FEB – Fresenius Environmental Bulletin founded jointly by F. Korte
Transcription
FEB – Fresenius Environmental Bulletin founded jointly by F. Korte
FEB – Fresenius Environmental Bulletin founded jointly by F. Korte and F. Coulston Production by PSP – Parlar Scientific Publications, Angerstr. 12, 85354 Freising, Germany in cooperation with Lehrstuhl für Chemisch-Technische Analyse und Lebensmitteltechnologie, Technische Universität München, 85350 Freising - Weihenstephan, Germany Copyright © by PSP – Parlar Scientific Publications, Angerstr. 12, 85354 Freising, Germany. All rights are reserved, especially the right to translate into foreign language. No part of the journal may be reproduced in any form- through photocopying, microfilming or other processes- or converted to a machine language, especially for data processing equipment- without the written permission of the publisher. The rights of reproduction by lecture, radio and television transmission, magnetic sound recording or similar means are also reserved. Printed in GERMANY – ISSN 1018-4619 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FEB - EDITORIAL BOARD Environmental Toxicology: Prof. Dr. H. Greim Senatskomm. d. DFG z. Prüfung gesundheitsschädl. Arbeitsstoffe TU München, 85350 Freising-Weihenstephan, Germany Chief Editor: Prof. Dr. H. Parlar Prof. Dr. A. Kettrup Institut für Lebensmitteltechnologie und Analytische Chemie TU München - 85350 Freising-Weihenstephan, Germany e-mail: [email protected] Institut für Lebensmitteltechnologie und Analytische Chemie TU München - 85350 Freising-Weihenstephan, Germany FEB - ADVISORY BOARD Co-Editors: Environmental Analytical Chemistry: Environmental Analytical Chemistry: Dr. D. Kotzias K. Ballschmitter, D - K. Bester, D - K. Fischer, D - R. Kallenborn, N D.C.G. Muir, CAN - R. Niessner, D - W. Vetter, D – R. Spaccini, I Via Germania 29 21027 Barza (Va) ITALY Environmental Proteomic and Biology: D. Adelung, D - G.I. Kvesitadze, GEOR A. Reichlmayr-Lais, D - C. Steinberg, D Environmental Proteomic and Biology: Environmental Chemistry: Prof. Dr. A. Görg J.P. Lay, D - J. Burhenne, D - S. Nitz, D - R. Kreuzig, D D. L. Swackhammer, U.S.A. - R. Zepp, U.S.A. – T. Alpay, TR V. Librando; I Fachgebiet Proteomik TU München - 85350 Freising-Weihenstephan, Germany Prof. Dr. A. Piccolo Università di Napoli “Frederico II”, Dipto. Di Scienze Chimico-Agrarie Via Università 100, 80055 Portici (Napoli), Italy Environmental Management: L.O. Ruzo, U.S.A - U. Schlottmann, D Prof. Dr. G. Schüürmann Environmental Toxicology: UFZ-Umweltforschungszentrum, Sektion Chemische Ökotoxikologie Leipzig-Halle GmbH, Permoserstr.15, 04318 Leipzig, Germany K.-W. Schramm, D - H. Frank, D - D. Schulz-Jander, U.S.A. H.U. Wolf, D – M. McLachlan, S Environmental Chemistry: Prof. Dr. M. Bahadir Managing Editor: Dr. G. Leupold Institut für Ökologische Chemie und Abfallanalytik TU Braunschweig Hagenring 30, 38106 Braunschweig, Germany Editorial Chief-Officer: Selma Parlar Prof. Dr. M. Spiteller Institut für Umweltforschung Universität Dortmund Otto-Hahn-Str. 6, 44221 Dortmund, Germany PSP- Parlar Scientific Publications Angerstr.12, 85354 Freising, Germany e-mail: [email protected] - www.psp-parlar.de Prof. Dr. Ivan Holoubek RECETOX_TOCOEN Kamenice 126/3, 62500 Brno, Czech Republic Marketing Chief Manager: Max-Josef Kirchmaier MASELL-Agency for Marketing & Communication, Public-Relations Angerstr.12, 85354 Freising, Germany e-mail: [email protected] - www.masell.com Environmental Management: Dr. H. Schlesing Secretary General, EARTO, Rue de Luxembourg,3, 1000 Brussels, Belgium Prof. Dr. F. Vosniakos Abstracted/ indexed in: Biology & Environmental Sciences, BIOSIS, C.A.B. International, Cambridge Scientific Abstracts, Chemical Abstracts, Current Awareness, Current Contents/ Agriculture, CSA Civil Engineering Abstracts, CSA Mechanical & Transportation Engineering, IBIDS database, Information Ventures, NISC, Research Alert, Science Citation Index Expanded (SCI Expanded), SciSearch, Selected Water Resources Abstracts T.E.I. of Thessaloniki, Applied Physics Lab. P.O. Box 14561, 54101 Thessaloniki, Greece Dr. K.I. Nikolaou Organization of the Master Plan & Environmental Protection of Thessaloniki (OMPEPT) 54636 Thessaloniki, Greece 0 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin CONTENTS FOREWORD 162 REVIEW ARTICLE RELATIONS BETWEEN ECOSYSTEM AND WIND ENERGY 163 İlhami Kiziroğlu and Ali Erdoğan ORIGINAL PAPERS INTEGRATION OF GIS AND REMOTE SENSING WITH THE USLE MODEL IN THE ASSESSMENT OF ANNUAL SOIL LOSS AND SEDIMENT INPUT OF ZINAV LAKE BASIN IN TURKEY 172 Hakan Mete Doğan, Orhan Mete Kılıç, Doğaç Sencer Yılmaz, Ekrem Buhan, Fatih Polat and Saliha Dirim Buhan ACCUMULATION AND BEHAVIOR OF SOME HEAVY METALS IN THE MAIN COMPONENTS OF ZINAV LAKE BASIN ECOSYSTEM 180 Fatih Polat, Hakan Mete Dogan, Ekrem Buhan, Orhan Mete Kılıç, Doğaç Sencer Yılmaz and Saliha Dirim Buhan COMPARATIVE ANALYSIS OF BIOTIC INDICES FOR EVALUATION OF WATER QUALITY OF ESEN RIVER IN SOUTH-WEST ANATOLIA, TURKEY 188 Bülent Yorulmaz, Atakan Sukatar and Murat Barlas DETERMINING OF AREAS WITH HIGH EROSION RISK IN KÜÇÜK MENDERES RIVER BASIN (WEST ANATOLIA, TURKEY) BY USING MULTI-CRITERIA DECISION MAKING METHOD 195 Ali Ekber Gülersoy and Mehmet Ali Çelik TROPHIC STATUS AND THREATS IN ZINAV LAKE (TOKAT/ TURKEY) 203 Saliha Dirim Buhan, Nihal Bektaş, Mehmet Ali T. Koçer,Hakan Mete Doğan, Ekrem Buhan and Fatih Polat APPLICATION OF MULTI-METAL BIOACCUMULATION INDEX AND BIOAVAILABILITY OF HEAVY METALS IN Unio sp. (UNIONIDAE) COLLECTED FROM TERSAKAN RIVER, MUĞLA, SOUTH-WEST TURKEY 208 Tuncer Okan Genç, Fevzi Yilmaz, Burak Evren İnanan, Bülent Yorulmaz and Gökhan Ütük HEAVY METAL ACCUMULATION IN BIOINDICATORS OF POLLUTION IN URBAN AREAS OF NORTHEASTERN POLAND 216 Zbigniew Mazur, Maja Radziemska, Joanna Fronczyk and Jerzy Jeznach HEAVY METAL CONTAMINATION OF PLANT RAW MATERIAL INTENDED FOR FOOD Elvyra Jariene, Honorata Danilcenk and Maria Jeznach 160 224 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin COPPER REMOVAL FROM CONTAMINATED GROUNDWATER USING NATURAL AND ENGINEERED LIMESTONE SAND IN PERMEABLE REACTIVE BARRIERS 228 Joanna Fronczyk, Maja Radziemska and Zbigniew Mazur THE SALINITY PROBLEM AT YELKOMA LAGOON (YUMURTALIK-ADANA) AND ITS RESTORATION BY MIXING WITH FRESHWATER FROM CEYHAN RIVER 235 Harun Aydin, Hüseyin Karakuş and Osman Erdem DETERMINING NATURAL AND CULTURAL CHANGES AROUND WETLANDS BY MEANS OF REMOTE SENSING TECHNIQUES: A CASE STUDY IN EGIRDIR LAKE 244 Namık Kemal Sonmez, Işın Onur and Sevda Altunbaş NOTICE ECOTOURISM, PROTECTED AREAS AND NATURE CONSERVATION 250 Nihan Yenilmez Arpa and Yusuf Ceran INDEX 258 161 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FOREWORD The view of humanity on the environment has grown in recent times in different dimensions. His relationship with the environment has led to different echo in the strata of society. Since the destruction of the environment on the one hand caused the emergence of the environmental crisis, on the other hand leads to reducing the chance of survival of future generations. To avoid this, each individual must look at life in our environment, and protect the creatures bear any responsibility. This matter needs to be seriously discussed and solutions need to be found both on universal and local level. International meetings have also the duty to keep such environmental problems before the eye, and allow the exchange of expert opinion scientists. The 7th International Symposium On Ecology And Environmental Problems will forward the following topics in the Symposium: Environmental Education; -Environmental Law and Philosophy;- Chemical and physical contamination and measures to be taken in the ecosystem; -Tourism and Environment; -Alternative and Green Energy; -Biodiversity; -Environment and Settlement;- Ecology and Economy Dilemma; -Energy and Environment; -Health, Nutrition and Environment; -Art and Environment: What should be done to create a platform for climate change. A certain consensus has to be made between the economic thinking and ecological thinking. The relationship between human health and pollution should be thoroughly demonstrated. The impact of genetically modified foods on the environment and not least on the health of humanity is discussed. To protect against the import of genetics-modified organism (GMO) must be made on a legal basis. The protection of the air, water and soil should be placed on the agenda and discussed in the context of ecological thinking. Some issues should be directed to the protection of biodiversity and nature protection. In addition, the method of using the optimal form of alternative energy sources must be carried forward. The 7th International Symposium On Ecology And Environmental Problems was organized by the Hacettepe, Akdeniz and Mehmet Akif Ersoy University with the Ministry of Forestry and Water Affairs in Turkey and 65 national-and international organisations in Manavgat/Antalya/Turkey from Dezember 18-21, 2013. The main results of the 7th Symposium are included in this issue of the international journal “Fresenius Environmental Bulletin”(FEB) and they will contribute undoubtedly to the advancement of the environmental scientific knowledge and hence, to the improvement of the environment. Prof. Dr. Ilhami KİZİROĞLU Chairman of the Symposium 162 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin RELATIONS BETWEEN ECOSYSTEM AND WIND ENERGY İlhami Kiziroğlu¹,* and Ali Erdoğan ² ¹ Hacettepe University, Faculty of Education, 06800 Beytepe, Ankara, Turkey ² Akdeniz University, Faculty of Science, Department of Biology, 07058 Antalya, Turkey Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey KEYWORDS: Wind turbines, wind energy, bird migration, monitoring program, bird deaths, bat deaths ABSTRACT The study explores the amount of energy production by wind turbines in Turkey, in Europe, and in several other countries around the world. Annual production of electric energy through the wind turbines in Turkey is only 2493 MW, which accounts for only 5.8% of the total energy consumption in the country. We discussed the possibilities of how this amount can be increased to 10%, over the next 35 years. Turkey, which has 502 bird species, is a part of the Palearctic, and is located on important bird migration routes. As a result, birds prefer the migration routes on the areas where the wind intensity is quite high. Certain areas in Turkey, such as Kapıdagi peninsula, Iskenderun, Izmir, Belen, or Adana, are located on high wind intensity routes. Continuous monitoring programs for migratory bird species must be carried out for several years before the wind turbines are built on such areas. In this work, we discussed the collision effects of wind turbines on birds and bats, based on information obtained from literature and field observations both in Turkey and in several other countries. For example, the wind turbines in four states in the eastern part of the United States have only 0.003% share for bird deaths in the region. Similarly, it was found that only 0.23 individual bats died per year by wind turbines in Brandenburg, Germany. Similarly, the death rates of birds and bats caused by wind turbines are quite low compared to other human factors in Turkey. The available data indicate that death rates of birds and bats by wind turbines in relation to the other factors (e.g. by clashing up against glass windows of buildings) is quite low. Therefore, public oppositions