art%3A10.2478%2Fs11532-014-0566-7

1. IntroductionMetals found in surface soil derive from rock and precipitation. Urban areas contain more anthropogenic metals due to higher population density, traffic 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. ReagentsAll chemicals were of analytical grade. High purity deionized water (conductivity 0.05 µS 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 preparationSampling 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: [email protected]

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.

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Cent. Eur. J. Chem. • 12(11) • 2014 • 1144-1151DOI: 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 analysisAir-dried soil samples were oven dried at 105ºC 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 flask then filtered through Whatman No. 42 filter paper. The pH of the first 25 mL of filtrate was measured. The remaining 75 mL was evaporated to dryness on a water bath, dissolved in 5 mL of 1:1 HNO3:H2O plus 5 mL of 1:1 HCl:H2O, then diluted to 25 mL [16].

2.2.2. Fruit and leaves analysisThe fruit and leaves were washed with distilled water to remove dust and parasites, dried at 105°C 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 muffle furnace at 450oC 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 HNO3 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. ApparatusAir-acetylene flame 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 analysis2.4.1. Calculation of oral intake of metals from soil through fruitsThe 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 significance 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 flow (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

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2.4.2. Calculation of health risk index of metal contamination of fruitsHealth risk was characterized by a Hazard Quotient (HQ) [20], the ratio between exposure and the reference oral dose (RfD).

HQ = DIM / RfD,

Where RfD 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 analysisPrincipal component analysis was used to reduce the dataset dimension and extract the statistical relationships. It was performed using software for Microsoft Excel® (XLSTAT 2014.2.03., Addinsoft SARL, Paris, France).

3. Results and discussion

3.1. Metal concentrations in soil, leaves and fruitResults of of Zn, Mn, Fe, Cu, Pb, Ni, Cu and Cd determinations in soil, leaves and fruit are shown in Table 3.

There were strong Pearson correlations between iron and manganese (0.914), nickel and manganese (0.934), nickel and iron (0.935); and good correlations between manganese and zinc (0.665), iron and zinc (0.705), nickel and zinc (0.649), lead and manganese (0.624), cadmium and manganese (0.730), cadmium and iron (0.791), copper and nickel (0.653), cadmium and nickel (0.729), and cadmium and copper (0.714).

The iron content was several times higher than that of the other metals, ranging from 20995.5 to 30007.6 mg kg-1 in soil, 173.3 to 745.57 mg kg-1 in leaves, and 123.8 to 292.1 mg kg-1 in fruit. The maximum Fe set by FAO/WHO (1984) [21] in edible plants is 20 mg kg-1. However, for medicinal plants WHO limits have not been established [22].

Zinc is important in protein synthesis enzymes, energy production, and in maintaining membranes. Zn concentrations ranged 19.54–68.89 mg kg-1 in soil, 9.43–28.63 mg kg-1 in leaves, and 2.82–18.48 mg kg-1 in fruit. According to the literature [23], soil Zn levels should be not greater than 200–300 mg kg-1. For a majority of species, symptoms of zinc deficiency appear with leaf concentrations of 20–30 mg kg-1. However, all Zn levels

we found were below those in the literature. The FAO/WHO limit (1984) is 27.4 mg kg-1 Zn [21] in edible plants.

Mn in soil varies from 114.71 to 410.52 mg kg-1, in leaves from 10.96 to 107.89 mg kg-1, and in fruit from 2.22 mg kg-1 (Cornus mas L., “Soko Banja”) to 25.21 mg kg-1 (Crataegus laevigata L., “Svrljig”)). The FAO/WHO [21] Mn limit in edible plants is 2 mg kg-1.

Copper ranges 9.48–21.46 mg kg-1 in soil, 3.49–16.27 mg kg-1 in leaves, and 2.57–10.38 mg kg-1 in fruit. According to Allaway [24] Cu in agricultural products should be between 4 and 15 mg kg-1, and FAO/WHO (1984) [21] recommends 3.00 mg kg-1 or less.

Cadmium was 0.36–1.41 mg kg-1 in soil, 0.60–1.85 mg kg-1 in leaves and 0.28–0.52 mg kg-1 in fruit. Maobe et al. [25] report FAO/WHO [25] cadmium limits of 0.21 mg kg-1 in edible plants. However, for medicinal herbs WHO, Canada, China and Thailand allow 0.3 mg kg-1 cadmium. Canadian cadmium limits in finished herbal products are 0.006 mg day-1 [26].

