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SP Shukla
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Abstract
Atmospheric particle characteristics and concentrations are critical in source apportionment analysis. Particulate matter (PM) levels (in Indian conditions) suggest significant seasonal variability. There could be several
reasons for this variability, including the variable meteorology, wind-driven dust, and atmospheric chemistry,
which is responsible for formation of secondary particles. To clearly establish the causeeffect relationship of
particulate levels and sources, PM10 (n 100) samples were collected at Kanpur, India, during 2000 to 2001.
The collected samples were analyzed for metals and water-soluble ions, and results were utilized for factor
analysis and source apportionment estimations with specific focus on secondary particles of fine mode. In the
three seasons studied, two important PM10 sources were soil-road dust (1547%) and inorganic secondary particles like (NH4) 2SO4 and NH4NO3 (2126%). Winter and monsoon conditions were conductive for formation
of secondary particles due to moderate temperatures and high relative humidity. The role of ambient ammonia was vital in overall atmospheric chemistry of secondary particulate formation. It is thus clear that control
of PM will require control of primary precursor gases like SO2 and NOx, including NH3.
Key words: PM10; atmospheric particle characteristics; apportionment analysis
Introduction
We could not find any study in India to examine the formation of secondary particles and identify their contribution
to PM10, and more importantly, identify the precursor
gaseous pollutants responsible for formation of secondary
particles. Because most of the secondary particles are formed
in fine mode, their associated health risk is high and their
control will require control of primary precursor gaseous
pollutants. The problems of apportionment of secondary
particles is further compounded, as no measurements of
PM2.5, left beside their composition, are done in India, which
must be true in most developing countries. If one could apportion the sources of secondary particles of fine mode from
the measurements of PM10 (which is routinely done) this
knowledge could be of immense utility for the control of
PM2.5.
The winter levels of PM were found to be less than those
in summer at each of the seven sampling locations in Delhi
during the year 1990 (Sharma et al., 1995). A 5-year-long
study (19811985) by the Central Pollution Control Board
(CPCB) at Agra concludes that PM levels were significantly
1Department
849
850
FIG. 1.
to December 2001 at Kanpur (longitude 88 22 E and latitude 26 26 N). Finally, efforts have been made to quantitatively apportion the sources contributing to the PM levels
and subsequently defining the role of NH3, SO2, and NOx in
formation of PM. The sampling site was a relatively clean
site in the city of Kanpur.
The technique of factor analysis-multiple regression (FAMR) (Kumar et al., 2001), a receptor model, was employed
to apportion the sources for PM. It may be noted that techniques like chemical mass balance will not work for apportioning secondary particles as these particles have no specific signatures at the source.
Study Design and Materials and Methods
Study area
The study area of Kanpur is situated at an approximate
distance of 435 km SE from Delhi on the right bank of river
Ganges. Kanpur is a representative site of the Ganga basin
(where new power plants are expected to come) in terms of
the weather conditions and atmospheric seasonal variability.
TABLE 1.
Sampling
seasons
Summer
Monsoon
Winter
851
not become dry. The walls of beaker were rinsed with 20 mL
Milli-Q water (conductivity 0.055 S cm1) and allowed to
stand for at least 30 min to allow the diffusion of acid from
the filter into the rinse. The sample was filtered through 0.22
micron filter paper and the filtrate was made up to 100 mL.
This sample was transferred to plastic bottles and refrigerated until further analysis.
Filter paper blanks and acid blanks were also taken
through the same procedure simultaneously. Al, As, Ba, Ca,
Fe, K, Mg, Mn, and Pb were determined in these acid-digested samples using flame atomic absorption spectrophotometer (AAS) (Model Varian SpectrAA 220FS and GBC
Avanta , Australia). As metal was determined using a
hydride generator (Model GBC HG3000) coupled with AAS.
Before analyzing the samples, the instrument was calibrated
for Al, As, Ba, Ca, Fe, K, Mg, Mn, and Pb. As per the U.S.
EPA method, a stock solution (of 1,000 ppm) was prepared
and diluted to the range of working standards for individual metals. The calibration graphs were prepared using these
working standards in the linear range of the optical density
(0.04 to 0.8). The instrument was calibrated at three different levels for each metal.
To examine the background metal contents of blank filter
paper (5% of total samples), exactly similar extraction and
analysis procedure was employed for blank filter papers. It
was found there was a large variation in the characteristics
of blank filter papers. To overcome the impact of background
elemental variability in the filter paper, the blank portion
(the border of filter paper unaffected by sampling due to top
plate holding the filter paper to the filter assembly) of each
PM10 laden filter paper was separately analyzed for getting
the concentrations of metals in the blank filter paper. For this
purpose, the blank portion of each PM10 laden filter paper
was cut and weighed separately. Corresponding blank corrections were incorporated in the data. The blank value, recovery, and detection limit of metals and ions in filter blank
is given in Table 2.
