Aerosol and Air Quality Research, 14: 1701–1713, 2014

Copyright © Taiwan Association for Aerosol Research

ISSN: 1680-8584 print / 2071-1409 online
doi: 10.4209/aaqr.2013.09.0288

Diurnal and Seasonal Characteristics of Aerosol Ionic Constituents over an Urban

Location in Western India: Secondary Aerosol Formation and Meteorological
Influence

A.K. Sudheer*, Ramabadran Rengarajan, Dipjyoti Deka, Ravi Bhushan, Sunil Kumar Singh,
Mohammed Yusuff Aslam†
Geosciences Division, Physical Research Laboratory, Ahmedabad, 380 009, India

ABSTRACT

Water-soluble ionic constituents (Cl–, NO3–, SO42–, Na+, NH4+, K+, Mg2+ and Ca2+) of PM2.5 were measured using
Ambient Ion Monitor coupled-to Ion Chromatography (AIM-IC) with a time resolution of one hour at Ahmedabad (an
urban location in a semi-arid region of western India) during summer and winter to study the diurnal and seasonal variations.
Maximum abundances of most of the species were observed during afternoon hours in summer, whereas minimum
concentrations were found during winter at the same local time. During summer, the concentration levels of most of the
constituents in a diurnal cycle are largely influenced by variations in the ambient relative humidity. During winter, the
emission strength and boundary layer dynamics impact the diurnal cycle. Secondary inorganic species like NH4+, NO3– and
SO42– exhibit significant differences in their relative abundances during winter and summer. Four factors have been
derived by Positive Matrix Factorization (PMF) analysis of the water-soluble ionic constituents. These are secondary, sea-
salt, mineral dust sources, while the fourth factor is associated with K+, which is likely to be due to emissions related to
biomass burning.

Keywords: Aerosol chemistry; PM2.5; Secondary aerosol; GEOTRACES.

