Introduction
Metals found in surface soil derive from rock and
precipitation. Urban areas contain more anthropogenic
metals due to higher population density, traffc intensity,
and proximity to industry. Their long-term deposition
may reduce soil buffering capacity and cause soil and
groundwater contamination [1].
Fruits accumulate soil metals during growth and
processing. As metals are not biodegradable they may
accumulate up the food chain. Although some are
micronutrients, in high concentrations they are toxic [2].
Increased environmental heavy metal concentrations
may lead to increased human intake, causing serious
illness [3-7].
Zinc, copper, iron, chromium and cobalt are essential
and become toxic only in high concentrations, while lead
and cadmium are highly toxic [8-11]. It is thus important
to monitor metals in soil, fruit and fruit products. Many
species of wild fruit used in nutrition and folk medicine
grow in southeast Serbia. Crataegus laevigata L., Cornus
mas L. and Prunus spinosa L. are widely used fresh
and as fruit juices, jams and teas. Their metal contents
must be controlled so they can be used for nutrition and
pharmaceuticals [12].
Fruit and leaves of wild Crataegus laevigata L.,
Cornus mas L. and Prunus spinosa L. from rural
southeast Serbia were analyzed (Table 1). Metals uptake
from soil to leaves and fruit was determined.
Relations among the data were examined by
principal component analysis (PCA) The health risk
index estimates the risk due to exposure.
2. Experimental procedure
2.1. Reagents
All chemicals were of analytical grade. High purity
deionized water (conductivity 0.05 S cm
-1
) was used
in solution preparation. Stock Cu, Mn, Zn, Fe, Pb, Ni
and Cd solutions (1 g L
-1
) were purchased from Merck
(Darmstadt, Germany).
2.2. Sample preparation
Sampling points were selected by a standard procedure
[16]. Points were at least 300 m from a main road,
100 m from a local road, and 5 m from a forest road
to avoid pollution from vehicle exhaust. Samples were
collected from wild-growing Crataegus laevigata L.,
Cornus mas L. and Prunus spinosa L. in southeast
Central European Journal of Chemistry
Metals content of soil, leaves
and wild fruit from Serbia
* E-mail: ba432@ymail.com
Received 1 November 2013; Accepted 8 February 2014
Abstract:
Versita Sp. z o.o.
Keywords: Wild fruit Soil metal Plant metal
Faculty of Sciences and Mathematics, University of Nis, 18000 Nis, Serbia
Sasa S. Randjelovic, Danijela A. Kostic,
Gordana S. Stojanovic, Snezana S. Mitic,
Milan N. Mitic, Biljana B. Arsic
*
, Aleksandra N. Pavlovic
Research Article
The concentrations of Zn, Mn, Fe, Pb, Ni, Cu and Cd in soil, leaves and edible wild fruit (Crataegus laevigata L., Cornus mas L. and
Prunus spinosa L.) from southeast Serbia were determined by atomic absorption spectroscopy. Metal translocations from soil to fruit
were calculated as well as their oral intake and health risk indices. Positive correlations were found among metal concentrations in soil,
leaves and fruit.
1144
Cent. Eur. J. Chem. 12(11) 2014 1144-1151
DOI: 10.2478/s11532-014-0566-7
S. S. Randjelovic et al.
Serbia (locations in Table 3) during September 2010.
Fruit and leaves were collected from the same plants.
Soil sampling followed a zigzag principle at a depth of
0-30 cm.
2.2.1. Soil analysis
Air-dried soil samples were oven dried at 105C for two
hours, then ground to pass through 2 mm sieves. Ten
grams of sample was suspended in deionized water in a
100 mL volumetric fask then fltered through Whatman
No. 42 flter paper. The pH of the frst 25 mL of fltrate
was measured. The remaining 75 mL was evaporated
to dryness on a water bath, dissolved in 5 mL of
1:1 HNO
3
:H
2
O plus 5 mL of 1:1 HCl:H
2
O, then diluted to
25 mL [16].
2.2.2. Fruit and leaves analysis
The fruit and leaves were washed with distilled water
to remove dust and parasites, dried at 105C for
24 h, and homogenized [16]. Standard AOAC (2000)
sample preparation was followed [16]. Accurately
weighed (1 g) sample in a silica crucible was ashed
in a muffe furnace at 450
o
C for 2 h and then 5 mL of
6 M HCl was added. Care was taken to ensure that all
ash came into contact with the acid. The sample was
digested on a hot plate to obtain a clear solution. The
residue was dissolved in 0.1 M HNO
3
and made up to
25 mL. Working standards were prepared by diluting
stock solutions with 0.1 M nitric acid. The blank was
deionized water.
2.3. Apparatus
Air-acetylene fame atomic absorption measurements
were made using a Varian SpectrAA 20
spectrophotometer. Working conditions and limits of
detection (3s criterion [17]) are shown in Table 2.
A Hanna Instruments pH meter was used to measure
pH. Sigma pH 7.00 0.01 and 4.00 0.01 calibration
buffers, were used. Milli-Q apparatus prepared high
purity deionized water.
2.4. Data analysis
2.4.1. Calculation of oral intake of metals from soil
through fruits
The daily intake of metals (DIM) from fruit was estimated
following Jolly et al. [18].
DIM = daily fruit consumption mean fruit metal
concentrations (mg day
-1
, fresh weight).
The daily fruit consumption was assumed to be
300 g per person [19].
Table 1. Therapeutic uses of plants.
Plant Binomial name Therapeutic signifcance Ref.
Hawthorn Crataegus laevigata L.
Treatment of atherosclerosis, relieves symptoms of angina pectoris and cardiac
arrhythmias, heart and menopausal problems.
[13]
Cornelian
cherry
Cornus mas L.
Astringent effect on the intestinal lining, treatment of diarrhea and other diseases of
the digestive tract
[14]
Blackthorn Prunus spinosa L. Treatment of skin problems, soothes stomach cramps [15]
Table 2. Working conditions and limits of detection.
Metal Calibration range
(mg L
-1
)
Limit of detection
(LOD) (mg L
-1
)
Wavelength
(nm )
Slit
(nm)
Acetylene fow
(L min
-1
)
Iron (Fe) 0.00-10.00 0.015 248.3 0.2 2.0
Copper (Cu) 0.00-1.00 0.007 324.8 1.0 1.8
Zinc (Zn) 0.00-5.00 0.021 213.9 0.5 2.0
Lead ( Pb) 0.00-1.00 0.002 217.0 1.0 1.6
Cadmium (Cd) 0.00-1.00 0.003 228.8 0.5 2.0
Manganese (Mn) 0.00-2.00 0.005 279.5 0.2 1.8
Nickel (Ni) 0.00-1.00 0.002 232.0 0.2 2.0
1145
Metals content of soil, leaves
and wild fruit from Serbia
2.4.2. Calculation of health risk index of metal
contamination of fruits
Health risk was characterized by a Hazard Quotient
(HQ) [20], the ratio between exposure and the reference
oral dose (R
f
D).
HQ = DIM / R
f
D,
Where R
f
D is the oral reference dose for the metal (mg
day
-1
), assuming 70 kg body weight. If HQ is less than 1
there will be no obvious risk. Although the HQ does not
quantitatively estimate the probability of negative health
effects, it provides an indication of health risk [18].
2.4.3. Statistical analysis
Principal component analysis was used to reduce
the dataset dimension and extract the statistical
relationships. It was performed using software for
Microsoft Excel