Pesticide residues in water and sediment of ergene river and tributaries in Turkey
* Author to whom correspondence should be addressed.
Sigma Journal of Engineering and Natural Sciences 2020, Vol. 38, Issue 1, pp. 361-370; doi.org/10.62051/ytu.sigma-journal-of-engineering-and-natural-sciences-pesticide-residues-in-water-and-sediment-of-ergene-river-and-tributaries-in-turk
Abstract
Keywords: Ergene River Basin; water – sediment quality; pesticide residues.
1. Introduction
Pesticides, which are being widely used to improve agricultural production, are a widespread group of chemical substances. However, these substances could be persistent in water and accumulative in sediment and also bioaccumulative in biota depending on their solubility. They are very hazardous even at low levels for living organisms, human and environment. The use of pesticides is a significant global concern today due to their toxicity and long persistence in the environment (Erkmen and Kolankaya, 2006; Chopra et al., 2010; Ccanccapa et al., 2016). Meriç River is a transboundary river and has a great importance for the Balkans. Ergene River, where is known as one of the most polluted aquatic habitats of Turkey, is the main branches of Meriç River. Ergene River is being threatened by industrial and domestic wastes *
Corresponding Author: e-mail: tokatlicem@gmail.com, tel: (284) 616 13 48 361
originating from regional factories and settlement areas and agricultural contaminants originating from intensive cultivation activates (Tokatlı, 2014; 2015; 2017; Tokatlı and Baştatlı, 2016). But maybe the most important factor on the pollution of this system is very weak environmental awareness in the local people (Tokatlı and Gürbüz, 2014). These organic and inorganic pollutions significantly threaten the water resources and soil of the basin and also human health, who lives in the Thrace Region. The main objective of this study was to determine the residues of 174 kinds of pesticides in the surface waters and sediments of Ergene River Basin and to evaluate the toxicological significance of the investigated contamination in the aquatic components of the basin including Meriç and Ergene Rivers and total of 10 significant tributaries of the basin.
2.1. Study area and collection of samples
Samples were collected from the middle of the rivers (over the bridges on the rivers) in spring (rainy) season of 2018, when the precipitation and surface runoff have increased significantly in the region. After a preliminary field study, 21 stations were selected on the Ergene River Basin considering the main basin components and pollution sources. 9 of the stations were located on the Ergene River, 2 of the stations were located on the Meriç River, 10 of the stations were located on the significant tributaries of Ergene River. Location information is given in Table 1 and map of study area is given in Figure 1. Water samples were collected 0.5 m below the water surface in 1 L pre-cleaned glass bottles and kept at 4 0C until the chemical analysis. Sediment samples were collected form the upper 10 cm of sediments with an ekman grab sampler in 1 L sterile glass bottles and kept at 4 0C until the chemical analysis. Water and sediment samples were collected. Table 1. Location information of selected stations Meriç and Ergene Rivers Station Location Kavacık E1 Muratlı E2 Karamusul E3 Eskibedir E4 Oklalı E5 Pehlivanköy E6 Uzunköprü E7 Yenicegörece E8 Adasarhanlı E9 Küplü M1 Sarıcaali M2
Tributaries Name of Potamic Safaalan Creek Çorlu Stream Ahmetbey Creek Köprüaltı Creek Ana Creek Hayrabolu Stream Büyükdere Creek Kuleli Stream Ana Stream Irrication Canal
Location Karlı Muratlı Ahmetbey Lüleburgaz Sinanlı Karakavak Babeski Kumköy Bakışlar Küçükaltıağaç
Figure 1. Topographic map of Erg ene River Basin and selected stations
2.2. Pesticide analysis
QUECHERS (Quick, Easy, Cheap, Effective, Rugged, Safe) method has been applied for the extraction of pesticides in the sample and the determination of pesticides has been done by ZİVAK TANDEM GOLD LC-MS / MS device (the detection limit was 10 ppt) in Trakya University Technology Research and Development Application and Research Center (TÜTAGEM) (Schenck and Hobbs, 2004). The center has an international accreditation certificate within the scope of TS EN / ISO IEC 17025 issued by TÜRKAK (representative of the 363
World Accreditation Authority in Turkey). The element analyses were recorded as means triplicate measurements. Regarding the quality control procedures, parameters such as laboratory and field blanks, matrix spikes were evaluated. The reliability of the calibration method and sample preparation was evaluated on the spiked samples. The calibrated midpoints (10,000 ppt) were spiked with pesticide-free water, and QUECHERS stages were applied. As a result of the analysis, the recoveries were determined between 80 – 120%.