INTRODUCTION are secondary in nature, produced from precursor gases,

One of the major uncertainties in quantitative assessment
of climate change is the influence of atmospheric aerosol on
global climate by direct and indirect effects (IPCC, 2007).
Aerosol, mainly fine aerosol (PM2.5, particles < 2.5 µm
aerodynamic diameter) are also responsible for reduction
in visibility and have adverse health effects (Nel, 2005).
Fine particles are formed from a variety of natural and
anthropogenic sources and can be primary or secondary in
nature. In urban areas, large fraction of fine particulate is
water-soluble, where in inorganic ionic constituents
comprise a major portion. Inorganic constituents are
generally responsible for the hygroscopic nature of aerosol
and influences CCN activation, thereby having profound
impact on hydrological cycle on a regional scale. Major
water-soluble ionic species such as SO42–, NO3– and NH4+
†
Now at Indian Institute of Tropical Meteorology, Pune,
411 008, India
*
Corresponding author.
E-mail address: sudheer@prl.res.in
viz., SO2, NOx and NH3. Formation of secondary aerosol,
both organic and inorganic, has been recognized as a major
factor for air pollution over mega-cities (Guo et al., 2010;
Zhang et al., 2010).
Several studies addressing the chemical composition of
atmospheric particulate matter over Indian sub-continent, a
potential hot-spot region in terms of aerosol and pollutant
emission, have been reported (Ram et al., 2008; Kulshrestha
et al., 2009; Rengarajan et al., 2011; Ram et al., 2012). This
region is characterized by high loading of both natural and
anthropogenic aerosol during different seasons. In addition,
this region is a potential source for variety of constituents
transported to surrounding remote oceanic regions under
favourable meteorological conditions (Kumar et al., 2008;
Cherian et al., 2010; Kumar et al., 2012), which have
significant impact on surface ocean biogeochemistry.
Northwestern arid and semi-arid regions of India are known
for high amount of mineral aerosol, especially during summer
(Kumar and Sarin, 2009). During summer monsoon (June–
September), most of the continental region is influenced by
sea-salt aerosol transported by trade winds. During winter
(December–January), anthropogenic emission from various
sources is enhanced and surface meteorological condition
is conducive for entrainment of pollutants in a shallow
1702 Sudheer et al., Aerosol and Air Quality Research, 14: 1701–1713, 2014
boundary layer, which is a regular phenomenon over Indo-
Gangetic Plain (Tare et al., 2006). The observed seasonal
and inter-annual variability have been attributed to changes
in meteorological conditions, emission source strength and
changes in atmospheric processes. Significant day-night
variability in aerosol ionic constituents has been reported
indicating a prominent role of atmospheric processes on
abundances of various aerosol constituents on shorter
timescales (Ram and Sarin, 2011). Filter sampling technique
employed in various studies integrating long period (12–24
hours or more) limits opportunity to understand variability
in aerosol constituents at shorter timescales and relation of
particle composition to emissions, transport pattern and
meteorological conditions. It may also be noted that these
techniques are having positive as well as negative artifacts
which are difficult to quantify. Since emission,
meteorological changes and atmospheric processes occur in
timescales substantially shorter than 24 hours, highly time-
resolved intensive measurements of aerosol constituents
and related species are essential to study physical and
chemical transformation processes as well as transport
pattern of continental aerosol (Uematsu et al., 1992). In
addition, diurnal trend in aerosol optical depth and single
scattering albedo are considered largely due to relative
humidity (RH) changes (Ramana et al., 2004). However,
aerosol composition, number density and mass concentration
also have significant impact. Over the past decade, several
online measurement techniques were developed to overcome
limitations of integrated sampling and study the chemical
processes associated with aerosol particulate matter at
shorter timescales (Jayne et al., 2000; Weber et al., 2001;
Boring et al., 2002). Changes in aerosol chemistry which
is not observed using conventional filter based techniques
have been demonstrated by such studies (Weber et al.,
2003).
So far, there are no studies reported from the Indian sub-
continent and adjacent oceanic regions utilizing real-time
measurement of aerosol chemical constituents. Time-resolved
chemical composition has potential to provide insight into
diversity of aerosol sources from natural and anthropogenic
emissions as well as various chemical, physical and
thermodynamic processes within diurnal cycle especially
in the source region. In this paper, we present for the first
time, results from a semi-continuous (near real-time)
measurement of PM2.5 ionic constituents at an urban
location in semi-arid region of the western India, in order
to elucidate factors influencing diurnal variation in aerosol
major ionic constituents during summer and winter seasons.
METHODOLOGY
Sampling Site and General Meteorology
Measurements of PM2.5 ionic composition was performed
at Ahmedabad (22.0°N, 72.5°E), one of the largest cities in
western India. The observations were carried out in the
campus of Physical Research Laboratory located in western
zone of Ahmedabad. Population of Ahmedabad is ~6 million
with several small and large scale industrial establishments
situated within ~200 km from sampling site, mostly located
in south, south-west, east and north-east region of the city.
Two thermal power plants are situated in north and north-
east side within ~40 km distance of sampling location.
Potential local aerosol sources mainly consist of road traffic
with distinct diurnal variation, coal-based power plants and
industrial emissions. During winter, surface wind direction
over Ahmedabad is easterly or north-easterly and the sampled
air masses are generally of continental origin. Whereas during
summer, surface wind direction is westerly or south-westerly
and the air masses are predominantly of marine origin.
Local meteorological parameters (RH, temperature and
wind direction) during the observation period are depicted
in Fig. 1.
Near-real Time Measurement of PM2.5 Ionic Composition
Ionic composition of PM2.5 was measured with hourly
time resolution using an ambient ion monitor (AIM, model
URG 9000D, URG corporation, USA). AIM system was
operated during summer from June 5 to July 4, 2012 and
during winter from December 22, 2011 to January 16,
2012. This instrument mainly consists of two components:
1) Sample collection unit and 2) sample analysis unit and
the entire set up is similar to that described by Markovic et
al. (2012). PM2.5 separation is achieved by a sharp cut off
cyclone inlet (URG Inc. USA) operating at a flow rate of 3
L/min. Ambient air is taken using 1 m long inlet connected
to a diffusion-based parallel plate wet denuder. Cellusep®
membrane is used for the separation of gaseous components
like SO2, NOx, NH3, HNO3, HCl in the parallel plate denuder.
5 mM hydrogen peroxide in de-ionized water is used as
denuder solution. A steam jet aerosol collector, a modified
design of Khlystov et al. (1995), is placed downstream of
denuder for collection and extraction of aerosol particles.
The water extract from the steam jet aerosol collector is
subsequently filtered through an inline PTFE filter (Pall
Life Sciences) and simultaneously analyzed for major cations
and anions by two ion chromatographs (Model ICS-1100,
DIONEX, USA). The denuder solution is also analyzed for
cations and anions. All analysis is completed in one hour,
thus, providing the aerosol ionic composition data with an
hourly time resolution. For analysis of anions, Dionex AS-
14A and AG-14A columns were used and for cations CS-12A
and CG12A were used along with the appropriate electrolytic
suppressors. The conductivity detectors used for detection
and quantification of various analytes were calibrated with
laboratory-made standard solutions and commercially
available Merck® Ion chromatography standards. Standards
solutions were periodically injected to check the consistency
of sensitivity of the detectors. Air flow rate is frequently
checked using a calibrated flow meter.
Data Quality
To verify the efficiency with which interfering gaseous
species such as NH3, SO2, HCl, HNO3 and NOx, are removed
by diffusion denuder, a quartz fiber filter (Tissuquartz, Pall
Life Sciences, 0.3 µm, 99.9% retention; fixed in a 47 mm
diameter filter cartridge) was connected at the inlet and the
cation and anion concentrations were monitored in denuder
solution and steam jet solution. Concentrations of Cl–, SO42–
 Sudheer et al., Aerosol and Air Quality Research, 14: 1701–1713, 2014 1703

50

30
Temperature (oC)

Temperature (oC)
40

20
30

10 20

100 100
Relative Humidity (%)

Relative Humidity (%)

80 80

60 60

40 40

20 20

300 300
Wnd direction

Wnd direction
200 200

100 100

0 0

3/11 /11 /11 /12 /12 /12 /12 /12 /12 /12 /12 /12 /12 /12 /12 /12
/2 /27 /31 /04 /08 /12 /16 /04 /08 /12 /16 /20 /24 /28 /02 /06
12 12 12 01 01 01 01 06 06 06 06 06 06 06 07 07
90 50 90
Relative Humidity(%)

Relative Humidity(%)
Temperature (oC)

Temperature (oC)

80 80
30
70
40 70
60
60
20 50
30 50
40
40
30
10 20 30
20
10 20
0 2 4 6 8 10 12 14 16 18 20 22 24 0 2 4 6 8 10 12 14 16 18 20 22 24

