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Environmental Pollution 154 (2008) 254e263

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Heavy metal (Cu, Zn, Cd and Pb) contamination of vegetables

in urban India: A case study in Varanasi
Rajesh Kumar Sharma a, Madhoolika Agrawal a,*, Fiona M. Marshall b
a
Ecology Research Laboratory, Department of Botany, Banaras Hindu University, Varanasi 221005, India
b
SPRU, Freeman Centre, University of Sussex, Brighton, BN1 9QE, United Kingdom
Received 12 January 2007; received in revised form 26 September 2007; accepted 7 October 2007

Atmospheric depositions can significantly increase the heavy metal concentrations in vegetables during marketing.

Abstract

The contributions of heavy metals in selected vegetables through atmospheric deposition were quantified in an urban area of India. Depo-
sition rate of Zn was recorded maximum followed by Cu, Cd and Pb. The concentrations of Zn and Cu were highest in Brassica oleracea, Cd in
Abelmoschus esculentus and B. oleracea, while Pb was highest in Beta vulgaris. Heavy metal pollution index showed that B. oleracea was max-
imally contaminated with heavy metals followed by A. esculentus and then B. vulgaris. The results of washing showed that atmospheric depo-
sition has contributed to the increased levels of heavy metals in vegetables. Both Cu and Cd posed health risk to local population via test
vegetables consumption, whereas Pb posed the same only through B. oleracea. The study concludes that atmospheric depositions can elevate
the levels of heavy metals in vegetables during marketing having potential health hazards to consumers.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Atmospheric depositions; Heavy metals; Vegetables; Health risk; Heavy metal pollution index

1. Introduction The uptake and bioaccumulation of heavy metals in vegeta-

The contamination of vegetables with heavy metals due to
soil and atmospheric contamination poses a threat to its quality
and safety. Dietary intake of heavy metals also poses risk to
animals and human health. Heavy metals such as Cd and Pb
have been shown to have carcinogenic effects (Trichopoulos,
1997). High concentrations of heavy metals (Cu, Cd and Pb)
in fruits and vegetables were related to high prevalence of up-
per gastrointerestinal cancer (Turkdogan et al., 2002). For
most of the people, the main route of exposure to heavy metals
is through the diet except occupational exposures at related in-
dustries. Regulations have been set up in many countries and
for different industrial set up to control the emission of heavy
metals.
* Corresponding author. Tel.: þ91 542 2368156; fax: þ91 542 2368174.
E-mail address: madhoo58@yahoo.com (M. Agrawal).
bles are influenced by a number of factors such as climate, at-
mospheric depositions, the concentrations of heavy metals in
soil, the nature of soil on which the vegetables are grown
and the degree of maturity of the plants at the time of harvest
(Lake et al., 1984; Scott et al., 1996; Voutsa et al., 1996). Air
pollution may pose a threat to post-harvest vegetables during
transportation and marketing, causing elevated levels of heavy
metals in vegetables (Agrawal, 2003). Elevated levels of heavy
metals in vegetables are reported from the areas having long-
term uses of treated or untreated wastewater (Sinha et al.,
2004, 2005; Sharma et al., 2006, 2007). Other anthropogenic
sources of heavy metals include the addition of manures, sew-
age sludge, fertilizers and pesticides, which may affect the up-
take of heavy metals by modifying the physico-chemical
properties of the soil such as pH, organic matter and bioavail-
ability of heavy metals in the soil. Whatmuff (2002) and
McBride (2003) found that increasing concentrations of heavy
metals in soil increased the crop uptake.

0269-7491/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envpol.2007.10.010
 R.K. Sharma et al. / Environmental Pollution 154 (2008) 254e263 255

