EVALUATING THE HEAVY METALS IN DUST POLLUTION IN CABBAGES IN KASTRIOT, KOSOVO

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1 Journal Journal of Chemical of Chemical Technology Technology and Metallurgy, and Metallurgy, 52, 5, 52, 2017, 5, EVALUATING THE HEAVY METALS IN DUST POLLUTION IN CABBAGES IN KASTRIOT, KOSOVO Kaltrina Jusufi 1, Majlinda Vasjari 2, Bardha Korça 1 1 University of Prishtina Hasan Prishtina Faculty of Natural Science and Mathematics Department of Chemistry, str. Nëna Tereze nr Prishtina, Kosovo kaltrinajusufi@gmail.com 2 University of Tirana, Department of Chemistry Faculty of Natural Sciences Tirana, Albania Received 20 February 2017 Accepted 06 May 2017 ABSTRACT This study was focused on heavy metal (Cr, Cd, Cu, Zn and Ni) accumulation in cabbage from the agricultural area of Kastriot, Kosovo. Washed and unwashed cabbage samples were analyzed to identify the presence of dust particle pollution. The samples were treated in a microwave system in the presence of HNO 3 and H 2 O 2. Then the heavy metal content was determined by ICP-AES technique. The range of Cr presence was from 0.02 mg kg -1 to 1.7 mg kg -1, that of Cd - from 0.11 mg kg -1 to 0.29 mg kg -1, that of Cu - from 1.74 mg kg -1 to 9.49 mg kg -1, that of Zn - from 4.13 mg kg -1 to mg kg -1, while that of Ni - from 0.37 mg kg -1 to 2.35 mg kg -1. The results obtained suggest that more attention should be paid to areas where coal ashes and wastes are deposited in Kosovo. Keywords: heavy metals, plants, pollution, ICP-AES technique. INTRODUCTION Anthropogenic activities including mining, industry, agriculture and an increase of the urbanization level have altered the environment significantly throughout the world [1-2]. Toxic metals are introduced into the environment from different sources such as industrial and municipal waste, automobile emissions, mining activities, etc. [3]. The mobility of heavy metals from soil into the food chain and their subsequent bioaccumulation has increased the attention they receive as major environmental pollutants [4-5]. It is well recognized that heavy metal pollution released in any form into the environment easily ends in food because of plant absorption, wind or any other form of storage in agricultural land. Heavy metals pose a serious threat to human health, living organisms and natural ecosystems because of their toxicity, persistence and bioaccumulation characteristics. Accumulation of heavy metals in arable soils poses a 956 potential risk to food chain contamination, and consequently to human health. To prevent this risk, assessment of heavy metal accumulation in soil is required [6-7]. Cabbage is a cool seasoned plant with a high tolerance for cold [8]. It has a thick stem, gray-green leaves and four petals in its flowers. Cabbage leaves are red or green, smooth or wrinkled. They are low in carbohydrate, calories and fats; however, they are a good source of protein containing all the essential amino acids, especially those of sulfur amino acids [9]. The environment in the region of Kastriot has been subjected for decades to heavy metal emissions coming from the power plants complexes of Kosovo. Anthropogenic pollution affects the redistribution of heavy metals in soil and ecosystems of the region and incorporates them into the atmosphere. The production of many crops in this region is dangerous because of potential penetration of heavy metals into the food chain and the living organisms. This investigation is aimed to identify the

2 Kaltrina Jusufi, Majlinda Vasjari, Bardha Korça presence of dust particle pollution in cabbage from the agricultural area of Kastriot, Kosovo EXPERIMENTAL Study of the area The research study showed heavy metals contamination of the cabbage grown in different locations in the vicinity of power plants in Kosovo. The sampling locations referred to the power plants complexes surroundings. Initially the soil was monitored [10]. Then cabbage samples taken from those areas were analyzed in a dry state by standard methods. The content of Pb, Cd, Zn, Cu, Cr, and Ni was determined by ICP AES technique. The latter was also applied to soil analysis. Aiming a comparison samples from an unpolluted zone in rural Kosovo, far from power plants, were studied. Sample collection and preparation The samples were stored in polyethylene bags and were transported to the laboratory. They were divided into two parts - unwashed leaves of the plant were placed in a dish, while leaves washed with doubly distilled water and were cut to small pieces using a clean knife were placed in another one. After drying at 65 0 C for 24 h then at C for 4 h - 5 h, the samples were ground into a fine powder and digested in a microwave system. RESULTS AND DISCUSSION Table 1. ph values and humus percentage in soil. ph KCl in ph H 2 O Table 1 shows the results referring to soil ph and humus percentage in it. Table 2 presents the highest and the lowest values of heavy metals content in the cabbage samples studied. Letter W stands for washed cabbage samples, while the abbreviation UW stands for the unwashed one. The figures given below refer to each element present in the washed (W) and unwashed (UW) cabbage samples. On one hand this is done to provide a comparison, while on the other - to outline the dust impact. The results presented in Table 2 and Fig. 1 show that chromium content ranges from 1.70 mg kg -1 in the unwashed to 0.3 mg kg -1 in the washed samples. The in % humus Table 2. The highest and the lowest heavy metals content in washed and unwashed cabbage samples. No. Cr No. Cd No. Cu No. Zn No. Ni mg/kg mg/kg mg/kg mg/kg mg/kg Highest UW W Lowest UW W

