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Ecological Indicators 48 (2015) 358–364

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Ecological Indicators
journal homepage: www.elsevier.com/locate/ecolind

Geochemical baseline determination and pollution assessment of
heavy metals in urban soils of Karachi, Pakistan
Zahida Karim *, Bilal Aslam Qureshi, Majid Mumtaz
Department of Chemistry, University of Karachi, Karachi 75270, Pakistan

A R T I C L E I N F O

A B S T R A C T

Article history:
Received 23 April 2014
Received in revised form 23 August 2014
Accepted 24 August 2014

Karachi is one of the most populated urban agglomerations in the world. No categorical study has yet
discussed the geochemical baseline concentrations of metals in the urban soil of Karachi. The main
objectives of this study were to establish geochemical baseline values and to assess the pollution status of
different heavy metals. Geochemical baseline concentrations of heavy metals were estimated using the
cumulative frequency distribution (CDF) curves. The estimated baseline concentrations of Pb, Cr, Cu, Zn
and Fe were 56.23, 12.9, 36.31, 123.03 and 11,776 mg kg1, respectively. The pollution status of heavy
metals in urban soils was evaluated using different quantitative indices (enrichment factor–EF, Geoaccumulation Index–Igeo, and pollution index–PI). Enrichments factors of the selected heavy metals
determined by using Fe as a normalizer showed that metal contamination was the product of
anthropogenic activities. The urban soils of Karachi were found to have a moderate to moderately severe
enrichment with Pb, whereas Cr and Cu has moderate and Zn has minor enrichment. Igeo results indicated
moderate soil contamination by Pb at some of the sampling locations. PI for Pb, Cr, Cu and Zn was found in
the range of 0.04–3.42, 0.19–1.55, 0.27–2.45 and 0.32–1.57, respectively. Large variations in PI values of Pb
revealed that soil in those areas of the city which are influenced by intensive anthropogenic activities
have exceptionally high concentrations of Pb. The findings of this study would contribute to the
environmental database of the soil of the region and would also facilitate both at the local and the
international scales, in a more accurate global environmental monitoring, which will eventually facilitate
the development of management and remediation strategies for heavy metal contaminated urban soil.
ã 2014 Elsevier Ltd. All rights reserved.

Keywords:
Cumulative frequency distribution (CDF)
curves
Enrichment factor (EF)
Geochemical baseline concentration
Karachi
Pollution assessment
Urban soil

1. Introduction
Soils in the urban environment tend to be affected by a wide
range of anthropogenic activities. Vehicular emissions, industrial
wastes and wastewater sludge have a noticeable impact on the
heavy metal contamination of urban soils (Li et al., 2004; Ali and
Malik, 2011; Wang et al., 2012; Kardel et al., 2012). Non-exhaust
emissions due to wear and tear of vehicle parts such as brake, tire
and clutch are an important source of trace metals in the urban
environment (Thorpe and Harrison, 2008; Pant and Harrison,
2013). Industrial sources for the heavy metal (Cu, Pb, Zn and Cr)
contamination in the urban soil include electroplating, petrochemicals, dyes, pigments, ceramic, tanning and textile industries.
Contamination of urban soils by heavy metals is therefore a matter
of major concern at local, regional and global level owing to its
adverse effect on the urban ecosystem.

* Corresponding author. Tel.: +92 3002382208.
E-mail address: zkareem@uok.edu.pk (Z. Karim).
http://dx.doi.org/10.1016/j.ecolind.2014.08.032
1470-160X/ ã 2014 Elsevier Ltd. All rights reserved.

There are very limited published data on the soil contamination in
urban areas of Pakistan. Malik et al. (2010) investigated the metal
contamination in urban soil of Sialkot and concentrations of Cd, Ni,
Cr, Zn, and Pb were found to exceed the permissible limits of surface
soils. Spatial distribution of metals in top soils of Islamabad also
revealed elevated concentrations of Pb, Ni, and Zn in built-up areas
and it was largely influenced by the vehicular emissions and waste
disposals (Ali and Malik, 2011). The spatial variation in the
concentrations of Cu, Zn and Pb metals seemed to be the result of
increased atmospheric deposition from road traffic in the urban soil
of Karachi (Karim et al., 2014). The potential health risk due to
lifetime exposure to Cu, Pb, Cr and Zn in urban soil of Karachi was
evaluated by Karim and Qureshi (2014). Risk assessment indicated
that the overall results for the carcinogenic risk were insignificant. It
was also found that children were more susceptible to noncarcinogenic health effects of trace metals compared to adults.
The geochemical or natural background is a relative measure to
differentiate between natural element or compound concentrations and anthropogenically-influenced concentrations in a given
environmental sample (Matschullat et al., 2000). Owing to the