Analysis of ions
The remaining half portion of PM10 filter papers were analyzed for water-soluble ions following the prescribed extraction procedure (Lodge, 1989). Half of the filter paper used
in the high-volume sampler was cut into small pieces into a
conical flask, and 80 mL of Milli-Q water was added. The
sample was agitated for 30 min and then digested at a temperature of 65 C for 3 h. Digested sample was again agitated for 30 min. Thereafter, the walls of beaker were rinsed
SAMPLING DETAILS
Sampling months
June, 2000
MarchJune
JulyOctober, 2000
JulyOctober, 2001
November, 2000February, 2001
NovemberDecember, 2001
OF
PM10
Parameter
measured
PM10 concentrations,
Al, As, Ba, Ca
Fe, K, Mg,
Mn, Pb, NH4,
F, Cl, NO3, and SO42
Number of
samples
26
41
33
852
Species
Blank value
(mg g1)
Recovery (%)
Detection limit
(mg L1)
Al
As
Ba
Ca
Fe
K
Mg
Mn
Pb
NH4
F
Cl
SO42
NO3
5.4
1.4
23.6
3.9
8.1
5.1
13.3
BDLa
BDLa
BDLa
BDLa
BDLa
BDLa
BDLa
92
85
88
91
96
86
94
97
97
85
97
97
97
90
0.020
0.035
0.045
0.002
0.006
0.002
0.001
0.003
0.020
0.10
0.10
0.10
0.25
0.20
aBDL,
[PM10]j C0 Ci [APCSi]j
(1)
i1
FIG. 2. Twenty-four-hour average ambient air PM10 concentration (g m3) at IITK (after removing outliers).
Summer (n 26)
(g m3)
22.15
0.54
9.10
21.33
2.08
0.62
5.19
0.16
0.22
1.76
0.76
2.06
7.52
10.25
853
7.23
0.44
4.85
8.65
0.87
0.18
1.81
0.05
0.11
0.83
0.32
1.26
2.64
2.54
Monsoon (n 41)
(g m3)
5.89
0.69
4.02
6.45
1.16
0.60
3.60
0.08
0.22
0.87
0.26
1.12
4.50
7.07
2.20
0.59
1.69
2.25
0.57
0.38
0.88
0.03
0.10
0.65
0.17
0.59
2.03
2.18
OF
VARIOUS SPECIES
AT
IITK.
Winter (n 33)
(g m3)
Other studies
(g m3)
14.67
0.37
3.24
14.15
1.15
1.08
2.78
0.09
0.32
5.52
0.30
1.33
18.02
10.10
5.08
0.29
1.26
3.79
0.45
1.89
0.91
0.03
0.13
1.90
0.09
0.49
5.91
2.74
aAbdul-Wahab and Yaghi (2004); bTripathi et al., (2004); cQuieterio et al., (2004); dHueglin et al., (2004); eChan et al., (1999); fTripathi et al.,
(1996).
AT
IITK.
Summer
(MarchJune)
Monsoon
(JulyOctober)
Winter
(NovemberFebruary)
30.60
51.30
0.67
29.70
73.80
0.50
18.00
62.80
0.43
854
FOR
AT
IITK.
Secondary particles
Coal combustion
0.85
0.02
0.63
0.88
0.84
0.55
0.77
0.62
0.34
0.35
0.52
0.02
0.34
0.37
4.65
33.24
33.24
0.39
0.19
0.17
0.36
0.33
0.62
0.02
0.35
0.16
0.89
0.10
0.71
0.88
0.83
3.76
26.83
60.07
0.02
0.76
0.46
0.00
0.05
0.47
0.14
0.02
0.59
0.17
0.55
0.08
0.19
0.04
1.77
12.62
72.69
Al
As
Ba
Ca
Fe
K
Mg
Mn
Pb
NH4
F
Cl
NO3
SO42
Eigenvalue
% variance
Cumulative % variance
TABLE 6.
FOR
AT
IITK.
Secondary particles
Fuel combustion
Miscellaneous
0.85
0.00
0.03
0.95
0.88
0.26
0.84
0.08
0.07
0.33
0.02
0.19
0.36
0.34
3.57
25.50
25.50
0.37
0.02
0.04
0.19
0.32
0.01
0.06
0.26
0.68
0.90
0.13
0.01
0.89
0.90
3.25
23.18
48.68
0.08
0.93
0.12
0.02
0.04
0.21
0.05
0.83
0.33
0.17
0.91
0.30
0.12
0.15
2.74
19.57
68.25
0.20
0.09
0.84
0.14
0.11
0.56
0.36
0.06
0.10
0.02
0.05
0.75
0.02
0.01
1.80
12.87
81.12
855
FOR
AT
IITK.