Local time (hours) Local time (hours)

(a) (b)
Fig. 1. Temporal variation in meteorological parameters during a) winter and b) summer sampling period.

and NO3– measured in particle channel are below detection conductivity detection method. Details of the procedure are
limits. Concentration of NH4+ is less than 5% of that observed discussed in earlier publications (Rengarajan et al., 2007;
in denuder solution confirming that more than 95% gaseous Kumar et al., 2012). Hourly data of AIM was averaged over
NH3 is removed by denuder. Typical concentration levels sampling duration of high-volume samplers for comparison
of NH4+ in steam jet solution during sampling is about two with filter-based measurements. Fig. S1 (Supplementary
order of magnitude higher than blank levels obtained with Materials) represents the comparison between filter-based
filter at the inlet. This confirms that gaseous components measurements and average of online measurements for all
like NH3, SO2 and NOx are effectively removed by parallel measured ionic constituents. The measurement uncertainty
plate wet denuder and their interference in the measured was 10% as depicted by error bars for each data points.
concentration of aerosol constituents is negligible. Ionic Na+, K+, Ca2+ and SO42– exhibit on an average good
constituents measured in denuder solution provide agreement between both the measurements. The
concentration of gaseous species like NH3 and SO2, but concentrations of NO3– and Cl– exhibit large scatter and
independent validation with parallel measurement of these show overall lower values for filter-based measurements.
constituents was not performed. Hence, discussion on This may be due to negative artifact of filter sampling
gaseous constituents is not presented in this paper. arising from low stability of constituents like NH4NO3 at
Fifteen PM2.5 samples were collected simultaneously with ambient temperatures during our observation (Schaap et
AIM data collection using high-volume (Thermo Scientific) al., 2004) and Cl– loss on particulate phase in presence of
sampler during the observation period in summer on stronger acidic species such as SO42–. NH4+ also exhibits
Tissuquartz filters (Pall Life Sciences) integrating typically deviation from the 1:1 line. Even though the high-volume
about 24 hours of sampling. The filters were sub-sampled samplers are not equipped with denuders for removing
and extracted with de-ionized water after 45 minutes interfering trace gas constituents, the inter-comparison of
ultrasonication. The water extract is analyzed on ion- SO42– measurements by both methods shows reasonably
chromatograph for anions and cations using suppressed good agreement. The positive artifacts from gaseous
1704 Sudheer et al., Aerosol and Air Quality Research, 14: 1701–1713, 2014

components on measurements are negligible and negative
artifact by volatilization is unlikely to occur during AIM
sampling. Hence, the data derived from AIM operation can
be considered with minimum sampling bias and measurement
artifacts with respect to these measured species.
Charge balance of anions and cations provides an
estimate of completeness and accuracy of measured ionic
constituents. Fig. S2 depicts the scatter plot between total
anion and cations measured by AIM-IC system. The aerosol
anions and cations show very good correlation (r = 0.962,
n = 692 and r = 0.988, n = 569 for summer and winter data,
respectively) with a slope of ~1 and negligible intercept
suggesting that on an average fine particulate matter is
neutral during our observation period. However, during
summer the scatter is larger compared to that in winter.
Cation excess may be due to the contribution of organic
acid ions, bicarbonate and, on some occasion, NO2– ions
that were not quantified in this study. Anion excess is due
to presence of significant amount of aerosol acidity since
H+ ions are not accounted in the charge balance.
RESULTS AND DISCUSSION
Temporal Variation of Ionic Constituents during Summer
Most of the constituents, especially those associated with
mineral dust, like Ca2+ and Mg2+, exhibit large variability
during initial few days of observation (Fig. 2). On June 13
and 16, light rain events were recorded at Ahmedabad.
Ca2+ and Mg2+ concentrations show minimum levels on
these days indicating their effective removal from ambient
air and decreased emission of mineral aerosol. From June
17 onwards, these constituents show distinct diurnal pattern
with minimum variability until July 2. On July 3 and 4,
anthropogenic constituents like SO42–, NO3–, K+, NH4+
show sudden increase with a large diurnal amplitude. Light
drizzles were recorded on these days also. Such temporal
variations, in general, can arise from changes in source
strengths of aerosol during the observational period, changes
in meteorological conditions, or transport of pollutants from
different source regions. There are three occasions when
the wind direction drastically changed in a diurnal cycle;
on June 12 and 16 as well as on July 3 (Fig. 1(a)). Rest of
the period, sampling location witnessed mostly consistent
local wind pattern and the observed variation in abundances
of chemical constituents were not controlled by wind pattern
and transport from local point sources. On June 12 night,
south-westerly winds changed to almost northerly but there
is no significant change in the concentration levels of various

14
12
12 8
NO3- (g m-3)

10 6
Cl- (g m-3)

8
4
6
4 2
2
0 0
8
30
20
SO42- (g m-3)

15 6
Na+ (g m-3)

10 4

5 2

0 0
20 3.0
16
12 2.5
NH4 (g m )

8
-3

K (g m )

2.0
-3

6
1.5
+

4 1.0
+

2 0.5
0 0.0
0.6 4
0.5
3
(g m )

(g m )
-3

-3

0.4

0.3 2
2+

2+

0.2
Mg

Ca

1
0.1

0.0 0
2

2
-1

-1

-1

-1

-1

-1

-1

-1

-1

-1

-1

-1

-1

-1
un

un

un

un

un

un

ul

un

un

un

un

un

un

ul
-J

-J
-J

-J

-J

-J

-J

-J

-J

-J

-J

-J

-J

-J
05

05
05

10

15

20

25

30

05

10

15

20

25

30

Fig. 2. Temporal variations in ionic constituents in PM2.5 during summer season.

