Water Air Soil Pollut (2008) 190:1325
DOI 10.1007/s11270-007-9575-x
Annual and Seasonal Variations of Trace Metals
in Atmospheric Suspended Particulate Matter
in Islamabad, Pakistan
Munir H. Shah & N. Shaheen
Received: 23 May 2007 / Accepted: 15 November 2007 / Published online: 6 December 2007
# Springer Science + Business Media B.V. 2007
Abstract Total Suspended particulate matter (TSP) in
urban atmosphere of Islamabad was collected using a
high volume sampling technique for a period of one
year. The nitric acidperchloric acid extraction method
was used and the metal contents were estimated by
atomic absorption spectrophotometer. The highest
mean concentration was found for Ca at 4.531 g/m3,
followed by Na (3.905 g/m3), Fe (2.464 g/m3), Zn
(2.311 g/m3), K (2.086 g/m3), Mg (0.962 g/m3),
Cu (0.306 g/m3), Sb (0.157 g/m3), Pb (0.144 g/m3)
and Sr (0.101 g/m3). On an average basis, the de-
creasing metal concentration trend was: Ca > Na >
Fe > Zn > K > Mg > Cu > Sb > Pb > Sr > Mn > Co >
Ni > Cr > Li > Cd Ag. The TSP levels varied from a
minimum of 41.8 to a maximum of 977 g/m3, with a
mean value of 164 g/m3, which was found to be
higher than WHO primary and secondary standards.
The correlation study revealed very strong correlations
(r>0.71) between FeMn, SbCo, NaK, MnMg,
PbCd and SbSr. Among the meteorological param-
eters, temperature, wind speed and pan evaporation
were found to be positively correlated with TSP, Ca,
Fe, K, Mg, Mn and Ag, whereas, they exhibited
negative relationships with relative humidity. On the
other hand, Pb, Sb, Zn, Co, Cd and Li revealed sig-
nificant positive correlations with relative humidity and
M. H. Shah (*) : N. Shaheen
Department of Chemistry, Quaid-i-Azam University,
Islamabad 45320, Pakistan
e-mail: munir_qau@yahoo.com
negative with temperature, wind speed and pan evap-
oration. The major sources of airborne trace metals
identified with the help of principle component anal-
ysis and cluster analysis were industrial emissions,
automobile exhaust, biomass burning, oil combustion,
fugitive emissions, resuspended soil dust and earth
crust. The TSP and selected metals were also studied
for seasonal variations, which showed that Na, K, Zn,
Cu, Pb, Sb, Sr, Co and Cd peaked during the winter
and remained lowest during the summer, while Ca, Fe,
Mg and Mn were recorded highest during the spring.
Keywords AAS . Cluster analysis . Meteorological
variations . Principal component analysis .
Seasonal variations . TSP . Trace metals
1 Introduction
Atmospheric total suspended particulate matter (TSP)
has been linked with a number of environmental and
human health effects on regional and global scales
(Dockery et al. 1993; Charlson et al. 1992; Dickerson
et al. 1997). Since TSP chemical composition is im-
portant in understanding the properties of ambient
suspended particles, including sources, chemical evo-
lution, optical properties and human health effects,
accurate determination of their chemical constituents is
critical.
The study of the large-scale influence of TSP
on the environment needs a deep knowledge of
14
particulate load and of chemical composition and
distribution in the atmosphere (WHO 2000). In the
last decade concern on airborne particulates in urban
areas led to a number of studies on the characteri-
sation of TSP. Epidemiological studies pointed out
a number of adverse health effects associated with
atmospheric particles as they are vehicles of toxic
substances (Dockery et al. 1993; Schwartz et al. 1996;
Samet et al. 2000). As a consequence of the growing
interest of the scientific community in chemical com-
position of particulates we started an extended study
on TSP to obtain statistically significant data on its
trace metal constituents. Indeed, previous short-term
studies carried out in this area (Shah et al. 2004, 2006;
Shaheen et al. 2005a, b) revealed elevated levels of
some toxic trace metals over a particular duration but
so far no study has been reported on their annual and
seasonal variations. These data stress the importance
of a deeper knowledge of TSP composition, as well as
their emission sources and of the role of atmospheric
dispersion conditions in the area.
During the present monitoring campaign mea-
surements of TSP composition were performed to
inter-relate the trace metal contents and the climatic
variables prevailing in the area during the study
period in a wider research context. Herein, we also
present seasonal variations of TSP measurements over
a 12-month study period conducted at the urban
locations of Islamabad and examine long-term trends
and short-term fluctuations in metal concentrations. In
addition, the metal content variations are investigated
in conjunction with the seasonal distributions to char-
acterize the significance of metallic constituents to
TSP and shed light on its sources and co-variation
mechanisms. The aim of the research was twofold:
(a) To assess concentration levels and sources of
selected metals in TSP and their seasonal variability;
(b) To study the role of climatic conditions on TSP
load and metal concentrations and to assess the
importance of seasonal meteorological variations on
particulate metal distributions.
2 Experimental
2.1 The Study Area
Islamabad, the capital city of Pakistan, is situated
500 m above sea level (Latitude 3349 N; Longitude
Water Air Soil Pollut (2008) 190:1325
7224 E) covering an area of about 900 km2 support-
ing a population of more than one million. It is 25 km
north of its twin city, Rawalpindi, with a population
of more than three million (Pakistan Bureau of
Statistics 2004). The inhabited land in Islamabad is
divided into residential, industrial, and commercial
sectors. The main industrial units are housed in
sectors I-9 and I-10 (Fig. 1). The major industries in
the industrial area include steel mills, marble facto-
ries, flour mills, oil and ghee units, soap/chemical
factories, ceramic, paint, pigment, and pharmaceutical
manufacturing plants, in addition to several other
small industrial units.
The climate of Islamabad can be divided into
four distinct seasons; warm and rainy summer (June
to August), followed by dry autumn (September to
November), cold and dry winter (December to Febru-
ary) and spring (March to May) (Khan 1991). Higher
precipitation was recorded for summer during the
monsoon while other seasons for the most part
remained dry and the predominant wind direction
was north-east.
2.2 Sampling
Two sampling locations were selected during the
present study; one at sector H-8 and other at Quaid-
i-Azam University, Islamabad, both representing the
typical urban areas. The sampling was performed on
regular 24-h basis, commencing at 08:00 h, during
June 2004May 2005. A total of 214 TSP samples
(111 from Quaid-i-Azam University and 103 from
sector H-8) were collected on cellulose and glass fibre
filters (20.425.4 cm) using high-volume samplers
(Thermo-Anderson, model GMWL-2000H, USA) at
a stipulated flow rate of 40 ft3/min (1.13 m3/min)
(Method IO-2.1 1999). The same methodology was
applied at both sampling stations and 2 to 3 TSP
samples per week were collected from each location.
The samplers were installed on the roof-tops, approx-
imately 15 m above the ground level and well cleared
from other buildings around.
2.3 Extraction Procedure and Analysis
TSP mass was determined gravimetrically prior to
analysis (Method IO-2.1 1999). For the metal esti-
mation, each filter was extracted by nitric acid
(Merck Suprapure 65%) and perchloric acid (Merck
Water Air Soil Pollut (2008) 190:1325
Fig. 1 Location of sampling sites (asterisk) and residential sectors (open box) in Islamabad
Suprapure 70%) mixture (10:1, v/v) (NIOSH Method-
7300 1984). The extracted solution was filtered with
washing by doubly distilled water and refrigerated in
pre-cleaned strong polyethylene bottle until analysed
(Gonzalez et al. 1997). Filter and reagent blanks were
also processed following the above procedure for
sample treatment. Metals were determined by Atomic
Absorption Spectrophotometer (Shimadzu, model
AA-670, Japan) following Method IO-3.2 (1999).
The metals estimated in blanks were <10% of the
sample average metal contents. The accuracy of
the method was evaluated using a standard reference
material (OL-96) obtained from National Institute of
Health (NIH), Islamabad, where inter-laboratory
comparison of the data was also exercised. Normally,
a maximum of 5% deviation was observed in the
results of the two laboratories. The results obtained
were comparable within 2% in the range of the
standard reference material used. The meteorological
parameters reflecting the prevailing atmospheric
conditions were recorded at Pakistan Agricultural
Research Council (PARC), Islamabad.
15
2.4 Statistical Analysis
Along with the basic statistical parameters and cor-
relation analysis, multivariate methods comprising of
Principal Component Analysis (PCA) and Cluster
Analysis (CA) were performed on the dataset using
the STATISTICA software (StatSoft, Inc. 1999). The
PCA was conducted using varimax normalized rotation
on the dataset and the CA was applied to the stan-
dardized matrix of samples, using Wards method and
the results are reported in the form of dendrogram.
3 Results and Discussion
3.1 Airborne Metal Distribution for the Annual Period
The TSP metal data estimated at the two sampling
locations were compared by t-Test (both one-tailed
and two-tailed at p<0.001) and no significant dif-
ferences were observed in any case. Therefore, the
entire data were cast together to avoid unnecessary
16 Water Air Soil Pollut (2008) 190:1325