Cultivation areas near highways are also exposed to atmo- infrequent premonsoon rains. Rainy season starts with onset of heavy monsoon
spheric pollution in the form of metal containing aerosols. towards the end of June and continue till mid October, ending up with 90%
annual rainfall within 4 months. During rainy season, the temperature varies
These aerosols can be deposited on soil and are absorbed by from a minimum of 24  C to a maximum of 36  C and relative humidity
vegetables, or alternatively deposited on leaves and fruits from 70 to 95%. During winter, the temperature ranges between 10 and
and then absorbed. Voutsa et al. (1996) have reported high ac- 25  C, relative humidity between 40 and 79% and occasional light rains are
cumulation of Pb, Cr and Cd in leafy vegetables due to atmo- received from retreating monsoons. January and June are the coldest and hot-
spheric depositions. Field studies have found positive test month, respectively, of the year. The predominant wind direction during
the study period was WeNW and the wind speed varied from 0.8 to
relationships between atmospheric metal deposition and ele- 8.8 km hr1 during the study period.
vated concentrations of heavy metals in plants and top soil Varanasi is one of the most densely populated cities of India. There are sev-
(Larsen et al., 1992; Sanchez-Camazano et al., 1994). The eral small scale industries dispersed in industrial areas of Shivpur, Chandpur,
levels of heavy metals in vegetables collected from peri-urban Maruadih, Lahartara and Diesel Locomotive Works. A number of brick indus-
areas of New Delhi were found to be high due to atmospheric tries are also located at the periphery of the city. Heavy traffic on narrow roads
leading to frequent traffic congestion is of common occurrence within the city.
deposition as well as due to use of contaminated water. The A reconnaissance survey was conducted to evaluate the land use, types of
magnitude of heavy metal deposition on vegetable surfaces market, traffic flow and consumption of vegetables grown locally prior to site
varied with morpho-physiological nature of the vegetables selection for collections of atmospheric bulk deposition and vegetable sam-
(Singh and Kumar, 2006). Jassir et al. (2005) have shown ples. The city was divided into 40 grids of 1 km2 and then 20 sampling loca-
that unwashed leafy vegetables sold on roadside of Riyadh tions were selected where vegetables grown in nearby peri-urban production
sites, are sold. These sampling locations were categorized into three groups
city, Saudi Arabia had higher levels of heavy metals as com- based on the types of market i.e. wholesale, retailer and vender. In the present
pared to washed leafy vegetables. Demirezen and Aksoy study, 55, 25 and 20% of the sampling locations represent retailer, wholesale
(2006) have reported higher concentrations of Pb, Cd and and vender markets, respectively. The magnitude of urban activities such as
Cu in Abelmoschus esculentus collected from urban areas of industrial, residential and commercial and vehicular density also varied be-
Kayseri, Turkey as compared to those from rural areas. The tween the sampling locations. The characteristics and relative position of sam-
pling locations are shown in Table 1 and Fig. 1, respectively.
partitioning of heavy metals is well known, with accumulation The common vegetables grown in the peri-urban areas of Varanasi and sold
of greater concentrations in the edible portions of leafy or root to the local markets exclusively are palak (Beta vulgaris L. var benghalensis cv
crops than the storage organs or fruits (Jinadasa et al., 1997; all green H1 Family: Chenopodiaceae), lady’s finger (A. esculentus L. Family:
Lehoczky et al., 1998; Sharma and Agrawal, 2006). Malvaceae), cauliflower (Brassica oleracea var botrytis Family: Brassicaceae),
Urban activities may significantly contribute to elevated cabbage (B. oleracea var capitata Family: Brassicaceae), tomato (Lycopersicon
esculentum Miller Family: Solanaceae) and radish (Raphanus sativus L. Fam-
heavy metal loads in atmospheric deposits and consequently ily: Brassicaceae). Other vegetables are mostly supplied from other areas of
in the edible portion of the vegetables. Thus the present study the country. These vegetables are covered with polyethylene sheets during
was conducted with the objectives (1) to quantify the levels of the transport from the production to market sites, but are exposed to urban
heavy metal (Cu, Zn, Cd and Pb) contamination in edible por-
tions of vegetables; (2) deposition rates of heavy metals Table 1
Characteristics of market sampling sites located in the urban area of Varanasi
through atmosphere; (3) to assess the health risk in urban in-
habitants via consumption of vegetables; (4) to assess the Serial no. Study sites Type of markets Land uses
heavy metal pollution index for comparison of total heavy 1 ShiD4 Retailer DPRA, HT, NIA
metal load at different sampling locations and (5) computation 2 LalG4 Wholesale DPRA, HT, NIA
3 NadF6 Retailer DPRA, HT
of relationships between the deposition rates and the concen-
4 AnaG7 Vender DPRA, HT, CA
trations of heavy metals in the vegetables to find out the con- 5 VisI7 Wholesale DPRA, HT, CA
tribution of atmospheric depositions to the levels of heavy 6 KasK7 Retailer SPRA, LT
metal contamination. A community acceptable technique of 7 LahE8 Vender DPRA, HT, NIA
washing the vegetables was also explored to quantify the at- 8 KabH8 Vender DPRA, HT, CA
9 ChanC9 Retailer DPRA, HT, CA, IIA
mospheric input of heavy metals through depositions. Pro-
10 RatG9 Retailer DPRA, HT, CA
duced data from this study would be helpful in formulation 11 DasI9 Wholesale DPRA, LT
of policies and programmes, in which food quality and its 12 MdcE10 Retailer DPRA, LT, NIA
safety could be prevented from the threats of heavy metal 13 KamG10 Retailer DPRA, HT, CA
contamination. 14 LakE11 Retailer DPRA, LT, NIA
15 SunF12 Wholesale DPRA, HT, CA
16 DlwC12 Retailer SPRA, LT, IIA
2. Materials and methods 17 KndG12 Retailer DPRA, HT, CA
18 KarF13 Retailer DPRA, LT, CA
2.1. Study area and sampling locations 19 ChaF8 Wholesale DPRA, HT
20 LanH12 Vender DPRA, HT
The present study was carried out from March 2003 to February 2004 in DPRA ¼ densely populated residential area.
the urban areas of Varanasi, located (lat 25 180 N, long 83 010 E and alt NIA ¼ near industrial area.
76.19 m) in the eastern Gangetic plains of India. The climate of the region HT ¼ heavy traffic.
is dry tropical with three distinct seasons i.e. summer, rainy and winter. The CA ¼ commercial area.
summer season (MarcheJune) in Varanasi is usually dry, associated with SPRA ¼ sparsely populated residential area.
strong hot winds, high temperature during the day ranging from a minimum LT ¼ low traffic.
of 30  C to a maximum of 45  C, relative humidity from 25 to 45% and IIA ¼ in industrial area.
256 R.K. Sharma et al. / Environmental Pollution 154 (2008) 254e263
Fig. 1. Map showing the relative position of sampling locations.
atmosphere at the time of marketing. The selected vegetables (B. vulgaris, A.
esculentus and B. oleracea) for the present study are morphologically different
from each other. B. vulgaris is a leafy vegetable with large leaf area, smooth
leaf surface and sold in the market in the form of compact bundles, therefore
less chances of post-harvest contamination. A. esculentus is a fruit vegetable
having hairy ridged and rough surface area more vulnerable to particulate de-
position. B. oleracea is an inflorescence having large exposed rough surface
area. Both A. esculentus and B. oleracea are kept open in big baskets during
marketing, therefore more in contact with urban atmospheric depositions.
2.2. Sampling and pre-treatment
Samples of edible portions of vegetables (2 kg each of B. vulgaris and
A. esculentus and 1 unit of B. oleracea) were collected from three different
outlets in each market locations. The samples were collected once in a month
between March 2003 and February 2004 for B. vulgaris, between March and
November 2003 for A. esculentus and between October 2003 and February
2004 for B. oleracea. Samples were kept in pre-distilled water rinsed polyeth-
ylene bags and pined up to avoid the excess deposition. Then the samples were
brought back to laboratory, chopped into small pieces and oven dried at 80  C
till the constant weight was achieved.
To assess the effects of washings on the removal of heavy metals from the
vegetable surfaces, samples of vegetables (4 kg each of B. vulgaris and
A. esculentus and 2 units of B. oleracea) were collected from selected sam-
pling locations (KabH8, ChanC9, RatG9, LanH12 and ChaF8). The samples
of each sampling location were separately divided into two groups. First group
was kept as such for oven drying, whereas other group was washed with clean
tap water according to the normal household technique. After draining the ex-
cess water samples were chopped into small pieces and oven dried at 80  C till
the constant weight was achieved. The dry vegetable samples were powdered
with a stainless steel blender and passed through a 2 mm size sieve. The sam-
ples were then kept at room temperature for further analysis.
Bulk atmospheric depositions (wet þ dry) were collected on monthly basis
using a stainless steel funnel of 30 cm diameter fitted on polyethylene bottle
previously rinsed with deionised water from March 2003 to February 2004
from 18 market sampling locations (Serial no.: 1e18; Table 1) using the
method described by Singh and Agrawal (2005). At locations LanH12 and
ChaF8, bulk deposition measurements could not be performed due to spoilage
of collection units.
2.3. Analytical procedure for heavy metal analysis
Tri-acid mixture, 15 ml (70% high purity HNO3, 65% HClO4 and 70%
H2SO4; 5:1:1) were added to the beaker containing atmospheric deposits and
heated at 80  C till the solution became transparent (Allen et al., 1986). The re-
sulting solution was cooled and filtered through Whatman no. 42 filter paper. The
filtered solution was finally maintained to 50 ml using deionised water and kept
at room temperature for further analysis of heavy metals. For the heavy metal
analysis of dry vegetable, 1 g sample was taken into a 100 ml acid washed beaker
and 15 ml of tri-acid mixture was added (Allen et al., 1986). The mixture was
 R.K. Sharma et al. / Environmental Pollution 154 (2008) 254e263 257