_1)TD$IG] Fig.. food and 359 dairy products etc. industrialization and urbanization. automobiles. Cr. 1 represents the most urbanized part of the city. Zn and Pb). no categorical study has yet discussed the geochemical baseline concentrations of metals in the urban soil of Karachi (Pakistan). 2. Zn and Pb was therefore log-transformed prior to the CDF plotting. chemicals. rubber. The reverse convention. Study area and sampling sites. comprising 20 administrative towns with population densities ranging from 10. The normality of the distribution of metals’ data was investigated by performing one-sample Kolmogorov–Smirnov test (or the K–S test of normality).. Then. leather tanning. Chen et al. Soil samples at depth of 0–10 cm were collected from 30 different sampling locations. It was found that datasets of metals were either normally (for Cr and Fe) or log-normally distributed (for Cu. paints and pigment... geo-accumulation index (Igeo). Fig. The findings of this study would therefore facilitate the concerned authorities for monitoring the impact of anthropogenic activities on heavy metal contamination of urban soil and for the development of proper management strategies for urban environment pollution control and for the remediation of heavy metal contaminated soils of Karachi city. 2013). Karim et al. Blonda and Valenzano. 1. ceramics. 2001). because statistically it is 95% of the expected range of background concentrations (Gough et al. Several studies were conducted in different regions of the world to estimate geochemical background and baseline concentration of heavy metals (Wei and Wen 2012. CDF curves for Fe and Cr were drawn by [(Fig. 1999. The CDF curves were drawn by statistical software Minitab 161. Five replicate samples were collected from each sampling site within a 2 m  2 m grid using a stainless steel auger. The cumulative frequency distribution (CDF) curves of the metal’s data sets were used to estimate baseline metal concentrations. practically it is almost impossible to quantify a true background value beyond doubt. and pollution index (PI).. The total number of vehicles registered in Karachi till 2011 were 2. paper. Usually. 1994. plastic.. Karim et al. pharmaceutical. Geochemical baseline concentration is therefore more useful. Materials and methods Karachi is the largest city of Pakistan in terms of population. can also be used if percentile/s following certain sample value is to be found. cement.000 km2 to almost 100. a CDF curve is plotted with the data on abscissa and the corresponding estimated percentiles on ordinate. ground and passed through a 2mm nylon sieve. However. The main objectives of this study were to estimate the baseline values and pollution status of different heavy metal in urban soils of Karachi using enrichment Factor (EF). thoroughly mixed to obtain a bulk composite sample.6 million. The data of Cu.Z. Samples were air-dried. / Ecological Indicators 48 (2015) 358–364 natural variability and widespread anthropic input. 2014) and analysed by using an AAnalyst 700 Perkin–Elmer Flame atomic absorption spectrometer. . 2013.000 km2 (Karim et al. Facchinelli et al. Total concentrations of Pb. Cu. Major industries include textile. 2014). as in the present study. 2006. Zn and Fe in soil samples were determined using a strong acid (HNO3–HClO4) pseudo-total digestion method (Lee et al. The city has an estimated population of over 18 million.. Rodrigues et al.