repetition and overlap. The basic statistical distribu- concentration, starting from Mn (0.079 g/m3) and
tion parameters related to the TSP levels estimated terminating at Ag (0.004 g/m3). Overall, on an aver-
during the present study are given in Table 1. The age basis, the data revealed the following decreasing
TSP varied from a minimum of 41.8 to a maximum of pattern of metal concentration: Ca > Na > Fe > Zn >
977 g/m3, with a mean value of 164 g/m3. Larger K > Mg > Cu > Sb > Pb > Sr > Mn > Co > Ni > Cr >
variations and non-normal distribution in TSP level Li > Cd Ag.
were found during the present study as manifested by The average metal concentrations in airborne TSP
large SD value on one hand and higher skewness on can be compared with the safe limits proposed by
the other. The mean level (164 g/m3) was found to international agencies. WHO and USEPA standards
be higher than the WHO primary (80 g/m3) and for atmospheric Pb, Mn, Cr, Ni and Cd are 0.500,
secondary (60 g/m3) standards (WHO 2000). 0.150, 1.10, 0.00038 and 0.005 g/m3, and 1.500,
The distribution of selected trace metals in a total 0.500, 0.100, 0.00024 and 0.006 g/m3, respectively
of 214 airborne TSP samples collected and analysed (WHO 2000; ATSDR 2002). During the present
during the study period are also given in Table 1 in study, average concentrations of Pb (0.144 g/m3),
terms of basic statistical parameters. The highest Mn (0.079 g/m3 ), Cr (0.010 g/m 3) and Cd
mean concentration was found for Ca at 4.531 g/m3, (0.004 g/m3) were found to be within the range of
followed by Na (3.905 g/m3), Fe (2.464 g/m3), Zn WHO and USEPA standards. However, the average
(2.311 g/m3), K (2.086 g/m3) and Mg (0.962 g/m3). Ni level (0.024 g/m3) was 63 times higher than the
Thus, of all the metals, Ca, Na, Fe, K, Zn and Mg proposed WHO standard and about 100 times higher
emerged as dominant metals in the airborne par- than the USEPA standard (WHO 2000; ATSDR 2002).
ticulate samples; the remaining metals being at the Likewise, average concentrations of Cd and Ni were
sub-microgram levels. Among other metals, the 7.3 and 6.1 times higher than those recommended by
estimated mean levels of Cu, Sb, Pb and Sr were the European Community (EC 2000). Similarly, the
0.306, 0.157, 0.144 and 0.101 g/m3, respectively. safe limit range for cancer is laid down for Cd between
The remaining metals (Mn, Co, Ni, Cr, Li, Cd and 0.24 and 0.55 ng/m3 (EC 2000); the mean concentra-
Ag) were found to follow a sequence of decreasing tion of the metal in the atmosphere of Islamabad is
4 ng/m3. The comparative elevated TSP metal concen-
trations in the local atmosphere may be attributed to
Table 1 Statistical distribution of airborne TSP and selected the difference in number of samples as during the
trace metal levels (g/m3, where applicable) during the study
period (n=214) present study 214 TSP samples were collected and
analysed while the WHO levels referred to annual
Range Mean Median SD Skewness mean values.
TSP 41.8977 164 140 108 3.1
The individual variability in airborne metal con-
Ca 0.06511.52 4.531 3.792 2.262 1.550 centrations could be examined through either respec-
Na 0.03314.56 3.905 3.197 3.142 0.775 tive ranges or standard deviation (SD) values listed
Fe 0.08811.20 2.464 2.220 1.622 1.526 in Table 1. The maximum dispersion around the
K 0.00812.32 2.086 1.214 2.408 1.659 mean value was noted in the case of Na, Ca, K and
Zn 0.02213.25 2.311 1.733 2.280 1.679 Zn, followed by Fe, Mg and Cu to a lesser extent.
Mg 0.01215.98 0.962 0.295 1.746 4.457 Thus, compared with other metals Mg, Na, Zn, K, Ca,
Cu 0.0237.516 0.306 0.177 1.471 9.266
Fe and Cu showed a broader range of extremum
Pb 0.0050.895 0.144 0.100 0.136 2.104
Sb 0.0021.937 0.157 0.093 0.222 4.800 levels, with the recorded maximum concentrations at
Sr 0.0041.476 0.101 0.070 0.160 5.647 15.980, 14.564, 13.254, 12.317, 11.523, 11.200 and
Mn 0.0050.529 0.079 0.063 0.065 2.977 7.516 g/m3, respectively. The overall distribution of
Co 0.0030.689 0.033 0.011 0.064 6.103 metals in the TSP samples remained, in general, far
Ni 0.0020.137 0.024 0.019 0.021 1.969 from a normal distribution, as projected by the skew-
Cr 0.0010.080 0.010 0.008 0.009 3.157 ness values, notably high for Cu, Co, Sr, Sb, Mg, Cr,
Li 0.0020.023 0.005 0.005 0.003 1.818
Mn and Pb. This indicated a non-normal metal distri-
Cd 0.0010.019 0.004 0.003 0.003 1.860