then digested at 80  C till the transparent solution was achieved. After cooling, 2.5.4. Heavy metal pollution index (HPI)
the digested samples were filtered using Whatman no. 42 filter paper and the To compare the total heavy metal load through vegetables or atmospheric
filtrate was diluted to 50 ml with deionised water. depositions at different sampling locations, heavy metal pollution index (HPI)
Determination of the heavy metals such as Cu, Zn, Cd and Pb in the filtrate was calculated using the equation given by Usero et al. (1997).
of vegetables and atmospheric deposits was achieved by atomic absorption
spectrophotometer (Model 2380 PerkineElmer Inc., Norwalk, CT, USA).
The instrument was calibrated using manually prepared standard solution of HPI ¼ ðCf 1  Cf 2  Cf 3  /  Cf n Þ1=n
respective heavy metals. General purpose reagent cadmium nitrate of a mini-
mum purity of 99% was used in the preparation of the solution used to spike where Cf is the concentration of n heavy metals in vegetable samples or atmo-
the samples for Cd. An analytical grade of a nitrate salt of Pb and granules of spheric depositions.
Cu and Zn were used in the preparation of solutions used in the spiking of
samples for Pb, Cu and Zn. Acetylene gas was used as the fuel and air as
the support. An oxidizing flame was used in all cases. Table 2 shows different
parameters at which the instrument was set for each metal.
2.6. Statistical analyses

