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Environ Monit Assess (2010) 164:101110 DOI 10.

1007/s10661-009-0878-9

Impact of overland trafc on heavy metal levels in highway dust and soils of Istanbul, Turkey
Mert Guney Turgut T. Onay Nadim K. Copty

Received: 10 October 2008 / Accepted: 10 March 2009 / Published online: 4 April 2009 Springer Science + Business Media B.V. 2009

Abstract The purpose of this study was to investigate the impact of overland trafc on the spatial distribution of heavy metals in urban soils (Istanbul, Turkey). Road dust, surface, and subsurface soil samples were collected from a total of 41 locations along highways with dense trafc and secondary roads with lower trafc and analyzed for lead (Pb), zinc (Zn), and copper (Cu) concentrations. Statistical evaluation of the heavy metal concentrations observed along highways and along the secondary roads showed that the data were bimodally distributed. The maximum observed Pb, Zn, and Cu concentrations were 1,573, 522 and 136 mg/kg, respectively, in surface soils along highways and 99.3, 156, and 38.1 mg/kg along secondary roads. Correlation analysis of the metal concentrations in road dust, surface and 20-cm depth soils suggests the presence of a common pollution source. However, metal concentrations in the deeper soils were substantially lower than those observed at the surface, indicating low mobility of heavy metals, especially for Pb and Zn. A modied kriging approach that honors the bimodality of the data was used to estimate the spatial distribution of the surface concentrations

of metals, and to identify hotspots. Results indicate that despite the presence of some industrial zones within the study area, trafc is the main heavy metal pollution source. Keywords Heavy metal Soil pollution Geostatistics Overland trafc Urban soils

Introduction Pollution from overland transportation is an inevitable environmental consequence of increasing commercial and industrial activity in developing areas, especially in large metropolitan areas around the world. The rapid growth in overland transportation activities within many urban centers is causing the release of numerous pollutants to the environment, including heavy metal emissions to the atmosphere and its deposition to nearby roadside soils. Heavy metals are naturally found in various amounts in water, air, soils, and sediments. Anthropogenic sources from various industrial activities such as mining, foundries, smelters, combustion, and trafc contribute to the amounts of heavy metals in various media (Al-Khashman 2004). Although some heavy metals are essential for vital processes in many living organisms, including humans (Juvanovic et al. 1995; Lapitajs

M. Guney T. T. Onay N. K. Copty (B) Institute of Environmental Sciences, Bogazici University, 34342 Bebek, Istanbul, Turkey e-mail: ncopty@boun.edu.tr

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et al. 1995), these metals are generally toxic when their concentrations exceed certain thresholds. The most common heavy metals introduced to the environment by overland transportation are lead (Pb), zinc (Zn), and copper (Cu; Kim et al. 1998; Sezgin et al. 2003; Banerjee 2003; Li et al. 2004). Use of leaded gasoline is primarily responsible for the Pb exposure (Chen et al. 2005), while tire wear and corrosion of roadside safety fences contribute to Zn pollution (Blok 2005). Cu is mainly released from the wear of brake linings, which is also an important source of Pb and Zn (SEHPA 2001). All three metals are deposited in the form of dust and can form aerosols when resuspended (Han et al. 2007). Moreover, platinum group elements (Pt, Pd, Rh, Ru, and Ir) originating from catalytic converters have been detected in limited amounts (in the order of micrograms per kilogram) in highway dusts and plants (Djingova et al. 2003; Hooda et al. 2008). Field investigations have shown that soil pollution by heavy metals is generally concentrated in the rst few meters to tens of meters on either side of the road pavement and then sharply decreases with distance from the road (Olajire and Ayodele 1997; Blok 2005). Several studies have reported that heavy metals tend to accumulate within the top 30 cm of soil despite decades of exposure from trafc (e.g., Teutsch et al. 2001; Turer et al. 2001). However, soil penetration of metals may increase when the soil is disturbed due to tillage or trafc (Panichayapichet et al. 2007). Geostatistics is a powerful analysis tool that has been used in numerous studies for the evaluation of the spatial distribution and behavior of heavy metals in urban areas. Applications ranged from environmental risk assessment (Liu et al. 2006) to the calculation of anthropogenic stock (Saby et al. 2006) and the identication of the spatial patterns of pollutants in urban areas (Tong and Lam 2000; Charlesworth et al. 2003; Imperato et al. 2003; Yongming et al. 2006; Zhang 2006). Istanbul, with a population exceeding ten million, is one of the largest metropolitan areas of the world. It is located along the shores of the Bosphorus Strait which connects the Black Sea to the Marmara Sea and divides the city into a European district and an Anatolian or Asian district (Fig. 1). These two districts are