bution influenced by an uptake and/or depletion of
Ag 0.0020.013 0.004 0.003 0.002 1.560
metals in particulate matter by random processes
Water Air Soil Pollut (2008) 190:1325
(Shah et al. 2006; Shaheen et al. 2005a; Kim et al.
2002a; Samura et al. 2003); the attributes to these
could be traced in anthropogenic sources that are
examined in the forthcoming sections.
The percentile distributions of the selected metals
are also presented as box and whisker plot in Fig. 2.
All metals were found to exhibit large variations in
their minimum, maximum, 25th percentile, 75th per-
centile and median values except for Li and Ag which
showed a narrow distribution. A relatively symmetric
distribution pattern was found in case of Mg, Sr, Mn
and Cr thus manifesting their consistently varying con-
centrations in the TSP samples. Pb and Zn revealed
almost similar distribution pattern while the other
metals exhibited large asymmetry in their distribution
(Kim et al. 2002a).
3.2 Meteorological Variations During
the Study Period
Data cast in Table 2 listing meteorological parameters
pertaining to the study period provide a comparative
detail on this aspect. Accordingly, the maximum tem-
perature ranged from 9.0 to 42.0C, with a mean
value of 28.3C, while the minimum from 0 to 28.0C,
with a mean value of 14.5C. The average tempera-
ture was associated with random variations extending
from 7.0 to 32.0C, with a mean value of 21.4C.
Average relative humidity, featuring an important
aspect of local meteorology, varied between 21 and
100%, measured on fore-noon (RH 8:00) and after-
noon (RH 14:00) basis. The mean RH 8:00 values
were comparatively higher (79.0%), while those of
RH 14:00 were lower (46.7%). The sunshine had a
mean time of 7.69 h on daily basis, marked with
average pan evaporation of 4.32 mm/day indicating
10.000 Min-Max
25%-75%
Metal Level (g/m3)
Median value
1.000
0.100
0.010
0.001
Ca Fe Zn Cu Sb Mn Ni Li Ag
Na K Mg Pb Sr Co Cr Cd
Fig. 2 Box and Whisker plot showing the airborne metal
distribution patterns for the study period
17
mostly humid conditions prevailed. The annual aver-
age rainfall was 16.19 mm only, which indicated an
overall dry seasonal spell in an area, which normally
used to have an average of 250 mm annual rain
during the past several years (Khan 1991). Low wind
velocities were encountered during the sampling
period; the wind pattern remained steady and the
days were mostly non-windy, with mean wind speed
of about 0.65 m/s. The wind direction was predom-
inantly north-east during the study period (Fig. 3).
Comparative seasonal variations in the meteorological
conditions are also shown in Table 2.
3.3 Correlation Study of TSP and Metals
for the Annual Period
The correlation coefficient matrix given in Table 3, with
bold r values significant at p<0.001, showed some
strong mutual correlations between the pairs of metals
in terms of their concentrations. Strong correlations
emerged between FeMn (r=0.88), SbCo (r=0.86),
NaK (r=0.77), MgMn (r=0.76), PbCd (r=0.73),
SbSr (0.71), FeMg (r=0.68), CuSb (r=0.60), Sr
Co (r=0.58), NaAg (r=0.53), CaK (r=0.51), NaZn
(r=0.51), KAg (r=0.50) and CuSr (0.49). Other
notable correlations were shown by CaNa, CaFe,
CaMg, CaMn, KZn, ZnAg, CuLi, PbLi, SbLi,
MnLi, CrAg and LiCd, all being significant at p<
0.001. Overall, the metal correlation data (Table 3)
helped to isolate some metal groups that could be used
as pointers to common sources of their distribution in
TSP (Fang et al. 2000; Kim et al. 2002a; Gotschi et al.
2005). Based on these correlation coefficients the
metals could be divided into four groups showing
mutual relationships: CaMgFeMn; NaKZnAg;
PbCd; CuSbSrCo. The first group is mainly
originating from the earths crust as well as some
industrial emissions, the second group is contributed
by re-suspended soil dust, excavation activities and
biomass burning, the third group is chiefly emanating
from automobile emissions and the fourth group is
mainly associated with fugitive emissions (Shah et al.
2006; Kim et al. 2002b; Mishra et al. 2004; Shaheen
et al. 2005a). A few negative correlations listed in the
Table (e.g., between CaLi, CaCd and KLi) sig-
nified no apparent relationship of these metals in air-
borne particulates.
Investigating possible metal-to-TSP correlations
was an important part of the present study since the
18 Water Air Soil Pollut (2008) 190:1325