against wind turbines are not well justified. Considering the ever lasting energy needs of mankind and environmental deterioration due fossil fuels and nuclear energy, establishment of wind turbines as green energy sources must be encouraged in appropriate places accomponied by bird observation programs along with recommended implementations proposed by ornitology reports. * Corresponding author 1. INTRODUCTION The energy need of countries is steadily increasing. This need is met mainly by traditional sources of energy, as well as coal, petroleum and natural gases. About 81% of energy used on earth derives from the classic energy sources, namely, fossil fuels energy. Also, everlasting negative effects of nuclear power plants on the environment have not yet been eliminated; nevertheless, 6.2% of energy in the world is met by nuclear energy sources [1]. The increasing trend towards the use of fossil energy sources around the world has also accelerated their negative influences on environment and human health. All of these factors result in various social and economic problems, including climate change on global scale. The energy consumption in Turkey as well as in many other countries of the world is met mostly by the fossil sources. Because Turkey depends on imports for most of its energy requirements and allocates about 72% of its budget for this purpose, and needs to eliminate the negative environmental effects of fossil fuels, the country needs to invest for alternative energy sources. Turkey has a great chance for alternative green energy and, in this respect, has to activate its solar energy and wind energy potentials [2-4]. Also Hötker [5] has suggested that, as already known before, wind turbines have smaller impact on breeding birds than on migrant birds [6-8]. Intensive use of fossil fuels as energy sources has been the major cause of global climate change, and this destroyed the balance of the environment due to resulting CO2 derivatives [9, 10]. In particular, lives of almost all living things have been distorted and influenced through the negative impacts of fossil energy in the environment and the ecosystems. In recent years, wind energy appears to be replacing the place of the primary energy sources. According to Moidl et al. [11], about 86 000 MW of wind energy has been produced per year in Europe. A medium-sized wind turbine produces enough energy per year to meet the needs of more than 1250 houses. By the year 2020, the European 163 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin Union countries aim to increase the amount of wind energy to meet 20% of their annual energy consumption [12]. This article evaluates the current situation of wind energy in Turkey, Europe and several other countries around the world. Although expansion of wind energy seems to be inevitable, the impact of this energy source on the environment also needs to be investigated. This article covers the relationships between wind turbines and their environments, specifically the effects of wind turbines on birds and bats. 2. THE CURRENT SITUATION OF WIND ENERGY PRODUCTION IN THE WORLD, EUROPE AND TURKEY The amount of electrical energy from the wind was 40 000 MW in the world, in 2003. Following the announcement of the law on renewable energy in 2004, amount of wind energy has increased considerably within a relatively short time. As one result, amounts of CO2 emission in the world were reduced by about 32 700 000 tonnes (www.igwindkraft.at/fakten). In Tables 1 and 2, the highest wind energy producing countries (and few others for comparative purposes) are presented in their wind energy production, in 2011, 2012 and 2013 (end of June). In 2013, five countries in the world have produced more than 10,000 MW of wind energy. Together, these five countries produced over 215 726 MW of energy which accounts for 73% of all WE in the world. Here, China is the first one with 80 824 MW (26.7%), the United States is the second with 60 009 MW (17.6%), Germany is the third with 32 422 MW (12.0%), Spain is the fourth with 22 907MW (8.8%), and India is the fifth (19 564 MW, 6.8%) (Table 1). According to the data from wind farm Atlas TURSAT-2012/2 [4], the amount of energy produced by wind turbines in Turkey is 2041.35 MW with additional 452.65 MW under process of construction. It can be said that the amount of current wind energy production was increased by two times in 2010. The amount of electrical energy consumed per year in Turkey is about 43,000 MW. The amount of wind energy represents only 5.8% of the electrical energy consumed in Turkey. The country must strive to raise this amount to at least 10% in a very short time. On the continental scale, European countries produce 32.5% of the world wind energy production, Asian countries 34.6%, North Americab countries 22.4%, and other countries 8.8 % (Table 2). The European Union countries get only 10% of their energy needs through the wind. It is expected that the share of renewable energies (including wind energy) in the total energy production in the European Union will raise to 20% by 2020. However, propor- TABLE 1 - The first fifteen wind energy producing countries in the world in 2011, 2012 and 2013 (Status: end of June) and the status of Turkey (from: [13-14 ]). Rank Name of the country Total capacity in June 2013 (Megawatts) (=MW) Capacity increase (MW) in the first half of 2013 Total capacity at the end of the 2012 (MW) Capacity increase (MW) in the first half of 2012 Total Capacity at the end of the year 2011(MW) Increase in wind energy capacity from the end of 2011 by the end of June, 2013 Growth Growth Rate (MW) % 18 460 22.8 13 090 21.8 3 347 10.3 1 411 5,4 3684 18.8 3592 37.4 1538 18.3 1181 15.1 1 313 20,0 651 14.2 185 4.1 1268 31.2 833 27.2 1359 48.7 154 5.8 712.35* 65.1 7 426 28.3 58 538 19.8 1 China 80 824 5 500 75 324 5 410 62 364 2 USA 60 009 1,6 60 007 2 883 46 919 3 Germany 32 422 1 143 31 308 941 29 075 4 Spain 22 907 122 22 785 414 21 673 5 India 19 564 1243 18 321 1 471 15 880 6 UK 9610 1331 8228 822 6018 7 Italy 8415 273 8152 320 6877 8 France 7821 198 7623 650 6640 9 Canada 6578 377 6201 246 5265 10 Denmark 4578 416 4162 56 3927 11 Portugal 4564 22 4542 19 4379 12 Sweden 4066 526 3743 2798 13 Australia 3059 475 2584 2226 14 Brazil 2788 281 2507 118 1429 15 Japan 2655 41 2614 2501 Turkey * 2041.35+452,6¹= 2494** 712.35* 1329 Other Countries 26 204 2030 24 174 3026 18 778 TOTAL 296 255 13 980 282 275 16 376 237 717 End of 2011199 739 Increase Increase % End of 2013 318 000 118 261 37,2 *: Turkey Wind Farm Atlas TURSAT_2012\2 (Turkish Wind Energy Atlas_2012\/as of July 2, 2012; * *) as of the end of June 2013 after construction, WEC production Megawatt (MW) 164 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 2 - World wind energy (WE) production on continental bases in June (Sources: [14, 15]. Countries By Continents European Countries Asian Countries The Countries of North America Other Countries TOTAL Wind Energy (WE) Production In MW 2010-2012 From 2012 to the % Increase End of June in 2013 86.075 96 877 32,5 58.641 103 043 34,6 44.189 66 587 22,4 21 023 26 204 8,8 292 711 tion of fossil fuels energy (coal, natural gas and oil) in the total energy consumption in the Union is still more that 70%. It means that it will take much longer time to replace fossil fuel energy by renewable energy sources. Therefore, it appears necessary that each country in the Union should take initiatives to take necessary steps on this important issue. In its 2012 report WWEA indicated that wind energy production in Europe will double in the next five years. [16], at Global Wind Energy Council on the European wind energy Conference and exhibition in Copenhagen, noted that worldwide wind energy production in 2011 increased 40 500 MW (which amounts to 20% increase), and this increases is expected to be even more in the year 2012. Here the leading country is China. Despite the fact that Europe is a leading continent with 96 600 MW, China alone is approaching to Europe with 82 000 MW. About 80 countries in the world, 20 of which with wind energy center (WEC) capacity of more than 1000 MW, have been producing and using wind energy. Especially, nuclear power plant accident in Fukushima in 2011 has been an influential factor to avoid nuclear energy and, at the same time, to urge the development of renewable energy sources. The tsunami and earthquake completely immobilized few of the 55 nuclear reactors in Japan. However, all of the 190 WEC started to fully operate within short time following the earthquake disaster. Similarly, a wind turbine, which is 300 km away from the center of earthquake and hit by five-meter-high tsunami waves, started to operate again only three hours after the tsunami hits. Fossil energy sources have multidimensional negative impacts on the environment. In addition, their prices are steadily increasing and creating various economic crisis. All these are the indicators why alternative energy sources should be sought and encouraged. The argument that the fossil energy is cheaper than renewable energy is a wrong statement when considered in wide time and space perspectives. For example, each person in Europe, on the average, spends about 700 euros every day for the fossil energy [17]. Germany plays a leading role in Europe in using the wind energy. Currently, there are twenty-five thousand wind energy turbines in Germany, and these turbines are producing more electrical energy than the electrical energy produced by 30 nuclear reactors [18]. Therefore, replacing new technological applications instead of the old technology for wind energy turbines are on the agenda [18]. The WE Production From 2010 to the % Increase End of June 2013 10 802 11.2 16 968 16.5 22 398 33.6 5 181 19.8 same argument is supported by “http:\\ www. Wind-Energie.de-Portal”. Indeed, numbers of WECs using the old technology established since 2002 have been decreasing each year. This is attributed to low capacities of old technologies of wind turbines. For this reason, developments of new technologies on wind turbines have been in process in Gemany. Therefore, establishment of wind turbines with old technology is not recommended in Turkey. In particular the low capacity 2.5 and 3.5 MW wind energy should not be used (see for example: http://www. enercon.de/ de-de/23mw.htm). 3. BIRD MIGRATION PERIODS AND MIGRATION ROUTES IN TURKEY Common migration routes of birds proceed north to south (or vice versa), depending on season, either in spring or late summer [3, 19-22]. Spring migration season over Turkey starts in March and lasts until the end of May. Autumn migration starts at the end of August and continues until the end of October. One of the most important migration routes in Turkey comes from Europe and goes through Bosphorus strait in the western part of the country. The other equally important route comes from Caucasia and goes over Artvin Province in the eastern part. Both of these routes are used mainly by storks and some predatory birds. The third route, which is of great importance mainly for cranes and common quail, comes over Black Sea and crosses the Anatolian peninsula [19-22] (Map 1 a and b). Monitoring programs need to be established and continued in areas with high wind intensities where WECs are already present and/or to be established (for examples, areas such as Kapıdağ peninsula, Iskenderun, Izmir, Adana and Belen, Map 1 a and b). In Map 1b, the localities of WEC and the most important routes of migratory birds are specified. An important route for migratory birds (especially of storks, Eurasian buzzard, black kite, short-toed snake eagle, European honey buzzard, greater spotted eagle, lesser spotted eagle and white pelicans) is located in the north of Istanbul. After 2-year monitoring of a wind turbine in the area, only a few dead seagulls were found, but no dead storks nor birds of prey were observed.That does not mean that in the course of time, no collision of birds of prey to WEC with twelve turbines in Arnavutköy at Istanbul will occur. 