 Sudheer et al., Aerosol and Air Quality Research, 14: 1701–1713, 2014 1705

constituents. However, long range transport may influence 0.4

the observed concentrations, since the impact of sea-salt (a)

aerosol is conspicuous from June 16 onwards up to July 2. 0.3
r = 0.95
During these days, prevailing wind direction changed from

Mg2+ (g m-3)

south-westerly to westerly. This period is characterized by
strong correlation between Na+ and Mg2+ indicating their 0.2
common sources most likely to be sea-salt aerosol, whereas
during initial days up to June 16, Ca2+ and Mg2+ were
correlated indicating mineral dust as a major source. On July 0.1

3 and 4, the anthropogenic constituents like SO42–, NO3–

and NH4+ increased by more than factor of 5, whereas Na+, 0.0
Mg2+, Ca2+ decreased significantly. This indicates that 0.0 0.5 1.0 1.5 2.0 2.5 3.0
anthropogenic sources situated in eastern region of sampling Na+ (g m-3)
4
location have influenced the aerosol composition during the
reversal of wind direction on these days. Cl– concentrations (b)
show a reverse trend compared to constituents like Mg2+, Na+ 3

and Ca2+ and are closely associated with the anthropogenic

Ca2+ (g m-3)

components.
2
General wind direction changed from southerly to westerly
from June 17 onwards, which is reflected in the Na+ and
Mg2+ concentrations. These constituents typically originate 1
from sea-salt emission and the sampling location is influenced
by long-range transport of marine aerosols. Na+ and Mg2+
exhibit a good correlation (Fig. 3(a)) indicating their common 0

sources, where as Ca2+ and Na+ do not show such significant

0.0 0.5 1.0 +
1.5 -3
2.0 2.5 3.0
Na (g m )
correlation (Fig. 3(b)). Ca2+ is considered typically originating 4

from mineral dust and the contribution of Na+ from dust

(c)
sources can be neglected. Since Mg2+ and Ca2+ also show a 3
similar trend (Fig. 3(c)), some amount of Mg2+ is expected
Ca2+ (g m-3)

to be derived from dust as well. Thus, Na+ is the most

suitable species to be used as sea-salt tracer. Even though 2

the average Cl–/Na+ ratio is ~1.7, close to seawater ratio

(1.8), it shows a large variability (Keene et al., 1986).
1
Especially during July 2 to July 4, it increased drastically
to more than 10 and there was a corresponding change in
wind direction during these days. During these days, the 0
location was influenced largely by anthropogenically derived 0.0 0.1 0.2 0.3 0.4 0.5 0.6

aerosol as evident from higher abundances of NO3–, SO42–
and K+. Hence, it can be inferred that anthropogenic
sources (like industrial emissions and/or waste incineration)
are significantly affecting the observed Cl– abundances
when the winds are not near westerly or south-westerly.
Mönkkönen et al. (2004) reported higher aerosol number
concentration over Delhi, a polluted urban location in north
India, during week days compared to weekends. Data
collected at Ahmedabad during summer suggests that there
is no significant difference between week days and weekends
in concentrations levels or diurnal pattern of ionic
constituents of PM2.5. This demonstrates that variation in
traffic emission do not influence considerably on temporal
changes in the observed concentration levels or diurnal
pattern at the sampling site.
Diurnal Variations in Summer
In general, local wind direction did not influence the
concentration levels or relative abundances of ionic
constituents at Ahmedabad on a diurnal scale. This suggests
that the local point emissions are not significant in influencing
the observed aerosol composition and it can be considered
Mg2+ (g m-3)
Fig. 3. Scatter plot between Na+ and Mg2+, Ca2+ and Na+,
Ca2+ and Mg2+.
as a representative site for urban background condition.
NH4+, SO42– and NO3– concentrations are substantially
higher during afternoon hours, showing an increase from
10:00 hours onwards and reached maximum at ~14:00–
16:00 hours then decreased to background level by ~20:00
hours (Fig. 4). Similar patterns were observed with other
constituents also, may be due to the combined result of
many factors like aerosol sources, source strength, removal
mechanisms and surface meteorology. Concentrations of
SO42– and NO3– are expected to be higher during periods
conducive for more photochemical production and hence it
is expected to be high during day time (Seinfeld and Pandis,
1998). However, day and night temperature differences
can cause boundary layer changes and low concentration
may be observed during the day due to dilution effect,
which is in contrast to the observed pattern at Ahmedabad.
The observed trend is possible, when contribution from
1706 Sudheer et al., Aerosol and Air Quality Research, 14: 1701–1713, 2014

4 5

4
3

NO3 (g m )
Cl (g m )

-3
-3
3
2
2

-
-

1
1

0
10 0

8
1.5
SO4 (g m )
-3

Na (g m )
-3
6
1.0
2-

+
0.5
2

0 0.0

3 0.6
NH4 (g m )
-3

K (g m )
-3

2 0.4
+

1 0.2

0 0.0

0.3
1.5
(g m )