Secondary
particles
0.84
0.08
0.21
0.77
0.87
0.12
0.76
0.20
0.24
0.48
0.17
0.80
0.48
0.35
4.05
28.94
28.94
0.29
0.73
0.17
0.42
0.30
0.03
0.40
0.82
0.02
0.72
0.79
0.09
0.71
0.77
4.00
28.58
57.52
0.33
0.23
0.62
0.34
0.28
0.84
0.40
0.36
0.86
0.36
0.13
0.04
0.36
0.42
2.92
20.82
78.34
TABLE 8.
version of NH3, NOx, and SO2 and, hence, this source can be
identified as the secondary particles.
Pb is associated with leaded gasoline (used at the time
of this study period) vehicular emissions. During the sample collection period, gasoline supply was not fully unleaded in Kanpur city. Hence, the factor comprising Pb can
be identified with vehicular emissions. Mn is normally associated with ferrous metal processing. Hence, cluster containing Mn can be traced as a complex mixture of metal
working emissions. There are several small- and mediumscale industries located in the receptor domain (although
FOR
AT
IITK.
Secondary
particles
0.84
0.08
0.81
0.87
0.87
0.10
0.83
0.81
0.04
0.02
0.75
0.61
0.01
0.50
5.42
38.71
38.71
0.41
0.07
0.21
0.37
0.07
0.13
0.18
0.21
0.41
0.96
0.07
0.13
0.95
0.74
3.02
21.54
60.25
0.14
0.53
0.07
0.13
0.16
0.75
0.05
0.35
0.70
0.22
0.34
0.05
0.23
0.14
1.76
12.60
72.84
856
INTERPRETATION
OF
FACTOR LOADINGS
TO
Soil & road dust (Kumar et al., 2001; Salvador et al., 2004)
Secondary particles (Salvador et al., 2004)
Vehicular emission (Kumar et al., 2001)
Coal combustion (Kumar et al., 2001)
Diesel combustion (USEPA, 1993)
Biomass burning (Godoy et al., 2005)
Marine aerosol (Harrison et al., 1996)
Metallurgical aerosol (Harrison et al., 1996)
Liu et al. (2003) classified the factor (PC) loadings as strong, moderate, and weak corresponding to
absolute loading values of 0.75, 0.750.50, and 0.500.30.
in the downwind direction). As is emitted during combustion of coal, firewood, and refuse burning (Sadasivan
and Negi, 1990; Kumar et al., 2001). A coal-based thermal
power plant (200 MW) is situated at a distance of about 3
FIG. 3.
FIG. 4.
857
For combined samples: PM10 28.8 27.6*APCS1
23.3*APCS2 9.4*APCS3
Percent contribution from each source (factor) can be calculated from the above models. For example, for the summer
season percent contribution from first factor (soil and road
dust) for the jth observation will be [ (29.1*APCS1)j*100/
(PM10)j]. The average percent contribution by a source in a
season can be calculated by taking average of the percent
contribution for all observations for that source.
Based on the above models, the estimated PM10 was plotted vs. observed PM10 (Fig. 3a to 3d). These figures signify
that computed and observed data of PM10 compare well
(R2 0.86). It may be seen that constant [C0 in equation (1)]
is estimated as a significant number indicating 26 to 43% contribution from the sources not apportioned by this exercise
these are referred to as other sources. These may include
long-range transport, refuse, and agricultural residue burning, tyre wear, industrial emission, etc.
Quantitatively, the percentage contribution of sources/
factors for different seasons and for combined samples was
calculated by seasonal models mentioned above, and the
same is presented graphically in Fig. 4a to 4d.
Figure 4 signifies that local soil and road dust (15 to 47%)
and secondary particles (21 to 26%) are the key sources in
all three seasons. It is interesting to note that in the winter
season when the PM10 levels are relatively lower than summer, the contribution of soil and road dust becomes smaller,
and the contribution of secondary particles and vehicular
source tend to become important (18%).
Formation of secondary products like SO42 and NO3 is
quite complex, as it depends not only on the concentration
of precursor pollutants but also on temperature and relative
858
FIG. 5. (a) Contribution of soil and road dust (combined samples). (b) Contribution of secondary particles (combined
samples). (c) Contribution of vehicular and biomass burning emission (combined samples).
859
argued that within a season vehicular contribution should
remain quite similar. No specific inventory is available, but
for sure, biomass burning in the urban area and burning of
agricultural residue in the field (to clear the field for next
crop) is a common practice, and thus emissions due to biomass burning in winter are going be significantly large. This
is reflected in high peaks of the contribution in the winter
season, which is in line with the segregated seasonal observation (Fig. 4c).