165 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin The height of wind energy facilities, especially in areas on migration routes for migratory birds, can present some disadvantages. They act as obstacles in the sky for free movement of birds. Therefore, wing rotors reaching heights of 80-100 m (modern wind turbines can reach up to 200 m) should be questioned. They may or may not be harmful to the bird’s navigation, depending on whether they are on migration routes or not. Maps 1a and 1 b show the overlapping between the flyway of migratory birds and the distribution of wind turbines. For example, in recent years, RES tribunes were built in Kapıdağ peninsula, which is used by white pelicans as migration route. Monitorings have just been started in these localities. Therefore, relevant results have not yet published. Here, Annual Mean Wind Speed (m/s) at 30m Migratory Routes Of Birds Shown On Turkish Annual Mean Wind Speed Map Red lines represent primary migratory routes while blue lines represent less used secondary migrotary routes. Blue arrows represent north‐south oriented migrations occuring without a certain route. Migratory Routes Of Birds Shown On Turkish Wind Power Plant Atlas Red lines represent primary migratory routes while blue lines represent less used secondary migrotary routes. Blue arrows represent north‐south oriented migrations occuring without a certain route. MAP 1 - a) Migratory routes of birds shown b) on Turkish annual mean wind speed map (red lines represent primary migratory routes while blue lines represent less used secondary migrotary routes. Blue arrows represent north-south oriented migrations occuring without a certain route. White arrow is representing Belen Pass). 166 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin the altitude of migration route is very important in that radar records cannot be used for low-flying birds. Therefore, radar data sets for the low flying birds are questioned whether they could be suitable [23]. Dürr (2013-2014) [43] has given a number of deaths of birds and bats by years as reported by various sources in several European countries and several states in Germany. Such results are not present for Turkey, mainly because there are no sufficient and reliable monitorings and records on such deaths. This study evaluates the general information available so far. The flying altitude of birds is very variable. In general, small birds fly close to the ground level [24]. Flight altitude could be quite high for large bird species. Birds migrating at night can achieve greater height than birds flying at day time [24]. Bird species flying by wing flapping prefer to fly at lower altitudes than the birds flying through the help of air drafts. Birds flying against wind direction also prefer to fly at lower altitudes. Bird species that prefer wind direction coming behind during migration can achieve 400, 700, 900 m above ground level. It was stated that this level is achieved especially during the autumn migration [25-26] (s. Map 1 a and 1 b). birds are able to assess the technical structures not as a threat or danger. In particular, they can see wind turbines as not being a problem in the region and in the thickets of semi-open areas [6]. Because birds have their own internal biological clock, they can easily adapt to new conditions and then exhibit almost natural behavior [3, 8, 31-33]. In Denmark [34] and Germany [35], it has been found, according to the radar measurements, that birds change their flight direction before reaching 100 to 200 m close to the rotor of a WEC, and can thus avoide any probable damage. The birds can adapt to the regions where WEC power plants are installed, in the course of time. However, such cases need to be further clarified in further works and continued monitoring of the respective areas. According to (http://www.wind-energie.de/en/topics/ protection-of-birds) portal, Arctic geese used to reach altitudes of 500-1000 m, but now they fly about 30-100 m above ground level around the cities. This is especially common when organisms do not change their body temperature according to the ambient conditions (homoiothermal) [33]. Even it is known that some species of migratory birds are able to prefer a new route with new conditions instead of going through a distorted geographic area. 4.2 Death Impact on Birds 4. DEATHS OF BIRDS AND BATS BY WIND ENERGY TURBINES During a monitoring of a wind-turbine-farm on Belen Pass by Hatay [27] (Map 1a), flight altitudes of the following bird species were determined: white stork, lesser spotted eagle, greater spotted eagle, crane, short-toed snake-eagle, western marsh harrier, Eurasien hobby, Eurasian sparrowhawk, European honey buzzard, northern harrier, common buzzard, long-legged buzzard, common kestrel and European beeeater. It was noted that common kestrel, Eurasian sparrowhawk, however, flew above the height of the turbine more than the smaller bird species, over 300 NN or 500 m of sea level. This means that wind turbines have negative impacts on the life of few small bird species. It appears that wind energy expansion seems to be inevitable; therefore, the potential impacts of these facilities on bird species should be investigated before constructions. In this context, the primary concern focuses on the relationship between WEC and birds and bats [28, 29]. In addition, bird species show intra-species variation in their behavioural patterns. For this reason, the respective species of migratory birds, especially on the optimal migrational zones, need to be monitored. To prevent the negative effects of wind turbines on the environment, various investments have been made in different countries. In spite of this, the prevailing public opinion and concerns are that wind energy power plants cause deaths of larger birds and bats. 4.1 The Dilemma of Bird Deaths and Wind Power Plants Isselbächer [30] pointed out that the wind turbines have minimal negative impact on native birds. It is because The numbers of deaths of birds by WEC are not greater than with other human activities. In this context, one of the most extreme examples is as follows: in Sweden, 43 bird died in one night on a WEC, which was under illumination but not in operation [36]. Similaly, the number of bird deaths by various human-related factors in the United States exceeds millions, or even billions. In four States in the eastern part of the USA, the proportion of bird deaths by WEC accounts only for 0.003% of all bird deaths in the region [37]. A study by [38] has shown that, through the various means, 20 million birds are killed each year. Such deaths were mostly due to glass constructions on buildings in residential, high voltage lines, communication lines and traffic. In other words, the deaths of the birds by the WEC rotors is much lower than the deaths by various other human factors. According to a study by [39], each year, 60 to 80 million individual birds die by vehicles in traffic, 98 to 980 million by clashes against the glasses on buildings, and 4 to 50 millions by communication lines. On the other hand, in the same study, it was highlighted that the number of birds killed by WEC is only 10-40 thousand in a year. As it is seen, the bird deaths from wind turbines compared to the other sectors are rather small. It was also found that the numbers of birds and bats killed by WEC in Turkey is much lower than the deaths by other sectors; for example, through the traffic [40]. For these reasons, the number of birds and bats killed by WEC alone must not prevent the development of this alternative energy source. Also, it is assumed that the number of bird deaths from clash against glass windows of buildings is much larger in Turkey than deaths due to WECS. Therefore, it is suggested that bird pictures must be glued on the glasses so that the birds avoid clashing against the glass windows and walls of particu- 167 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin larly tall official buildings. If it is assumed that one bird dies by hitting windows of every single house, it can be estimated that the number of birds dying in Germany becomes enormous [41]. It was found out by Hötker et al. [42] that between 1989 and 2004, 269 individual birds were killed by WEC. Among them, red kite with 41 and buzzard with 27 individuals reached the highest numbers. It was also found that the number of birds killed by the WEC plants, near a village (Fehmarn, Germany), representing an important bird migration route between Scandinavia and Central Europe, was only 13 individuals [44]. This number was much lower than the results obtained from WEC farms located in the western part of SchleswigHolstein and in Netherlands [45-47]. Birds dying by WEC in Fehmarn compared to traffic was quite low. The results of the studies cited above indicate that bird deaths due to WEC installations is much lower than the bird deaths caused by other human activities. If one makes a comparison between the mortality rate of birds and bats by traffic and by WEC installations in Turkey, it could easly be stated that WEC installation is almost innocent [40]. 4.3 The Bat Deaths by Wind Energy Centers Glasner [26] indicates the number of bats killed per year in a wind farm is 0.23 individual in Brandenburg in Germany. It was reported that three individuals of serotine bat (Eptesicus serotinus) died in a year in North RhineWestphalia in Germany, and the number of deaths of noctule (Nyctalus noctula) was larger [48]. The important reason for low bat deaths was that bats in the air will not move when the rotors operate at high speeds [49]. Also in August and September wind speed is quite low (5.5 m/sec) and the rotors are closed down at this period. However, there is a possibility that bats die when the rotors exert a pressure on them as it was observed in Canada [50]. It can well happen in other countries, too. Indeed, hundreds of dead bats were observed on a WEC TABLE 3 - Bird deaths caused by the WEC (SVLU, GV, Brandenburg, 7th October 2013, Dürr) (http://www.mugv.brandenburg.de/cms/detail.php/bb2.c.451792.de) [43]. Species/Countries Bubulcus ibis Anas platyrhynchos Gyps fulvus H.albicilla Milvus milvus M.migrans Buteo buteo Falco tinnunculus L.arus ridibundus L. argentatus L.fuscus Sterna hirundo Apus apus Alauda arvensis Delichon urbica Emberiza calandra Sturnus vulgaris Countries Total (Europa union) (B) (G) 48 76 (S) 96 36 1877 (F) (UK) 2 87 213 13 4 22 66 13 245 21 2 5 55 220 14 328 72 2 33 787 45 1 200 5 4 154 1 2 75 73 20 72 89 19 23 37 1 28 162 2 26 60 2 8 59 539 878 122 1698 1305 3020 121 1757 1844 3892 243 (B) Belgium; (G) Germany; (S) Spain; (F) France; (UK) United Kingdom; NL) np=Nonpassers. (Nl) (N) 7 2 1 39 3 9 36 1 4 29 8 1 1 2 1 14 46 16 119 102 110 133 148 126 Netherlands; (N) Norway; (P) 4 1 (Sw) TOTAL 100 185 1882 24 157 12 246 101 3 3 281 20 321 474 2 889 211 155 5 3 181 22 219 40 6 134 20 212 2 115 141 68 p 2004 59 62 np 6671 200 130 8675 (P) Portugal; (Sw) Sweden; p= Passers; TABLE 4 - Types of bat species died due to WEC in various countries ([43] (Dürr, 2013). Countries B G S F UK NL P Species Nyctalus noctula 689 1 12 10 1 N. leislerii 99 19 39 58 152 Eptesicus isabellinus 117 1 Pipistrellus pipistrellus 409 211 226 24 14 200 P. pygmaeus 503 76 34 24 TOTAL 6 1982 1219 743 199 22 689 (B) Belgium; (G) Germany; (S) Spain; (F) France; (UK) United Kingdom; (NL) Netherlands, (P) Portugal; (Sw) Sweden 168 Sw TOTAL 1 746 371 118 10195 144 5024 1 1 11 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin farm near Brandenburg, Germany. It was soon understood that the deaths were not due to physical harm to the bats, but rather due to pressure on bats while they were resting under standstill rotors [43] (Table 4). 