(g m )
-3

-3

0.2
1.0
2+

2+
Mg

Ca

0.1
0.5

0.0 0.0
0 4 8 12 16 20 24 0 4 8 12 16 20 24
Local time (hours) Local time (hours)
Fig. 4. Diurnal variation in ionic constituents of PM2.5 during summer.

secondary formation to the variability in concentrations of
SO42– and NO3– dominates over dilution effect due to
dispersion. The constituents like Ca2+, Mg2+ and Na+ have
distinctly different sources compared to that of secondary
species. Ca2+ can be closely associated with mineral dust,
whereas Na+ and major fraction of Mg2+ are generally sea-
salt derived, but their diurnal trend is similar to that of
NH4+, SO42– and NO3–. From this observation, it may be
inferred that the emission strength is not the only
controlling factor for the observed trend.
Diurnal variations of PM2.5 and BC mass concentrations
over Ahmedabad and southeastern Tibetan Plateau have
been reported by earlier studies (Ramachandran and Rajesh,
2007; Engling et al., 2011). Minimum concentrations at
about 14:00 hours and two peaks at ~8:00 hours and 22:00
hours has been observed and is attributed to the combination
of emission as well as boundary layer dynamics. These
reasons are very unlikely to cause different diurnal trends
of NH4+, SO42–, NO3–, Ca2+, Mg2+ and Na+ during summer in
our study. The observed pattern of ionic constituents at
Ahmedabad is similar to that of BC reported from Manora
Peak, a high altitude site in Himalayan region, northern India
(Pant et al., 2006). The atmospheric processes causing this
variability should be different, as similar boundary layer
dynamics is not operative at both the sites. Inconsistent
diurnal variation in PM2.5 mass and chemical constituents
were reported by Lee et al. (2007) from Gosan supersite in
Jeju Island. PM2.5 mass reaches maximum during afternoon
while major constituents shows different diurnal pattern
which is attributed to changes in transport of different air
masses towards the sampling site. Such conspicuous changes
in the wind pattern or air mass trajectory are not observed
during our study and not a plausible reason for the observed
diurnal trend.
 Sudheer et al., Aerosol and Air Quality Research, 14: 1701–1713, 2014
Hygroscopic nature of water-soluble ionic constituents
can cause hygroscopic growth and preferential increase in
deposition rate of these species under higher RH conditions
compared to non-hygroscopic particles. Fig. 1(a) shows the
typical diurnal variation in RH, which is opposite to the
trend observed for ionic constituents. The average RH for the
entire observation period is ~59%, ranging from 27 to 100%.
Minimum RH observed in average diurnal cycle is at 16:00–
17:00 hours, overlapping with maximum concentrations for
inorganic constituents. Hence, the removal process by
deposition can be lower at afternoon hours during summer
and is likely to be a major controlling factor for the diurnal
variations in concentrations of ionic constituents at this
location. Constituents like NH4+, NO3– and SO42– show
~100% or more increase during noon compared to
constituents like Ca2+, Mg2+ and Na+ showing an increase
of 30–50%. This suggests that enhanced production also
contribute significantly to the increase in NH4+, NO3– and
SO42– concentrations during afternoon hours. Major source
of K+ is biomass burning emissions and hence, major
fraction of it may be associated with carbonaceous particles
at this site. Freshly produced carbonaceous aerosol can be
hydrophobic in nature which gets converted to hydrophilic
with aging. Hence, removal process of K+ bearing particles
could be different compared to other ionic constituents. In
24-hour cycle, their removal efficiency may not be a
dominant factor, leading to a different diurnal trend for K+
with respect to other species.
Cl– concentration shows an inverse trend in diurnal cycle
compared to NO3– and SO42–, because Cl– is preferentially
degassed as HCl from sea-salt particles in presence of
strong acidic species (Hsu et al., 2007; Sarin et al., 2010).
During summer period, the sea-salt contribution to the
ionic constituents is significant as the prevailing wind
direction is westerly or southwesterly bringing marine air
masses to the sampling site. These sea-salt particles can
undergo aging processes under polluted environment
resulting significant depletion of Cl–. Cl– deficit (Cl–deficit)
is calculated assuming Na+ is exclusively of marine origin
as follows:
Cl–deficit = 1.8 × [Na+] – [Cl–] (1)
where [Na+] and [Cl–] are measured concentrations of Na+
and Cl–. Cl–deficit exhibits an excellent correlation with
NO3– (r = 0.93) indicating major role of nitric acid vapors
in degassing HCl from sea-salt particles. The observed Cl–
deficit ranges from 10% to 45% with an average value of
25% and the highest percentage depletion is observed
during afternoon hours when the acidic species reached
maximum value. The observed Cl–deficit ranges from 0.02 to
1.3 µg/m3. Assuming steady state condition for total chlorine
from sea-salt aerosol, degassed HCl concentrations equivalent
to Cl–deficit is calculated, which will be lower limit from sea-
salt origin. Estimated HCl mixing ratio ranges from ~0.02
ppbv to ~0.9 ppbv in the ambient air. This range is similar
to the reported concentration levels of HCl in a typical urban
atmosphere. Hence, HCl release from sea-salt particles is
likely to be a major source to ambient HCl vapours in this
1707
region during summer. It has major implication on trace
gas chemistry and secondary organic aerosol formation in a
polluted atmosphere involving NOx, O3, VOCs and CO,
because HCl can act as a potential source for Cl free radical
through hydrogen abstraction reaction with OH radical
(Lawler et al., 2009).
Temporal Variation of Ionic Constituents during Winter
Fig. 5 shows the temporal variations of PM2.5 ionic
constituents during winter. The measured concentration
levels are conspicuously higher during this period compared
to those during summer, presumably due to shallow boundary
layer and enhanced emissions particularly from biomass
burning sources. For example, average concentration of
SO42– is 5.7 ± 2.5 and 4.7 ± 5.8 µg/m3 during winter and
summer, respectively. Corresponding average concentration
of NO3– is 5.0 ± 2.7 and 2.1 ± 5.8 µg/m3, respectively. All
the constituents show a large variability during the
observation period with distinct diurnal pattern. Variation
in ionic constituents in fine aerosol does not show dependence
on local wind direction similar to the case observed during
summer. Hence, during winter also, local emission from
point sources does not seem to influence the measured
concentrations of aerosol constituents. In general, winds
were northerly and north-easterly, largely carrying polluted
continental air-masses to the sampling site, whereas it is
reversed during summer period. Hence, the concentration
of marine aerosol is very low during this time period,
which is evident from the concentration levels of Na+.
During summer, the concentration of Na+ varied from near
detection limit to ~3.5 µg/m3, whereas during winter it was
found to be < ~1 µg/m3. Temporal trends of Mg2+ and Na+
are not similar unlike during summer, whereas similar
temporal trend of Mg2+ and Ca2+ indicates that they can be
largely from mineral aerosol. There is no systematic change
in wind direction for extended duration during the sampling
period and hence influence of long-range transport of air
masses and associated variation in aerosol constituents is not
observed during winter. During week days and weekends,
observed concentrations of ionic constituents remain similar
and the influence of change in traffic emission sources may
not have significantly affected the temporal variation of these
constituents. Throughout the study period, daily diurnal
patterns of various constituents do not vary, suggesting that
these observations are characteristic of a large spatial scale
and not considerably impacted by local plume emissions.
Hence, this data set can be considered as a typical
representative of ionic concentration of fine particulates
during winter in this region.
Diurnal Variation in Winter
Diurnal variation of ionic constituents during winter is
presented in Fig. 6. The abundances of various constituents
exhibit typically two maxima, one in the morning and
another at night time. There is no general variation in wind
direction, consistent with changes in the aerosol ionic
concentrations. Similar trend has been reported for BC
mass concentration from various locations during winter
including Ahmedabad (Ganguly et al., 2006; Ramachandran
1708 Sudheer et al., Aerosol and Air Quality Research, 14: 1701–1713, 2014

