sum of anions) varies from 0.66
to 1.05 at Allahabad. However, the average /+ ratio
(0.90 0.13) and average HCO3 concentration (10.3 3.4
g/m3) suggest the alkaline nature due to the presence of
significant amount of mineral dust (also supported by high
concentrations of Ca2+ at Allahabad; Table 2). In addition,
the long-range transport of aerosol from the Thar Desert (in
western India) and African Deserts was observed during the
sampling period at Allahabad (Ram and Sarin, 2010). This
conclusion was also corroborated by high concentrations of
unidentified matter (UM), especially in Allahabad samples
and the contribution of mineral aerosol can be as high as
50% of the TSP mass at Allahabad (Fig. 3).
The scatter plot between the equivalent concentrations
of NH4+ and SO42 at Allahabad and Hisar is shown in Fig.
7(a). Also, 0.5:1 and 1:1 equivalent lines for the existence
of ammonium sulfate [(NH4)2SO4] and ammonium bisulfate
[NH4HSO4], respectively are shown in the figure. A
significant correlation between NH4+SO42 (R2 = 0.66, n =
61; Fig. 1) and NH4+/SO42 equivalent ratio 1 suggest
near-complete neutralization of sulphuric acid by ammonia.
Typically, NH3 neutralizes particle-phase sulfuric acid to
form ammonium sulfate and ammonium bisulfate. The
NH4+/SO42 equivalent ratio varies from 0.2 to 3.6 (av.: 1.3
0.6) at Hisar whereas it varies from 0.6 to 1.2 (av.: 0.9
0.2) at Allahabad. The observed equivalent ratios suggest
their probable existence as ammonium sulfate [(NH4)2SO4],
[NH4HSO4] and NH4NO3 salts in the urban environment of
the IGP. The formation of NH4NO3 involves the
heterogeneous reaction on existing primary and secondary
aerosol particles. A short-living complex, formed by proton
transfer from HNO3 to NH3, produces an ion-pair of
(NH4+) and (NO3) under high relative humidity conditions.
The data points with NH4+/SO42 equivalent ratios greater
than unity indicate the presence of excess-NH3 gas which
can neutralize nitric acid. The major sources of gaseous
ammonia (NH3) are human and animal excretion during
the metabolism processes; and those emitted from industrial
activities and fertilizers (urea, ammonium phosphate) used
for agriculture purposes in the IGP (Ram et al., 2010). The
gaseous ammonia is trapped in the lower atmosphere due to
the shallow boundary layer height and provides ammoniarich environment during fog-haze conditions. In contrast,
data points with NH4+/SO42 equivalent ratios less than
unity, especially Allahabad samples, suggest NH3-deficient

Table 4. Intercomparison of nitrogen and sulfur oxidation ratios during clear days, haze and fog events.
NOR##
SOR##
Clear
Haze
Fog
Clear
Haze
Fog
Allahabad
Dec-04
0.25 0.08 0.20 0.04 0.33 0.11 0.39 0.05 0.45 0.12 0.52 0.15
Hisar
Dec-04
0.23 0.15 0.30 0.04 0.39 0.08
winter-2002
0.06
0.15
0.08
0.15
Guangzhou
summer-2002
0.04
0.22
0.1
0.16
Beijing
2001-04
0.18
0.29
0.17
0.27
Guangzhou Dec 07Jan 08
0.09
0.24
0.22
0.29
##
Nitrogen and sulfur oxidation ratios.
Site

Time-period

Reference
This study
This study
Tan et al. (2009)
Tan et al. (2009)
Wang et al. (2006)
Jihua et al. (2009)

Ram et al., Aerosol and Air Quality Research, 12: 359370, 2012

environment and the possible association of NO3 with Ca2+

and Mg2+ as calcium nitrate [Ca(NO3)2] and [Mg(NO3)2],
respectively. This is further reflected by the scatter plot
between NH4+ and [NO3 + SO42] at the two sampling sites
(Fig. 7(b)). All the data points, except one, fall below the line
with slope of unity indicating that ammonia is not sufficient to
completely neutralize the acidic gaseous species and invoke
the possible role of mineral aerosol toward the neutralization
process. The scatter plot between [Ca2+ + NH4+] and [NO3
+ SO42] indicate nearly complete neutralization of acidic
species (Fig. 7(c)). Furthermore, we have calculated the
neutralization by the cations (NH4+, Ca2+ and Mg2+) during
clear days, haze and fog events, and neutralization factors
(NF; defined as the equivalent ratio of cation to the acidic
species) are presented in Table 3. Although, ammonia is the
major neutralizing agent of the acidic species at Allahabad
and Hisar; Ca2+ is the second neutralizing agent. In addition,
the neutralization by Ca2+ becomes more prominent during
clear days at both the sampling sites (Table 3).

367

CONCLUSIONS AND IMPLICATIONS

Mass concentrations of carbonaceous and inorganic
species, together with the oxidation ratios of SO2 and NO2,
studied during wintertime, have led us to infer that organic
matter is a major constituent of aerosol (~2530% of TSP
mass) in the Indo-Gangetic Plain. Water-soluble inorganic
species contribute ~20 and 25% of the TSP mass at
Allahabad and Hisar, respectively. A factor of 23 increase
in the mass concentration of secondary inorganic aerosols
(NH4+, SO42 and NO3) is observed at the sampling sites in
the IGP during haze and fog events. The scattering
coefficient is relatively higher at urban sites in the IGP and
is closely related to meteorological conditions and aerosol
chemical composition. Carbonaceous and inorganic aerosols,
associated with high mass scattering efficiencies, contribute
significantly to total aerosol mass and scattering coefficient
(as evident from the present study). Therefore, the reduction
of carbonaceous and inorganic aerosols could effectively
improve the visibility over the Gangetic plain during
wintertime.
The sulphur and nitrogen oxidation ratios (SOR and NOR)
are significantly higher during haze and fog events indicating
enhanced oxidation efficiency of precursor gases of SO42
and NO3. Secondary inorganic aerosol contributes ~65 and
70% of the WSIS mass at Allahabad and Hisar, respectively.
The prevailing meteorological conditions (higher RH) and
the presence of high levels of pollutants and condensation
nuclei may be a likely cause for the fog-haze formation
over the IGP which is also favoured under secondary
aerosol formation and their hygroscopic growth during the
wintertime. Subsequently, changes in morphological features
and physico-optical properties of ambient aerosol in the
presence of high concentrations of acidic species of the
IGP requires detailed investigation in order to understand
optical properties and their impact on radiation budget and
regional climate.
ACKNOWLEDGEMENT
Technical help provided by UC Kulshreshtha in collection
of aerosol sample at Allahabad is highly appreciated. The
authors would like to acknowledge the financial support
provided from ISRO-GBP office (Bengaluru, India). We are
thankful to two anonymous reviewers for their constructive
comments and suggestions to our manuscript.
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Received for review, July 22, 2011
Accepted, February 15, 2012