5. CONCLUSIONS AND RECOMMENDATIONS In the USA, it is considered that wind turbines can be deadly for birds and bats, and the focus has been on how to prevent such deaths. This will take 1- to 1-year periods of monitoring on seven thousand wind turbines and over one thousand observations [51]. Observations indicated that birds of prey species are the most affected by deaths through the clash with rotor blades. Through observations and scientific studies, it has been established that maximum 0.5 bird per turbine is under threat in Germany [52-54]. However, certain bird species, such as common quail, corncrake, common buzzard, long-legged buzzard, Eurasian sparrowhawk, short-toed snake-eagle, red kite, crane, and various duck species are affected by wind energy rotor blades. Therefore, it appears necessary to monitor and study how bird species breeding in the close vicinity of WEC installations are affected. Such monitoring studies around WEC installations should also continue on non-migratory birds as well as migatory birds both during the summer, spring and autumn periods. The location of WEC installations must be inspected and monitored by ornithologists, at least for 1- to 2-year periods before the WEC establishments and during the WEC operations [3, 27, 55-57]. Several studies by ornithologists showed that bird species exhibit certain intraspecific variation in their behvioural patterns, which may results in changes of their interaction with WEC areas. It appears that WEC areas should be studied and monitored due to ornithological reasons for the period of at least 2 years before and after the WEC establishments [3, 27, 55-57]. Although the available data strongly indicate that bird deaths caused by wind turbines are almost negligible compared to deaths caused by other human activities, it is still necessary to obtain new data by continual monitoring and additional studies. Dürr [43] has presented various data (see Tables 3 and 4) and evaluated them in his study. When some bird species, such as storks, pelicans, red kites, sea eagles, buzzards and bee-eaters, are considered in Bosphourus and Belen Pass in Turkey, similar evaluations as by Dürr [43] seem to be not possible at this stage, because there are not enough data based on monitoring and field observations. As such data become available, we will be able to make more reliable assessments whether or not the WECs have negative, positive, or neutral impact on the birds. The candidate zones where WEC facilities to be established need to be investigated in terms of predatory and, especially, in terms of migratory birds. On this context, especially predatory bird species in danger of extinction should be given special consideration in monitoring programs. When the results of such studies become apparent, people will be able to better understand that WEC installations are not as harmful to bird populations as it has been thought. As the establishment of WEC plants extended, it is expected that harming affects of fossil fuels energy and nuclear energy on our environment would decline rapidly. Energy resources other than coal reserves in Turkey are rather limited. Turkey has to meet about 72% of its energy needs through paying foreign exchange money. At present, annual energy consumption in Turkey is about 43 000MW. By 2023, it is expected that this amount will double. To meet the growing needs, Turkey has to make investments for alternative energy sources. As seen in Table 1, the amount of wind energy production in Turkey has reached 1329 MW in recent years. On the other hand, potential wind energy sources in Turkey are estimated to be about 40 times higher, i.e. around 40 000 to 50 000 MW. Another advantage of Turkey in terms of energy system is that the country has been surrounded by seas, and efficient WECs can also be established in offshore areas. 169 The authors have declared no conflict of interest. REFERENCES [1] EA (2008) Key World Energy Statistics 2008, Paris, Cedex 2008. [2] Turan, L. and Kiziroğlu, I. (2006) Rüzgâr Santralleri, Kuşlar Ve Türkiye. XVII. Ulusal Biyoloji Kongresi,2006,Aydın [3] Kiziroğlu,, İ.(2013) Alternatif Enerji Kaynağı Olarak Rüzgar Enerjisi ve Ekosistem İlişkisi. 6. Mühendislik ve Teknoloji Sempozyumu 25-26 Nisan 2013, Çankaya Üniversitesi/Ankara,107-112. [4] Turkiye Ruzgar Santralleri Atlası TURSAT_2012/2 (Turkish Wind Energy Atlas_2012/2) [5] Hötker, H. (2006) Auswirkungen des “Repowering” von Windkraftanlagen auf Vögel und Fledermaeuse. NABU, 40 pp. [6] Horch, P. and Keller, V. (2005) Windkraftanlagen und Vögel - ein Konflikt? Eine Literaturrechrche. Schweizerische Vogelwarte Sempach, Sempach. [7] Langston, R.W.H. and Pullan, J.D. (2003) Wind farms and birds: an analysis of the effects of wind farms on birds, and guidance on environmental assessment criteria and site selection issues. Report written by Bird Life İnternational on behalf of the bern Convention, Sandy. [8] Reichenbach, M. (2003) Windenergie und Vögel-Ausmass und planerische Bewaeltigung Dissertation. Technische Universitaet, Berlin [9] Pall, P., T. DA. Aina., Stone, PA. Stott, T. Nozawa, AGJ. Hilberts, D. Lohmann, MR. Allen (2011) Anthropogenic greenhouse gas contribution to flood risk in England and Wales in autumn 2000. Nature 470,382-385 [10] Stott, P. A., M. Allen, N. Christidis, R. Dole, M. Hoerling, C. Huntingford, P. Pall, J.Perlwitz, and D. Stone (2011) Attribution of Weather and Climate-Related Extreme Events. 44pp. conference2011.wcrp-climate.org. © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin [11] Moidl, M. S., U. Naeher and G. Scholz (2011) Die starken Zahlen der Windkraft. IMPRESSUM, Wien. [12] www.igwindkraft.at/fakten. [35] Bergen, F. (2001) Untersuchungen zum Einfluss der Errichtung und des Betriebs von Windenergieanlagen auf Vögel im Binnenland. Dissertation, Ruhr Universität Bochum. [36] Karlsson, J. (1983) Birds and windpower, pp.12. [13] http://www.igwindkraft.at/redsystem/mmedia [14] WWEA (2012) 2012 Half-year Report. World Wind Energy Association. www.wwindea.org, [15] WWEA (2013) 2013 Half-year Report. World Wind Energy Association. www.wwindea.org, [16] Sawyer, S. (2012) GWEC(Global Wind Energy Council). [17] Engel, (2012) GWEC(Global Wind Energy Council). [37] National Academy of Sciences. (2007) Environmental impacts of wind-energy projects (Washington, DC: National Research Council). [38] Arup, O. (2002) Bird Collision With Manmade Structures ,Report No. 3 On Ecological Survey Results (Ref. 076). Agreement No. CE 39/2001, Shenzhen Western Corridor Investigation And Planning. Ove Arup & Partners Hong Kong Limited, February 2002, 26pp+App.A-Z [18] Maas, N. (2008) Der Repoweringmarkt für Windkraftanlagen in Deutschland. Bachelor of Engineering (B.Eng.) Nico Maas, FB Energie Gebaeude Umwelt, Münster. [39] Reichenbach, M and Steinborn, H. (2008) Brutvögel und Feldermäuse im Bereich der geplanten Erweiterung des Windparks Westerburg/Charlottendorf Ost. Faunistisches Gutachten . [19] Kiziroğlu, İ. (1994) Türkiye’nin Yerli ve Göçmen Kusları Haritası. Atlas ve Tempo Dergisi Eki olarak. [40] Kiziroğlu, İ., Turan, L. and Erdoğan, A. (2013) Biological diversity in Turkey and threats on it. (F-2012-528)/ Fresenius Environmental Bulletin 22(3), 770-778.. [20] Kiziroğlu, İ. (1995) Türkiye’nin Yerli ve Göçmen Kusları Haritası. Atlas ve Tempo Dergisi Eki olarak. [21] Kiziroğlu, İ.(2008) Türkiye Kusları Kırmızı Listesi. Red Data Book for Birds of Türkiye. Ankamat Mat., Ankara, 151 pp. [22] Kiziroğlu, İ. (2009) Türkiye Kusları Cep Kitabı. Pocketbook for Birds of Türkiye. Ankara, Ankamat Matbaacılık, 568 pp. [23] Gatter, W. (2000) Vogelzug und Vogelbestaende in Mitteleuropa. Aula, Wiesbaden. [24] Berthold, P. (2000) Vogelzug-Steuerung und Evolution aus heutiger Sicht.Sber.Ges.Naturf.Freunde Berlin (N.F.)39, 4352. [25] Bruderer, B. and Liechti, F. (2004) Welcher Anteil ziehender Vögel fliegt im Höhenbereich von Windturbinen? Der Ornithologische Beobachter 101, 327-335. [26] Glasner, W. (2009) Faunistische Untersuchungen zur Windkraftnutzung im Aachener Norden. Zum Einfluss des weiteren Ausbaus der Windenergie auf Vögel und Fledermäuse - Gutachten im Auftrag des LA Landschaftsplanung, Oktober 2009, 114 pp. [27] Erdoğan, A., A. Aslan, H. Sert, S. Kaçar and H. Karaardıç (2010) Hatay-Senköy'de Kurulması Planlanan Rüzgâr Enerji Santralinin Yaz Ve Sonbahar Kus Göç Hareketleri Üzerine Olası Etkilerinin Değerlendirmesi, 60 pp. [28] Bach, L. (2001) Fledermäuse und Windenergienutzung – reale Probleme oder Einbildung? Vogelkdl. Ber. Niedersachs, 33, 119-124 [29] Bach, L. and Rahmel, U. (2006) Fledermäuse und Windenergie – ein realer Konflikt? Inform.d.Naturschutz Niedersachs.26.Jg.N147–52. [30] Isselbächer, K. and Isselbächer, T. (2001) Vogelschutz und Windenergie in Rheinland-Pfalz. Gutachten im Auftrag des LfUG, Oppenheim. [31] Kiziroğlu, İ. (2001) Ekolojik Potpuri. TAKAV Yay., Ankara, 265 pp. [32] Kiziroğlu, İ.(2014) Ekolojik Potpuri. 2. Ankamat Mat. Baskıda.(in pres),465pp, Ankara. [33] Kiziroğlu, İ. (2010) Genel Biyoloji. Canlılar Bilimi. VII Baskı: Okutman Yayıncılık. Ankara; 610 pp.7.Baskı. [34] Pedersen, M.B. and Poulsen, E. (1991) Avian responses to the implementation of the Tjaereborg Wind Turbine at the Danish Wadden Sea . Dan. Wildtundersogelser 47,1- 44. 170 [41] Richarz, K. and Limbrunner, A. (2003) Fledermäuse. FrankhKosmos [42] Hötker, H., Thomsen, K.M. and Köster, H. (2004) Auswirkungen regenerativer Energiegewinnung auf die biologische Vielfalt am Beispiel der Vögel und der Fledermäuse –Fakten, Wissenslücken, Anforderungen an die Forschung, ornithologische Kriterien zum Ausbau von regenerativen Energiegewinnungsformen. Endbericht. Michael-Otto-Institut im NABU. [43] Dürr, T. (2013) Daten aus der zentralen Fundkartei der Staatlichen Vogelschutzwarte im Landesamt für Umwelt, Gesundheit und Verbraucherschutz Brandenburg zusammengestellt: Tobias Dürr; Stand vom: 07. Oktober 2013). Daten aus der zentralen Fundkartei der Staatlichen Vogelschutzwarte im Landesamt für Umwelt, Gesundheit und Verbraucherschutz Brandenburg Stand: 25. September 2013, Tobias.Dürr. [email protected]. http://www.mugv.brandenburg.de/cms/detail.php/bb2.c.451792.de [44] Grünkorn, T. (2010) “Hotspot Fehmarn“ ausgewählter Ort 2010, „www.land-der-ideen.de“ Preisträger des Wettbewerbes der Deutschen Bank. [45] Grünkorn, T., A. Diederichs, D. Poszig, B. Diederichs and G. Nehls (2005) Entwicklung einer Methode zur Abschätzung des Kollisionsrisikos von Vögeln an Windenergieanlagen. Untersuchungen im Auftrag des Landesamtes für Naturschutz des Landes Schleswig-Holstein. *pdf bei „www.bioconsult-sh.de“ [46] Grünkorn, T., A. Diederichs, D. Poszig, B. Diederichs and G. Nehls (2009) Wie viele Vögel kollidieren mit Windenergieanlagen? Natur und Landschaft 7, 309-314. *pdf bei http.www.bioconsult-sh.dewww.bioconsult-sh.de [47] Krijgsveld, K.L., K. Akershoek, F. Schenk, F. Dijk and S. Dirksen (2009) Collision risk of birds with modern large wind turbines. Ardea 97(3) 357–366. [48] Brinkmann, R. (2006) Auswirkungen von Windkraftanlagen auf Fledermäuse. Naturschutz- Info 2/2006 + 2/2006. [49] Brinkmann, R. and Schauer-Weißhahn, H. (2006) Untersuchungen zu möglichen betriebsbedingten Auswirkungen von Windkraftanlagen auf Fledermäuse im Regierungsbezirk Freiburg. Studie im Auftrag des Regierungspräsidiums Freiburg. [50] Brahic, C. (2008) Wind turbines make bat lungs explode. New scientist, Aug 2008. [51] Orloff, S. and Flannery, A. (1992) Wind turbine effects on avian activity, habitat use and mortality in Altamont Pass and Solano County wind resources areas 1989-1991. California Energy Commission, Bio-Systems Analysis, Tiburón, Califonia. 49. © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin [52] Winden, J., Spaan, A.L. and Dirksen, S. (1999) Nocturnal collision risks of local wintering birds with wind turbines in wetlands. Bremer Beiträge für Naturkunde und Naturschutz 4, 3338. [53] Green, R. E. (1999) Survival and dispersal of male Corncrakes Crex crex in a threatened population. Bird Study 46 (supplement), 218-229. [54] Everaert, J. (2003) Collision victims on 3 wind farms in Flanders (Belgium) in 2002.1nstituut voor Naturbücher, Brüssel. [55] Daulton M. (2007) Congressional Testimony on Benefits of Wind Power Before the Committee on Natural Resources Subcommittee on Fisheries, Wildlife and Oceans Impacts of Wind Turbines on Birds and Bats May 1, 2007 [56] Telleria, J.L. (2009) Potential impacts of wind farms on migratory birds crossing Spain Bird Conservation International 19, 131-136. (http://www.wind-energie.de/en/topics/protection-of-birds), [57] www.gwec.net,www.ruzgarenerjisibirligi.org.tr,www.tr.wikipedia.org,www.igwindkraft.at/fakten,http://eie.gov.tr http://www.nabu.de/aktionenundprojekte/weissstorchbesenderung/#karte,www.oekostrom.at,www.aae.at,www.naturkraft.at Received: April 03, 2014 Revised: August 04, 2014 Accepted: August 13, 2014 CORRESPONDING AUTHOR Ilhami Kiziroğlu Dicle Caddesi, No. 2006532 Beysukent/Ankara TURKEY Phone +903122351336 E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 163 - 171 171 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin INTEGRATION OF GIS AND REMOTE SENSING WITH THE USLE MODEL IN THE ASSESSMENT OF ANNUAL SOIL LOSS AND SEDIMENT INPUT OF ZINAV LAKE BASIN IN TURKEY Hakan Mete Doğan1*, Orhan Mete Kılıç1, Doğaç Sencer Yılmaz1, Ekrem Buhan2, Fatih Polat3 and Saliha Dirim Buhan4 1 4 Gaziosmanpaşa University, Agricultural Faculty, Soil Science Department, GIS&RS Unit, Taşlıçiftlik, Tokat/Turkey 2 Gaziosmanpaşa University, Agricultural Faculty, Aquaculture and Fisheries Department, Tokat/Turkey 3 Gaziosmanpaşa University, Almus Vocational School, Tokat/Turkey Gebze Institute of Technology, Faculty of Engineering, Environmental Engineering Department, Gebze/Kocaeli/Turkey Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey ABSTRACT The effects of annual soil loss on Zinav Lake Basin located in Tokat Province of Turkey were researched. The annual soil loss of the study area was modelled and mapped by using the Universal Soil Loss Equation (USLE), Geographic Information Systems (GIS) and remote sensing (RS). Employing the USLE model, precipitation (R), the degree of slope and length of slope (L and S), soil erodibility (K), vegetation cover-land use (C), and soil conservation (P) factors were separately calculated and transformed to raster maps in GIS environment. Then, all produced factor map layers were multiplied each other to develop an annual soil loss raster map. Annual sediment input was calculated by utilizing Roehl sediment delivery ratio and developed annual soil loss raster map. The mean annual soil loss of the study area was determined as 0.037 t.ha-1year-1. Erosion risk classes of the study area were determined according to European Environment Information and Observation Network for Soil (EIONET-SOIL) Erosion Map, and summarized as five classes including the 0-0.5, 0.5-1.0, 1.0-2.0, 2.0-5.0 and 5.0-7.1 t.ha-1year-1 intervals. Sediment delivery ratio and mean annual sediment input were determined as 44.67% and 0.181 t.ha-1year-1, respectively. KEYWORDS: EIONET-SOIL, Geographic Information Systems, erosion, K-factor, modelling, LANDSAT-7 ETM+, soil accumulation, Zinav Lake. 1. INTRODUCTION Soil erosion, as a result of anthropogenic activity, in excess of accepted rates of natural soil formation, causing * Corresponding author a deterioration or loss of one or more soil functions [1]. It is a gradual process that occurs when the impact of water or wind detaches and removes soil particles, causing the soil to deteriorate. The most importantly, erosion generates many environmental problems such as removal and disappearance of the productive top soil [2, 3], corruption of river regimes [4], destruction of wetlands [5], short reservoir life and water pollution [6]. Therefore, soil deterioration and low water quality due to erosion and surface runoff have become the most fundamental problems that threat ecosystems and life world-wide [3]. The spatial identification of erosion risk areas has a high priority to combat erosion and is a prerequisite for sustainable ecosystem. The Universal Soil Loss Equation (USLE), developed by the United States Department of Agriculture (USDA) in 1930s, has been a widely used mathematical model that describes soil erosion processes [7, 8]. The USLE played critical roles in soil and water resource conservation and nonpoint source pollution assessments, including: sediment load assessment and inventory, conservation planning and design for sediment control, and for the advancement of scientific understanding [9, 10]. A GIS is a tool that integrates hardware, software, and data for capturing, managing, analyzing, and displaying all forms of geographically referenced information [11]. As a modern and powerful tool GIS allows us to view, understand, question, interpret, and visualize the spatial data in many ways [12]. Rise and significant improvements in GIS and RS, as well as the advances made in computing power have assisted in the orientation of modelling efforts towards the spatial attributes of erosion processes and features [13]. In the past decade, many researchers integrated the USLE with GIS in order to calculate and map soil losses properly [6, 8, 14-16]. GIS for water erosion modelling caused the consequences such as facilitating multiplesource data mixing, creating a computing environment for 172 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin potential model rescaling and increasing complexity in datamethod relations [17]. Zinav Lake is the biggest natural lake in Tokat Province and Kelkit Basin of Turkey. The lake has regional and national importance because of its natural structure, biological diversity, and unique landscape values. However, the lake and the lake basin are under the pressure of several threats such as anthropogenic and natural hazards. One of these pressures is soil accumulation towards the lake due to erosion. Although ecologists in the area have been aware this accumulation process, there is not any study to quantify this accumulation until now. This is a critical subject for the lake management in the future. In this study, we aimed to research the effects of annual soil loss and sediment input on Zinav Lake. For this purpose, we employed the USLE model, GIS and RS to calculate and map soil loss and to determine sediment input of Zinav Lake Basin. 2. MATERIAL AND METHODS The study area is located in the Central Black Sea Region of Turkey. Zinav Lake Basin is situated in the northwest district of Reşadiye county of Tokat province. The precise position of study area can be described as between the 37o13’-37o21’ East longitudes and 40o32’-40o23’ North latitudes (Figure 1). The total study area is determined as 98.01 km2, and Zinav Lake surface area covers an area of 0.34 km2. The highest and lowest points of the basin are 1648 m and 451 m, respectively. The lowest point is located in the vanishing point of Zinav Lake and Kelkit River. In the study area, the average annual temperature is 10.3oC, and average annual rainfall is 482 mm. The majority of rains fall in the spring. From time to time, less intense but prolonged rains occur in the study area. Zinav Lake is located FIGURE 1 - Location and topographic features of the study area 173 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin at higher elevation comparing to the Reşadiye county centre (Figure 1). For this reason, the lake and surrounding area receive more snow fall compared with the centre of Reşadiye county, and this snow is long lasting. Both spring rains and leaked water from the melting snow cause increasing water level in Zinav Lake. This situation promotes erosion and landslides in the study area [18]. The sedimentation is transferred to the lake by Kelkit river and side gutters around the lake. Main vegetation of the study area is degraded oak and pine forests. The soils of the study area have been considered to the Brown Forest Soil major group. This major group corresponds to Eutric Cambisols (CM) according to the WRB Map of World Soil Resources [19-21]. This soil group holds soils with incipient soil formation. Beginning transformation of soil material is evident from weak, mostly brownish discolouration and/or structure formation below the surface horizon [20, 21]. The main land covers of the study area are forest, rangeland, water surfaces (Lake Zinav) and rocky areas. The soil erosion indicator adopted in this study is the estimated soil loss expressed in ton per hectare per year (t ha-1 yr-1) as described in detail by Huber et al. [22]. We followed a methodology that integrates the USLE model with GIS and RS to determine soil erosion. The USLE model (1) below predicts soil losses depending on rainfall, soil, and vegetation characteristics [10]. In this model (1), A is the annual soil loss (t ha-1 yr-1); R is the rainfall-runoff erosivity factor (MJ mm ha−1 h−1 yr−1); K is the soil erodibility factor (t ha h ha−1 MJ−1 mm−1); L is the slope length factor; S is the slope steepness factor; C is the covermanagement factor; and P is the support practice (soil conservation) factor. L, S, C, and P are unit-less as factors. A R * K * L * S *C * P (1) Basically, R (rainfall-runoff erosivity) factor shows the effects of annual independent rainfalls to soil loss. Duration and the amount of rainfall, kinetic energy of raindrops, and the diameters of raindrops are the main factors that affect R factor [23]. We utilized rain data from Reşadiye meteorological station to calculate R factor. This rain data contains the average monthly rainfall data between 1970 and 1992. The Modified Fournier Index (MFI) equation (2) below have been used to calculate R factor [24-26]. In this equation (2), Pi is the total rainfall (mm) in the ith month, P is the average annual rainfall (mm). 