25 20

20 16

NO3- (g m-3)

Cl- (g m-3)
15 12

10 8

5 4

0 0
20 2.0
SO42- (g m-3)

15 1.5

Na+ (g m-3)

10 1.0

5 0.5

0 0.0
20 2.0

16
1.5
NH4+ (g m-3)

K+ (g m-3)
12
1.0
8
0.5
4

0 0.0
0.25 2.5

0.20 2.0
Mg2+ (g m-3)

Ca2+ (g m-3)

0.15 1.5

0.10 1.0

0.05 0.5

0.00 0.0
1

2
-1

-1

-1

-1

-1

-1

-1

-1

-1

-1
an

an

an

an

an

an
ec

ec

ec

ec
-D

-D

-D

-D
-J

-J

-J

-J

-J

-J
02

07

12

02

07

12
23

28

23

28

Fig. 5. Temporal variation in ionic constituents during winter.

and Rajesh, 2007). The reason for such a pattern is largely
due to stable and shallow boundary layer during the night
and dilution effect during the day. This indicates that the
variability is largely controlled by the atmospheric boundary
layer dynamics, causing nighttime peak due to lower
boundary layer height and morning increase due to
fumigation effect. Fig. 1 depicts the variation in the observed
RH during the study period. In comparison to that observed
during summer, the RH is relatively low, ranging from
~11% to ~95% with an average value of 50%. This causes
lower hygroscopic growth and consequently deposition of
hygroscopic particles from the ambient air is not likely to
be a major factor in controlling the ambient concentration.
Formation processes for secondary aerosol constituents
like NH4+, SO42– and NO3– are expected to be high during
daytime, when photochemical activity is at its maximum,
but the effect due to boundary layer dynamics dominates in
deciding overall concentration of these species, which is
evident from the noon time low concentrations of these
species.
Secondary Inorganic Aerosol: Seasonal Characteristics
NH4+, NO3– and SO42– constitute the major fraction of
secondary inorganic aerosol produced by oxidation of NOx
and SO2 and subsequent neutralization with ambient gaseous
ammonia or scavenging by existing particles (Seinfeld and
Pandis, 1998). In general, concentration levels of these
species are relatively lower during summer than winter.
The average concentration of NH4+ during summer is 1.2
µg/m3 and average NH4+/SO42– equivalent ratio is 0.63,
indicative of ammonium-poor condition causing NH4+ and
SO42– could exist in the form of NH4HSO4. Fig. 7(a) depicts
scatter plot between NH4+ and SO42–, exhibiting a good
correlation for all data points with NH4+ concentration less
than 200 neq/m3. During July 3 and 4 (when RH was high
and intermittent rain was recorded), the data exhibit a
different trend with excess NH4+ with almost quantitative
neutralization of SO42–.
During winter, the average NH4+ concentration is 4.6 µg/m3
and NH4+/SO42– ratio is 2.2, suggesting an ammonium-rich
environment. Significant quantity of NH4NO3 is likely to
be present in particulate form during this period. Plot between
NH4+ and SO42– is given in Fig. 7(b) indicating more scatter
compared to summer period, probably due to significant
fraction of total NH4+ is associated with NO3– during this
period.
 Sudheer et al., Aerosol and Air Quality Research, 14: 1701–1713, 2014 1709