3. Results And Discussion
The mean values of the pesticide residues recorded in water and sediment of the Ergene River Basin components are given in Table 2 and 3. The proportional values of pesticides detected in water and sediment and the mean values of the total pesticide loads detected in Meriç and Ergene Rivers and tributaries of the basin are given in Figure 2 and 3. Table 2. Mean pesticide accumulations in waters of basin components (ppb) Potamic Safaalan Creek
Pesticide Propamocarbhydrochloride Carbendazim Imazalil Forchlorfenuron-706 Carbendazim Acetamiprid Forchlorfenuron-706 Carbendazim Thiamethoxam Acetamiprid Forchlorfenuron-706 Azoxystrobin Pymetrozine Carbendazim Thiamethoxam Acetamiprid Forchlorfenuron-706 Azoxystrobin Carbendazim Forchlorfenuron-706 Acetamiprid Carbendazim Dimethoate Forchlorfenuron-706 Methamidophos Mexacarbate Prometon Propamocarbhydrochloride
Pesticide Residue Propamocarb0.2066 hydrochloride Carbendazim 12.0250 Acetamiprid 0.0731 Forchlorfenuron-706 0.4817 Carbendazim 1.5696 Thiamethoxam 0.0968 Forchlorfenuron-706 0.5146 Carbendazim 0.1251 Acetamiprid 0.0239 Forchlorfenuron-706 0.2730 Carbendazim 0.1039 Forchlorfenuron-706 0.0506 Pymetrozine 0.0367 Carbendazim 2.0559 Thiamethoxam 0.3284 Acetamiprid 0.1114 Forchlorfenuron-706 0.1125 Azoxystrobin 0.1934 Carbendazim 1.0734 Forchlorfenuron-706 0.2646 Secbumeton 0.0461 Spiroxamine 0.3816 Terbumeton 0.0596 Thiabendazole 0.04334 Thiacloprid 0.074 Thiamethoxam 0.0717 Thiophonate Methyl 0.17135 Tricyclazole-753
Table 3. Mean pesticide accumulations in the sediments of basin components (ppt) Potamic
Pesticide Carbendazim Acetamiprid Thidiazuron-747 Imazalil Azoxystrobin Epoxiconazole Tebuconazole Prochloraz Propiconazole Pymetrozine Carbendazim Thiamethoxam Acetamiprid Imazalil Cyproconazole Azoxystrobin Epoxiconazole Prochloraz Tebuconazole Propiconazole Pymetrozine Carbendazim Thiamethoxam Acetamiprid Imazalil Azoxystrobin Epoxiconazole Prochloraz Tebuconazole Propiconazole Carbendazim Thiamethoxam Acetamiprid Imazalil Chlorotoluron Cyproconazole Azoxystrobin Epoxiconazole Prochloraz Tebuconazole Propiconazole Difenoconazol Acetamiprid Azoxystrobin Carbendazim Diuron Epoxiconazole
Residue 1.2990 2.0028 0.7223 1.5116 7.9727 20.1094 73.2832 1173.5320 15.4181 3.5472 4.9622 0.1538 5.2478 1.6263 1.8751 26.5398 38.9446 585.2052 165.1282 74.2774 3.8740 2.1633 0.4436 3.4751 0.7772 2.7806 7.2947 149.7365 36.8510 6.9100 2.5415 0.3885 0.1119 2.0258 0.2702 1.4835 25.1946 17.3496 45.2769 17.8928 10.2578 11.0282 0.372795 7.684818 4.630187 0.690328 5.198424 365
Pesticide Carbendazim Thiamethoxam Acetamiprid Imazalil Azoxystrobin Epoxiconazole Tebuconazole Prochloraz Propiconazole Carbendazim Clothianidin Acetamiprid Imazalil Cyproconazole Azoxystrobin Epoxiconazole Prochloraz Tebuconazole Propiconazole Difenoconazol Carbendazim Acetamiprid Imazalil Cyproconazole Azoxystrobin Epoxiconazole Prochloraz Tebuconazole Propiconazole Difenoconazol Carbendazim Acetamiprid Imazalil Chlorotoluron Cyproconazole Azoxystrobin Epoxiconazole Prochloraz Tebuconazole Metconazole -718 Propiconazole Difenoconazol Carbendazim Imazalil Azoxystrobin Prochloraz Tebuconazole
Residue 2.3964 0.1228 0.0277 2.2038 127.0282 6.1998 19.0737 212.4226 4.0181 3.6511 0.8572 0.2820 0.9941 0.9890 16.1187 8.3246 36.2022 13.2834 8.7658 5.4184 1.1758 0.3274 1.8707 0.3613 16.4166 6.8362 32.0535 8.3549 6.2555 13.6894 0.8968 0.6616 4.9117 0.9103 1.0787 26.6647 9.7438 90.3261 18.8510 2.5984 14.9129 4.5181 0.4466 0.9124 0.7944 90.8343 4.2461
Imazalil Methamidophos Prochloraz Propamocarbhydrochloride Propiconazole Pymetrozine Spiroxamine Tebuconazole Tetraconazole Thiabendazole Thidiazuron-747 Tricyclazole-753 Acetamiprid Azoxystrobin Carbendazim Chlorotoluron Cyproconazole Dimoxystrobin-688
Propiconazole Propamocarbhydrochloride Carbendazim Thiabendazole Acetamiprid
Imazalil Azoxystrobin Epoxiconazole Prochloraz Tebuconazole Propiconazole Diuron Epoxiconazole Fluometuron Imazalil Prochloraz Propiconazole Tebuconazole Thiamethoxam