2).95. the inflexion points in a curve were determined by examining the CDF vs. For assessing the soil contamination by heavy metals.360 Z. 2. . for the metals Cu. The plot of the regression line thus obtained was overlapped with the respective CDF curve. which was considered to be the baseline value for the metal (Fig.05 and R2 > 0. Igeo for every metal in each sample was estimated. the linear portion of the CDF curve between the two inflexion points was used. For this.90 to extract the inflexions. / Ecological Indicators 48 (2015) 358–364 plotting the metal concentrations on the ordinate and the estimated % CDF on the abscissa. Wei and Wen (2012) used the linear regression parameters of P < 0. Igeo was calculated as:   Cn (1) Igeo ¼ log2 1:5Bn where Cn is the concentration of heavy metal in soil. Ni is the reference metal or the “normalizer’s” concentration in the ith sample. both the upper and the lower extreme values from the coordinate data were omitted until the remaining data met the said criterion of linearity. log10 of the metal’s concentration was plotted on the y-axis with decimal coordinates._2)TD$IG] Fig. Cb is the metal’s baseline concentration and Nb is the [(Fig. Karim et al. metal/log-metal data under linear regression model for P < 0. Cumulative frequency distribution curves of selected heavy metals.05 and R2 > 0. Bn is the geochemical background or baseline value of the same metal in the soil. Zn and Pb. To find the baseline value for each metal. The EF values for the metals in different soil samples were calculated as follows: EF ¼ C i =Ni C N OR i  b Ni =Nb Ni C b (2) where Ci is the metal’s concentration in the ith sample. In this study. and the upper end of the CDF curve that “first deviates” from the regression line was chosen as the upper inflexion point. Enrichment factor (EF) was used in the present study to find if the metal enrichment in soil has occurred.

3.0 mg kg1.1. Although there has been a decline in lead vehicle emission since leaded gasoline was phased out. a significant reservoir of lead still . According to Han et al.64 mg kg1 and 1793 to 14. CV of heavy metals were found in the order of Pb > Cu > Cr > Zn > Fe.. 9. p ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi n (4) PLI ¼ PI1  PI2  PI3    PIn where n is the number of pollutants assessed (i. 3. respectively. an extension of ArcView3.49 to 20. / Ecological Indicators 48 (2015) 358–364 [(Fig. Enrichment Factors (EF) for heavy metals across the study area. PI ¼ Cn Bn (3) where Cn is a metal’s/pollutant’s concentration and Bn is the baseline concentration of that metal in soil._3)TD$IG] 361 Fig.10 mg kg1. waste incineration and industry (Koz et al.84 to 193.96 to 89.e. 4) and PIi is the single factor pollution index of each metal. Single factor pollution indices (PI) and the pollution load index (PLI) were calculated for every sample to investigate the level of pollution of the urban soils of Karachi. Concentration of heavy metals in soil samples Concentration of Pb.21 software was used. Results and discussion 3. Table 1 presents concentrations of these metals in different studies that are reported in the urban soils worldwide.. Karim et al. (2006) coefficient of variation (CV) values of heavy metals dominated by natural sources are relatively low.800 mg kg1. while CV values of heavy metals affected by anthropogenic sources are quite high (Guo et al. The main sources of lead in the urban environment are the combustion of leaded fuel. For the spatial representation of EF of heavy metals in the soil (Fig. 2012).Z. Cu. The calculated values of EF for each of the sampling location were spatially interpolated by the method of inverse distance weight (IDW) to get a surface with varying intensities of color/shades. representing variation of EF between any two sampling locations. 2008). normalizer’s baseline concentration. Zn and Fe was found in the range of 2. Cr.5 mg kg1. 39.19 to 192.. Lead pollution is associated with urbanization and density of population. 2. 3). Spatial Analyst1.

