Water pollution studies in the rivers of the Edirne Region– M. Serdal Sakcali,1 Ruya Yilmaz,2 Salih Gucel,3∗ Celal Yarci,4 and Munir Ozturk5 1Fatih University, Faculty of Science & Arts, Buyukcekmece, , Turkey 2Trakya University, Faculty of Agriculture, Tekirdagı,˘ Turkey 3Near East University, Institute of Environmental Sciences, Nicosia, Cyprus 4Marmara University, Faculty of Science & Arts, Goztepe, Istanbul, Turkey 5Ege University, Botany Department, Bornova–35100, Izmir, Turkey ∗Corresponding author: [email protected]

Physico-chemical parameters of Tunca, Merich, and Ergene rivers, in the Edirne region of Turkey, were investigated. Studies were carried out during 1998–2004 and the data obtained were compared with EU threshold levels. The results showed that the total concentrations of P, Pb, Cu, Ni, Mn and Co were higher than these threshold levels. There is an urgent need for Turkey to limit water pollution from a wide range of dangerous substances, particularly at a time when it is being considered as an EU candidate. Turkey will be required to achieve a satisfactory status in its waters by 2015, in particular in the waters of the rivers investigated in this paper that border and . Levels of pollutants which pose a significant risk to the aquatic environment need to be monitored and strictly controlled.

Keywords: Tunca, Merich, Arda, Ergene, physico-chemical, trace metals

Introduction they contain trace elements in concentrations above acceptable limits (Sawidis et al., 1995; Zhulidov, The excessive use of natural resources and ef- 1996; Shine et al., 1998; Yevseev and Krasovskaia, fluents resulting from human activity are damag- 2001). One of the states in Turkey facing this sit- ing aquatic habitats. As a result, mechanical, physi- uation is Edirne. The area is particularly important cal, chemical, organic and biological characteristics for the production of sunflowers, rice and wheat of waters have been adversely affected (Aksoy and all of these agriproductions are using water et al., 2005; Cetin et al., 2000; Ozturk et al., 2005; from four rivers: Arda, Ergene, Tunca and Merich Okonkwo and Mothiba, 2005). The pollutants com- (Fig.1). Indiscriminate discharge of various types ing from anthropogenic sources, surface and urban of effluents from different industries and domestic stormwater runoff containing metals from roadways sewage entering these transboundry rivers leads to and atmospheric fallout, domestic wastewater efflu- heavy pollution, which can produce detrimental ef- ents, industrial effluents and waste sludges enter the fects on water quality, agriculture, and in the long irrigation waters and are transported to the agri- run to human beings (Euroconsult, 2001; Sandwith cultural fields. These polluted waters may produce et al., 2001). During this study the variations in harmful effects on living organisms, particularly if the physico-chemical parameters of Arda, Ergene,

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Aquatic Ecosystem Health & Management, 12(3):313–319, 2009. Copyright C 2009 AEHMS. ISSN: 1463-4988 print / 1539-4077 online DOI: 10.1080/14634980903133757

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Figure 1. Study area with the locations of the rivers and sampling points.