8 10

8
6

NO3- (g m-3)

Cl (g m )
-3
6
4
4
-

2
2

0
9 0
0.6

8 0.5
SO42- (g m-3)

Na+ (g m-3)

0.4

6
0.3
5
0.2
4
0.1
3
8 0.0
1.5

6 1.2
NH4+ (g m-3)

K+ (g m-3)

0.9
4

0.6
2
0.3

0
0.15 0.0
1.8

0.12 1.5
Mg2+ (g m-3)

Ca2+ (g m-3)

1.2
0.09
0.9
0.06
0.6

0.03
0.3

0.00 0.0
0 4 8 12 16 20 24 0 4 8 12 16 20 24
Local time (hours) Local time (hours)
Fig. 6. Diurnal variation in ionic constituents of PM2.5 during winter.

Positive Matrix Factorization (PMF) Analysis
PMF is a receptor model widely used in the source
apportionment studies of atmospheric aerosol in the absence
of source profile information (Lee et al., 2003; Jeong et al.,
2008; Karanasiou et al., 2009; Sudheer and Rengarajan,
2012). EPA PMF 3.0.2.2 was used in this study in order to
assess temporal variability of various source contributions to
water-soluble inorganic constituents during the observation
period. Details of the model have been described elsewhere
(Kim et al., 2003; Norris et al., 2008; Sudheer and Rengarajan,
2012). Number of factors from 3 to 7 was examined using
linearity of fit by the residual distributions along with
interpretability of the resulting profiles (Kim et al., 2003).
PMF analysis yielded four factors each for both summer and
winter samples (Table 1). For the summer data, Factor 1
has dominant loading from NO3–, SO42– and NH4+ signifying
the secondary sources. Factor 2 has 78% loading from Na+
and 70% from Mg2+, suggesting this factor corresponds to
sea-salt emission. The third factor is characterized by 58%
loading from Ca2+, which can be considered as mineral dust
sources. The fourth factor corresponding to 54% loading
from K+ and 40% loading from Cl–. There is no significant
loading from other species and K+ is usually emitted from
biomass burning, hence, this factor may correspond to
biomass burning emission. Fig. 8(a) depicts the temporal
variation of various factor contributions to PM2.5 water-
soluble constituents during our observation. On an average,
secondary sources contribute 23% of total water-soluble
inorganic constituents during the observation period in
summer. Sea-salt and mineral dust fractions constitute 29 and
25% respectively. Temporal variation in sea-salt contribution
is found in good agreement with Na+ concentration.
The major three factors identified (factors 1, 2 and 3,
Table 1) for winter are secondary sources, sea-salt, and
1710 Sudheer et al., Aerosol and Air Quality Research, 14: 1701–1713, 2014

250 during winter is substantially higher compared to summer.

r = 0.84 (a) Meteorological conditions and ammonium-rich environment
200 are conducive for secondary production of inorganic ionic
constituents and could result in high abundance of these
species in fine aerosol.
NH4 (neq m )
-3

150

CONCLUSION
+

100

Temporal as well as diurnal variations of PM2.5 water-

50 soluble ionic constituents during summer and winter have
been studied from Ahmedabad, an urban location situated in
0
semi-arid region of western India, based on semi-continuous
0 50 100 150 200 250 300 measurement for the first time. The results show distinctly
2-
SO4 (neq m ) -3 different diurnal patterns of various constituents during
1000
summer and winter. During summer, the concentration levels
of most of the constituents in a diurnal cycle are largely
r = 0.75 (b) influenced by ambient relative humidity variation possibly
800
due to hygroscopic growth and deposition processes. The
secondary species like SO42–, NO3– and NH4+ are also
NH4 (neq m )
-3

600 influenced by photochemical production during day-time.

Comparison with variability in other aerosol parameters
and trace gases from earlier studies indicate that the diurnal
+

400
variability observed during winter is mainly modulated by
boundary layer dynamics. Secondary inorganic species,
200
viz. NH4+, NO3– and SO42– exhibit significant differences
in their relative abundances during winter and summer.
0 PMF analysis of the water-soluble ion data yielded four
0 100 200 300 400
factors, identified as secondary, sea-salt, mineral dust sources
and a source associated with K+, which is likely to be
2- -3
SO4 (neq m )

Fig. 7. Scatter plot between NH4+ and SO42– during (a)
summer and (b) winter.
mineral dust for the measured ionic constituents. The
secondary source factor is having loading from K+, hence
it is not fully resolved from biomass burning sources as
obtained for summer. The fourth source is associated with
K+ (10% loading) and Cl– (43%). Factor 4 for summer
season is characterized by K+ and Cl– loading. Cl– also is
associated with biological systems along with K+ and it is
reasonable to consider this factor representing biomass
burning emission. Temporal variation of various factors
contribution to measured ionic constituents is depicted in
Fig. 8(b). Percentage contribution of secondary sources
biomass burning emission. Since diurnal variation of aerosol
constituents, number density and mass concentration may
have significant impact on diurnal trend in aerosol optical
depth and single scattering albedo, incorporation of such
real-time measurements and delineation of controlling
factors of the variability in radiative transfer calculations
might result in more realistic aerosol forcing estimates.
AKNOWLEDGEMENT
Authors would like to gratefully thank Ministry of Earth
Sciences, Government of India, under GEOTRACES
programme for funding of this project. Authors are thankful
to Dr. K.P. Subramanian (PRL) for providing laboratory
space for conducting experiments.