Table 2 Summary of meteorological parameters recorded during the study period

Annual Summer Autumn Winter Spring

Range Mean Range Mean Range Mean Range Mean Range Mean

Max. T (C) 9.042.0 28.3 28.542.0 33.5 22.035.0 29.4 9.023.5 17.0 20.038.0 33.2
Min. T (C) 0.028.0 14.5 18.028.0 23.7 3.526.0 17.5 0.011.0 4.5 8.025.0 15.6
Avg. T (C) 7.032.0 21.4 25.833.8 28.6 12.830.0 23.5 7.016.0 10.6 16.531.0 24.4
RH 800 (%) 27.0100 79.0 66.0100.0 84.9 61.0100.0 85.0 79.0100.0 97.2 27.0100.0 63.9
RH 1400 (%) 10.0100 46.7 10.084.0 59.4 26.091.0 50.8 36.0100.0 59.1 14.074.0 32.2
Avg. RH (%) 21.0100 62.9 45.592.0 72.2 44.595.5 67.9 63.5100.0 78.2 21.087.0 48.2
Sunshine (h) 0.012.50 7.69 0.0010.80 7.43 0.2010.50 7.55 0.5010.00 6.29 0.0012.50 8.17
Wind speed (m/s) 0.052.09 0.65 0.481.56 0.83 0.241.53 0.55 0.05 0.68 0.31 0.212.09 0.85
Pan evap. (mm/day) 0.0212.13 4.32 1.1010.31 5.02 0.508.60 3.66 0.023.65 1.19 1.7711.70 5.95
Rain fall (mm) 0.30101.8 16.2 4.8036.00 20.66 3.10101.8 26.38 0.3028.40 10.33 0.7035.46 9.99

precise nature of mutual relationship between a metal
and particulate matter could play a pivotal role
towards its atmospheric distribution. The TSP showed
very strong correlations with Fe (r=0.89), Mg (r=
0.76) and Mn (r= 0.94) and significant positive
correlations were noted for TSP with Ca and Li, as
reported in Table 3.
3.4 TSP and Metal Correlations with Climatic
Parameters for the Annual Period
The data pertaining to the TSP and metal correlations
with climatic parameters are provided in Table 4. The
correlation coefficient values shown in bold were
all significant at p<0.001. Based on this correlation
study, the metals could be grouped in three categories.
The first one showed significant positive correlations
Fig. 3 Mean wind direction during the study period
with temperature (min., max. and Avg.) and negative
correlations with relative humidity (8:00, 14:00 and
Avg.) included Ca, Fe, K, Mg, Mn and Ag (Vallius
et al. 2005; Querol et al. 1998; Colombo et al. 1999;
Fang et al. 2004; Shaheen et al. 2005a). The second
one exhibited positive relationships with RH and
negative with temperature exemplified by Sb, Pb, Zn,
Co, Li and Cd (Jonsson et al. 2004; Kim et al. 1997),
while the third group of metals (Cr, Cu, Sr, Ni and
Na) showed no specific pattern with respect to tem-
perature and RH. Also, significant metal correlations
were observed for sunshine and pan evaporation
which in fact, could be taken as composite parameters
representing the overall dry or wet conditions prevail-
ing in the atmosphere. Wind speed affected the dis-
tribution of trace metals appreciably as Ca, Na, Fe, K,
Mg, Mn and Ag revealed a positive relationship while
Pb, Sb, Co, Li and Cd manifested a dilution effect of
wind speed on these metal levels (Jonsson et al. 2004;
Fang et al. 2004; Kim et al. 2002a; Ragosta et al.
2002; Vallius et al. 2005). Furthermore, all metals
were found, in general, to be negatively correlated
with rainfall signifying its scavenging effect (Shaheen
et al. 2005b; Kim et al. 1997; Hrsak et al. 2001;
Quiterio et al. 2004). The examination of the dataset
regarding correlations of TSP with climatic param-
eters (Table 4) evidenced that TSP was significantly
and positively correlated with maximum and average
temperature at r=0.34 and r=0.28, respectively. The
RH (8:00, 14:00 and Avg.) showed a strong inverse
relationship with TSP (Sharma et al. 2005) while
rest of the parameters did not show any significant
correlation.
Water Air Soil Pollut (2008) 190:1325 19

Table 3 Correlation coefficient matrix (bold values are significant at p<0.001) for airborne TSP and trace metals during study period
(n=214)

Ca Na Fe K Zn Mg Cu Pb Sb Sr Mn Co Ni Cr Li Cd Ag

Na 0.34
Fe 0.35 0.00
K 0.51 0.77 0.01
Zn 0.04 0.51 0.07 0.27
Mg 0.44 0.11 0.68 0.15 0.02
Cu 0.09 0.16 0.02 0.10 0.23 0.04
Pb 0.14 0.01 0.04 0.14 0.23 0.01 0.18
Sb 0.17 0.05 0.08 0.18 0.03 0.21 0.60 0.20
Sr 0.04 0.12 0.06 0.02 0.07 0.08 0.49 0.23 0.71
Mn 0.38 0.08 0.88 0.02 0.12 0.76 0.04 0.10 0.06 0.08
Co 0.11 0.04 0.10 0.11 0.13 0.18 0.15 0.10 0.86 0.58 0.05
Ni 0.00 0.06 0.21 0.06 0.13 0.03 0.13 0.06 0.25 0.27 0.19 0.22
Cr 0.25 0.23 0.14 0.19 0.06 0.22 0.02 0.03 0.01 0.04 0.20 0.08 0.23
Li 0.25 0.20 0.25 0.41 0.19 0.23 0.39 0.43 0.34 0.04 0.29 0.16 0.14 0.17
Cd 0.23 0.08 0.02 0.12 0.42 0.00 0.18 0.73 0.13 0.09 0.00 0.06 0.02 0.07 0.41
Ag 0.36 0.53 0.18 0.50 0.39 0.24 0.24 0.05 0.04 0.04 0.15 0.16 0.05 0.36 0.02 0.03
TSP 0.31 0.06 0.89 0.05 0.13 0.76 0.04 0.11 0.01 0.13 0.94 0.01 0.19 0.14 0.36 0.05 0.10

3.5 Source Apportionment chemical and physical characteristics of the partic-

Source apportionment of airborne metals refers to
the quantitative estimation of the contribution from
different source categories to the concentration of
measured variables in atmosphere. It is based on
ulate matter and temporal co-variation of measured
variables. This procedure can be divided into iden-
tification of the sources and to apportionment of
the measured variables to these sources. In principle,
the source apportionment methods are normally

