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Heavy Metals As Main Polluting Factors in the Mirusha, Stanishor and Morava Rivers in the Municipality of Gjilan, Kosovo

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Heavy Metals As Main Polluting Factors in the Mirusha, Stanishor and Morava Rivers in the Municipality of Gjilan, Kosovo Beluli VM, Mulliqi I. JOTCSA. 2019; 6(2): 89-96. RESEARCH ARTICLE Heavy metals as main polluting factors in the Mirusha, Stanishor and Morava rivers in the Municipality of Gjilan, Kosovo Valdrin M. Beluli1* , Ismet Mulliqi2 1University of Tirana, Faculty of Natural Sciences, Department of Industrial Chemistry, Boulevard Zogu I, Tirana, Albania 2University of Mitrovica "Isa Boletini", Faculty of Food Technology, Department of Technology, Ukshin Kovaqica,40000 Mitrovica, Kosovo Abstract: Pollution with the heavy metals of Kosovo's rivers has been and continues to be a serious concern not only for the population, but also for responsible institutions that deal with environmental protection in our country. Based on this fact and our doubts regarding the quality of the river waters of the Municipality of Gjilan, we were motivated to conduct a study of the quality of the Mirusha, Stanishor and Morava river waters. During our research, we have set eight monitoring points for determining the exact level of concentration of heavy metals in the river waters quoted above. The heavy metals analyzed in this study were: Pb, Hg, Mn, Cu, Fe, Ni, Cr, Cd, Zn and Ba. The analytical technique used to determine the concentration of heavy metals was ICP-OES. The obtained results show that Fe, Mn and Ba exceed the allowed level at several monitoring points of the Mirusha and Stanishor rivers and appears in the degree of pollution with these metals of Morava river waters. The presence of heavy metals in the waters of these rivers negatively affects habitat waters and indirectly human health. Therefore, the identification and then suggestions regarding elimination of polluting sources are the subject of this study. Keywords: Rivers, pollution, heavy metals, ICP-OES. Submitted: November 28, 2018. Accepted: February 11, 2019. Cite this: Beluli V, Mulliqi I. Heavy metals as main polluting factors in the Mirusha, Stanishor and Morava Rivers in Gjilan, Kosovo. JOTCSA. 2019;6(2):89–96. DOI: https://dx.doi.org/10.18596/jotcsa.489098. *Corresponding author. E-mail: [email protected]. INTRODUCTION the pollution of the Mirusha, Stanishor, and Morava Rivers. Analysis of the heavy metals of these rivers Gjilan is a municipality in the Republic of Kosovo. is indispensable to have sufficient chemical evidence Lastly the number of food industries has begun to on how the concentration of heavy metals increases grow every year and more and normally with the each and every year in these rivers. Kosovo from rise of the economy of this city the livelihood has the state budget allocates a lot of money on become bigger in this city, this means that the environmental issues but as a result it is not known number of inhabitants in Gjilan municipality has why Kosovo as a state, namely Gjilan with a major started to increase the population. economic development, have a problem with wastewater see Figure 1. Gjilan has a problem of wastewater treatment due to deficiency of plants and this is the main factor of 89 Beluli VM, Mulliqi I. JOTCSA. 2019; 6(2): 89-96. RESEARCH ARTICLE Figure 1. Description of the pollutant causes of rivers in Gjilan municipality, laboratory analysis of heavy metals and discussion of results. Mirusha and Stanishor rivers are surface waters, protection of rivers in this state, but the problem is characterized by low volumes during the summer that many industries producing different products season, while during the winter season the waters and do not follow the rules for wastewater of these rivers are more voluminous. These two treatment. In the past decade, the concentration of rivers flow into the river with a fast flow which is metals in the rivers of Kosovo was reported to be "Morava e Binçës". These rivers are very chemically higher than normal and the detectable polluted with heavy metals because domestic and concentration of metals in some rivers was found to industrial wastewater are discharged in these rivers exceed the health standard limits. as we cite above, see Figure 2. The spring of the Mirusha River is in the village of Koretisht and this Environmental pollution is a significant problem in spring is called church water, but the problem is that modern society (2). Heavy metals are naturally urban and industrial wastewater are discharged in occurring elements that have a high atomic weight this river. The Stanishor river is also a polluted river, and a density at least 5 times greater than that of but the spring of the Stanishor river is not water. Their multiple industrial, domestic, contaminated with wastewater. Morava River agricultural, medical and technological applications belongs to the Black Sea basin. It also flows