12 MFI Pi 2 / P (2) its topography, geology, vegetation, and soil characteristics to find the best placement of sampling sites. Considering this stratification, a total of 70 sampling sites were randomly distributed within these strata. Soil samples were collected with a small shovel to the depth of 15–20 cm. During the soil sampling process, the soil sampling procedures were utilized [28, 29]. The soil samples (̴ 2.0 kg) were taken into a plastic bag and labelled. Organic matter, texture, and very fine sand fraction were determined through the laboratory analyses. We measured soil organic matter content (%) by following the modified Walkley–Black wet oxidation procedure [30], and determined the texture by utilizing the Bouyoucos hydrometer method [31, 32]. Structure codes were determined during the field studies, and permeability values were calculated by using SPAW hydrology software [33]. On the basis of these calculated values, K factor values were determined by using the following equation (3) [8, 10, 23]. In this equation (3), K is soil erodibility factor (t ha h ha−1 MJ−1 mm−1), M is the product of the primary particle size fractions ((% modified silt or the 0.002-0.1 mm size fraction) * (% silt + % sand)), OM is organic matter content (%), s is structure type code, and p is permeability class code. Using this equation (3), K factor values of 70 soil samples were calculated. Then, a K factor raster map was developed by using ordinary kriging method with spherical variogram in ArcGIS software [12]. In the interpolation process, we used the highest precision for derived coverage, and single precision for new coverage. (3) L (length of slope) factor is the horizontal distance from the starting point of surface runoff to the point that water flow concentrated to a particular canal [10]. We determined the length of slope (L) and the degree of slope (S) factors by using the digital elevation model (DEM). For this purpose we digitized the topographic map of the study area with 1/25000 scale, and developed a DEM from this digitized topographic map. We utilized DEM to generate elevation and slope raster maps with 10x10m grid size in ArcGIS. Then, we calculated L factor values from the created raster maps by using raster calculator function of ArcGIS and the equation (4) below [10, 34, 35]. In equation (4): L is the length of slope factor, λ is the length of slope (m), and m is a dimensionless exponent. Coefficient m depends on the slope steepness value and gets 0.5 (slope >5%), 0.4 (slope=4%), and 0.3 (slope <3%) values [10, 34, 35]. 1 L ( / 22 .1) m K (soil erodibility) factor defines the effects of soil features and soil profile characteristics to soil loss. In this study, K factor was calculated by using the laboratory analysis results of 70 geo-referenced soil samples that we collected by following the stratified random sampling design [27]. For this aim, we stratified the study area according to K 2.1 10 4 (12 OM ) M 1.14 3.25( s 2) 2.5( p 3) / 100 * 0.1317 (4) S (degree of slope) factor shows the effect of slope to erosion. S factor was calculated by using slope raster map, the equations (5, 6) below and raster calculator function of ArcGIS. In equations (5, 6): S is the degree of slope factor, Ɵ is the angle of slope, and s refers to the land slope. If the 174 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin land slope is smaller than 9% (s<9%), equation 5 is valid. If the land slope is equal or bigger than 9% (s≥9%), equation 6 is used [10, 35, 36]. S 10.8Sin 0.03 (5) S 16.8Sin 0.05 (6) C (vegetation cover-land use) factor reflects the impacts of surface roughness, plant cover and management practices. Protection of top soil because of vegetative cover or surface roughness is evaluated in C factor [10]. In this study, C factor was calculated by utilizing geo-referenced land observations, available land cover and forest maps. We also utilized a LANDSAT-7 ETM+ satellite image taken on 18 September 2012. The image was corrected by using a gap fill method [37] before analyzing. Then, the image was subset to obtain the area of interest (AOI) image by using a vector AOI created from the border map of the study area. Consequently, a subset image was created in ERDAS Imagine software [38]. Utilizing this prepared image, the normalized difference vegetation index (NDVI) values were calculated. NDVI index equation (7) used in this process was given below [39-42]. In this equation (7): B3 and B4 are LANDSAT-7 ETM+ bands 3 and 4, respectively. NDVI ( B 4 B3) /( B 4 B3) (7) In ERDAS Imagine, NDVI values were stretched to an unsigned 8-bit image varying between 0 and 256. Utilizing geo-referenced land observations, available land cover and forest maps, we classified produced NDVI map in 5 classes including water surface or rocky areas (NDVI: 0-87), weak grasslands (NDVI: 88-114), moderately dense rangelands (NDVI: 115-148), moderately dense oak forest (NDVI: 149189), dense forest (NDVI: 189-255). With this classification, we also updated the land cover map of the study area. Utilizing land cover map, we determined C factor value of each class [43]. For this aim, 0.000, 0.280, 0.042, 0.011, and 0.003 C factor values were assigned to water surface or rocky areas, dense forest, moderately dense oak forest, moderately dense rangelands, and weak grasslands land cover classes, respectively. (SDR) is the ratio between sediment export and annual soil loss in a catchment [44]. We calculated SDR by utilizing the Roehl Equation (8) below [44, 45]. In this equation (8), SDR is sediment delivery ratio, A is the Zinav Lake Basin area (km2). Multiplying SDR with mean annual soil loss, we determined sediment input of Zinav Lake Basin. SDR 36( A) 0.20 3. RESULTS Produced raster map layers of K, L*S, and C factors are shown in Figure 2. R (62.30 MJ mm ha−1 h−1 yr−1) and P (1.00 unit-less) layers are constant and uniform in the study area. For this reason R and P were not shown up in Figure 2. However, pixel values of K factor (soil erobility) raster map changed between 0.00571 and 0.01320 t ha h ha−1 MJ−1 mm−1 (Figure 2a) with a 0.00789 t ha h ha−1 MJ−1 mm−1 mean value. L and S factors were expressed together as the L*S raster map with the changing pixel values between 1.29 and 42.50 (Figure 2c) with a 19.03 mean value. In C factor raster map (Figure 2d), pixel values varied between 0.000 and 0.280 with a 0.037 mean value. The annual soil loss (t.ha-1year-1) raster map, developed by multiplying the raster maps of all factors (R, K, L*S, C, and P) in ArcGIS, was shown in Figure 3. Pixel values of this raster map changed between 0.0 and 7.1 t.ha1 year-1 with a 0.037 mean value (Figure 3). We classified the annual soil loss raster map using the class intervals of European Environment Information and Observation Network for Soil (EIONET-SOIL) Erosion Map [8]. Covered area by erosion risk classes were summarized in Table 1. Spatial distribution of erosion risk classes showed that 84.89% of the study area in 0.0-0.5 t.ha-1year-1 risk class. This was followed by the 2.0-5.0 (6.02%), 0.5-1.0 (4.54%), 1.0-2.0 (2.30%) and 5.0-7.1 (1.90%) erosion classes (Table 1). Remaining cover area (0.35%) is the lake surface. TABLE 1 - Cover areas of determined soil loss and sediment input classes Soil Loss (t.ha-1year-1) 0.0-0.5 0.5-1.0 1.0-2.0 2.0-5.0 5.0-7.1 Lake TOTAL We considered P (soil conservation) factor as 1, because there is no soil conservation application in the area [10]. All calculated factors (R, K, L*S, C, and P) were transformed to raster map layers by using 10x10 m grid size in ArcGIS software [12]. Using map calculation functions, all map layers were multiplied each other to develop annual soil loss (A) raster map in ArcGIS. Some parts of erosion in a catchment area are hold by stream bed, the end of slope, and surface pits. Some parts, however, are exported or delivered. This delivered portion is important, because this is the portion that will negatively affect the lake through time. The sediment delivery ratio (8) Sediment Input (t.ha-1year-1) 0.00-0.22 0.22-0.45 0.45-0.89 0.89-2.23 2.23-3.16 Cover Area (km2) 83.20 4.45 2.25 5.91 1.86 0.34 98.01 Cover Area (%) 84.89 4.54 2.30 6.02 1.90 0.35 100.00 The mean annual soil loss of the total study area (98.01 km2) was determined as 0.037 t.ha-1year-1. The SDR was calculated as 44.67%. The mean annual sediment input of Zinav Lake Basin was determined as 0.181 t.ha-1year-1 by multiplying SDR with mean annual soil loss. The annual sediment inputs of the study area were also shown in Figure 3. 175 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FIGURE 2 - Raster map layers of R (a), K (b), L*S (c), C (d), and P (e) factors. FIGURE 3 - Raster map layer of the annual soil loss (t.ha-1year-1) and annual sediment input (t.ha-1year-1). 176 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin (Project No: ÇAYDAG- 1110Y117); and Orhan Mete Kılıç for his technical assistance as a part of his Ph.D. thesis. 4. DISCUSSION AND CONCLUSION In shallow lake ecosystems, the sediment plays an important role in the overall nutrient dynamics [46]. The deposition rate of lake sediments is controlled by many factors such as lake morphology (area, depth, shoreline’s length), water circulation, climate conditions, area and land use in the catchment [47, 48]. Erosion is one of the key factors that drive sediment delivery ratio and sediment input. Higher values of these variables will most likely stress the lake ecosystems and give a chance to be filled through time [3, 6]. Therefore, the information about soil loss and sediment input of a lake basin plays a crucial role in lake management process. The early identification of areas susceptible to erosion is an essential step to take necessary precautions. The USLE model is one of the most widely used mathematical model that describes soil erosion processes [7, 8]. The sediment delivery ratio (SDR) developed by Roehl (1962) is the ratio between sediment export and total soil loss in a catchment [44, 45]. Utilizing the USLE and SDR annual soil loss and sediment input values of a lake basin can safely be calculated. Integration of this model with GIS and RS opened the ways to develop precise raster maps of these variables [6, 14-16]. In this study, annual soil loss and sediment input of Zinav Lake Basin were mapped by using the USLE, Roehl`s SDR, GIS and RS. Integration the USLE model with GIS and RS tools simplified the mapping process in a reliable and fast way. Our study showed that majority of the study area (84.89%) was in 0.0-0.5 t.ha-1year-1 class. This was found to be the lowest erosion rate compared to EIONETSOIL Erosion Map [8]. Although higher erosion rates (2.0-5.0 and 5.0-7.1) covered small portions (6.02% and 1.90%) of the lake basin area, the majority of these kinds of areas were found close to the northwest of Zinav Lake. The erosion rate of 5.0-7.1 t.ha-1year-1 was reported as very critical level according to some researchers in Turkey [49-52]. It was also reported that this is the highest level determined in Europe (Italy- 6.60 t.ha-1year-1) [8]. Sediment input from these kinds of areas changed between 0.89-2.23 and 2.23-3.16 t.ha-1year-1 in the study area. In the studies combating erosion, priority should be given to these areas. With some measures such as forestation of degraded forest, rehabilitation of the side gutters, improvement of the infrastructure of nearby settlements, and developing a lake management plan, Zinav Lake and the surrounding area will be able to maintain its existence for future generations without losing its importance and naturalness. ACKNOWLEDGEMENTS The authors thank to the Scientific and Technical Research Council of Turkey (TÜBİTAK) for project funding 177 