Tunca and Merich rivers were investigated, to deter- The pH was measured on site with a portable mine the pollution status and safety levels of these pH/◦C-meter (Handylab 1 SCHOTT). The DO was irrigation waters. measured on site by means of a portable oxygen- meter, type WTW OXI-320. Measurements were Materials and methods calibrated using Winkler titration (Parsons et al., 1984; Bode and De Bruin, 1990). The study area, Edirne, with a total area of 23 The water samples were transferred to the labo- 2 485 km , lies in the European part of Turkey. It ratory in a portable refrigerator, where they were fil- is surrounded by the Black Sea and Bulgaria in the tered (0.45 µm) and stored in a refregirator (+4◦C). north, the Bosphorus in the east, Marmara Sea in the For the cation analysis, samples were acidified with south, the in the south-west and Greece HNO3 Merck to a pH below 2. Measurements were in the west. There are four major rivers; Merich, repeated twice during the sampling day to avoid Tunca, Arda and Ergene in this area (Fig.1). Water the fluctuations of the physico-chemical parame- from these rivers is used to irrigate the fertile agri- ters arising from temperature differences. Chemi- cultural land around Ergene basin (Anon., 2005). cal oxygen demand (COD) and nitrates were de- The 492 km long Merich () River with a termined by colorimetry (EPA 410.4, EPA 353.2, 3 −1 flow rate of 157 m sec originates in Bulgaria, respectively) and the determination of sulfates fol- enters Turkey, and a 185 km track constitutes the lowed the turbidimetric method (SM 4500-SO4-E). state border between Turkey and Greece, reaching A blank was used before starting measurements and the Aegean Sea in around the Bay of Saros. repeated after every 10 samples. Analysis methods River Tunca, with a length of 289 km and flow rate were tested with certified reference materials (for 3 −1 of 22 m sec also originates in Bulgaria, entering trace elements SRM NIST 1640). The detection lim- Turkey at Suakacagi Village (Edirne), joining the its for each of the elements were determined using Merich in Bulbul Adasi (Edirne). River Arda, also the lowest concentration of each of the elements that originating in Bulgaria, enters Turkey in Pazarkule gave the least detectable signal using flame AAS and joins the river Merich under the Marsh Bridge for Cd, Cu, Pb and Zn. Six replicates of each of in Edirne. The 283 km long river Ergene with a flow these concentrations were prepared and analysed. 3 −1 rate of 14 m sec , together with its tributaries, Physical and chemical parameters were determined rises in Karatepe-Saray at the base of the Istranca according to the methods outlined in detail in the Mountains and joins the river Merich in the Bala- handbooks of US EPA (1993) and APHA (1989). bancik Village-Ipsala located in the south of Edirne. Water samples were collected randomly from fif- Results teen sampling stations located at these four rivers, on a yearly basis during 1998–2004 (Fig.1). Fresh The flow rates of Merich, Tunca and Ergene surface water (from a depth of 0.5 m) was collected Rivers are presented in Fig. 2a. Values recorded for from each site over a period of six years (1998– Merich River are higher than those from Tunca and 2004) using 1 liter polypropylene sampling bottles. Ergene rivers. The means of twelve months for each

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Figure 2. (a) Mean annual water flow (m3h−1) of the rivers, (b) Annual record of floods in the Meric¸ and its tributaries.

year reveal that the highest flow rate was in 1998 the second highest value for these rivers. The pH in (628.416 m3 h−1) in the Merich because of precip- Tunca ranged between 6.8 and 8.16 and in Ergene itations above the mean. The data for Arda was not between 6.41 and 8.41. Where the three rivers meet recorded because it is just 1 km long. The floods that and join Merich River, the pH varies between 6.5 and occur around these rivers, in particular the Merich 8.2 (Fig. 3). The lowest value among the sampling River, are a great problem in the region (Fig. 2b). stations (6.1) was recorded for Merich in 2003 at Altough the strength of the floods in the last few station 12 (Kuplu). The highest value of pH (8.4) years has been comparably weaker than in 1984, was measured at station 9 (Uzunkopru) in 2002. the financial damage in both Turkey and Greece has The average values for each river were 7.16 (Arda), increased. Furthermore, these floods pose a great 7.48 (Tunca), 7.47 (Ergene) and 7.22 (Merich). risk for the of Edirne as well as its suburban agricultural areas. Sulphate (SO4) −1 pH The lowest value of SO4 (47mgL )was recorded in the Arda in 2003 and the highest in Er- The lowest pH was measured at Arda (5.5) in gene in 2001 (235 mg L−1). The average values of 1998 and the highest (8.4) in Ergene in 2002. The Arda were very low during 1998–2003, whereas the abnormal pH value below 6 could be attributed to the values of the Ergene are the highest of all. In Tunca overuse of fertilizers in agricultural areas. In 2001 and Merich the values ranged between 88 to 184 mg −1 however, the pH of Arda gave a peak value of 8.22, L . The average SO4 values of the rivers Arda,

Figure 3. Annual pH fluctuations in the rivers.

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Figure 4. Annual (a) Sulphate (SO4), (b) Nitrogen fluctuations in the rivers.

