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Stanislav Frančišković-Bilinski 1 , Fatbardh Gashi 2 , Halka Bilinski 1

Establishing Of Monitoring Network On Kosovo Rivers (Drini I Bardhë, Morava E Binçës, Lepenc And Sitnica ). Stanislav Frančišković-Bilinski 1 , Fatbardh Gashi 2 , Halka Bilinski 1 1 Institute “Ruđer Bošković”, Division for Marine and Environmental Research, Zagreb, CROATIA

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Stanislav Frančišković-Bilinski 1 , Fatbardh Gashi 2 , Halka Bilinski 1

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  1. Establishing Of Monitoring Network On Kosovo Rivers (Drini I Bardhë, Morava E Binçës, Lepenc And Sitnica) Stanislav Frančišković-Bilinski1, Fatbardh Gashi2, Halka Bilinski1 1Institute “Ruđer Bošković”, Division for Marine and Environmental Research, Zagreb, CROATIA 2Faculty of Natural Science, Department of Chemistry, University of Pristine, KOSOVO

  2. Introduction Overexploitation of nature and uncontrolled use of natural resources, including inadequate processing of industrial wastes have caused large contamination of world ecosystems by toxic metals (Hg, Pb, Cd, Cu, Zn, Ni, Mn). Decomposition of organic matter and pollution due to anthropogenic activity are the main sources of pollution of water and stream sediments (Montgomery, 1996). It is known that nature has developed best “auto purification” mechanisms, but it is extremely important to have knowledge about precipitation, dissolution, adsorption and redox processes, which regulate water-sediment system. Sediments containing toxic heavy metals, in addition to river waters, are important for studying water pollution. Based on combined results, it is possible to propose protection and detoxification measures of affected locations.

  3. The aim... ...of the current work is to perform, a systematic research on rivers Drini i Bardhë, Morava e Binçës, Lepenc and Sitnica. These rivers, which belong to different watersheds, have drainage basins that cover a large area of Kosovo, being as well of supra-regional interest. The sampling sites in rivers are geographically positioned using GIS (Geographic Information System). The results were interpreted using modern statistical methods that can be used to locate polluted regions with anomalous element concentration values. Selected locations, where certain toxic elements should be monitored and remediation possibly performed, were highlighted. We aim to suggest a permanent network of monitoring stations situated at the whole course of the river, where authorities concerned will continue the regular water and sediment monitoring, applying WFD (Water Framework Directive) in Kosovo.

  4. Study area The study area with the sampling locations is shown in Figure 1. Details about all sampling sites are presented in Table 1. The area covers all four main drainage basins of Kosovo: the rivers Drini i Bardhë, Morava e Binçës, Lepenc and Sitnica. Kosovo is located between 41°51’ - 43°16’ N and 20°01’ - 21°48’ E. It is mainly situated on two plains, surrounded by mountains; the Dukagjin (Metohija) Plain at 330-550 m and the Kosovo Plain at 500-600 m above the sea level.

  5. Table 1Sampling stations on rivers of Kosovo with detailed locality description

  6. Sampling, sample preparation and experimental methods Sampling of stream sediments within the drainage basins of the main Kosovo rivers was performed in September 2004, during relatively warm and dry weather with low water levels. Samples were dried in air. Coarse material was separated using a sieve of 40 mesh and afterwards with the standard sieve of 63 μm. Sediments were analyzed using Inductively Coupled Plasma Mass Spectroscopy (ICP-MS). Sampling of water was performed in October 2005 at the same locations. Ecotoxic elements were analyzed using three comparative methods: Anodic Stripping Voltammetry (ASV), Atomic Absorption Spectrophotometry (AAS) and Ultraviolet-Visible (UV-VIS) Spectrometry.

  7. Statistical methods Program Statistica 6.0 (StatSoft, 2001) was used in statistical calculations of this work, such as: frequency histograms and two dimensional box plot diagrams for determination of anomalies (extremes and outliers) for solution data. Outlier values are between 1.5 and 3 and extreme values above 3 standard deviations.