. 1997. Cu. Baptista et al. The hotspots in the EF map of Pb are located adjacent to the roads having intensive traffic congestion during peak hours.. 2013 Present study impact in urban soil of the city. Zechmeister et al.00 70. it is practically not possible to determine a “natural background” which strictly refers to the pristine geochemical composition of soil..7 283. 2005.00 39.69 386. Spain Novi Sad. 2010 Acosta et al...90 21. 2005). 0.776 mg kg1. 2000.. an attempt was therefore made to estimate “anthropic background” instead of natural. 3 presents EF values for Pb.26–4.00 41. The estimated baseline concentrations of Pb.00 125.. Conrad and Chisholm-Brause. respectively. 2000) Background concentration Pb Cr Cu Zn Fe 56. Cu. 2012 Rizo et al.0 88.362 Z.06–7.. 3. 2008 Christoforidis and Stamatis. China Murcia. 2009 Malkoc et al. Rubio et al. As no Table 2 Comparison of estimated regional baseline values (milligrams per kg of dry weight) with the values published in the literature.30 97.. Cu and Zn.. Balls et al. Fe (Schiff and Weisberg.30 3.70 64..00 26. the enrichment factor (EF) was used to assess the level of contamination and the possible anthropogenic Fe – – – – – – 35.46–2.00 9. / Ecological Indicators 48 (2015) 358–364 Table 1 Average heavy metal concentrations (mg g) in urban soils from different cities in the world. Esen et al. Pant and Harrison.. Cr and Zn in urban atmosphere is the traffic (Kemp. 2009. 36.50 107.0 65.90 28.70 31. 2010 Sun et al.0 28.90 11. Karim et al.30 181.9 36.5. Cuba Karachi..15 and 2. 2011).90 232.00 94. Zn also has a small spatial variation in EF values. Zn compounds have also been extensively used as antioxidants and as detergent/dispersant improvers for lubricating oils (DeMiguel et al.5 indicate the metal is entirely from crustal materials or natural processes.. whereas EF values greater than 1. Cr and Zn pollution (Garg et al.. yet its lowest variability ensures that it is less vulnerable to anthropic changes. 2006 Shi et al. Fe and Cr in urban soil of Karachi were estimated using the methods of normalization and cumulative frequency curve method (Fig.31 123. 1999. City/Country Heavy metals Reference Pb Cr Cu Zn Palermo.00 199. with slightly higher EFs in south-east of the studied area. Zn and Fe are 56..79 301. The estimated baseline values were also compared with those reported in the literature (Table 2) These anthropic background values were then used for the pollution assessment of selected heavy metals in urban soils of Karachi. 2000.60 214.80 98..40 354.40 151.33 51.5 and 1. Zwolsman et al. Determination of baseline values In Karachi due to rapid increase in industrialization and urbanization in recent decades and widespread anthropic input.76 respectively.60 49. and Zn. and Zn were found in the range of 0.40 54. 2003.7 122.48 and 6.10 – 77.0 – .25 172. Daskalakis and O’Connor. S7 and S30 with EFs 2.0 140.0 36. Cr. This shows that the Cr and Cu contents of the soils of Karachi city are mostly around the baseline value. 12.9. 2012). Enrichment factor In the present study. Cr and Cu had moderate enrichment in soils only at locations S3. Christophoridis et al. EF values between 0..00 111.23. 1996) is generally used.00 99. 2000).0 83. Spain Eskisehir. Geochemical baseline concentrations of Cu.9 94.00 23..40 20. and that some enrichment is probably due to the unidentified anthropogenic point sources. Fe was used as a conservative tracer to differentiate natural from anthropogenic components. 2004.72 – – – – 8962.65 – 16.50 39.. 2009 Franco-Uria et al.93 75. Pakistan 253. Turkey Shenyang.2.41 and 0. “Geochemical baseline” represents background conditions that contain a certain degree of human impact on the environment (Darnley. 2002 Li et al.60 111. 2).0 – 85. Meza-Figueroa et al.52 present in the roadside soils due to its long half-life of several hundred years..5 suggest that the sources are more likely to be anthropogenic (Zhang and Liu 2002. 2010. 2008).. 123.50 140. 0. 2013). with EF > 2..2 54. Al (Sinex and Wright.0 36.31.80 42. In the present study. 2005 Yuangen et al. Serbia Las Tunas City. 1997. 2009.665.. The EF values for Pb at some sampling sites were found to be the highest among the metals i. S6 and S26.0 100.31 59. the geochemical normalization of the metal data to a conservative element... Cu.00 23. 2002) Background values (Crommentuijn et al.. Fe has highest concentration in all soil samples. 2004 Lee et al. Mucha et al.3–3. and S5 and S24 respectively. Heavy metal Present study Baseline values (Mico et al. Pb.30 445.03 and 11. Ghrefat et al. 3.3. Italy Hong Kong Seoul City.02 16.. 1995. and total organic carbon (Rubio et al. Korea Aberdeen City.0 – 36. Cr. 2011). as it compensates for any variation in the soil texture and composition (Abrahim and Parker.23 12. 2000.03 11776 28. Fig. UK Shanghai. In the present study.10 97. Ghrefat et al.. Greece Galicia.39 respectively. Cr.10 182.. Wei and Wen.33 respectively and S4 and S29 with EFs 7. The normalized EF can be used for the geospatial analysis of soil chemistry of large areas.26 19149.0 34.1 – 26.48. 2007) Baseline values (Gjoka et al. 2009. 1988.84 Manta et al.29 21.26 8. and its non-correlation to the other heavy metals also makes it a good choice for the study of metals like Pb Cr. China Kavala. 2002). Zn. Cevik et al.e.00 2. The main source of Cu. 2011 Skrbic and Mladenovic. EF for Pb. Zechmeister et al. 1997. Scotland. The wear and tear of vehicle brake pads is the major contributor of Cu. In order to calculate the EF. 2011) Background values (Atanassov and Terytze.