Ergene, Tunca and Merich were 78.262, 177.70, age DO values of Arda, Ergene, Tunca and Merich 119.048 and 138.655 mg L−1 respectively (Fig. 4a). Rivers were 11.381, 5.928, 10.517 and 11.381 mg L−1 respectively. Total nitrogen Nitrogen fluctuations in the rivers are shown in Chemical Oxygen Demand (COD) Figure 4b. The peak values were recorded in Ergene The COD values on a yearly basis are given in River. Despite the low values of 1998 (3.7 mg L−1), −1 Figure 5b. High values were observed in Ergene in 2001 the value abruptly went up to 17 mg L . − River (132.2 and 133.3 mg L 1). The values in the This could be due to the nitrogen content of textile other three rivers were very close to each other and effluents. In the other three rivers the values were − changed between 3.7 to 20.6 mg L 1. The average stablearound1to2mgL−1. A little activity was seen COD values of the rivers Arda, Ergene, Tunca and at Tunca River during 2002–2004. It went down to −1 −1 Merich were 7.437, 94.573, 13.247 and 17.024 mg 0.1mgL in 2003 but rose to 4.5 mg L in 2004. − L 1 respectively. Average values of total nitrogen for Arda, Ergene, Tunca and Merich were 1.124, 9.771, 2.139 and 2.904 mg L−1 respectively. Copper (Cu) Dissolved oxygen (DO) Cu concentrations of the four rivers are shown in Figure 6a. The highest level of Cu was measured − DO fluctuations along the rivers are shown in in Tunca (0.43 mg L 1) in 2000, whereas in 1998 − Figure 5a. The highest value (13.7 mg L−1)was it was below 0.1 mg L 1. The lowest value of Cu − − recorded in the Merich in 2004, while the lowest was recorded from the Tunca (8.5 × 10 3 mg L 1) was observed in Ergene River (3.0 mg L−1). Aver- in 2003. The average Cu concentration of the rivers

Figure 5. Annual (a) Dissolved Oxygen (DO), (b) Chemical Oxygen Demand (COD) fluctuations in the rivers.

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Figure 6. Annual changes in the, (a) Cu, and (b) Zn, concentrations in different rivers.

Arda, Ergene, Tunca and Merich were 0.035; 0.019; Iron (Fe) 0.213 and 0.111 mg L−1 respectively. The highest level of Fe was found in the Ergene (0.222 mg L−1) and the lowest in Arda (0.123 mg Zinc (Zn) L−1). The average concentrations in the rivers Arda, Ergene, Tunca and Merich were 0.123, 0,222, 0.169 The highest level of Zn was measured in the Arda and 0.136 mg L−1 respectively. (0.1 mg L−1) in 1998 and the lowest in Ergene (5 × 10−4 mg L−1) in 2000 (Fig. 6b). The second highest value was recorded for the Tunca (0.08 mg L−1)in Chrome (Cr) 2003. The average concentrations of the rivers Arda, The highest level of Cr was measured in the Ergene, Tunca and Merich were 0.058, 0.010, 0.023 Tunca (0.071 mg L−1) and the lowest in Merich −1 and 0.020 mg L respectively. (0.003 mg L−1). The average concentrations in the rivers Arda, Ergene, Tunca and Merich were 0.004, −1 Biological Oxygen demand 0,022, 0.071 and 0.003 mg L respectively. (BOD5) Sodium (Na)

The highest level of BOD5 was found in Ergene The highest level of Na was in the Ergene −1 (33.146 mg L ) and the lowest in Tunca (0.68 mg (140.612 mg L−1) and the lowest in Arda (13.594 mg −1 − L ). The values of BOD5 in Merich and Arda were L 1). The average concentrations in the rivers Arda, −1 5.224 and 3.071 mg L respectively. Ergene, Tunca and Merich were 13,594, 140,612, 28,736 and 20,478 mg L−1 respectively. Lead (Pb) Manganese (Mn) The highest levels of Pb were found in the Merich −1 The value of Mn was highest in Ergene (0.490 (0.92 mg L ), in 1999 and the lowest in Arda (5.5 −1 −1 × 10−3 mg L−1) in 2004. The average Pb concentra- mg L ) and lowest in Arda (0.052 mg L ). The tions in the rivers Arda, Ergene, Tunca and Merich average concentrations in the rivers Arda, Ergene, were 0.02, 0.22, 0.05 and 0.235 mg L−1 respectively. Tunca and Merich were 0,052, 0,490, 0,181 and 0,091 mg L−1 respectively. Nickel (Ni) Cobalt (Co) The highest level of Ni was measured in the Er- The highest level of Co was measured in Arda gene (0.33 mg L−1) in 2001 and the lowest in Tunca (0.314 mg L−1) and the lowest in Tunca (0.259 mg (0.014 mg L−1) in 2003. The average concentrations L−1). The average concentrations in the rivers Arda, in the rivers Arda, Ergene, Tunca and Merich were Ergene, Tunca and Merich were 0,314, 0,268, 0,259 0.089, 0.200, 0.102 and 0.137 mg L−1 respectively. and 0,271 mg L−1 respectively.