Mean, median and range were calculated using statistical package, SPSS
2.4. Quality assurance 11.0 (SPSS USA). Linear regression analysis was used to compute the rela-
tionships between the deposition rate and the concentrations of heavy metals
Blanks (5% tri-acid mixture) and quality control standards were measured in edible portions of different vegetables.
at every five samples to detect contamination and drift. The elemental concen-
trations of procedural blanks were generally <5% of the mean analyte concen-
trations for all the metals. Precision and accuracy of analyses were also 3. Results
ensured through replicate analyses of samples against standards reference ma-
terial (SRM-1570) of National Institute of Standard and Technology for all the
3.1. Deposition rate of heavy metals
heavy metals. The results were found to be within 2% of certified values.

2.5. Data analyses

2.5.1. Calculation of atmospheric deposition rate of heavy metals
To calculate the daily atmospheric depositions of heavy metals per unit area
(mg m2 d1), the measured heavy metal concentrations in the solution (HM) in
mg l1 was divided by the number of sampling days (n), exposed to the ambient
environment and cross sectional sampling area of the jar [A (pr2)] in m2.

HM
Deposition rat mg m2 d1 ¼
½A  n
Site wise variations in deposition rates of heavy metals
along with heavy metal pollution index (HPI) are presented
in Table 3. The deposition rate of Cu, Zn, Cd and Pb
(mg m2 d1) ranged from 4.19 to 38.93, 20.0 to 372.0, 0.32
to 11.33 and not detected to 11.67, respectively, during the
study period. HPI showed maximum value at ChanC9 (3.84)
and minimum at LakE11 and KndG12 (2.64). The deposition
rate of Zn was highest followed by Cu, Cd and Pb.

2.5.2. Calculation of daily intake of heavy metals from vegetable surfaces Table 3
deposits Atmospheric deposition rates of heavy metals (mg m2 d1) and heavy metal
The daily intake of heavy metals from vegetable surface atmospheric de- pollution index (HPI)
posits via consumption of unwashed vegetables was calculated by multiplying Sites ID Heavy metals HPI
daily vegetable consumption rate (mg person1 d1) with mean atmospheric
Cu Zn Cd Pb
depositions on vegetable surfaces. Daily vegetable consumption was obtained
from survey conducted in the study area. Mean atmospheric deposits on veg- ShiD4a 18.80 159.06 4.13 4.80 3.63
etable surfaces were obtained by subtracting mean concentrations of heavy LalG4 18.54 74.12 3.54 5.22 3.35
metals in washed from that of unwashed vegetables. NadF6 19.30 227.62 3.36 2.75 3.50
AnaG7 15.88 219.27 5.34 2.37 3.53
2.5.3. Calculation of health risk index of heavy metal contamination VisI7 20.70 185.80 4.31 2.18 3.46
The health risk index was calculated as the ratio of estimated exposure due KasK7 18.71 169.67 4.68 2.35 3.45
to daily heavy metal intake through vegetables and reference dose oral (RfDo, LahE8 20.51 169.94 5.39 2.69 3.57
U.S. Environmental Protection Agency (USEPA), 2002; Cui et al., 2004). Es- KabH8 23.37 207.31 5.24 3.29 3.74
timated exposure is obtained by dividing vegetable consumption rate  mean ChanC9 25.38 225.01 5.91 3.40 3.84
heavy metal concentrations in unwashed vegetables by safe limit of heavy RatG9 18.29 213.58 5.48 2.95 3.65
metals (Indian standard; Awashthi, 2000). An index more than 1 is considered DasI9 17.63 222.35 3.60 2.27 3.42
as not safe for human health. MdcE10 15.05 90.23 4.87 2.55 3.21
KamG10 14.74 89.09 3.24 2.19 3.02
LakE11 11.27 68.09 2.23 1.59 2.61
Table 2
SunF12 18.19 111.23 2.12 2.77 3.10
Wavelength and detection limits of each heavy metal measured by Atomic
DlwC12 19.39 59.96 1.73 2.17 2.77
Absorption Spectrophotometers (Model 2380 PerkineElmer Inc., Norwalk,
KndG12 15.99 44.15 1.91 2.00 2.61
CT, USA)
KarF13 20.47 59.63 1.92 1.27 2.64
Element Wavelength (nm) Detection limits
Meanb 18.45 144.23 3.83 2.17
(mg ml1)
Median 18.65 138.71 3.55 2.26
Cadmium 288.8 0.0005 Range 4.19e38.93 20.00e372.00 0.32e11.33 nde11.67
Copper 324.8 0.001
nd ¼ Not detected.
Lead 213.3 0.01 a
Number of samples collected from each site in a year (n ¼ 12).
Zinc 213.9 0.0008 b
Total number of samples (n ¼ 216).
258 R.K. Sharma et al. / Environmental Pollution 154 (2008) 254e263