connected to each other by two highway suspension bridges: the Bosphorus Bridge which receives an annual average trafc load of about 209,000 vehicles/day and the Fatih Sultan Mehmet Bridge which carries 173,000 vehicles/day (Turkish General Directorate of Highways 2006). Although Istanbul is an important transportation center, no study on the extent of soil metal pollution due to trafc can be found in the literature. The only related published study investigated metal pollution in street dust at 14 locations on an 18 km span of a highway located in the European district of the city (Sezgin et al. 2003). The study reported elevated concentrations of Pb, Zn, and Cu in dust, with maximum values of 555.4, 1,852.0, and 1,358.5 mg/kg, respectively. The purpose of this study is to assess the impact of overland trafc on soil heavy metal (Pb, Zn, and Cu) pollution in the Anatolian district of Istanbul, Turkey. Specically, the aims of the study are (1) to determine the level of pollution of the selected metals in dust and soils along major highways and secondary roads, (2) evaluate the statistical distribution of metal pollution in the study area, (3) statistically compare the spatial distribution of the different heavy metals and identify potential pollution sources, and (4) identify hotspots within the study area using geostatistics.

Materials and methods Sampling procedure The study area comprising of the Anatolian district of the city of Istanbul is shown in Fig. 1. The district contains numerous residential and commercial zones and a complex transportation network including the two suspension bridges that connect the Anatolian and European districts of the city. The Anatolian district also includes a number of industrial zones which are mostly located along the eastern part. Road dust and soil samples were taken from a total of 41 locations within the area. Twenty locations were adjacent to one of the six highways (having four or more lanes and high speed, dense trafc) in the district. At each of these 20 locations, dust samples were taken from the

Environ Monit Assess (2010) 164:101110 Fig. 1 Map of the city of Istanbul and the study area showing the sampling locations

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road pavement, while soil samples were collected within 1-m distance from the edge of the pavement. Surface soil samples were taken from the top 02 cm of soil, while the subsurface (20-cm depth) samples were from collected from depths of 1921 cm. From the 21 locations next to the secondary roads (side roads having at most four lanes and low speed, light trafc), only surface soil samples (02 cm, n = 21) were taken within 1-m distance from the end of the pavement. All samples were taken and processed as duplicates. Soil samples were taken without disturbing the soil with a specially manufactured sampling device consisting of a piston inside a steel cylinder. The device was driven into the soil with the help of a hammer, and the sample was removed from the cylinder by the piston with minimal disturbance to protect the soil prole. Dust samples were col-

lected by using a brush and a shovel. All samples were preserved in sealed plastic bags until the time of analysis. Metal content EPA Method 3050B (USEPA 1996) was used for the analysis of the collected dust and soil samples. According to the procedure, samples were dried, crushed, and sieved (sieve size 2 mm) before the analysis. Acid digestions of samples were performed with HNO3 and HCl. The recovery rates of metals for the method are reported in the protocol as 97% for Pb, 99% for Zn, and 94% for Cu (USEPA 1996). Digestates were ltered and heavy metal concentrations in digested samples were determined by using a ame atomic absorption spectrophotometer device (Perkin Elmer

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AAnalyst). All samples were analyzed in duplicates. Detection limit for Pb, Zn, and Cu for atomic absorption spectrophotometry device was 1.5 g/L. The relative standard deviation values for the duplicate samples were below 15% (13.3% for Pb, 14.2% for Zn, and 6.7% for Cu, for samples from the highways; 3.3% for Pb, 2.1% for Zn, and 4.6% for Cu, for samples from secondary roads). Statistical analysis To evaluate the heavy metal pollution, statistical analysis of the Pb, Zn, and Cu concentration data in dust, surface soils, and 20-cm depth soils was performed. The analysis included the descriptive statistics for the three datasets and correlations of co-located metal concentrations to assess the signicance of vehicular trafc on heavy metal pollution of urban soils and to assess the relative vertical transport of the different metals. The spatial variability of the surface soil data was analyzed using a modied ordinary kriging algorithm. Ordinary kriging is a linear spatial interpolator that estimates spatial data at unsampled locations using a linear weight function of adjacent data points (Cressie 1990). The weights are compared based on the semi-variogram function which is a measure of the spatial variability of the data as a function of distance. The geostatistical program used to compute the semi-variogram and perform the ordinary kriging is GSLIB (Deutsch and Journel 1998) which is extensively used in soil pollution, mining and groundwater problems. Because the observed heavy metal concentration data may show multimodality due to differences in trafc loads, using the entire data set from the highways and secondary roads jointly in kriging may lead to inaccurate results. To overcome this, an indicator function was incorporated into the ordinary kriging. The surface pollution data were divided into two subsets and separate semivariograms were computed for each. The following indicator function was dened: I(x, y) = 1 If the unsampled location (x, y) and the data point are within the same subset (i.e., both along the highways or both near secondary roads)