3 Journal of Chemical Technology and Metallurgy, 52, 5, 2017 Fig. 1. Chromium content in mg kg -1 in washed and unwashed cabbage samples. Fig. 2. Cadmium content in mg kg -1 in washed and unwashed cabbage samples. latter value is in the interval of 0.2 mg kg mg kg -1 reported [10] for washed cabbage samples. It is reported [11] that the average cadmium concentration in plants, affected by soil ph, is in the interval of 0.1 mg kg mg kg -1. The results obtained in this study show that cadmium content varies from 0.29 mg kg -1 to 0.16 mg kg -1 in the washed samples, i.e. it does not exceed the amount pointed above by more than 0.8 mg kg -1. The content of Cu in the samples investigated varies between 2 mg kg -1 and 20 mg kg -1. This value is not exceeded in any cabbage sample. The content of zinc is higher than that of the other elements. It results from the high amount of zinc in the soil samples from this area [12]. Zinc is an essential element but it could be toxic in large amounts [13]. Zn content usually ranges from 15 mg kg -1 to 50 mg kg -1. The values found in this study do not exceed 50 mg kg -1. Ni content ranges from 0.1 mg kg - to 5 mg kg -1 in plants grown in uncontaminated soils [10, 14-16]. The values in this study are in the interval from 2.32 mg kg -1 to 1.58 mg kg -1. It should be mentioned that all heavy metals in high concentrations are toxic. What separates the limit of essential metals from that of toxic elements depends on the concentration and amount of the metal that is taken with food [17]. It is recognized that the content of heavy metals is much higher in unwashed cabbage samples when compared to that in washed one [18-19]. Fig. 6 presents 958

4 Kaltrina Jusufi, Majlinda Vasjari, Bardha Korça Fig. 3. Copper content in mg kg -1 in washed and unwashed cabbage samples. Fig. 4. Zinc content in mg kg -1 in washed and unwashed cabbage samples. Fig. 5. Nickel content in mg kg -1 in washed and unwashed cabbage samples. 959

5 Journal of Chemical Technology and Metallurgy, 52, 5, 2017 Fig. 6. Heavy metals content in mg kg -1 in unwashed and washed cabbages samples taken from an unpolluted zone. data referring to samples gathered in a pollution- free zone about 40 km away from the power plant complexes. This is done aiming a comparison and a verification that the contamination reported is due to the use of coal for electric energy generation. Determination of the soil amount of heavy metals is the basis for determining the degree of pollution and suitability of the land for cultivation of crops. The bioavailability and bioaccumulation of heavy metals in plants is directly related to their concentration and mobility on land, the plants genetic properties and other ecological factors. The concentration of metals in plants increases with soil ph increase [20-22]. The juxtaposition of the data referring to the soil and the cabbage samples studied shows that the heavy metals content in the soil is higher than that in cabbage [23]. This is most probably due to root activity, which seems to act as a barrier for metals translocation [24-25]. CONCLUSIONS The results obtained in this study show the minimum and maximum content of heavy metals in washed and unwashed cabbage samples. It is found that in any case the heavy metals content follows the line Zn > Cu > Ni > Cr > Cd. It is also found that the unwashed samples are more contaminated than the unwashed one indicating that the dust from this area can significantly affect heavy metal pollution. Our findings lead to the conclusion that monitoring heavy metal content in food production sites is crucial for assessing health hazards to human beings. Bioremediation of the polluted soils should be considered. REFERENCES 1. A. Radjenovic, G. Medunic, Adsorptive removal of Cr(VI) from aqueous solution by carbon black, Journal of Chemical Technology and Metallurgy, 50, 1, 2015, P. Wang, S. Zhang, C. Wang, J. Hou, P.Ch. Guo, Zh.P. Lin, Study of heavy metal in sewage sludge and in Chinese cabbage grown in soil amended with sewage sludge, African Journal of Biotechnology, 7, 9, 2008, B. Balabanova, T. Stafilov, R. Šajn, K. Bačeva, Spatial Distribution and Characterization of Some Toxic Metals and Lithogenic Elements in Topsoil and Subsoil from Copper Mine Environs, International Journal of Environmental Protection, 3-9, 2013, M. Jaishankar, B.B. Mathew, M.S. Shah, K.R.S. Gowda, Biosorption of Few Heavy Metal Ions Using Agricultural Wastes, Journal of Environment Pollution and Human Health, 2, 1, P.C. Nagajyoti, K.D. Lee, T.V.M. Sreekanth, Heavy metals, occurrence and toxicity for plants: a review, Environ. Chem. Lett., 8, 3, 2010, E. Kasa, P.F. Henningsen, R.A. Duering, B. Gjongecaj, F. Gjoka, Mobility of heavy metals in arable 960