Table 4 Correlation coefficient matrix (bold values are significant at p<0.001) for TSP and trace metals with meteorological
parameters during the study period (n=214)

Max. T Min. T Avg. T RH 800 RH 1400 Avg. RH SS WS PE RF

TSP 0.34 0.18 0.28 0.28 0.37 0.36 0.11 0.25 0.27 0.07
Ca 0.50 0.38 0.47 0.60 0.33 0.52 0.24 0.55 0.63 0.07
Na 0.01 0.16 0.08 0.30 0.20 0.27 0.04 0.24 0.16 0.23
Fe 0.49 0.33 0.44 0.41 0.43 0.47 0.16 0.24 0.34 0.07
K 0.27 0.19 0.25 0.46 0.17 0.34 0.07 0.43 0.42 0.09
Zn 0.21 0.30 0.28 0.26 0.12 0.32 0.02 0.07 0.15 0.14
Mg 0.36 0.29 0.34 0.44 0.33 0.43 0.07 0.34 0.34 0.01
Cu 0.13 0.19 0.16 0.16 0.02 0.09 0.01 0.18 0.18 0.07
Pb 0.26 0.33 0.31 0.28 0.04 0.18 0.02 0.24 0.30 0.23
Sb 0.34 0.35 0.36 0.35 0.13 0.27 0.03 0.31 0.38 0.16
Sr 0.11 0.19 0.15 0.15 0.03 0.07 0.03 0.15 0.15 0.05
Mn 0.39 0.26 0.35 0.31 0.37 0.38 0.14 0.23 0.28 0.07
Co 0.34 0.34 0.36 0.29 0.11 0.22 0.04 0.24 0.36 0.05
Ni 0.03 0.08 0.06 0.15 0.10 0.14 0.02 0.10 0.09 0.01
Cr 0.00 0.07 0.03 0.05 0.09 0.03 0.06 0.10 0.08 0.05
Li 0.32 0.30 0.33 0.38 0.12 0.27 0.14 0.43 0.49 0.39
Cd 0.34 0.41 0.40 0.31 0.09 0.22 0.05 0.29 0.35 0.18
Ag 0.30 0.20 0.26 0.35 0.17 0.29 0.23 0.33 0.36 0.11
20 Water Air Soil Pollut (2008) 190:1325

3
Linkage Distance (Pearson r)
2
1 the metal data of the study period with corresponding
0 tive variance. An examination of the Table showed
Sb Cu Pb Mg Fe Ni Sr K Ca
Co Li Cd Zn Mn Cr Ag Na
Fig. 4 Cluster Analysis (Wards method) of airborne selected
metals for the study period
used to identify the combined effect of several mea-
sured variables and the influence of external param-
eters on given distributions. In accordance, two
multivariate statistical methods were applied for
source identification and apportionment during the
present study, namely; Principal Component Analysis
(PCA) and Cluster Analysis (CA) (Hair et al. 1998;
Jalkanen and Manninen 1996; Ragosta et al. 2002;
Senaratne and Shooter 2004; Yongming et al. 2006; Shah
et al. 2006).
The CA related to metal data for the study period is
presented in the form of dendrogram in Fig. 4. The
primary cluster pairs were observed for CoSb, Li
Cu, PbCd, FeMn, CrNi and NaK, with a total of
six clusters representing six significant sources of the
selected trace metals in local atmosphere. Table 5
presents the Principal Component (PC) loadings for
eigen values and variances. Six PCs with eigen values
greater than 1.0 were extracted with 79.4% cumula-
maximum variance of 20.6% was contributed by PC 1
which had higher PC loadings for Fe, Mn, Mg
and Ca, with significant contribution from Li. This
revealed close association of Fe, Mn, Mg and Ca in
TSP in the atmosphere, mainly contributed by earth
crust (Ragosta et al. 2002; Cohen 1999; Gonzalez
et al. 1997) and the industrial units, such as cement
and marble industries (Quiterio et al. 2004; Shah et al.
2006). The PC 2 showed higher loadings for Sb, Co
and Sr with significant contributions from Cu and Ni,
originating from fugitive emissions as pointed out
earlier (Moreno-Grau et al. 2002; Yongming et al.
2006; Veranth et al. 2003; Garcia et al. 2004). Third
PC revealed maximum loadings in favour of Na, K,
Ca, Ag and Zn. It might be contributed by excavation
activities, biomass burning and re-suspended soil
dust, duly supported by literature reported data (Smith

Table 5 Principal compo-

nent loadings of the air- PC 1 PC 2 PC 3 PC 4 PC 5 PC 6
borne trace metals for the
study period Eigen values 3.508 3.184 2.594 2.126 1.083 1.011
% Total variance 20.6 18.7 15.3 12.5 6.37 5.94
% Cumul. variance 20.6 39.4 54.6 67.1 73.5 79.4
Ca 0.493 0.015 0.538 0.239 0.071 0.243
Na 0.041 0.093 0.904 0.086 0.017 0.056
Fe 0.915 0.011 0.007 0.022 0.075 0.021
K 0.028 0.039 0.886 0.101 0.008 0.230
Zn 0.134 0.190 0.504 0.461 0.161 0.401
Mg 0.857 0.169 0.148 0.006 0.033 0.078
Cu 0.018 0.433 0.098 0.049 0.078 0.793
Pb 0.063 0.160 0.037 0.879 0.014 0.022
Sb 0.112 0.897 0.072 0.075 0.091 0.327
Sr 0.068 0.874 0.077 0.059 0.071 0.102
Mn 0.951 0.027 0.055 0.051 0.119 0.001
Co 0.123 0.843 0.079 0.054 0.182 0.067
Ni 0.106 0.345 0.117 0.058 0.597 0.100
Cr 0.116 0.075 0.250 0.075 0.863 0.096
Li 0.252 0.057 0.348 0.458 0.268 0.595
Cd 0.033 0.033 0.011 0.924 0.028 0.089
Ag 0.168 0.109 0.708 0.003 0.181 0.360
Water Air Soil Pollut (2008) 190:1325 21

et al. 1996; Cohen 1999; Quiterio et al. 2004; Shaheen
et al. 2005a). The PC 4 exhibited higher loadings for
Pb and Cd along with Zn and Li, believed to originate
from automobile emissions and road dust (Ragosta
et al. 2002; Kim et al. 2002b; Gonzalez et al. 1997;
Shah et al. 2006). The PC 5 pointed out higher
loadings for Ni and Cr, mainly emanating into the
local atmosphere from the crude oil combustion
and metallurgical units housed in the industrial area
of Islamabad. The PC 6 manifested the combined
contribution of Cu and Li with considerable load-
ings from Zn, Sb and Ag, most likely finding