As a result of this study, from investigated 174 kinds of pesticides in Ergene River Basin, a total of 19 pesticide varieties were found in water and a total of 26 pesticide varieties were found in sediment and the most widely used pesticide varieties in the region are carbendazim and prochloraz (Figure 2). It has been also recorded that pesticide accumulations detected in the Ergene River Basin, especially in the Ahmetbey Creek, Çorlu Stream and Ergene River, were found to be in quite high levels (Figure 3). According to the Water Pollution Control Regulation in Turkey, Safaalan Creek, Ahmetbey Creek, Büyük Creek, Kuleli Stream and Irrigation Canal have I. Class water quality; Köprüaltı Creek, Ana Creek, Hayrabolu Stream and Meriç River have II. Class water quality; and Çorlu Stream and Ergene River have III. Class water quality in terms of total pesticide contents, in general (Turkish Regulations, 2015). In a study, which was performed in Meriç Delta, organochlorine pesticide accumulations in surface water, sediment and fish tissues were investigated. In contrast to the results of the present study, it was indicated that, Meriç Delta was declared as low contaminated of organochlorine pesticide residues (Erkmen and Kolankaya, 2006).
Prochloraz 69% Figure 2. Total pesticide rates detected in water (up) and sediment (down) According to the results of many researches, it was clearly revealed that even trace doses of pesticides, which are threaten ecosystem integrity due to their stable structure and lipophilic character, are significant toxicants for biological organisms. Pesticides also tend to bioaccumulate and biomagnify and transferred to higher trophic levels through several food chains. As a result of this biomagnification they may lead to toxicity in non-target organism and even in human (Ogunfowokan et al., 2012; Masia et al., 2013; Wang et al., 2013). Ergene River Basin receives many point contaminant inputs like discharge of effluent from factories and industrial wastes by means of especially Çorlu and Çerkezköy settlement areas located on the east part of the basin and non-point inputs like intensive agricultural activities conducted almost all around the basin (Sungur et al., 2014; Sari et al., 2016; Tokatli, 2018). Agricultural activities carried out in the region have been generally performed in the form of monoculture applications for many years. This situation causes the agricultural pests to have significant resistance gains over time and to increase the amount and quantity of pesticides used by the local producers every year. The detected data of this study clearly reveals that agricultural runoff is a major contamination source for all the aquatic components of the Ergene River Basin and use of 367
unconscious pesticides may cause significant health problems not only for the ecosystem but also for the local people in the near future.
Figure 3. Total pesticide residues in Meriç – Ergene Rivers (left) and tributaries (right) (ppb)
4. Conclusions
In this study, pesticide residues in water and sediment of Ergene River Basin components including 10 significant tributaries were investigated. As a result of this investigation, agricultural pressure on the abiotic components of the Ergene River Basin was clearly revealed. Çorlu Stream and Ahmetbey Creek were found to be the most polluted ecosystems among the investigated basin components and fungicides mainly carbendazim and prochloraz were found to be the most widely used pesticide variety in the Ergene River Basin. It was also revealed that the basin has II. – III. Class water quality in terms of total pesticide concentrations, in general. For the protection and improve the quality of this significant river ecosystem, which is known as the lifeblood of the Thrace Region, monoculture practices in agricultural aplications should be changed and the farmers should be encouraged to polyculture practices. Also use of unconscious chemical fertilizers and pesticides should be avoided by giving the necessary training and environmental awareness for local people.
Acknowledgements
The authors would like to thank for the financial and technical supports supplied by Trakya University, Turkey. This investigation has been supported by the project numbered as 2017/211 accepted by Trakya University, Commission of Scientific Research Projects.
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TOKATLI, C. Pesticide residues in water and sediment of ergene river and tributaries in Turkey. Sigma Journal of Engineering and Natural Sciences 2020, Vol. 38, pp. 361-370. https://doi.org/10.62051/ytu.sigma-journal-of-engineering-and-natural-sciences-pesticide-residues-in-water-and-sediment-of-ergene-river-and-tributaries-in-turk