Nickel was detected in soil (8.25–25.22 mg kg-1), and low soil lead concentrations were found at “Svrljig” and “Soko Banja.” Neither was detected in leaves or fruit. Maobe et al. [25] report FAO/WHO [21] Pb limits in edible plants of 1.63 mg kg-1.

Other authors have presented similar findings. In unpolluted Indian soil the average zinc concentration was 89.65 mg kg-1, copper was 27.41 mg kg-1 and Cd was 1.28. In one location the average zinc concentration in plants was about 25.30 mg kg-1, copper about 16.72 mg kg-1 and cadmium about 0.20 mg kg-1 [7]. Soil metals in northwestern Romania vary from 66.3 to 238.1 mg kg-1 (Cu), 108–397 mg kg-1 (Pb), and 0.48 to 3.12 mg kg-1 (Cd). Plant metal concentrations from this area are 2.64 to 19.55 mg kg-1 (Cu), 0.26 to 3.24 mg kg-1 (Pb) and 0.09 to 4.21 mg kg-1 (Cd) [24].

Reiman et al. determined metals in birch, ash, and fern leaves. Their results were higher than ours: iron was 20–400 mg kg-1, zinc was 15.3–864 mg kg-1, manganese was 20–55.91 mg kg-1, and cadmium was 0.02–1.47 mg kg-1 [16].

We have recently reported correlations among phenols content, metals and antioxidant activity of plant extracts used in traditional Serbian medicine [27]. However, since the metals content of flowers were determined, comparisons cannot be made.

3.2. Soil metals uptake to leaves and fruitPlant uptake of trace metals depends on soil pH, soil organics, and soil type, but the metals concentration in the soil is the dominant factor [28]. The relationships among metals concentrations in soil, foliage, and fruit may be summarized by species-specific plant uptake

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Table 3. Mean metal concentrations in soil, leaves and wild fruit.

Location Fruit Sample Zn(X±U)

mg kg-1

Mn(X±U)

mg kg-1

Fe(X±U)

mg kg-1

Pb(X±U)

mg kg-1

Ni(X±U)

mg kg-1

Cu(X±U)

mg kg-1

Cd(X±U)

mg kg-1

Pukovac

Crataegus laevigata L.

Soil 25.31±0.76 249.3±7.48 21184.5±423.7 - 20.03±0.60 21.46±0.43 0.40±0.008

Leaves 23.60±0.47 40.55±0.81 189.76±3.79 - - 16.01±0.32 0.13±0.023

Fruit 11.50±0.35 5.47±0.16 145.6±2.91 - - 4.97±0.09 0.10±0.008

Prunus spinosa L.

Soil 28.92±0.87 298.1±8.94 20995.5±419.9 - 25.22±0.76 18.47±0.37 0.54±0.011

Leaves 27.80±0.56 48.19±0.96 216.99±4.34 - - 14.75±0.29 0.35±0.037

Fruit 14.78±0.44 6.94±0.21 162.8±3.26 - - 6.62±0.13 0.22±0.006

Cornus mas L.

Soil 20.43±0.61 213.89±6.42 22592.3±451.8 - 21.63±0.65 17.22±0.34 0.50±0.010

Leaves 20.40±0.60 36.44±0.73 173.3±3.47 - - 13.21±0.26 0.22±0.024

Fruit 9.68±0.29 5.23±0.16 138.9±2.78 - - 5.01±0.10 0.08±0.009

Mokra


Soil 24.65±0.74 246.78±7.40 21604.6±432.1 - 12.25±0.37 11.93±0.24 0.53±0.011

Leaves 9.43±0.19 25.78±0.51 219.05±4.38 - - 10.16±0.20 0.23±0.019

Fruit 6.06±0.18 4.69±0.14 182.7±3.65 - - 7.96±0.16 0.09±0.007

Prunus spinosa L.

Soil 65.74±1.97 300.68±9.02 26934.3±538.7 - 19.40±0.58 18.16±0.36 0.69±0.014

Leaves 14.28±0.28 60.18±1.20 745.57±14.91 - - 11.92±0.24 0.31±0.021

Fruit 4.26±0.13 2.67±0.08 164.5±3.29 - - 9.73±0.19 0.20±0.006

Cornus mas L.