6 6

Na Level (g/m )
Ca Level (g/m )

3
3

4 4

2 2

0 0
Summer Autumn Winter Spring Summer Autumn Winter Spring

4 3.0
Fe Level (g/m3)

K Level (g/m )
3 3
2.0
2
1.0
1

0 0.0
Summer Autumn Winter Spring Summer Autumn Winter Spring

3.0 2.0
Mg Level (g/m )
Zn Level (g/m )

3
3

1.5
2.0
1.0
1.0
0.5

0.0 0.0
Summer Autumn Winter Spring Summer Autumn Winter Spring

0.6 0.3
Pb Level (g/m )
Cu Level (g/m )

3
3

0.4 0.2

0.2 0.1

0.0 0.0
Summer Autumn Winter Spring Summer Autumn Winter Spring

0.4 0.2
Sb Level (g/m )

Sr Level (g/m )
3

0.3

0.2 0.1

0.1

0.0 0.0
Summer Autumn Winter Spring Summer Autumn Winter Spring
Fig. 5 Seasonal variations in individual trace metal levels (SE) during the study period
22 Water Air Soil Pollut (2008) 190:1325

their way from electrical/cable manufacturing plants highest average TSP was found during the spring at
(Ragosta et al. 2002; Manoli et al. 2002). The PCA 212 g/m3. The comparatively lower TSP levels
findings were well supported by CA, as depicted in during the summer and winter were mainly due to
Fig. 4. the excessive precipitation during the monsoon of
summer and occasional precipitation during the
3.6 Seasonal Variations in Airborne TSP cold winter, whereby the suspended particles were
and Metal Levels washed down from the atmosphere (Khan 1991). An
examination of the data in Fig. 5 showed that Co, Sb,
During the present study a total of 214 TSP samples Cu, Cd, Pb, K, Sr and Na exhibited comparatively
were collected, 51 during the summer, 52 during higher mean concentrations during winter, while
the autumn, 54 during the winter and 57 during the lower concentrations were recorded in summer. On
spring. Lowest mean TSP was recorded during the other hand, Mg, Mn, Fe and Ca revealed elevated
summer and winter followed by autumn, while the average levels during spring and Ni and Cr showed

0.12 0.09
Mn Level (g/m )

Co Level (g/m )
3

3
0.08 0.06

0.04 0.03

0.00 0.00
Summer Autumn Winter Spring Summer Autumn Winter Spring

0.04 0.03
Cr Level (g/m )
Ni Level (g/m )

3
3

0.03
0.02
0.02
0.01
0.01

0.00 0.00
Summer Autumn Winter Spring Summer Autumn Winter Spring

0.009 0.008
Cd Level (g/m )
Li Level (g/m )