  8. Results and discussion Results of major and trace elements in stream sediments (fraction <63 μm) represent the first database of stream sediment analysis in Kosovo. The database was published by Gashi et al. (2009). The data were used in statistical calculation and in physico-chemical assessment of sediment quality. Anomalous geochemical data (extremes and outliers) for both toxic and lithogenic elements were calculated, using experimental data and boxplot approach (Tukey, 1977). Concentrations of toxic elements (Cu, Zn, Cd, Pb and Mn) determined by comparative techniques give useful information about temporary contamination of water at each sampling location. However, the point source of pollution can be better located from sediment analysis. Using experimental data obtained by AAS method and boxplot approach, anomalous values (extremes and outliers) in waters were determined. Summarized complete data were submitted in extensive paper by Gashi et al. (2010).

  9. Classification of river waters in Kosovo, based on trace metal indicators, is presented in Table 2. The locations S5 having category V is in accord with determination of anomalous concentrations. For most metal indicators, waters are from II to IV category. Classification of waters was tentatively performed using available standards in Croatia (Narodne novine, 107/95, 1998). Manganese concentration of 50 μgdm-3 was recommended by EPA, based on aestetics, not on toxic effects or human health. Manganese is not a priority pollutant according to EPA. It should be mentioned that concentrations of manganese in the lower flow of Drini (D4, D5) in Morava (M1-M5) in Lepenc (L3) and especially in Sitnica (S1-S5) are above the value recommended by EPA. Location M1 deserves further study with respect either to possible ore deposits, or to weathering processes.

  10. Table 2 Classification of river waters in Kosovo, based on trace metal indicators

  11. In Table 3 are presented anomalous values of ecotoxic elements determined in sediment and in water of the main rivers in Kosovo. In Drini i Bardhë River only one anomalous value (for Mn) was found in sediment D1 in the upper stretch. This value is significantly higher than the concentration present in average Earth crust (1000 ppm) or in basalt (1700 ppm). This highest value of Mn at D1 is supposed to come from ore mineralization. In Morava River two anomalous values for Cd were found in sediments at locations M4 and M5. The second one is close to the border of Serbia. The value found is causing significant toxic effects. In the same river, anomalous values of Cd, Cu an Mn were found in water at the station M1. The values are above permanent toxic levels. As there is no source of pollution, it is assumed that found concentrations are of geological origin. In Lepenc River no anomalous values were found. In Sitnica River two locations are extremely polluted. Anomalous values of Cd, Pb and Zn were found in sediments and of Pb in water at location S2 (Fushë Kosovë). Anomalous values of Cu, Cd, Pb and Zn, far exceeding the values causing significant toxic effects were found in sediments at location S5 (Mitrovicë), which is about 50 km upstream from the border of Serbia. In waters at the same location anomalous concentrations of Zn and Cd were found, which are higher than in a river of V water class.

  12. Table 3Anomalous values of eco-toxic elements (Cu, Cd, Pb, Zn, Mn) determined in sediment and water of rivers in Kosovo

  13. In Table 4 is presented an overview of concentrations (μgdm-3) of ecotoxic elements determined in waters of the main rivers of Kosovo by different authors, quoted within the table title. There is hardly visible any agreement among the authors, except of the values found by Rugova (1977) and the values of Gashi et al. (2010) in Sitnica River. The reason can be that either concentrations have been changing with time, or the determination was not accurate. Our results from Gashi et al. (2010) seem to be more reliable, as measurements were done by three different techniques, which are in accord.

  14. Table 4An overview of concentrations (μgdm-3) of eco-toxic elements determined in waters of the main rivers (D=Drini i Bardhë, M=Morava e Binqës, L=Lepenc and S=Sitnica) of Kosovo by different authors: [1] Rugova (1977); [2] Bacaj and Branica (1983); [3] Rugova et al. (1989); [4] Rugova et al. (2003); [5] Arbneshi et al. (2004); [6] Berisha et al. (2008); [7] Gashi et al. (2010), accepted

  15. Conclusions A monitoring network on four main rivers of Kosovo (Drini i Bardhë, Morava e Binçës, Lepenc and Sitnica), which are of supraregional interest, is suggested using locations where sediments and waters have been studied. Statistical methods were applied to find anomalous values in sediments and waters. From these results locations were suggested where integrated water resources management should be performed by local authorities.