Soil 19.54±0.59 139.57±4.19 21882.5±437.6 - 8.25±0.25 16.93±0.34 0.94±0.019

Leaves 6.89±0.14 10.96±0.22 229.70±4.59 - - 12.99±0.26 0.54±0.028

Fruit 2.82±0.08 2.25±0.07 123.8±2.48 - - 10.38±0.21 0.38±0.007

Svrljig


Soil 39.52±1.18 257.46±7.72 21681.3±433.6 1.21±0.02 18.00±0.54 11.70±0.23 0.46±0.009

Leaves 18.70±0.37 97.08±1.94 181.75±3.63 - - 10.19±0.20 0.26±0.012

Fruit 16.49±0.49 25.21±0.76 176.5±3.53 - - 6.62±0.13 0.16±0.007

Prunus spinosa L.

Soil 40.36±1.21 284.57±8.54 25318.1±506.4 1.08±0.02 16.12±0.32 9.48±0.19 0.46±0.009

Leaves 21.51±0.43 107.89±2.15 316.11±6.32 - - 6.78±0.14 0.23±0.017

Fruit 15.62±0.47 8.34±0.25 251.3±5.03 - - 5.64±0.11 0.13±0.006

Cornus mas L.

Soil 36.11±1.08 232±6.96 22556.4±451.1 1.12±0.02 13.01±0.39 12.50±0.25 0.40±0.008

Leaves 19.12±0.38 85.9±1.72 294.75±5.89 - - 9.17±0.18 0.24±0.015

Fruit 16.54±0.49 7.99±0.24 205.5±4.11 - - 7.21±0.14 0.14±0.007

Aleksinac


Soil 22.16±0.66 224.73±6.74 28307.4±566.1 - 13.60±0.41 10.29±0.21 0.52±0.010

Leaves 17.35±0.35 26.71±0.53 336.37±6.73 - - 8.69±0.17 0.24±0.016

Fruit 13.59±0.41 10.63±0.32 256.5±5.13 - - 7.25±0.14 0.12±0.007

Prunus spinosa L.

Soil 20.48±0.61 249.28±7.48 28226.5±564.5 - 15.35±0.46 13.27±0.26 0.47±0.009

Leaves 19.29±0.39 49.73±0.99 346.08±6.92 - - 6.30±0.13 0.25±0.023

Fruit 13.67±0.41 5.05±0.15 222.7±4.45 - - 4.85±0.09 0.13±0.007

Cornus mas L.

Soil 68.89±2.07 114.71±3.44 30007.6±600.1 - 13.70±0.41 16.95±0.34 0.53±0.011

Leaves 23.85±0.48 30.17±0.60 283.55±5.67 - - 16.27±0.32 0.27±0.031

Fruit 13.05±0.39 2.85±0.08 177.8±3.56 - - 7.47±0.15 0.14±0.009

Soko Banja


Soil 39.69±1.19 258.93±7.77 27993.3±559.9 1.28±0.02 16.05±0.48 11.32±0.23 0.41±0.008

Leaves 28.63±0.57 48.20±0.96 348.96±6.98 - - 7.81±0.16 0.21±0.022

Fruit 17.25±0.52 10.78±0.32 272.8±5.46 - - 6.52±0.13 0.09±0.008

Prunus spinosa L.

Soil 42.64±1.28 410.52±12.32 29501.6±590.0 1.26±0.02 20.65±0.62 14.56±0.29 0.55±0.011

Leaves 23.56±0.47 59.15±1.18 358.07±7.16 - - 9.92±0.19 0.24±0.013

Fruit 18.48±0.55 5.99±0.17 292.1±5.84 - - 6.84±0.14 0.13±0.007

Cornus mas L.

Soil 33.87±1.02 253.65±7.61 24352.6±487.1 1.46±0.03 11.95±0.36 10.94±0.22 0.44±0.009

Leaves 26.35±0.53 27.60±0.55 549.6±10.99 - - 3.49±0.07 0.19±0.014

Fruit 14.46±0.43 2.22±0.07 221.7±4.43 - - 2.57±0.05 0.12±0.007

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Table 4. PUF values.

Location PUF Zn Mn Fe Pb Ni Cu Cd

Pukovac

Crataeguslaevigata L.

Soil-leaves 0.933 0.163 0.009 - - 0.45 0.65

Soil -fruit 0.4544 0.0219 0.0069 - - 0.23 0.25

Leaves-fruit 0.4873 0.1349 0.7673 - - 0.3104 0.77

Prunus spinosa L.

