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 Abstract The main goal of this work was to establish a monitoring network on main rivers of Kosovo. We aim to apply WFD (Water Framework Directive) in Kosovo as soon as possible, and our research could be the first step towards it. Waters of the rivers Drini i Bardhë, Morava e Binçës, Lepenc and Sitnica, which are of supra-regional interest, are investigated systematically. Statistical methods are applied to find locations where integrated water resources management can be suggested. Sediments of these rivers were also investigated at the same monitoring points and results have recently been published by us. In this paper we present results of mass concentrations of ecotoxic metals: Cu(II), Pb(II), Cd(II), Zn(II) and Mn(II) in waters of four main rivers of Kosovo. Results of anomalous concentrations of ecotoxic metals in water are compared with anomalous concentrations of the same elements found in sediments. In Drini i Bardhë River the only anomalous value (for Mn) was found in sediment. In Morava e Binçës extreme values of Cd were found in sediments at the lower stretch of the river. In water anomalous values of Cd, Cu and Mn were found at the upper stretch of the river, which are above permanent toxic values. In Lepenc River anomalies were not found, indicating uncontaminated river. Sitnica River is still polluted at two locations, although most of the industry is closed. Anomalous values of Cd, Pb and Zn were found in sediments and of Pb in water at location S2 (Fushë Kosovë); at location S5 (Mitrovicë) anomalous values of Cu, Cd, Pb and Zn were found in sediments and of Cd and Zn in water. Continuation of water and sediment monitoring by Kosovo authorities is highly recommended. Possible remediation at critical locations on Sitnica and Morava e Binçës rivers would be desirable. Keywords: monitoring network, Water Framework Directive, rivers of Kosovo, ecotoxic metals, pollution 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. 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. 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’ BALWOIS 2010 - Ohrid, Republic of Macedonia - 25, 29 May 2010 1 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. Figure 1. Study area with sampling stations BALWOIS 2010 - Ohrid, Republic of Macedonia - 25, 29 May 2010 2 Table 1 Sampling stations on rivers of Kosovo with detailed locality description Sample River Locality Flowing to Watershed Coordinates Height Possible river of above pollution sea level sources (m) D1 Drini i Radavc Fierza Adriatic 42º44’12” N 734 - Bardhë (Albania) Sea 20º18’19” E D2 Drini i Katundi i ri Fierza Adriatic 42º34’36” N 487 Road Bardhë (Albania) Sea 20º19’37” E D3 Drini i Klina Fierza Adriatic 42º42’36” N 348 Road; waste Bardhë (Albania) Sea 20º34’26” E water from Klina D4 Drini i Bridg Fierza Adriatic 42º22’08” N 319 Road Bardhë Fsheji (Albania) Sea 20º32’50” E Gjakovë D5 Drini i Nashec, Fierza Adriatic 42º14’21” N 287 Settlement Bardhë Prizren (Albania) Sea 20º38’52” E M1 Morava e Binçë J. Morava Black Sea 42º17’01” N 538 - Binçës (Serbia) 21º21’44” E M2 Morava e Kllokot J. Morava Black Sea 42º22’15” N 477 Agriculture; Binçës (Serbia) 21º24’14” E waste water from Vitina M3 Morava e Partesh J.Morava Black Sea 42º23’58” N 471 Settlement; Binçës (Serbia) 21º28’03” E agriculture M4 Morava e Dobërçan J. Morava Black Sea 42º28’02” N 450 Waste water Binçës (Serbia) 21º34’56” E from Gnjilane M5 Morava e Kormini i J. Morava Black Sea 42º29’41” N 421 Road Binçës ulët (Serbia) 21º35’39” E L1 Lepenc Brod Vardar Aegean 42º16’17” N 646 - (Macedonia) Sea 21º07’51” E L2 Lepenc Kovaçec Vardar Aegean 42º14’25” N 478 Silicapor (Macedonia) Sea 21º14’24” E factory L3 Lepenc Kaqanik Vardar Aegean 42º12’59” N 466 Lime factory (Macedonia) Sea 21º15’12” E L4 Lepenc Elez Han Vardar Aegean 42º09’07” N 399 Settlement (Macedonia) Sea 21º17’34” E L5 Lepenc Elez Han Vardar Aegean 42º08’27” N 361 Cement factory (Macedonia) Sea 21º17’49” E S1 Sitnicë Lipjan Ibri Black Sea 42º31’23” N 535 Agriculture; (Kosovo) 21º06’09” E waste water from Lipljani S2 Sitnicë Fushë Ibri Black Sea 42º37’14” N 528 Settlement; Kosovë (Kosovo) 21º04’11” E flotation waste S3 Sitnicë Obiliq Ibri Black Sea 42º46’00” N 510 Thermo power (Kosovo) 21º00’23” E plant; waste water from Pristine S4 Sitnicë Vuqiternë Ibri Black Sea 42º50’15” N 492 Tin factory (Kosovo) 20º55’35” E S5 Sitnicë Mitrovicë Ibri Black Sea 42º53’48” N 480 Settlement; (Kosovo) 20º52’58” E phosphate and accumulator factory 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). BALWOIS 2010 - Ohrid, Republic of Macedonia - 25, 29 May 2010 3 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. 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. 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). 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