Table 1. Factor profile (% Species) derived from PMF analysis of water-soluble constituents. Summer - factor 1:
secondary, factor 2: sea-salt, factor 3: mineral dust, factor 4: biomass burning. Winter - factor 1: secondary + biomass
burning, factor 2: sea-salt, factor 3: mineral dust, factor 4: biomass burning.
Summer Winter
Factor 1 Factor 2 Factor 3 Factor 4 Factor 1 Factor 2 Factor 3 Factor 4
Cl– 0.0 59.7 0.0 40.3 8.4 34.4 13.8 43.3
NO3– 43.1 36.3 20.6 0.0 75.3 5.2 0.0 19.5
SO42– 49.6 28.4 14.6 7.4 73.4 0.0 14.3 12.2
Na+ 5.03 77.7 14.1 3.2 23.0 44.1 32.9 0.0
NH4+ 69.9 12.4 0.0 17.7 69.1 4.6 1.1 25.2
K+ 8.18 0.0 37.3 54.5 45.5 14.6 29.9 10.0
Mg2+ 2.57 69.9 27.5 0.0 27.7 3.0 69.3 0.0
Ca2+ 0.00 39.8 58.0 2.2 22.9 0.0 77.1 0.0
 Sudheer et al., Aerosol and Air Quality Research, 14: 1701–1713, 2014 1711

25 50
Factor 1 (a) Factor 1 (b)
20 40

15 30

10 20

5 10

0 0
30
Factor 2 25
Factor 2
12
20
8 15
10
4
5
0 0
20 20
Concentration (g m )

Concentration (g m )
-3

-3
Factor 3 Factor 3
16
15
12
10
8
5
4

0 0
30 40
Factor 4
25 Factor 4
30
20
15 20
10
10
5
0 0
2

2
-1

-1

-1

-1

-1

-1

-1

-1

-1

-1

-1

-1
un

un

un

un

un

un

ul

ec

ec

an

an

an
-J

-D

-D

-J

-J

-J
-J

-J

-J

-J

-J

-J

05

02

07

12
05

10

15

20

25

30

23

28

Fig. 8. Temporal variation of various factor contributions to PM2.5 water-soluble ionic constituents during (a) summer and
(b) winter sampling period.

SUPPLEMENTARY MATERIALS Asia Biomass-burning Season. Tellus Ser. B 63: 117–128.

Supplementary data associated with this article can be
found in the online version at http://www.aaqr.org.
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Supplementary Materials

3.0

2.5 a 3 b

NO3 -AIM (g m )

-3
Cl -AIM (g m )
-3

2.0
2
1.5

1.0

-
1
-

0.5

0.0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0 1 2 3
- -3 - -3
Cl -Filter (g m ) NO3 -Filter (g m )
10 3.0

c 2.5
SO42--AIM (g m-3)

8 d
Na -AIM (g m )
-3
2.0
6
1.5
4
1.0
+

2
0.5

0 0.0
0 2 4 6 8 10 0.0 0.5 1.0 1.5 2.0 2.5 3.0
2- -3 + -3
SO4 -Filter (g m ) Na -Filter (g m )
2.5 1.0

e f
NH4+-AIM (g m-3)

2.0 0.8
K -AIM (g m )
-3

1.5 0.6

1.0 0.4
+

0.5 0.2

0.0 0.0
0.0 0.5 1.0 1.5 2.0 2.5 0.0 0.2 0.4 0.6 0.8 1.0
+ -3 + -3
NH4 -Filter (g m ) K -Filter (g m )
0.5 3.0

2.5 h
Mg -AIM (g m )

g
Ca -AIM (g m )

0.4
-3

-3

2.0
0.3
1.5
0.2
1.0
2+

2+

0.1
0.5

0.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
2+ -3 2+ -3
Mg -Filter (g m ) Ca -Filter (g m )
Fig. S1. Scatter plot of measured ionic constituents between the averaged concentration from AIM
measurement and filter based measurement. Error bars indicate 10% uncertainty for AIM and filter
measurements.
 1.2
Summer
0.8
 Cations ( Eq m )
-3
0.6

0.4

c = 0.011
0.2 m = 0.967
r = 0.963

0.0
0.0 0.2 0.4 0.6 0.8 1.2
-3
1.2  Anions ( Eq m )
Winter
 Cations ( Eq m )

1.0
-3

0.8

0.6

0.4 c = 0.062
m = 1.036
r = 0.989
0.2

0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2

 Anions ( Eq m-3)
Fig. S2. Scatter plot between measured total anions and total cations showing the charge balance
during winter and summer observation period.