I(x, y) = 0

If the unsampled location (x, y) and the data point are not within the same subset

The modied ordinary kriging equation, thus, becomes


n

C (x, y) =
i=1

i C (xi , yi ) I (xi , yi )

(1)

Where C(x, y) is the estimated concentration at any location, i is the weight for a given location, C(xi , yi ) is the concentration, and I(xi , yi ) is the value of indicator function (equal to 0 or 1). The rst subset in this study is included in the 50-m wide zone from either side of the highways (Fig. 1), where extensive pollution due to the trafc activity is expected to occur. The second subset is collected from the rest of the area, which is dominated by a thick web of secondary arterials and streets with less dense trafc.

Results and discussion Statistical characteristics of the heavy metal concentration data The statistical data are presented for the highways and secondary roads separately because of the large differences observed (Table 1). The results show that Pb concentrations in dust and surface soil samples from the highways were signicantly higher than concentrations from the secondary roads. The Pb concentrations in the highway dust and surface soil samples were also elevated compared to the 20-cm depth soil samples from highway soils. The maximum Pb concentration in the dust samples collected along the highways was 1,087 mg/kg of dry soil, observed in the arterial carrying trafc to the rst suspension bridge joining the two districts. The average Pb concentration in highway dust was 177 mg/kg. The highest concentration of Pb in surface soil samples and in the 20-cm depth samples was 1,573 and 302 mg/kg, respectively, with both samples located along the same arterial. The corresponding average Pb concentrations were 191 and 81.2 mg/kg, respectively. These results suggest that the major

Environ Monit Assess (2010) 164:101110 Table 1 Descriptive statistics of metal concentrations data (mg/kg dry soil) Dust samples (highways, n = 20) Avg Max Min Pb Zn Cu 177 245 111 1086 521 299 12.5 87.0 14.0 Surface soil samples (highways, n = 20) Avg Max Min 191 255 68.7 1573 522 136 21.1 93.4 21.4 20-cm depth soil samples (highways, n = 20) Avg Max Min SD 81.2 211 47.0 302 450 94.1 10.1 47.2 12.6 82.7 109 20.7

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SD 230 91.6 75.5

SD 355 120 35.3

Surface soil samples (secondary roads, n = 21) Avg Max Min SD 29.7 96.6 23.4 99.3 155 38.1 8.1 45.2 11.0 25.1 29.1 7.2

pathway for the transport of Pb is through release into the atmosphere, followed by deposition and accumulation of metals in dust form and in surface soils, with limited downwards migration through the top soil. Although the use of leaded gasoline in Turkey has substantially decreased in 1990s and was banned in 2002, Pb concentrations in dust and soil remain high showing the persistence of the Pb in soils. A similar pattern was observed for Zn and Cu concentrations. The highest levels of pollution of Zn were observed in dust and surface soil samples from the highways with very close averages (245 and 255 mg/kg, respectively) and maximum values (521 and 522 mg/kg, respectively). Cu pollution was observed only in some locations along highways, with maximum and average Cu concentrations in the surface soil samples of 136 and 68.7 mg/kg, respectively. These values were higher than the Cu concentrations in the 20-cm depth samples from highways (maximum of 94.1 mg/kg and average of 47.0 mg/kg) and in the surface soils of secondary roads (maximum and average of 38.1 and 23.4 mg/kg, respectively). Similar studies conducted on urban soils from other major cities around the world (Table 2) indicate that heavy metal contamination in soils and highway dusts of urban areas generally exhibits a wide range in the concentration, varying from a few milligrams per kilogram to thousands of
Table 2 Summary of results from other selected studies Location Population Details