  16. From comparison of anomalous values of ecotoxic elements (Cu, Cd, Pb, Zn, Mn) determined in sediment and in waters, it was concluded that Lepenc River (flowing to FYROM) is almost uncontaminated. In the Drini i Bardhë River flowing toward Albania concentration of Mn should be especially monitored, both in sediments and in water. In the lower stretch of Morava e Binqës extreme values of Cd were found in sediments at the lower stretch of the river and in water of Cd, Cu and Mn in the upper stretch. Sitnica is the most polluted river in Kosovo, especially at Fushë Kosovë and Mitrovicë, what is in agreement with the finding of all previous authors. Possible remediation at critical locations on Sitnica and Morava e Binqës, flowing towards Serbia, would be desirable.

  17. Acknowledgements This paper is a part of PhD Thesis of Fatbardh Gashi, defended at the University of Pristina, Kosovo, in June 2006 (supervisor Dr. Halka Bilinski, from the Ruđer Bošković Institute, Zagreb, Croatia). Special thanks go to the collaborators of the Faculty of Natural Science, Department of Chemistry and Geography, University of Pristina for useful discussions. Part of the work and preparation of the manuscript was partly financed through the projects of Croatian Ministry of Science Education and Sport No. 0098041 and No. 098-0982934-2720.

  18. References Arbneshi, T., Bajraktari, N., Korqa, B., Lajqi, A., 2004: Contamination of the river Bel Drim and streams at the region of Orahovo (in Maced.). 2nd congress of ecologists of the Republic of Macedonia with international participation, Skopje, 578-582. Bacaj, M., Branica, M., 1983: The determination of lead concentrations in the water of the rivers Sitnica and Ibar using anodic stripping voltammetry (in Croat.). The Bulletin of the Chemist and Technologists of Kosova, Vol. 3/1, 27-32. Berisha, L., Arbneshi, T., Rugova, M., 2008: The level concentration of lead, cadmium, copper, zinc and phenols in the water river of Sitnica. BALWOIS 2008 – Ohrid, Republic of Macedonia – 27, 31 May 2008, 1-7. Gashi, F., Frančišković-Bilinski, S., Bilinski, H., 2009: Analysis of sediments of the four main rivers (Drini i Bardhë, Morava e Binçës, Lepenc and Sitnica) in Kosovo. Fresenius Environmental Bulletin, 18(8), 1462-1471. Gashi, F., Frančišković-Bilinski, S., Bilinski, H., Troni, N., Bacaj, M., Jusufi, F., 2010: Establishing of monitoring network on Kosovo rivers: preliminary measurements on the four main rivers (Drini i Bardhë, Morava e Binçës, Lepenc and Sitnica). Accepted in Env.Monit.Assessment. Montgomery, J.M., 1996: Water treatment, principles and design. John Wiley & Sons, New York. Rugova, M., 1977: Polarographic determination of traces of Cd, Pb and Cu in waters of the river Sitnica (in Croat.). M.Sc. Thesis, University of Zagreb, Croatia. Rugova, M., Jusufi, S., Gjeqbitriqi, T., Hasimja, H., 1989: Determination of heavy metals (Pb, Cd, Cu and Zn) in contaminated rivers of SAP Kosovo (in Croat.). Bilten Jugoslavenskog društva za zaštitu voda, 82-84, 34-38. Rugova, M., Jusufi, S., Lajqi, A., Arbneshi, T., 2003 : Water quality of the Sitnica River. 3rd Croatian conference of waters, Osijek, Croatia, 28-31 May 2003, 883-888. StatSoft, Inc., 2001: STATISTICA (data analysis software system), version 6. http://www.statsoft.com Tukey, J.W., 1977: Exploratory data analysis. Reading: Addison-Wesley.

  19. Drini i Bardhe river

  20. Lepenc River

  21. Sitnica River

  22. Morava e Binces River

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