3
3

0.006
0.006
0.004
0.003
0.002

0.000 0.000
Summer Autumn Winter Spring Summer Autumn Winter Spring

0.006
Ag Level (g/m )
3

0.004

0.002

0.000
Summer Autumn Winter Spring
Fig. 5 (continued)
Water Air Soil Pollut (2008) 190:1325
maximum mean concentrations during summer. In
case of Li, Zn and Ag almost comparable contribu-
tions were observed for the four seasons.
The seasonal variations of individual mean metal
levels (SE) during the study period are depicted in
Fig. 5. In the case of Ca, minimum mean concentra-
tion was found in summer, with increasing trend in
following seasons resulting in maximum mean levels
in spring. The average Na concentrations were found
to follow the decreasing order: winter > spring >
autumn > summer; same was the trend for K, Zn and
Sr. This showed the inverse relationship of these
metal levels with the temperature, duly supported by
the data given in Table 4. Mean Fe levels were
estimated to be higher in spring (Kim et al. 2002a, b),
followed by autumn, whereas, lower and comparable
concentration levels were observed during winter
and summer; same was the case for Mg and Mn.
Variations in average levels of Cu, Pb and Cd
exhibited the following pattern during the study
period: summer spring < autumn < winter, once
again manifesting a negative interactions with the
temperature (Kim et al. 1997, 2002b; Mishra et al.
2004). Much elevated levels of Sb were observed
during winter; but remained comparable for other
seasons. Cobalt showed a similar distribution pattern
as that of Sb which could be attributed to some com-
mon source of the two metals in TSP (Kim et al.
2002a). The mean distribution of Ni and Cr were
different from previously described cases, in that
comparable levels were encountered for all seasons
except summer which showed maximum levels, thus
revealing a direct relationship with temperature,
sunshine and pan-evaporation (Kim et al. 2002b).
The Li levels were found to be higher in autumn,
followed by winter and summer, while the minimum
levels were observed in spring. The case of Ag was
unique as it showed comparable average levels during
summer, autumn and winter with slightly higher mean
levels in spring, during the study period. The disper-
sion of the metals levels around the mean values,
evidenced by relevant SE, was noted highest during
spring for Ca, Na, Fe, K and Mg. However, for other
metals such as Cu, Pb, Sb, Sr, Co and Cd higher SE
was observed during winter, the data thus revealed
quite divergent metal distributions during the specific
seasons.
It could be concluded that the lower temperature
favoured the distribution of Na, K, Zn, Cu, Pb, Sb, Sr,
23
Co and Cd while elevated temperature appeared to
have some positive influence on Fe, Mg, Mn, Ni and
Cr (Querol et al. 2000). All selected metals showed
substantial spread around mean values, shown by
their respective SE values indicating some random
contributions from different sources.
4 Conclusions
During the present study, average TSP levels (164 g/m3)
were found to be higher than WHO primary and sec-
ondary standards. Dominant trace metals estimated in
the local atmosphere were Ca at 4.531 g/m3, Na at
3.905 g/m3, Fe at 2.464 g/m3, Zn at 2.311 g/m3, K
at 2.086 g/m3 and Mg at 0.962 g/m3, on an average
basis. Mean Ni (0.024 g/m3) and Cd (0.004 g/m3)
concentrations were many times higher than interna-
tional standards, whereas, Pb (0.144 g/m3), Mn
(0.079 g/m3) and Cr (0.010 g/m3) levels were found
to be within the safe range. The correlation study
revealed a number of strong correlations between
different metal pairs, pointing towards their proba-
ble common origin in the atmosphere. Among the
trace metals, Ca, Fe, K, Mg, Mn and Ag were
found to be positively correlated with the temper-
ature and negatively with the relative humidity,
while, Sb, Pb, Zn, Co, Li and Cd revealed an
opposite behaviour. Wind speed and direction were
also affecting the metal distribution significantly.
Similarly, suspended particulates were positively cor-
related with temperature, wind speed and pan evap-
oration but naively with relative humidity. The source
apportionment by Principle Component Analysis and
Cluster Analysis demonstrated the major contribu-
tions of trace metals from industrial emissions,
automobile exhaust, biomass burning, re-suspended
soil dust, crude oil combustion, metallurgical emis-
sions, fugitive emissions and earth crust. The seasonal
variations revealed that comparatively higher concen-
trations of Co, Cu, Cd, Pb, K, Sb, Sr and Na were
observed during the winter, while Mg, Mn, Fe and Ca
exhibited higher concentrations during the spring.
Mean TSP levels were found to be maximum during
the spring followed by autumn, winter and summer.
Acknowledgements The Research Fellowship awarded by
Quaid-i-Azam University to carry out this project is thankfully
acknowledged. We are also grateful to Chief, Public Health
24
Department, National Institute of Health, Islamabad, for
provision of SRM and inter-laboratory comparison of the data.
Thanks are also due to Pakistan Agricultural Research Council
(PARC) officials for providing the meteorological data.
References
ATSDR (2002). Regulations and guidelines applicable. Agency
for Toxic Substances and Disease Registry. Retrieved from
http://www.atsdr.cdc.gov/toxprofiles/tp11-c8.pdf.
Charlson, R. J., Schwartz, S. E., Hales, J. M., Cess, R. D.,
Coakley, J. A., Hansen, J. E., et al. (1992). Climate forcing
by anthropogenic aerosols. Science, 255, 423430.
Cohen, D. D. (1999). Seasonal and regional variations in
ambient fine particle concentrations and sources in New
South Wales, Australia A seven year study. International
Conference on Urban Climatology, 16.
Colombo, J. C., Landoni, P., & Bilos, C. (1999). Sources,
distribution and variability of airborne particles and
hydrocarbons in La Plata area, Argentina. Environmental
Pollution, 104, 305314.
Dickerson, R. R., Kondragunta, S., Stenchikov, G., Civerolo,
K. L., Doddridge, B. G., & Holben, B. N. (1997). The
impact of aerosols on solar ultraviolet radiation and
photochemical smog. Science, 278, 18211832.
Dockery, D. W., Pope III, C. A., Xu, X., Spengler, J. D., Ware,
J. H., Martha, E. F., et al. (1993). An association between
air pollution and mortality in six US cities. New England
Journal of Medicine, 329, 17531759.
EC (European Commission) (2000). DG environmental working
group on arsenic, cadmium and nickel compounds, Ambient
air pollution by As, Cd and Ni compounds. Position Paper
(Final Version), October.
Fang, G. C., Chang, C. N., Wu, Y. S., Wang, V., Fu, P. P. C.,
Yang, D. G., et al. (2000). Study on particulate and
metallic elements variation at day-time and night-time
periods in urban atmosphere. Toxicological and Environ-
mental Chemistry, 76(12), 8394.
Fang, G. C., Wu, Y. S., Haung, S. H., & Rau, J. Y. (2004). Dry
deposition (downward, upward) concentration study of
particulates and heavy metals during daytime, night time
period at the traffic sampling site of Sha-Lu, Taiwan.
Chemosphere, 56, 509518.
Garcia, J. H., Li, W. W., Arimoto, R., Okrasinski, R., Greenlee,
J., Walton, J., et al. (2004). Characterization and impli-
cation of potential fugitive dust sources in the Paso
del Norte region. Science of the Total Environment, 325,