Auckland. The IPI is classified as: IPI  1 low level of pollution. PLI > 5 very highly polluted (Zhang et al. Geo-accumulation index and pollution index Igeo results for Pb.J. PI and IPL values of heavy metals in 30 soil samples are summarized in Fig. battery leaks/spills etc. 1 < PLI  2 moderately to unpolluted. Parker. the source of Zn at those locations might be of geogenic origin. Cr. Cr.45 and 0. 4. It is revealed that the study area is not contaminated with respect to Cr. Environ.57 respectively.7377 and 0. Exposure to Pb contaminated urban soil can cause deleterious health effects in humans. however some of the sampling locations showed moderate soil contamination by Pb.4. and Zn are found in the range of 0. Cu. This indicated that overall situation of the urban soils in Karachi is showing low level of heavy metal pollution.55.42.04–3. PLI = 0 background concentration.S. 2 < IPI  5 high level of pollution.27–2.32–1. 0. 2011). 2008. 3.. PI for Pb. especially in children.Z.._4)TD$IG] 363 2 1 0 Sampling location Igeo -1 Cu Igeo -2 Zn Igeo -3 Fe Igeo -4 Pb Igeo -6 Cr Igeo S1 S2 S3 S4 S5 S6 S7 S8 S9 S10 S11 S12 S13 S14 S15 S16 S17 S18 S19 S20 S21 S22 S23 S24 S25 S26 S27 S28 S29 S30 -5 Fig. 227–238. Large variations in PI values of Pb in soil revealed that in those areas of the city which are influenced by intensive anthropogenic activities had exceptionally high concentrations of Pb. 5. Assess. 0. Conclusion This study is the first comprehensive attempt to establish the baseline concentration of a number of heavy metals of toxicological importance in the urban soils of Karachi. G. 136. 0 < PLI  1unpolluted. Anthropogenic activities including vehicular emission like engine exhausts. IPI > 5 extreme high level of pollution (Wei and Yang. brake wear. and the industrial emissions are the most important sources of lead contaminated soil in the study area.809 respectively. and Zn are presented in Fig. 2 < PLI  3 moderately polluted. These results suggest the need to develop proper management strategies to reduce the human health risk associated with the heavy metal contaminated urban soil. 0. PI and PLI of selected heavy metals. Pollution load index is a simple comparative means for assessing the level of heavy metal pollution. The integrated pollution index (IPI) is defined as the mean value of the pollution index. 4 < PLI  5 highly polluted. References Abrahim. It further aims to assess the pollution status of the urban soil through various geochemical and geo-statistical methods. 4. Assessment of heavy metal enrichment factors and the degree of contamination in marine sediment from Tamaki Estuary. Cu. Cr and Cu has minor to moderate and Zn has minor enrichment. and Zn. point sources were identified around the hotspots (showing only minor enrichment) in EF map of Zn.19–1. P.722. In this study. 1 < IPI  2 moderate level of pollution. / Ecological Indicators 48 (2015) 358–364 [(Fig. PLI values were found greater than 1 on those sampling locations that were either the industrial sites or the areas that were situated at high vehicular traffic zones like major roundabouts or busy road junctions of Karachi city.M.217 to 1. Igeo values of heavy metals at different sampling locations. PLI values varied from 0. . [(Fig.. 0. The IPI of Pb. 3 < PLI  4 moderately to highly polluted. Large variations in PI values of Pb suggested that the areas of the city characterized by high traffic loads have exceptionally high concentrations of Pb in soil._5)TD$IG] Fig. Cu. 5.42. and Zn calculated are 0.740. Igeo results also indicated that some of the sampling locations showed moderate soil contamination by Pb. New Zealand. Monit. 2010). soils of some locations of Karachi were found moderately to moderately high enriched with Pb. Karim et al. Cr. Cu. 4. From the EF estimates.

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