Table 4 Table 5
Heavy metal concentrations (mg g1 dry weight) and heavy metal pollution Heavy metal concentrations (mg g1 dry weight) and heavy metal pollution
index (HPI) of B. vulgaris index (HPI) of A. esculentus
Sites ID Heavy metals HPI Sites ID Heavy metals HPI
Cu Zn Cd Pb Cu Zn Cd Pb
ShiD4a 34.32 59.51 2.50 1.69 2.99 ShiD4a 55.90 93.62 1.71 1.52 3.14
LalG4 34.64 59.35 1.83 1.60 2.87 LalG4 41.19 76.59 3.02 1.49 3.16
NadF6 35.08 64.87 1.72 1.24 2.80 NadF6 34.28 68.43 1.46 1.23 2.75
AnaG7 29.15 58.40 3.13 1.42 2.95 AnaG7 27.02 58.98 2.18 1.23 2.76
VisI7 28.82 55.70 1.49 1.63 2.73 VisI7 26.67 94.39 2.41 1.11 2.91
KasK7 29.14 53.58 2.03 1.54 2.80 KasK7 28.44 79.80 2.64 1.25 2.94
LahE8 37.09 73.86 1.94 1.74 3.01 LahE8 37.67 70.40 2.07 1.19 2.90
KabH8 27.08 51.05 1.92 1.52 2.74 KabH8 42.24 84.34 3.30 1.59 3.25
ChanC9 34.90 77.88 3.67 1.58 3.19 ChanC9 23.91 51.77 3.90 1.72 2.98
RatG9 27.68 56.88 1.93 1.43 2.76 RatG9 31.11 55.73 2.86 1.73 2.99
DasI9 35.25 55.01 1.58 1.30 2.73 DasI9 21.03 91.39 1.82 1.28 2.77
MdcE10 35.25 71.57 1.87 1.54 2.93 MdcE10 43.76 74.40 1.84 1.51 3.01
KamG10 42.18 49.68 1.63 1.55 2.83 KamG10 55.90 74.09 1.24 1.19 2.88
LakE11 27.65 50.48 1.63 1.50 2.68 LakE11 25.87 86.03 1.64 1.22 2.77
SunF12 26.45 63.42 1.46 1.36 2.68 SunF12 31.32 81.76 1.60 1.48 2.87
DlwC12 23.58 61.57 1.68 1.69 2.75 DlwC12 20.40 72.79 1.67 1.31 2.67
KndG12 22.66 56.55 1.71 1.58 2.69 KndG12 22.90 95.99 1.24 1.27 2.69
KarF13 20.64 54.38 1.45 1.67 2.61 KarF13 19.78 79.66 1.00 1.15 2.48
Meanb 30.64 59.61 1.95 1.53 2.82 Meanb 32.74 77.20 2.08 1.36 2.88
Median 27.80 51.20 1.60 1.40 Median 24.95 65.25 1.60 1.20
Range 15.20e96.20 30.10e163.20 0.10e11.20 0.80e2.90 Range 10.00e111.20 29.20e189.10 0.40e9.20 0.50e3.10
Safe limitc 30 50 1.5 2.5 Safe limitc 30 50 1.5 2.5
Safe limitd 40 60 0.3 5 Safe limitd 40 60 0.3 5
a a
Number of samples collected from each site in a year (n ¼ 36). Number of samples collected from each site in a year (n ¼ 27).
b b
Total number of samples (n ¼ 648). Total number of samples (n ¼ 486).
c c
Indian standard (Awashthi, 2000). Indian standard (Awashthi, 2000).
d d
FAO/WHO standard (Codex Alimentarius Commission, 1984). FAO/WHO standard (Codex Alimentarius Commission, 1984).