along have led to their wide distribution in the the Danube River, and this is very worrying with the environment; raising concerns over their potential Morava River polluting scale. The description of the effects on human health and the environment (3). sampling place in the Mirusha, Stanishor and Heavy metals are natural components of the earth’s Morava rivers is very important to understand the crust, and natural concentrations of heavy metals in degree of pollution of the heavy metals of these soils tend to remain low. However, anthropogenic rivers that we have analyzed. (1). inputs of several heavy metals into waters greatly exceed natural inputs. This problem is more Determining heavy metals is not an easy procedure, prominent in cities, since cities have a high density so we have to be careful about sample preparation of anthropogenic activities and populations (4). and instrument work, so that there is no deviation After taking the metal from the human body, it is of the results. For the determination of heavy difficult for the metals to be completely metals, we used ICP- ICP-OES Optima 2100 DV, metabolized. They may accumulate in soft tissues while mineralization of the sample is realized with or in the bones, causing toxic effects. In the BERGHOF Speedwave MWS-3 +. With the ICP-OES human body, metals can insert adverse effects on we have analyzed these heavy metals such as: Pb, cellular organelles and components, as well as Hg, Mn, Cu, Fe, Ni, Cr, Cd, Zn and Ba. The Republic enzymes involved in metabolism, detoxification, of Kosovo, especially the Ministry of Environment, and DNA damage repair (5). has many laws and regulations regarding the 90 Beluli VM, Mulliqi I. JOTCSA. 2019; 6(2): 89-96. RESEARCH ARTICLE Figure 2. Rivers Stanishor, Mirusha and Morava in the southeast of Kosovo in the municipality of Gjilan. EXPERIMENTAL containers, after that the samples are ready to undergo the digestion-mineralization procedure or Sampling in the area as an important step in aqua regia. The method used for this performance the analysis of heavy metals is EPA 3015. Sampling is an important part of chemical analysis and should always be carried out under the From the filtered solution, 50 mL of water sample is supervision of the analyst. The reliability of an taken and discharged into Teflon® DAP 100 that analytical result depends on the accuracy of the was cleaned very well. This Teflon® digestion is analytical determination as well as from that added to 4-5 mL of HNO3 65% and 1 mL of HCl 35% sampling. It is rightly said that "a wrong sample (US EPA Method 3015, 1994). Teflon® dishes are can’t be answered fairly". The water sample for placed in the positions, provide Teflon® for the rotor chemical analysis must complement these pipes, the Teflon® samples are closed to prevent requirements; to be representative of the water any problem due to the high pressure used by this system being studied, not to suffer from sample mineralization instrument. Microwave oven contamination and loss of the sample being is started and the program for the respective analyzed during transport and not to undergo method is selected (8): the first stage temperature chemical composition changes during storage (6). reaches 145°C, pressure at 30 bar. This stage lasts The sampling method (1669) is that of “Sampling for 5 minutes and the power is at 80%. In the Ambient Water for Trace Metals at EPA Water second stage, the temperature rises to 170 °C, the Quality”. pressure remains at 30 bar again, while the time of this stage lasts for 10 minutes and the power is at Preparation of samples for analysis 80%. In the third stage, the temperature continues The samples were mineralized in a “Speedwave to rise to 190 °C, the pressure remains at 30 bar Four” microwave mineralizer by Berghof (7). In the again, while the duration is 15 minutes and the experimental work phase of this research, the power is at 80%. At the fourth and fifth stages, the analysis of the samples of Mirusha, Stanishor and temperature drops to 100 °C, while pressure is at 0 Morava river waters of the municipality of Gjilan was bar and time decreases in 10 minutes and the power carried out at the eight sites we have taken for study is 0%. see the Table 2. Sample preparation is a critical step in any analytical performance. Sample preparation After finishing the mineralization, the microwave means the dissolution and digestion of organic and switches off (BERGHOF Speedwave MWS-3+), until inorganic samples in closed or open systems by all data (temperature, pressure and time) are stored applying thermal energy or radiation (UV or in the database, the Teflon® dishes are removed microwave) digestion, in the closed system, is from the microwaves, placed in a desiccator to cool carried out at high temperature and pressure. This to the room temperature. Samples prepared technique is more efficient than digestion in the according to the procedure described above are open system.
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