95112.
Gonzalez, E. B., Garda, J. M. A., Velasco, E. S., & Mahia, P. L.
(1997). Metals in airborne particulate matter in La Coruna
(NW Spain). Science of the Total Environment, 196(2),
131139.
Gotschi, T., Arx, M. E. H., Heinrich, J., Bono, R., Burney, P.,
Forsberg, B., et al. (2005). Elemental composition and
reflectance of ambient fine particles at 21 European
locations. Atmospheric Environment, 39, 59475958.
Hair Jr., J. F., Anderson, R. E., Tatham, R. L., & Back, W. C.
(1998). Multivariate data analysis (p. 7305th ed.).
Englewood Cliffs, NJ: Prentice-Hall.
Water Air Soil Pollut (2008) 190:1325
Hrsak, K., Sisovic, A., Skrbec, A., & Sega, K. (2001). Seasonal
differences in the levels of suspended particulate matter and
heavy metals in the vicinity of waste dump. Atmospheric
Environment, 35, 35433546.
Jalkanen, L., & Manninen, P. (1996). Multivariate data analysis
of aerosol collected on the Gulf of Finland. Environmetrics,
7, 2738.
Jonsson, P., Bennet, C., Eliasson, I., & Lindgren, E. S. (2004).
Suspended particulate matter and its relations to the urban
climate in Dar es Salam, Tanzania. Atmospheric Environ-
ment, 38, 41754181.
Khan, F. K. (1991). Geography of Pakistan: Environment,
people and economy. Karachi: Oxford University Press.
Kim, K. H., Kim, D. S., & Lee, T. J. (1997). The Temporal
variabilities in the concentrations of airborne Lead and its
relationship to aerosol behaviour. Atmospheric Environ-
ment, 31(20), 34493458.
Kim, K. H., Lee, J. H., & Jang, M. S. (2002a). Metals in
airborne particulate matter from the first and second
industrial complex area of Taejon city, Korea. Environ-
mental Pollution, 118, 4151.
Kim, K. H., Lee, H. S., Youn, Y. H., Yun, S. T., Ro, C. U., &
Oh, J. M. (2002b). Studies of spatial variabilities of
airborne metals across four different land-use types. Water,
Air and Soil Pollution, 138(104), 724.
Manoli, E., Vousta, D., & Samara, C. (2002). Chemical
characterization and source identification/apportionment
of fine and coarse air particles in Thessaloniki, Greece.
Atmospheric Environment, 36, 949961.
Method IO-2.1 (1999). Sampling of ambient air for total
suspended particulate matter (SPM) and PM10 using high
volume sampler. In Compendium of methods for the
determination of inorganic compounds in ambient air,
EPA/625/R-96/010a. US-Environmental protection agency,
Cincinnati, OH.
Method IO-3.2 (1999). Determination of metals in ambient
particulate matter using Atomic Absorption (AA) spec-
troscopy. In Compendium of methods for the deter-
mination of inorganic compounds in ambient air, EPA/
625/R-96/010a. US-Environmental protection agency,
Cincinnati, OH.
Mishra, V. K., Kim, K. H., Hong, S., & Lee, K. (2004). Aerosol
composition and its sources at the King Sejong Station,
Antarctic peninsula. Atmospheric Environment, 38, 4069
4084.
Moreno-Grau, S., Cascales-Pujalte, J. A., Martinez-Garcia,
M. J., Angosto, J. M., Moreno, J., Garcia-Sanchez, A.,
et al. (2002). Relationships between levels of lead,
cadmium, zinc, and copper in soil and settleable particu-
late matter in Cartagena (Spain). Water, Air and Soil
Pollution, 137, 365383.
NIOSH Method-7300 (1984). NIOSH manual of analytical
methods. Cincinnati: National Institute of Occupational
Safety and Health.
Pakistan Bureau of Statistics (2004). Statistical year book.
Islamabad: Government of Pakistan.
Querol, X., Alastuey, A., Lopez-Solar, A., & Plana, F. (2000).
Levels and chemistry of atmospheric particulates induced
by a spill of heavy metal mining wastes in the Donana
area, Southwest Spain. Atmospheric Environment, 34,
239253.
Water Air Soil Pollut (2008) 190:1325
Querol, X., Alastuey, A., Puicercus, J. A., Mantilla, E., Ruiz, C. R.,
Lopez-Soler, A., et al. (1998). Seasonal evolution of
suspended particles around a large coal-fired power station
Chemical characterization. Atmospheric Environment, 32,
719731.
Quiterio, S. L., Silva, C. R. S., Arbilla, G., & Escaleria, V.
(2004). Metals in airborne particulate matter in industrial
district of Santa Cruz, Rio de Janeiro, in an annual period.
Atmospheric Environment, 38, 321331.
Ragosta, M., Caggiano, R., DEmilio, M., & Macchiato, M.
(2002). Source origin and parameters influencing levels of
heavy metals in TSP, in an industrial background area of
Southern Italy. Atmospheric Environment, 36, 30713087.
Samet, J. M., Dominici, F., Curriero, F. C., Coursac, I., &
Zeger, S. L. (2000). Fine particulate air pollution and
mortality in 20 US cities, 19871994. New England
Journal of Medicine, 343, 17421799.
Samura, A., Al-Agha, O., & Tuncel, S. G. (2003). Study of
trace and metals in rural and urban aerosols of Uludag and
Bursa (Turkey). Water, Air and Soil Pollution-Focus, 3,
109126.
Schwartz, J., Dockery, D. W., & Neas, L. M. (1996). Is daily
mortality associated specifically with fine particles? Journal
of Air and Waste Management Association, 46, 927939.
Senaratne, I., & Shooter, D. (2004). Elemental composition in
source identification of brown haze in Auckland, New
Zeland. Atmospheric Environment, 38, 30493059.
Shah, M. H., Shaheen, N., & Jaffar, M. (2006). Characterization,
source identification and apportionment of selected metals
in TSP in urban Islamabad, Pakistan. Environmental
Monitoring and Assessment, 114(13), 573787.
Shah, M. H., Shaheen, N., Jaffar, M., & Saqib, M. (2004).
Distribution of lead in relation to size of airborne particulate
matter in Islamabad, Pakistan. Journal of Environmental
Management, 70(2), 95100.
25
Shaheen, N., Shah, M. H., & Jaffar, M. (2005a). A study of
airborne selected metals and particle size distribution in
relation to climatic variables and their source identifica-
tion. Water, Air and Soil Pollution, 164(14), 275294.
Shaheen, N., Shah, M. H., Khalique, A., & Jaffar, M. (2005b).
Metal levels in airborne particulate matter in urban
Islamabad, Pakistan. Bulletin of Environmental Contami-
nation and Toxicology, 75, 739746.
Sharma, R., Pervez, Y., & Pervez, S. (2005). Seasonal
evaluation and spatial, variability of suspended particulate
matter in the vicinity of a large coal-fired power station in
India A case study. Environmental Monitoring and
Assessment, 102, 113.
Smith, D. J. T., Harrision, R. M., Luhana, L., Casimiro, A. P.,
Castro, L. M., Tariq, M. N., et al. (1996). Concentrations
of particulate airborne polycyclic aromatic hydrocarbons
and metals collected in Lahore, Pakistan. Atmospheric
Environment, 30, 40314040.
StatSoft, Inc. (1999). STATISTICA for windows. Tulsa, OK:
Computer Program Manual.
Vallius, M., Janssen, N. A. H., Heinrich, J., Hoek, G.,
Ruuskanen, J., Cyrys, J., et al. (2005). Sources and
elemental composition of ambient PM2.5 in three European
cities. Science of the Total Environment, 337, 147162.
Veranth, J. M., Pardyjak, E. R., & Seshadri, G. (2003). Vehicle-
generated fugitive dust transport: Analytic models and
field study. Atmospheric Environment, 37, 22952303.
WHO. (2000). Guidelines for air quality. World Health
Organization, Geneva. Retrieved from http://www.who.
int/environmentalinformation/Air/Guidelines/aqguide7.
pdf.
Yongming, H., Peixuan, D., Junji, C., & Postmentier, E. S.
(2006). Multivariate analysis of heavy metal contamina-
tion in urban dusts of Xian, Central China. Science of the
Total Environment, 355, 176186.