3.2. Heavy metal concentrations in vegetables 3.4. The risk index for local population

The concentrations of Cu, Zn, Cd and Pb and HPI of B.
vulgaris, A. esculentus and B. oleracea are given in Tables
4e6, respectively. The mean concentrations of heavy metals
were highest for Zn, followed by Cu, Cd and Pb. Among the
vegetables, mean concentrations of Zn and Cu were highest
in B. oleracea but mean Cd concentration was highest both
in A. esculentus and B. oleracea. Mean Pb concentration
was highest in B. vulgaris. The maximum value of HPI
was recorded at ChanC9 for B. vulgaris, at KabH8 for A. es-
culentus and at VisI7 for B. oleracea, whereas minimum
values of HPI for all the vegetables were observed at
KarF13 (Tables 4e6).
3.3. Human exposure to heavy metals through
atmospheric deposition on vegetable surfaces
Washing of vegetables reduced the concentrations of heavy
metals (Table 7). Concentrations of Cu and Pb reduced maxi-
mally due to washing in B. oleracea, whereas concentrations
of Zn and Cd reduced maximally in A. esculentus among the
vegetables. Daily intake of heavy metals through atmospheric
deposition via consumption of vegetables was found maxi-
mum for B. oleracea followed by A. esculentus and then
B. vulgaris (Fig. 2).
Estimated exposure and risk index due to heavy metal con-
tamination of vegetables to local population were given in
Table 8. Cd and Cu contamination posed risk to local popula-
tion through vegetable consumption. The risks from Cd
and Cu due to consumption of vegetables were higher for
B. oleracea followed by A. esculentus and least for B. vulgaris.
Intake of Pb through consumption of B. oleracea also posed
risk to local population. Zn intake through these vegetables,
however, did not pose any risk to local population.
4. Discussion
Peri-urban and urban areas of developing countries often
receive atmospheric depositions of heavy metals resulted in
contamination of fresh vegetables at the time of transportation
and marketing. Consumption of contaminated vegetables may
pose risk to human health. Heavy metals determined in differ-
ent vegetables showed that the concentrations of Cu, Zn and
Cd have often exceeded the safe limits of both Indian (Awash-
thi, 2000) and FAO/WHO (Codex Alimentarius Commission,
1984) standards. Pb concentration, however, did not exceed
the safe limit in any of the test vegetable. Exceedence of
safe limits was highest for B. oleracea, where 89% of the sam-
pling locations showed Cd safe limit exceedence of Indian and
 R.K. Sharma et al. / Environmental Pollution 154 (2008) 254e263 259

Table 6 concentrations of all the heavy metals in vegetables were re-

Heavy metal concentrations (mg g1 dry weight) and heavy metal pollution corded maximum at the sampling locations which are located ei-
index (HPI) of B. oleracea
ther in or near industrial areas such as ChanC9, ShiD4, LahE8
Sites ID Heavy metals HPI and LakE11 and at densely populated residential areas having
Cu Zn Cd Pb heavy traffic load i.e. KamG10, KabH8 and RatG9. The concen-
ShiD4a 46.86 86.76 2.08 1.30 3.07 tration of Cu (mg g1 dry weight) was found maximum in A. es-
LalG4 34.24 67.26 1.98 1.30 2.87 culentus (55.90) followed by B. oleracea (53.34) and B. vulgaris
NadF6 35.66 72.68 2.18 1.54 2.99 (42.18) at KamG10 which a retailer market situated in an area is
AnaG7 32.10 63.20 1.96 1.54 2.88
VisI7 44.26 100.68 2.50 1.30 3.16
having high population density and heavy traffic load.
KasK7 29.56 96.66 2.50 1.50 3.06 The results of linear regression analysis further showed that
LahE8 36.92 67.44 2.56 1.52 3.03 the deposition rate of Cu significantly influenced the level of
KabH8 39.00 67.64 3.08 1.30 3.06 Cu in B. vulgaris and A. esculentus, whereas the relationship
ChanC9 35.00 62.06 3.04 1.96 3.12 was insignificant in B. oleracea (Fig. 3). This indicated that
RatG9 30.02 57.88 2.34 1.68 2.91
DasI9 47.94 98.90 2.00 1.58 3.17
the increased level of Cu in B. oleracea may also be resulted
MdcE10 37.62 94.32 1.80 1.50 3.03 due to soil contamination, whereas atmospheric depositions
KamG10 53.34 70.28 1.48 1.30 2.93 have a major contribution to the elevated levels of Cu in
LakE11 43.04 102.06 1.60 1.18 2.98 A. esculentus and B. vulgaris. The positive and significant
SunF12 32.02 93.08 1.78 1.24 2.90 relationship between Zn deposition rate and concentration in
DlwC12 28.18 84.80 1.62 1.22 2.79
KndG12 24.90 75.76 1.46 1.38 2.72
B. vulgaris suggests a major contribution of aerial Zn deposi-
KarF13 24.78 68.98 1.52 1.16 2.64 tion in elevating concentrations of Zn in B. vulgaris, whereas
in A. esculentus and B. oleracea elevated Zn levels may have
Meanb 36.41 79.46 2.08 1.42 2.96
Median 34.85 73.20 1.95 1.40 a major contribution from production sites (Fig. 3). Atmo-
Range 20.50e71.20 45.30e141.30 1.10e4.50 0.90e2.20 spheric deposition rate of Cd showed a significant positive
Safe limitc 30 50 1.5 2.5 relationship with Cd concentration in B. vulgaris and B. oler-
Safe limitd 40 60 0.3 5 acea, which suggests that urban atmospheric deposits may be
a
Number of samples collected from each site in a year (n ¼ 15). the major source of Cd contamination in vegetables (Fig. 4).
b
Total number of samples (n ¼ 270). The atmospheric deposition rate of Pb showed a significant
c
Indian standard (Awashthi, 2000).
d negative and positive relationship with its concentration in
FAO/WHO standard (Codex Alimentarius Commission, 1984).
B. vulgaris and A. esculentus, respectively (Fig. 4). This sug-
gests that aerial deposition did not contribute to the Pb concen-
100% of FAO/WHO standards, whereas Cu and Zn showed ex- tration in B. vulgaris, but contributed to A. esculentus.
ceedence at 78 and 28% and 100 and 94% of the sampling lo- Heavy metal pollution index (HPI) was also found maxi-
cations. Cu, Zn and Cd concentrations were above the Indian mum for B. oleracea (HPI ¼ 2.96) followed by A. esculentus
and FAO/WHO standards at 45 and 6%, 94 and 28% and 83 (HPI ¼ 2.88) and B. vulgaris (HPI ¼ 2.82). Highest value of
and 100% of the sampling locations, respectively, in B. vulga- correlation coefficient (R2 ¼ 0.45; p < 0.01) for the relation-
ris, 50 and 28%, 100 and 83% and 78 and 100% of the sam- ship between HPI of deposition rate and B. oleracea suggests
pling locations, respectively, in A. esculentus. that among the test vegetables B. oleracea received maximum
The variations in the concentrations of the heavy metals in heavy metals through urban atmospheric depositions (Fig. 5).
vegetables may be ascribed to the heavy metals concentrations This may be due to higher surface area and direct exposure to
of soil, air and irrigation water of their production sites and urban atmosphere during the marketing. The lowest value of
also to the adsorption of heavy metals from aerial depositions correlation coefficient (R2 ¼ 0.39; p < 0.01) observed between
during transportation and marketing. The data produced in the HPI of deposition rate and B. vulgaris clearly showed lower
present study clearly showed that both the deposition rates and deposition of heavy metals on this plant. B. vulgaris is