milligrams per kilogram and that the heavy metal concentrations observed for Istanbul are comparable to that of other cities. While the Pb values in Istanbul are higher than all other urban areas (except Naples), the Zn and Cu concentrations are generally at the lower end. It is important to note that several factors inuence heavy metal concentration including population, trafc density, quality of the fuel used, proximity of the sampling location to the road, and type of the sample. Bimodal distribution of heavy metal concentration data Preliminary inspection of the surface data collected from the highways and secondary roads suggests that the two sets of data are signicantly different. This is also seen in Fig. 2, which shows the averages (bars inside the boxes), inner quartile ranges (top and bottom of the boxes), and maximum and minimums (the beginning and end of the whiskers) for the different metal concentrations. The results of the independent samples t test showed that the surface data collected from the highways and secondary roads are statistically different (t = 2.023 for Pb, 5.756 for Zn, and 5.635 for Cu; p < 0.05 for Pb, p < 0.01 for Zn and Cu). The data presented in Table 1 with Fig. 2, together with the results from the t test indicate that the metal pollution observed along highways

Pb (mg/kg) Zn (mg/kg)

Cu (mg/kg)

Reference

Istanbul, Turkey 10,018,735 Highway dusts 105.5555.4 190.91852.0 47.251358.5 Sezgin et al. (2003) Galway, Ireland 65,832 Highway surface soils 25543 23656 9271 Zhang (2006) Beijing, China 17,430,000 Urban surface soils 25.5207.5 25.7196.9 24.1457.5 Chen et al. (2005) Hong Kong 6,708,389 Urban surface soils 7.53496 23930 1.30277 Lee et al. (2006) Ibadan, Nigeria 2,550,593 Highway surface soils 205730 43.5213 8.9480.5 Olajire and Ayodele (1997) Naples, Italy 3,082,756 Urban surface soils 43420 302550 6.2286 Imperato et al. (2003)

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Fig. 2 Inner quartile ranges, maximums, and minimums of data from surface samples along highways and secondary roads

and secondary roads represent two statistically different populations, i.e., the data are bimodally distributed. Consequently, it would not be appropriate to consider all the data pooled together for determination of the semi-variogram and kriging. To address this issue, an indicator function is incorporated into the geostatistical evaluation of the data as previously described. Correlations between metal concentrations The Pearson correlations analysis (n = 20 for highways, n = 21 for secondary roads) indicate that Pb, Zn, and Cu dust concentrations are strongly correlated (r = 0.820 for PbZn, 0.693 for PbCu, and 0.605 for ZnCu couple; p < 0.05) which is an indicator that the metals in the soils may have originated from a common source. Among the surface data for the different metals,

there is also strong correlation between Pb and Zn (r = 0.746, p < 0.05) and between Zn and Cu (r = 0.735, p < 0.05) and a slightly lower correlation for Pb and Cu (r = 0.567, p < 0.05) which means these pollutants accumulate in a similar pattern within the soil surface. For the soil samples from 20-cm depth, only a strong correlation exists between Pb and Zn (r = 0.810, p < 0.05), while correlations of PbCu and ZnCu are weak (r = 0.210 and 0.302, respectively; p < 0.05). The Pearson correlations between metal concentrations determined from the samples collected from secondary roads are calculated as 0.424 for PbZn, 0.450 for PbCu, and 0.678 for ZnCu couples ( p < 0.05). These results show a moderate correlation between Pb, Zn, and Cu for surface soil samples. In comparison, these correlations are slightly weaker than the ones found for surface soil samples from highways.

Table 3 Correlations of metal concentrations across different media (dust and surface and 20-cm soils) along highways Soil samples (surface; n = 20) Pb Zn Cu Dust samples (n = 20) Pb Zn 0.957 0.663 0.540 0.716 0.580 0.478 Cu 0.688 0.497 0.366 Soil samples (20-cm depth; n = 20) Pb Zn Cu 0.846 0.869 0.677 0.649 0.937 0.745 0.045 0.273 0.698

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To statistically evaluate the extent of dust deposition and vertical prole of the metal concentrations in soils, Pearson correlations between metal concentrations observed across different media (dust, surface soil, and 20-cm depth soil samples) observed along the highways were computed and presented in Table 3. Metals in dust samples correlated moderately to very strongly to the surface soils, suggesting that there may be a common

source of contamination within the study area. Concentration of metals in surface soils and 20-cm depth soils were also strongly correlated, although the levels of contamination are much lower in the deeper soils. This indicates that surface contamination is the source of contamination of the deeper soils but that metal transport is a very slow process since the soils around highways has been exposed to the contamination for a long time.