There are not many studies in India on source apportionment of PM10. The study by Kumar et al. (2001) in Mumbai,
India, for source apportionment of PM was conducted for
traffic intersection. Their study indicated a major contribution of 3341% from road dust or soil, followed by contribution from vehicles and marine aerosols. Similar results are
found in this study that soil and road dust contribute about
15% (in winter), 46% (in summer) to ambient air PM10 levels.
Kumar et al. (2001) could not resolve the contribution of
secondary particles, as that will require measurements of water-soluble ions like NH4, NO3, and SO42 in atmospheric
particles. Although SO42 levels were measured, in the absence of other ions it was weakly related to the road dust
component and the authors enquired Sulphate in the atmosphere is generally assumed to be a secondary fine particle
aerosol component produced from gas to particle conversion
of SO2 and hence its association with crustal elements is
questionable and should have been identified as a separate
source.
In the research presented here, focus has been to understand the formation of secondary particles and their quantitative contribution to ambient levels of PM10. The NH4 ion
has correlated strongly with both SO42 and NO3 in all seasons, and through FA-MR, a group of these ions is identified as one of the main components (of PM10) in all seasons.
Seinfeld and Pandis (1986) have explained the vital role that
NH3 plays in neutralizing acidic substances such as H2SO4
and HNO3, mostly as a sole neutralizer of acidic species,
which leads to formation of secondary particles. It is also reported that available NH3 will be first taken up by H2SO4
and then the remaining NH3 will be available to react with
HNO3 to produce ammonium nitrate.
Soil analysis from the region showed Ca (0.3%), Al (1.5%),
Na (0.4%), Mg (0.08%), NH4 (0.01%), SO42 (0.02%), and
NO3 (0.002%). This soil analysis signifies two things: (1) the
markers taken for soil dust (Ca, Mg, Al) in identifying
sources for PM10 are from the local soil, and (2) contribution
of soil to NH4, SO42, and NO3 concentrations in PM10 is
TABLE 10.
TO
Pollutant
NO3
SO42
NH4
NO2
NH3
HNO3
5.95
5.11
4.10
3.81
5.70
0.74
1.66
1.57
0.99
3.89
6.0
2.16
860
insignificant. Thus, it can be said that NH4, SO42, and
NO3 are produced in the atmosphere (in fine mode) as secondary particles due to emissions from anthropogenic activities.
Further, the reaction rate constant of formation of ammonium nitrate aerosol is 2.04 104 m3 mol1 s1 (Baek and
Aneja, 2005) and for ammonium sulfate aerosol is 1.5 104
s1 (Harrison and Kitto, 1992). The rate constant of CaSO4
and MgSO4 formation is reported as 1.73 109 s1 by Pervez and Pandey (1992) while studying the marble damage
by SO2 acidity. As the reaction rate of CaSO4 and MgSO4 is
less (by several orders of 10) than that of ammonium nitrate
and ammonium sulfate aerosols, major portion of secondary
atmospheric particles will be (NH4)2SO4 and NH4NO3 and
in fine mode.
Because NH3 plays an important role, a study was taken
up recently at the same sampling location including the measurement of NH3 (Kishore, 2005). Table 10 presents the results of Kishore (2005) for parameters relevant to formation
of secondary particles.
In Table 10, NO3, SO42, and NH4 levels were statistically higher in the winter season compared to levels in summer, and HNO3 levels were higher in summer than in winter. The correlation between NH4 and SO42 and NH4 and
NO3 was in the range of 0.560.79 in winter (day and night)
and 0.750.88 (summer night); no correlation was found in
summer daytime. This study once again signifies the formation of secondary particles and vital role played by ammonia.
It may, therefore, be concluded that NH3 is playing a
significant role in formation of secondary particles that has
been seen through air quality sampling, receptor modeling, and also through the atmospheric chemistry. NH3
emitted due to anthropogenic activities is the major source
of NH4 in the atmosphere. The major sources responsible for NH3 emission are from the agricultural activities
(urea application) and intensive animal production facilities. India is primarily an agricultural economy, and it has
highest number of cattle population (an estimated 219.6
million cattle) in the world (http://dahd.nic.in/stat.htm).
No estimates of ammonia emission are available from the
study area. This study recommends that there is a need to
develop proper inventory of ammonia emission in India,
especially in the area where particulate pollution is high
to understand fully formation of secondary particles and
plan their control.
Conclusions
Simple source apportionment technique, factor analysismultiple regression, was applied to apportion the
sources of PM10 at a relatively less polluted site in Kanpur,
India. In three seasons studied, two important PM10
sources were soil-road dust (1547%) and inorganic secondary particles like (NH4)2SO4 and NH4NO3 (2126%).
Winter and monsoon conditions were conducive for formation of secondary particles due to moderate temperatures and high relative humidity. The main conclusion of
the research was that NH4 is a far more dominating ion
responsible for secondary particle formation; thus, the role
of ambient ammonia is most vital in overall atmospheric
chemistry of particulate formation.
861
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