Table 7
Effects of washings on heavy metals concentrations in vegetables
Heavy metals Vegetables (mg g1 dry weight)
B. vulgaris A. esculentus B. oleracea
UW W PR UW W PR UW W PR
Cu 38.29  0.94 29.50  0.61 23 13.80  0.30 9.18  0.62 33 41.13  1.33 20.27  0.44 51
Zn 75.23  2.52 47.70  0.75 37 59.05  2.89 28.10  1.99 52 76.89  1.39 54.33  1.08 30
Cd 2.68  0.21 1.53  0.05 43 3.23  0.15 1.01  0.16 68 3.31  0.17 1.31  0.06 60
Pb 2.00  0.04 1.31  0.03 35 1.71  0.06 1.21  0.03 30 1.75  0.05 0.91  0.04 48
UW ¼ unwashed.
W ¼ washed.
PR ¼ percent reduction.
260 R.K. Sharma et al. / Environmental Pollution 154 (2008) 254e263

Fig. 2. Daily intake of heavy metals via atmospheric deposits through vegetables.

commonly sold in form of compact bundles hence lower sur-
face area is available for heavy metal deposition (Fig. 5).
Reduction in heavy metal concentrations in vegetables due
to washing further suggests that atmospheric depositions on
vegetables during marketing are a major source of heavy metal
contamination in urban areas. The percent reductions in heavy
metal concentrations in vegetables at production sites were
less than 10% (data not shown; Agrawal, 2003), whereas the
same at market sites varied from 23 to 68%. The higher mag-
nitude of reductions in heavy metal concentrations at market
sites as compared to production sites clearly depicts that
post-harvest processes such as transportation and marketing
can elevate the levels of heavy metals in vegetables. The per-
cent reductions in heavy metal concentrations due to washing
of vegetables recorded during the present study were lower
than those reported by Singh and Kumar (2006). This can be
attributed to higher levels of atmospheric depositions of heavy
metals in peri-urban areas of Delhi, which is highly industrial-
ized as compared to Varanasi.
The percent reductions in heavy metal concentrations due
to washing were found highest for Zn and Cd in A. esculentus
and Cu and Pb in B. oleracea. Unwashed samples of B. oler-
acea, however, showed maximum concentrations of Cu, Zn
and Cd (Table 7). The order of percent reductions in heavy
metal concentrations due to washing was Cd > Zn > Pb > Cu
in B. vulgaris and A. esculentus and Cd > Cu > Pb > Zn in
B. oleracea, which suggests that maximum contribution
of Cd through atmospheric depositions. Singh and Kumar
(2006) also found that Cu concentrations reduced minimally
upon washing of B. vulgaris and A. esculentus in Delhi. B. vul-
garis and A. esculentus showed highest adsorption efficiency
for Cu, however, B. oleracea showed highest adsorption effi-
ciency for Zn. Singh and Kumar (2006), however, reported
the highest adsorption efficiency for Cd.
In the present study, the mean concentrations of Cu and Pb
(9.18 and 1.21 mg g1, respectively) in A. esculentus were found
lower than the concentrations reported in A. esculentus (37.54
and 10.7 mg g1, respectively for Cu and Pb) collected from
urban areas of Kayseri, Turkey (Demirezen and Aksoy, 2006).
The levels of Cd and Zn (1.01 and 28.10 mg g1, respectively)
were, however, higher in the present study as compared to those
reported in A. esculentus (0.58 and 15.54 mg g1, respectively)
by Demirezen and Aksoy (2006). When the concentrations of
heavy metals in the washed vegetable samples of the present
study were compared with the values of Singh and Kumar
(2006) from Delhi for the same heavy metals in same vegeta-
bles, it was observed that the concentrations of all the heavy
metals were higher in Varanasi as compared to Delhi. This