The authors have declared no conflict of interest. REFERENCES [1] Jones R.J.A., Verheijen F.G.A, Reuter H.I. and Jones A.R. (2008) Environmental Assessment of Soil for Monitoring Volume V: Procedures and Protocols. EUR23490 EN/5. Office for the Official Publications of the European Communities, Luxembourg: 165pp. [2] Reganold, J.P., Elliott, L.F. and Unger, Y.L. (1987) Long-term effects of organic and conventional farming on soil erosion. Nature, 330: 370-372. [3] Pimentel, D., Harvey, C., Resosudarmo, P., Sinclair, K., Kurtz, D., McNair, M., Crist, S., Shpritz, L., Fitton, L., Saffouri, R. and Blair, R. (1995) Environmental and economic costs of soil erosion and conservation benefits. Science, 267(5201): 11171123. [4] Benda, L., Miller, D., Bigelow, P. and Andras, K. (2003) Effects of post-wildfire erosion on channel environments, Boise River, Idaho. Forest Ecology and Management, 178: 105-119. [5] Uluocha, N.O. and Okeke, I.C. (2004) Implications of wetlands degradation for water resources management: Lessons from Nigeria. GeoJournal, 61(2): [6] Karabulut, M. and Küçükönder, M. (2008) Kahramanmaraş ovası ve çevresinde CBS kullanılarak erozyon alanlarının tespiti. KSÜ Fen ve Mühendislik Dergisi, 11(2): 14-22. [7] Hudson, N.W. (1993) Field Measurement of Soil Erosion and Runoff. Food and Agriculture Organization of the United Nations (FAO), Soils Bulletin 68, Rome: 141 pp. [ 8] Panagos, P., Meusburger, K., Liedekerke, M.V., Alewell, C., Hiederer, R. and Montanarella, L. (2014) Assessing soil erosion in Europe based on data collected through a European network. Soil Science and Plant Nutrition, 60(1): 15-29. [9] Wischmeier, W.H. and Smith, D.D. (1960) A universal soil-loss equation to guide conservation farm planning. Transactions of 7th International Congress of Soil Science, 1: 418-425. [10] Wischmeier, W.H. and Smith, D.D. (1978) Predicting Rainfall Erosion Losses: A Guide to Conservation Planning (Agriculture Handbook No. 537). USDA Science and Education Administration, US. Goverment Printing Office, Washington DC: 58 pp. [11] DeMers, N.M. (2009) Fundamentals of Geographic Information Systems, 4th Edition. John Wiley & Sons, New York: 443 pp. [12] ESRI (2005) ArcGIS 9, What is in ArcGIS 9.1. Environmental Systems Research Institute, Redlands California: 1-123. [13] De Jong, S.M. (1994) Applications of Reflective Remote Sensing for Land Degradation Studies in a Mediterranean Environment. PhD Thesis, Utrecht University. [14] Mati, B.M., Morgan, R.P.C., Gichuki, F.N., Quinton, J.N., Brewer, T.R. and Liniger, H.P. (2000) Assessment of erosion hazard with the USLE and GIS: a case study of the Upper Ewaso Ng'iro North basin of Kenya. International Journal of Applied Earth Observations and Geoinformation, 2(2): 78-86. [15] Cohen, M.J., Shepherd, K.D. and Walsh. M.G. (2005) Empirical reformulation of the universal soil loss equation for erosion risk assessment in a tropical watershed. Geoderma, 124(3-4): 235-252. © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin [16] Meusburger, K., Konz, N., Schaub, M. and Alewell, C. (2010) Soil erosion modelled with USLE and PESERA using QuickBird derived vegetation parameters in an alpine catchment. International Journal of Applied Earth Observation and Geoinformation, 12(3): 208-215. [17] Karydas, C.G., Panagos, P. and Gitas, I.Z. (2014) A classification of water erosion models according to their geospatial characteristics. International Journal of Digital Earth, 7(3): 229-250. [18] Zeybek, H.I. (2002) Sinan (Zinav) Gölü (Reşadiye-Tokat). Türk Coğrafya Dergisi, 38: 105-120. [19] FAO (1990) WRB Map of World Soil Resources. Food and Agriculture Organization of the United Nations, Rome. (available at online: www.fao.org/nr/land/soils/soil/wrb-soilmaps/wrb-map-of-world-soil-resources/en/) [20] Durak A. (1990) Clay mineralogy and classification of Brown soils and Gray-Podsolic soils of Tokat Region (in Turkish). Çukurova Üniversitesi, Ziraat Fakültesi Dergisi, 6(1): 275291. [21] FAO (2014) Mineral Soils Conditioned by Limited Age, Cambisols (CM). Lecture Notes on the Major Soils of the World. Food and Agricultural Organization Corporate Document Repository, Rome. (available at online: http://www.fao.org/docrep/003/ y1899e/y1899e08.htm) [22] Huber, S., Prokop, G., Arrouays, D., Banko, G., Bispo, A., Jones, R.J.A., Kibblewhite, M.G., Lexer, W, Möller, A., Rickson, R.J., Shishkov, T., Stephens, M., Toth, G., Van den Akker, J.J.H., Varallyay, G., Verheijen, F.G.A. and Jones, A.R. (eds) (2008) Environmental Assessment of Soil for Monitoring: Volume I Indicators and Criteria. EUR 23490 EN/1 Office for the Official Publications of the European Communities, Luxembourg, 339 pp. [23] Renard, K.G., Foster, G.R., Weesies, G.A., McCool, D.K. and Yoder, D.C. (1997) Predicting Soil Erosion by Water: a Guide to Conservation Planning with the Revised Universal Soil Loss Equation (RUSLE). Agriculture Handbook, Washington, 703 pp. [32] Gee, G.W. and Bauder, J.W. (1986) Particle Size Analysis. In A Klute (Ed.), Methods of Soil Analysis, Part 1- Physical and Mineralogical Methods, Second Edition, American Society of Agronomy Inc., Madison, Wisconsin , 383-411 pp. [33] Saxton, K.E. and Willey, P.H. (2004) Agricultural wetland and pond hydrologic analyses using the SPAW model. In: J.L. D'Ambrosio (Ed.), Self-Sustaining Solutions for Streams, Watersheds and Wetlands, Proceedings of the September 2004 Conference, American Society of Agricultural Engineers (ASAE), St. Paul, Minessota: 16-23 pp. [34] Okalp, K. (2005) Soil Erosion Risk Mapping Using Geographic Information Systems: A Case Study on Kocadere Creek Watershed, İzmir. M.Sc. Thesis, Middle East Technical University, Ankara. [35] Oguz, I. (2012) Analyzing variation of sediment yields in wet and drought years. Journal of Agricultural Sciences, 18(2): 146-156. [36] McCool, D.K., Brown, L.C., Foster, G.R., Mutchler, C.K. and Meyer, L.D. (1987) Revised slope steepness factor for the Universal Soil Loss Equation. Transactions of the American Society of Agricultural Engineers, 30(5): 1387-1396. [37] Bustillos, L.V. (2012) Gap Fill for Landsat 7 Images – A correction of SLC – off. [38] ERDAS (2003) Erdas Field Guide, Seventh Edition. Leica Geosystems, GIS and Mapping LLC, Atlanta Georgia: pp. 1-672. [39] Tucker, C.J. (1979) Red and photographic infrared linear combinations for monitoring vegetation. Remote Sensing of Environment, 8(2): 127-150. [40] Sabins, F.F. (1987) Remote Sensing Principles and Interpretation, 2nd Edition. Waveland Press Inc., New York: 449 pp. [41] Jensen, J.R. (1996) Introductory Digital Image Processing: A Remote Sensing Perspective, 2nd Edition. Prentice Hall, Englewood Cliffs, New Jersey: 316 pp. [42] Dogan, H. M. (2009) Mineral composite assessment of Kelkit River Basin by means of remote sensing. Journal of Earth System Science, 118: 701-710. [24] Renard, K.G. and Freimund J.R. (1994) Using monthly precipitation data to estimate the R-factor in the revised USLE. Journal of hydrology, 157(1-4): 287-306. [43] Haan, C.T., Bartfield, B.J. and Hayes, J.C. (1994) Design Hydrology and Seminetology for Small Catchments. Academic Press: USA. [25] İrvem, A., Topaloğlu, F. and Uygur, V. (2007) Estimating spatial distribution of soil loss over Seyhan River Basin in Turkey. Journal of Hydrology, 336(1-2): 30-37. [44] Kasai, M, Marutani, T., Reid, L.M. and Trustrum, N.A. (2001) Estimation of temporally averaged sediment delivery ratio using aggradational terraces in headwater catchments of the Waipaoa River, North Island, New Zealand. Earth Surface Processes and Landforms, 26: 1-16. [26] Oduro-Afriyie, K. (1996) Rainfall erosivity map for Ghana. Geoderma, 74(1): 161-166. [27] McGrew, J.C.Jr. and Monroe, C.B. (1993) Statistical Problem Solving in Geography. Dubuque, IA: Wm. C. Brown, 254 pp. [45] Roehl, J.E. (1962) Sediment sources areas, delivery ratios and influencing morphological factors. International Association of Hydrological Sciences Publication, 59: 202–213. [28] Atesalp, M. (1976) Soil and Water Sampling for Analysis, 1– 25. Ankara: Soil and Fertilizer Research Institute Press, General No.: 68, Farmer Pub. No: 3. [46] Søndergaard, M., Jensen, J.P. and Jeppesen, E. (2003) Role of sediment and internal loading of phosphorus in shallow lakes. Hydrobiologia, 506–509(1-3): 135–145. [29] Walworth, J.L. (2006) Soil Sampling and Analysis, 1–5. Tucson, AZ: Arizona Cooperative Extension, The University of Arizona, College of Agriculture and Life Sciences. [47] Noges, P., Tuvikene, L., Noges, T. and Kisand, A. (1999) Primary production, sedimentation and resuspension in large shallow Lake Vortsjarv. Aquatic Sciences, 61(2): 168-182. [30] Nelson, D.W. and Sommers, L.E. (1982) Total Carbon, Organic Carbon, and Organic Matter. In A. L. Page, R. H. Miller, and D. R. Keeney (Eds.), Methods of Soil Analysis, Part 2 – Chemical and Microbiological Properties, , 2nd ed. Madison, WI: American Society of Agronomy, 539–579 pp. [48] Ott, I., Rakko, A., Sarik, D., Noges, P. and Ott, K. (2005) Sedimentation rate of seston during the formation of temperature stratification after ice break-up in the partly meromictic Lake Verevi. Hydrobiologia, 547(1): 51-61. [31] Bouyoucos, G.J. (1951) A recalibration of the hydrometer method for making mechanical analysis of soil. Agronomy Journal 43: 434–438. 178 [49] Ozcan, A.U., Erpul, G., Basaran, M., Erdogan, H.E. (2008) Use of USLE/GIS technology integrated with geostatistics to assess soil erosion risk in different land uses of Indagi Mountain Pass-Çankırı, Turkey. Environmental Geology, 53(8): 1731-1741. © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin [50] Hacisalihoglu, S., Mert, A., Negiz, M.G. and Muys, B. (2010) Soil loss prediction using universal soil loss equation (USLE) simulation model in a mountainous area in Aglasun district, Turkey. African Journal of Biotechnology, 9(24): 35893594. [51] Gündoğan, R., Akay, A.E., Okatan, A., Yuksel, A. and Oguzkan, E.A. (2010). Land suitability evaluation for reducing soil losses in Kahramanmaras, Turkey. Fresenius Environmental Bulletin, 19(11a): 2678-2689. [52] Erkal, T., Unal, Y. (2012) Soil erosion risk assessment in the Sincanli Sub-Watershed of the Akarcay Basin (Afyonkarahisar, Turkey) using the Universal Soil Loss Equation (USLE). Ekoloji 21(84): 18-29. Received: April 03, 2014 Revised: May 21, 2014 Accepted: June 25, 2014 CORRESPONDING AUTHOR Hakan Mete Dogan Gaziosmanpaşa University Agricultural Faculty Soil Science Department GIS&RS Unit Taşlıçiftlik, Tokat TURKEY Phone: + 90 356 252 16 16 (internal: 2280) Fax: + 90 356 252 14 88 E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 172 - 179 179 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin ACCUMULATION AND BEHAVIOR OF SOME HEAVY METALS IN THE MAIN COMPONENTS OF ZINAV LAKE BASIN ECOSYSTEM Fatih Polat1, Hakan Mete Dogan2*, Ekrem Buhan3, Orhan Mete Kılıç2, Doğaç Sencer Yılmaz2 and Saliha Dirim Buhan4 1 Gaziosmanpaşa University, Almus Vocational School, Tokat/Turkey Gaziosmanpaşa University, Agricultural Faculty, Soil Science Department, GIS&RS Unit, Taşlıçiftlik, Tokat/Turkey 3 Gaziosmanpaşa University, Agricultural Faculty, Aquaculture and Fisheries Department, Tokat/Turkey Gebze Institute of Technology, Faculty of Engineering, Environmental Engineering Department, Gebze/Kocaeli/Turkey 2 4 Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey ABSTRACT Effects of Pb, Cu, Zn, Fe, Co, Al, and Cd on the ecosystem of Zinav Lake Basin in Turkey were investigated between 2011 and 2013. The ecosystem was handled in seven main components including fish, macrophyte, sediment, water, benthos, plankton, and soil. Heavy metal contents of the main components were determined by using Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) and field samples. Relationships among the heavy metal contents of ecosystem components were investigated by using correlation (Pearson) analysis. Hierarchical Clustering Analysis (HCA) was applied to delineate the similar subgroups of ecosystem components according to their heavy metal contents. Fe, Al and Zn were found maximum and Cd was found minimum in almost all ecosystem components except plankton. The accumulation order of heavy metal levels was found as soil > sediment > macrophyte > fish = benthos > water > plankton (except Fe). Al, Co, Cu, Fe, and Zn behave similar in the ecosystem. However, Pb and Cd did not show any similarities neither to each other nor to the others. KEYWORDS: Heavy metal, ecosystem, Hierarchical Clustering Analysis, Zinav Lake Basin. 