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Aluminium (Al) Sultan Marshes lay around 20.052, 5.299, 12.59 and 4.0mgL−1 respectively. Out of these, the values The highest level of Al was measured in Merich of Ni, Zn and Cu are higher than our findings but − (0.019 mg L 1) and the lowest in Arda (0.005 mg values of Pb are higher in the Edirne waters. The − L 1). The average concentrations in the rivers Arda, Cu concentration in the Tunca is a maximum of Ergene, Tunca and Merich were 0,005, 0,017, 0,012 0.213 mg L−1, around the threshold level of 0.2 set − and 0,019 mg L 1 respectively. by the (Aksoy et al., 2005). With regard to Ni the values recorded for Tunca are very Discussion high (8.958 mg L−1) in Tunca and for Ergene 0.270 mg L−1 (limit value being 0.2 mg L−1). The Mn Pollutants enter the aquatic environment from content in the Ergene (0.490 mg L−1) too is above a variety of sources including agriculture, indus- the standard value of 0.2 mg L−1. The Co content try and incineration. Chemical pollution can disrupt varies in different rivers but all values exceed the aquatic ecosystems by damaging or destroying habi- standard maximum values of 0.05 mg L−1. tats and the plants and animals that inhabit them, Concentrations of metals were determined in reducing biodiversity. Pollutants may accumulate in sediments from 34 sites in Texas-USA (Sharma the food chain and harm predators that consume et al., 1999). They have reported anomalies in metal contaminated prey (Europa Newsletter, 2006). The concentrations and have related this to sources such productive fertile plains of the state of Edirne are as military facilities, landfill leaching and municipal facing severe abiotic pressures. A steady increase in and industrial discharges. The same sources, except the pollution of the rivers that are used for the ir- military facilities, pollute Turkish rivers. rigation of agrilands pose a great threat. The rivers Cu and to a lesser extent Cr, were mainly as- Merich, Tunca and Ergene receive a pollution load sociated with the organic matter of the sediment, from Bulgaria as well as the industrial estates of whereas, Cd, Pb, Ni and Zn were related to the car- Tekirdag and Chorlu. According to the pollution bonate and Fe and Mn oxides content in the sedi- loads, the water quality values in the rivers Arda ments. These results are similar to those of Prego and Tunca are class II, in the river Merich class II et al. (1999), Palanques et al. (1999), Lau and Chu and III, in the river Ergene class III and IV (EU Di- (2000) and Demirezen and Aksoy (2006). rective, 2000). The use of these waters has already The values of COD are generally higher than started degrading surrounding land. BOD5 and this is a normal result. However, in the −1 The waters of the Merich are of class I and II Ergene the value of BOD5 lies around 33.6 mg L . −1 with regard to the NO3 content, but class IV from This value is above the standards of 8 mg L for the point of view of the ammonium nitrogen con- irrigation water. tent (World Health Organization, 1996). The Arda in general is classified as a class I and II inland wa- Conclusions ter source whereas the Tunca is regarded as class III and IV due to nitrate content and sodium values. If The values of total P, Pb, Cu, Ni, Mn and Co the irrigation water has heavy metals above stan- are relatively high in the rivers of the re- dard concentrations, this may lead to accumulation gion and the water of these rivers is used for irri- in the agricultural plants and enter the human body gation. The heavy metal contents, specially the Cr through consumed foods (Gambrell, 1994; Dauval- content, were attributable to anthropogenic origin. ter and Rognerud, 2001). The industrial effluents released from the tanner- The values of some parameters in the rivers of ies, plastic and chrome factories have considerably Edirne are high. In particular, the total P content in elevated the levels of Cr, Cd and Ni in water bod- the river Tunca is 2.838 mg L−1 and 0.526 mg L−1 ies. There is thus an urgent need for the application in the river Merich. According to criteria published of precautionary measures before these pollutants by the European Union (EPC, 2000), these values are accumulated in humans via the consumption of should be below 0.02 mg L−1. Maximum concen- agricultural products. trations of Pb, Cu, Cr, Co, Ni, Zn, Fe, Mn and Al According to international criteria (US EPA, should be 5.0, 0.2, 0.1, 0.05, 0.2, 2.0, 5.0, 0.2 and 1993), the 1700 ha wetlands of the Merich Delta, 5.0 mg L−1 respectively in any water system. including Gala and its adjacent lakes, can be clas- According to Aksoy et al. (2005), the values of sified as A class wetlands. The region also has B nickel, lead, zinc and copper in the waters of the class wetlands which should be protected. All these,

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