Table 8
Risk index for daily exposure to heavy metals via vegetables
Heavy metals RfDoa (mg person1 d1) Vegetables
B. vulgaris A. esculentus B. oleracea
Estimated exposure Risk index Estimated exposure Risk index Estimated exposure Risk index
(mg person1 d1) (mg person1 d1) (mg person1 d1)
Cu 4.00E02 4.17E02 1.04Eþ00 1.07E01 2.68Eþ00 2.99E01 7.49Eþ00
Zn 3.00E01 1.60E03 5.40E03 5.00E03 1.86E02 1.31E02 4.36E02
Cd 5.00E04 1.80E03 3.54Eþ00 4.50E03 9.07Eþ00 1.14E02 2.28Eþ01
Pb 3.50E03b 8.00E03 2.36E01 1.80E03 5.08E01 4.40E03 1.33Eþ00
a
U.S. Environmental Protection Agency (USEPA), 2002.
b
JECFA (1993).
 R.K. Sharma et al. / Environmental Pollution 154 (2008) 254e263 261

Fig. 3. Relationships between deposition rates of Cu and Zn and their concentrations in vegetables. (Bv ¼ B. vulgaris, Ae ¼ A. esculentus, Bo ¼ B. oleracea and
Dr ¼ deposition rates, NS ¼ not significant).

suggests that contribution of heavy metals through soils were
higher in Varanasi as compared to Delhi.
To assess the health risk associated with heavy metal con-
tamination of vegetables grown locally, estimated exposure
and risk index were calculated. The results showed that both
Cu and Cd contamination in vegetables had potential to pose
health risk to the local population. Pb, however, may only
pose risk through consumption of B. oleracea. Zn may not
have any risk to the local population through consumption
of these vegetables. Cui et al. (2004) have reported that local
residents of an area near a smelter in Nanning, China have
been exposed to Cd and Pb through consumption of vegetables
but no risk was found for Cu and Zn. From Fig. 2 it is clear
that B. oleracea posed a higher magnitude of threat to the local
population as heavy metal deposition on vegetable surfaces
was higher as compared to B. vulgaris and A. esculentus.
262 R.K. Sharma et al. / Environmental Pollution 154 (2008) 254e263

Fig. 4. Relationships between deposition rates of Cd and Pb and their concentrations in vegetables. (Bv ¼ B. vulgaris, Ae ¼ A. esculentus, Bo ¼ B. oleracea and
Dr ¼ deposition rates, NS ¼ not significant).

5. Conclusions
From this study, it can be concluded that urban activities in
Varanasi have elevated the levels of heavy metals in urban at-
mospheric deposits, which consequently increased the concen-
trations of heavy metals in test vegetables during marketing.
Variations in the magnitude of reductions in heavy metal con-
tamination due to washings of vegetables also depicted the
variations in heavy metal depositions at various market sites.
Vegetables sold in local markets of the city still looking
healthy and fresh, may pose a risk to human health particularly
due to Cu and Cd contamination. Based on HPI data it is clear
that B. oleracea is maximally contaminated with heavy metals
followed by A. esculentus and then B. vulgaris. Among the test
vegetables, B. oleracea can be used to monitor the contribution
of heavy metals through atmosphere. The study suggests that
washing technique can be used as a tool to assess the heavy
metals load in vegetables through atmospheric depositions.
The present study further suggested that to reduce the health
risk, vegetables should be washed properly before consumption
 R.K. Sharma et al. / Environmental Pollution 154 (2008) 254e263
Fig. 5. Relationships between heavy metal pollution index (HPI) of deposition
rates and HPI of vegetables. (Bv ¼ B. vulgaris, Ae ¼ A. esculentus, Bo ¼ B.
oleracea and Dr ¼ deposition rates).
as washing can remove a significant amount of aerial contami-
nation from the vegetable surface.
Acknowledgments
This research work was financially supported by the Depart-
ment for International Development (DFID), United Kingdom
(R7530). We thank the Coordinator, Central Instrumental Labo-
ratory, Department of Botany, BHU, Varanasi for the analyses of
heavy metals. Rajesh Kumar Sharma is thankful to DFID for
providing Junior Research Fellowship and CSIR, New Delhi,
India for providing Senior Research Fellowship.
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