Soil-leaves 0.93 0.16 0.01 - - 0.45 0.65

Soil -fruit 0.51 0.02 0.75 - - 0.36 0.40

Leaves-fruit 0.53 0.14 0.75 - - 0.45 0.63

Cornus mas L.

Soil-leaves 0.51 0.17 0.008 - - 0.76 0.57

Soil -fruit 0.47 0.025 0.006 - - 0.29 0.16

Leaves-fruit 0.47 0.14 0.8 - - 0.38 0.36

Mokra


Soil-leaves 0.383 0.104 0.01 - - 0.85 0.43

Soil -fruit 0.2458 0.0190 0.0085 - - 0.6672 0.17

Leaves-fruit 0.6426 0.1819 0.8340 - - 0.7834 0.39

Prunus spinosa L.

Soil-leaves 0.22 0.2 0.03 - - 0.81 0.45

Soil -fruit 0.07 0.009 0.006 - - 0.53 0.29

Leaves-fruit 0.30 0.044 0.22 - - 0.781 0.645

Cornus mas L.

Soil-leaves 0.35 0.078 0.01 - - 0.61 0.57

Soil -fruit 0.14 0.016 0.006 - - 0.61 0.40

Leaves-fruit 0.40 0.20 0.54 - - 0.79 0.71

Svrljig


Soil-leaves 0.473 0.3760 0.01 - - 0.65 0.56

Soil -fruit 0.4170 0.0979 0.0081 - - 0.5658 0.35

Leaves-fruit 0.8818 0.2598 0.9697 - - 0.6490 0.62

Prunus spinosa L.

Soil-leaves 0.53 0.37 0.012 - - 0.83 0.50

Soil -fruit 0.38 0.03 0.01 - - 0.59 0.28

Leaves-fruit 0.72 0.08 0.79 - - 0.82 0.56

Aleksinac

Cornus mas L.

Soil-leaves 0.53 0.37 0.013 - - 0.73 0.60

Soil -fruit 0.45 0.03 0.009 - - 0.58 0.35

Leaves-fruit 0.86 0.093 0.69 - - 0.78 0.58


Soil-leaves 0.61 0.12 0.012 - - 0.81 0.52

Soil -fruit 0.6133 0.0473 0.0090 - - 0.7046 0.23

Leaves-fruit 0.7833 0.3978 0.7625 - - 0.8343 0.50

Prunus spinosa L.

Soil-leaves 0.94 0.20 0.012 - - 0.475 0.53

Soil -fruit 0.66 0.02 0.008 - - 0.36 0.27

Leaves-fruit 0.71 0.10 0.64 - - 0.76 0.52

Cornus mas L.

Soil-leaves 0.35 0.26 0.01 - - 0.60 0.51

Soil -fruit 0.18 0.025 0.006 - - 0.44 0.51

Leaves-fruit 0.54 0.094 0.62 - - 0.46 0.29

Soko Banja


Soil-leaves 0.72 0.19 0.012 - - 0.69 0.51

Soil -fruit 0.4347 0.0416 0.0097 - - 0.5759 0.22

Leaves-fruit 0.6025 0.2236 0.7819 - - 0.8322 0.43

Prunus spinosa L.

Soil-leaves 0.55 0.144 0.012 - - 0.69 0.36

Soil -fruit 0.43 0.015 0.01 - - 0.47 0.24

Leaves-fruit 0.78 0.10 0.81 - - 0.69 0.65

Cornus mas L.

Soil-leaves 0.77 0.11 0.023 - - 0.32 0.43

Soil -fruit 0.43 0.009 0.009 - - 0.24 0.27

Leaves-fruit 0.55 0.08 0.40 - - 0.73 0.632

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factors (PUF), which measure the efficiency of metal accumulation [29]. They are defined by:

PUFsf = fruit concentration / soil concentrationPUFsl = leaf concentration / soil concentrationPUFlf= fruit concentration / leaf concentration

These factors are shown in Table 4.Cd, Cu and Zn are more efficiently concentrated in

leaves, while Mn and Fe are less so. Cu, Fe and Zn accumulate more in fruit than leaves, Mn and Cd much less so. Fe is deposited mostly in the fruit.