6 Kaltrina Jusufi, Majlinda Vasjari, Bardha Korça soils from bregu i Matit Plain, Albania, Carpathian Journal of Earth and Environmental Sciences, 9, 3, 2014, D. De Forest, K. Brix, W. Adams, Assessing metal bioaccumulation in aquatic environments: The inverse relationship between bioaccumulation factors, trophic transfer factors and exposure concentration, Aquat. Toxicol., 84, 2007, D.H. Callaway, K.O. Carpenter, Nutrition and Health, Saunders College Publishing, USA, 1981, 1, T. Coolong, Cabbage, Cooperative Extension Services, University of Kentucky- Agriculture Department, N.I. Ward, Trace Elements, Environmental Analytical Chemistry, Eds. F.W. Fifield, P.J. Haines, Blackie Academic and Professional, Champman and Hall, K.-Pendias, A.H. Pendias, Trace Elements in Soil and plants, CRC Press Inc., Bocca Raton, Florida, K. Jusufi, T. Stafilov, M. Vasjari, B. Korça, J. Halili, A. Berisha, Determination of heavy metals by ICP- AES in the agricultural soils surrounding Kosovo s power plants, Fresen. Environ. Bull., 25, 5, 2016, C. Carlon, M. D Alessandro, F. Swartjes, Derivation methods of soil screening values in Europe: a review of national procedures towards harmonization EUR, Scientific and Technical Research Series, Office for Official Publications of the European Communities, 2007, pp Brooks RR, Serpentine and its vegetation: a multidisciplinary approach. Dioscorides Press, Portland, OR, R.D. Reeves, The hyperaccumulation of nickel by serpentine plants. In: A.J.M. Baker et al. (ed.) The vegetation of ultramafic (Serpentine) soil, Andover, Hampshire, UK, 1992, pp U. Kukier, R.L. Chaney, In situ remediation of Niphytotoxicity for different plant species, J. Plant Nutr., 27, 2004, M.E.F. Conti, M. Carcea, Trace metals in soft and durum wheat from Italy, Food Additives and Contaminants, 17, 2000, E. Osma, M. Serin, Z. Leblebici, A. Aksoy, Heavy Metals Accumulation in Some Vegetables and Soils in Istanbul, Ekoloji, 21, 82, 2012, 1-8, doi: / ekoloji M.O. Akinola, T.A. Ekiyoyo, Accumulation of lead, cadmium and chromium in some plants cultivated along the bank of river Ribila at Odo-nla area of Ikorodu, Lagos state, Nigeria, Journal of Environmental Biology, 27, 3, 2006, U. Förstner, Metal speciation-general concepts and applications, International Journal of Environmental Analytical Chemistry, 51, 1-4, 1993, Z. Lončarić, B. Popović, K. Karalić, M. Rékási, V. Kovačević, Regression model for prediction availability of essential heavy metals in soils, 19th World Congress of Soil Science, Soil Solutions for a Changing World, Australia, 2010, Z. Lončarić, K. Karalić, B. Popović, D. Rastija, M. Vukobratović, Total and plant available micronutrients in acidic and calcareous soils in continental part of Croatia, Cereal Research Communications, 36, 2008, D. Demi rezen, A. Aksoy, Accumulation of heavy metals in Typha angustifolia (L.) and Potamogeton pectinatus (L.) Living in Sultan Marsh (Kayseri, Turkey), Chemosphere-Elsevier, 56, 2004, B.E. Davies, H.M. White, Trace element in vegetables grown on soils contaminated by base metal mining, Journal of Plant Nutrition, 3, 1981, A.A. Yusuf, T.A. Arowolo, O. Bamgbose, Cadmium, copper and nickel levels in vegetables from industrial and residential areas of Lagos City, Nigeria, Food & Chemical Toxicology, 41, 2003,

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