Fig. 3 Semi-variograms of the heavy metal surface data

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Geostatistical analysis The raw semi-variogram was determined using eight lags with a lag distance of 2.5 km, and a tolerance of 2 km was selected. An exponential model was used to t the raw semi-variogram:
h = 2 1 e( I )

(2)

Where is semi-variogram function, 2 is variance, h is the separation distance, and I is characteristic length parameter. The best t semivariogram model was determined by minimizing the squared sum of differences between the model and raw data. The raw semi-variograms along with the best t exponential curves are given in Fig. 3. The semi-variogram parameters are shown in Table 4. The results of ordinary kriging with the indicator function described in Materials and methods Section are given in Figs. 4, 5, and 6 for Pb, Zn, and Cu, respectively, based on the surface soils concentration data. These gures show the differences between the metal concentrations near highways and secondary roads. Due to the large variation of Pb concentrations in soils near highways roads and secondary roads, a logarithmic scale was used for better representation. A linear scale was used in the graphs for Zn and Cu. The overall results clearly exhibit the difference between concentrations of metals near the highways and the secondary roads. All three maps for metals of Pb, Zn, and Cu showed similar patterns of distribution, which is also an indicator of a common pollution source for these metals. For the highways, the highest concentrations were observed near the two arterials (upper left portion of the study area) carrying trafc to the two suspension bridges that join the European
Table 4 Best-t semi-variogram model parameters Variable Pb (Highways) Zn (Highways) Cu (Highways) Pb (Secondary roads) Zn (Secondary roads) Cu (Secondary roads) Nugget (ppm2 ) 0 9000 750 0 0 26.2 2 (ppm2 ) 119,819 13,681 1,183 602 804 49.8 I (km) 2.330 1.920 1.224 3.459 2.656 2.440

Fig. 4 Distribution of Pb in surface soils

and Asian portions of the city (see Fig. 1). Also the arterials and conjunctions close to these roads showed higher pollution values compared to other locations within the study area. For the areas around the secondary roads, elevated concentrations of Pb near the zone around the two arterials

Fig. 5 Distribution of Zn in surface soils

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Fig. 6 Distribution of Cu in surface soils

to the bridges was apparent. The reason for these elevated concentrations can be attributed to the increased trafc activity in the secondary roads connecting to the highways. Although the industrial activity within the Anatolian district of the city is mostly located in the eastern part of the study area, heavy metal levels in the soils of these regions were among the lowest. This indicates that these industrial areas are not a signicant source of heavy metal pollution. Therefore, it is concluded that the trafc activities are the primary source of heavy metal contamination in the study area.

tion between metal concentrations in dust, surface, and 20-cm depth soils indicate the presence of a common pollution source, namely overland transportation activities. The relatively low concentrations of heavy metals in the 20-cm soils (as compared to that observed in the dust and surface soils), coupled with the high correlation coefcients between the data from the different media, indicate high attenuation of heavy metals within the soil environment. Statistical testing of the data near the highways and the secondary roads showed that the two data sets are statistically distinct, which can be attributed to the fact that overland transportation within the study area is the main source of metal pollution in surface and near surface soils and pollution tends to be limited to short distance on either side of the roads. Because of the bimodality of the data collected along highways and along the secondary roads, indicator-based ordinary kriging was used to generate maps of the spatial variability of the heavy metal concentration, which showed that the highest levels of pollution were located near the arterials and conjunctions close to the two suspension bridges that connect the two districts of the city. Lower heavy metal concentrations were observed within the industrial zones located in the eastern portions of the city. These results show that overland trafc remains the main source of heavy metal pollution within the dust and urban soils of the city of Istanbul.
Acknowledgements The authors acknowledge the nancial support provided by Bogazici University Research Fund (Project No: 07Y101D).

Conclusions In this study, concentration data of selected heavy metals (Pb, Zn, and Cu) in dust, surface, and subsurface (20-cm depth) soils within the Asian district of Istanbul, Turkey were statistically analyzed to assess the impact of overland trafc on observed heavy metal levels. The data collected from 41 sampling points located throughout the study area showed extensive metal pollution in dust and surface soil samples near the highways compared to 20-cm depth soils and soils adjacent to secondary roads. The high levels of correlaReferences
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