3.3. Principal components analysisPrincipal components analysis extracted the principal relationships among the data [30,31]. Samples may then be classified by their metal distribution. The data matrix contained 45 rows (soil, leaves and fruit of three species from five areas) and seven columns (metal concentrations). Seven principal components were obtained to characterize the data. Their eigenvalues (4.871, 0.995, 0.462, 0.305, 0.258, 0.074, and 0.035) measure their relative contributions. As F1 and F2

together capture more than 80% of the variation, F3-F7 may be ignored (Fig. 1).

Some eigenvectors for factors (F1, F2, F3 and F4) are positive and some are negative. All data points make a positive contribution to F1. Fig. 2 shows the F1 – F2 plot.

Zinc content increases from left to right and manganese increases from bottom to top.

3.4. Daily metals intake from mixed fruitTable 5 shows the approximate daily metals intake from mixed fruit. These were calculated from average of the fruit metals contents (Table 3), assuming a daily fruit consumption of 300 g [19]. As fruit is mostly water, and the analyses are reported on a dry weight basis, these estimates of metal intake tend to be high. The metals intake is thus within various agencies’ recommended limits [32-36].

3.5. Potential health hazards (HQ)The hazard quotients (HQ) for Zn, Mn, Fe, Pb, Ni, Cu and Cd were 0.251, 0.425, 0.998, 0, 0, 0.664 and 0.639, decreasing Fe>Cu>Cd>Mn>Zn>Pb=Ni. The HQ value

Figure 1. Factors and cumulative variability (%).

Table 5. Estimated daily intake of metal (DIM) from fruit.

Metal Average fruit concentration (mg kg-1)

Daily Intake (mg)

RfD (mg day-1)

References

Zn 12.55 3.765 15.00 [18]

Mn 7.087 2.126 0.5-5.0 [18]

Fe 199.68 59.90 10.0-60.0 [18]

Pb 0 0 0.245 [35]

Ni 0 0 1.400 [34]

Cu 6.64 1.992 2.0-3.0 [18]

Cd 0.149 0.045 0.070 [34]

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for all the elements were below 1, suggesting that fruit consumption is safe.

4. ConclusionZn, Mn, Cu and Cd were determined in soil and wild fruits from southeast Serbia. Pb and Ni were found in soil but not in leaves or fruit. The ratios among metals concentrations in soil, leaf and fruit were calculated. Strong correlations among concentrations in soil, leaves and fruit were found. Principal component analysis proved useful in classifying samples.

The metal contents of Crataegus laevigata L., Cornus mas L. and Prunus spinosa L. pose no hazard to human health.

AcknowledgementsThis work was funded by the Ministry of Education and Science of the Republic of Serbia (Project No. 172047). Biljana Arsic thanks the Ministry of Science and Education, Republic of Serbia (Project No. 174007) for financial support.

M. Arora, B. Kiran, S. Rani, A. Rani, B. Kaur, N. Mittal, Food Chem. 111, 811 (2008) A.O. Isiaka, O.A. Al Moaruf, O.B. Muibat, O.I. Asiata, O.O. Nureni, Food Chem. 85, 67 (2004)S. Jabeen, M. Tahir Shah, S. Khan, M. Qasim Hayat, J. Med. Fruits Research 4(7), 559 (2010)S.A. Khan, L. Khan, I. Hussain, K.B. Marwat, N. Akhtar, Pak. J. Weed Sci. Res. 14(1-2), 101 (2008)K.R Sharma, M. Agrawal, M.F. Marshall, Food

Chem. Toxicol. 47, 83 (2009)Quality Control Methods for Medicinal Fruit Materials (World Health Organization, Geneva, 2011), apps.who.int/medicinedocs/documents/h1791e/h1791e.pdfR. Singh, D.P. Singh, N. Kumar, S.K. Bhargava, S.C. Barman, J. Environ. Biol. 421 (2010)M. Radivojevic, V.N. Bashkin, Practical Environmental Analysis (Royal Society of Chemistry, Cambridge, United Kingdom, 1999)

Observations (axes F1 and F2: 83,79 %)

45 44

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3938

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-2

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-4 -3 -2 -1 0 1 2 3 4 5

F1 (69,58 %)

F2 (1

4,21

%)

Figure 2. Principal component F1-F2 plot. Labeling: 1 means that it is the first sample from Table 3.

References

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[2]

[3]

[4]

[5]

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[7]

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