1. INTRODUCTION Heavy metal pollution of aquatic ecosystems is a potential problem [1]. Heavy metals may enter into aquatic ecosystems from several ways such as anthropogenic sources, industrial wastewater discharges, sewage wastewater, fossil fuel combustion and atmospheric deposition [2-6]. Trace amounts of heavy metals are always present * Corresponding author in fresh waters from terrigenous sources such as weathering of rocks resulting into geo-chemical recycling of heavy metal elements [7, 8]. Sometimes, trace elements may be immobilised within the stream sediments and thus could be involved in absorption, co precipitation, and complex formation [1, 9, 10]. Risk posed by sediment-associated chemicals to aquatic organisms is best understood through an evaluation of sediment quality which is known as the Sediment Quality Triad (SQT). SQT includes sediment chemistry, toxicity, and benthic community. Measurements of these three areas are integrated to reach conclusions based on the degree of risk indicated by each measurement and the confidence in each measurement [11]. Heavy metals such as cadmium (Cd), lead (Pb), copper (Cu) and zinc (Zn) are principal pollutants of aquatic ecosystems because of their environmental persistence, toxicity and great potential of accumulation in the food chains [12, 13]. The quantity and form of the element in water, sediment, or food will determine the degree of accumulation, and different aquatic organisms often respond to this external contamination in different ways [14]. Many heavy metals accumulate in the soil and sediments of water bodies. The lower aquatic organisms absorb and transfer them through the food chain to higher trophic levels. Some kinds of toxic sediments kill benthic organisms, reducing the food available to larger animals such as fish. Some contaminants in the sediment are taken up by benthic organisms in a process called bioaccumulation [15]. Therefore, the determination of heavy metals accumulation in the nutrient cycle, water, sediment and soil is very important. Zinav Lake is an important natural lake in Tokat Province and Kelkit Basin. The lake has regional and national importance. At present, the lake and the lake basin are under the threats of household discharge, spoiled water quality, incorrect fish species modifications, unsound land management, and forest destruction. Understanding the nature of 180 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin heavy metal pollution is important for sustainable management of the lake. Consequently, this study aimed to research accumulation and behavior of heavy metals in the ecosystem of Zinav Lake Basin. 2. MATERIAL AND METHODS This study was conducted in Zinav Lake Basin located in the Central Black Sea Region of Turkey (Figure 1). Zinav Lake is situated in the northwest district of Reşadiye county of Tokat province in Turkey. The precise position of study area can be described as between the 40o26’35”40o27’10” North latitudes and 37o16’05”-37o16’38” East longitudes. The study was performed at 5 stations on the lake and 3 stations around the lake (Figure 1), and field samples were collected between June 2011 and May 2013. Ecosystem in the lake basin was firstly divided into seven categories including (1) fish, (2) macrophyte, (3) sediment, (4) water, (5) benthos, (6) plankton, and (7) soil. Water samples were collected from the aforementioned stations, and were poured into 100 ml bottles after filtering. In order to perform heavy metal analysis, water samples immediately were acidized by adding 1 ml HCl (Merck). This prevented biological activities of bacteria and microorganisms, and did not allow metals to turn into other forms of metals. The treated samples were stored at +4 °C in the refrigerator until the analysis [16]. Sediment and soil samples were collected from each sampling site at a depth of 0 - 5 cm and stored in a plastic bottle. At least three composite soil and sediment samples were collected from each sampling stations. Each sediment and soil sample was airdried in the laboratory at room temperature and was passed through a 2 mm sieve before extraction. The dry weight of each sample was measured after 12 hours of drying in an oven at 105°C. At each sampling time, algae biomass samples from the same sites were collected using plankton nets (30 μm in mesh size) and about 100 g immediately stored in dry ice and later frozen at -20°C prior to heavy metal extraction. 250 ml of FIGURE 1 - Location, topographic features, and sampling stations of the study area. 181 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin water samples were collected and immediately fixed by a freshly prepared 0.7% Lugol’s solution and stored prior to phytoplankton identification and analysis. Other (benthos, fish species, macrophyte species) samples were stored in dry ice and later freezer at -80 ºC until analysis. 3. RESULTS During the sampling process, five fish species (Capoeta banarescui, Carassius auretus, Carassius carassius, Carassius gibelio, Squalius cephalus) and five macrophyte species (Myriophyllum spicatum, Nasturtium officinale, Phragmites australis, Potamogeton natans, Potamogeton pectunatus) were identified in the study area. The average heavy metal contents of ecosystem components and their ranges are given in Table 1 and Figure 2. The order of heavy metal concentrations was determined as Fe > Zn > Al = Cu = Pb = Co = Cd in water, Zn > Fe > Al > Pb > Co > Cu > Cd in fish species, Al > Fe > Zn > Cu > Pb > Co > Cd in macrophyte species, Fe > Cu > Pb > Al = Co = Zn = Cd in plankton, Fe > Al > Zn > Cu > Pb > Co > Cd in benthos, Al > Fe > Zn > Cu > Co > Pb > Cd in sediment, and Fe > Al > Zn > Cu > Co > Pb > Cd in soil. De-ionized water (18.2 MΩ) from a Milli-Q system (Millipore, Belford, MA, USA) was used to prepare all aqueous solutions. All mineral acids and oxidants (HNO3, HCl) used were of the highest quality (Suprapure, Merck, Darmsadt, Germany). All the plastic and glassware were cleaned by soaking (with contact) overnight in a 10% (w/v) nitric acid solution and then rinsed with deionized water. Heavy metal analysis was performed by using Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) equipment in the Soil Laboratory of Gaziosmanpaşa University, Tokat. After removing samples from the freezer, the samples were deforested for a while. From each sampled category, 1g amount was taken and soluted in 15 ml aqua regia (a mixture of 3 volume HCl and 1 volume HNO3) and dried to determine heavy metal (Pb, Cu, Zn, Fe, Co, Al, Cd) contents of the categories. After rinsing with 10 ml 2 M HNO3, the resulting suspension was filtered with the blue-band filter paper. Finally, filtered amount leaved to evaporate to reach 6-8 ml, and remaining amount (6-8 ml) was completed to 10 ml with distilled water. Heavy metal contents of prepared solution were determined in ICP-MS [17]. The order of heavy metal levels in the ecosystem components was found as soil > sediment > macrophyte > fish = benthos > plankton (except Fe) (Figure 3). Except plankton, Fe, Al and Zn were found maximum in almost all ecosystem components. On the contrary, Cd was determined as minimum. This status may be due to their common occurrence in the basic rock. Pearson correlation analysis results among heavy metal variables indicated statistically significant relationships (Table 2). Al showed strong positive correlations with Co (0.793), Cu (0.836), Fe (0.889) at 1% level. Strong positive correlations were also observed between Co and Cu (0.734); Co and Fe (0.827); Co and Zn (0.793); Cu and Fe (0.857); Fe and Zn (0.716) at 1% level. Pearson correlation analysis was adopted to analyse and establish inter-metal relationship of the lake water. Pearson correlation analysis was also employed to research the possible relationships between ecosystem components in respect to their heavy metal contents. Hierarchical Cluster Analysis (HCA) was performed to further classify the elements into groups representing different sources on the basis of similarities in their chemical properties [18]. HCA for identifying relatively homogeneous groups of variables were selected in this study by using an algorithm that starts with each variable in a separate cluster and combines clusters until only one is left. Before Cluster analysis, the variables were standardized by means of Z-scores; then Euclidean distances for similarities in the variables were calculated. A dendrogram was constructed to assess the cohesiveness of the clusters formed, in which correlations among ecosystem components can readily be seen. SPSS software [19] was employed for all statistical analyses. Pearson correlation analysis results among ecosystem components also indicated statistically significant relationships (Table 3). Water positively correlated with soil (0.752) and benthos (0.758) at 5% levels, and plankton (0.943) at 1% level. Soil showed strong positive correlations with sediment (0.946), benthos (1.000) and macrophyte (0.878) at 1% levels, and plankton (0.833) at 5% level. Strong positive correlations were also observed between sediment and benthos (0.945), sediment and macrophyte (0.985), benthos and macrophyte (0.878) at 1% levels. Finally, a positive relationship between benthos and plankton were found statistically significant (0.834) at 5% level. TABLE 1 - The average heavy metal contents (mg/kg) of ecosystem components in Zinav Lake. ECOSYSTEM COMPONENT WATER FISH MACROPHYTE PLANKTON BENTHOS SEDIMENT SOIL Al Cd Co Cu Pb Zn Fe 0.00 6.65 578.85 0.01 1124.15 11980.00 7802.33 0.00 0.13 0.22 0.01 1.08 0.00 0.02 0.00 0.63 0.81 0.01 2.11 5.48 6.09 0.00 0.47 1.98 6.03 9.16 55.48 27.92 0.00 1.36 1.45 3.34 3.89 0.05 3.86 0.03 34.08 28.71 0.01 47.65 78.08 83.28 0.08 11.56 402.37 960.00 1862.16 11105.80 12907.67 182 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FIGURE 2 - The heavy metal ranges in the Zinav Lake Basin FIGURE 3 - The heavy metal levels in the main ecosystem components of Zinav Lake 183 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 2 - Pearson Correlation Analysis results of heavy metal variables Al Cd Co 1.000 Al -0.018 1.000 Cd 0.252 1.000 Co 0.793** 0.028 Cu 0.836** 0.734** 0.054 Fe 0.889** 0.827** -0.165 0.395* 0.002 Pb 0.678** 0.311 Zn 0.793** **. Correlation is significant at the 0.01 level (2-tailed). *. Correlation is significant at the 0.05 level (2-tailed). Cu Fe 1.000 0.857** 0.136 0.628** 1.000 0.045 0.716** Pb Zn 1.000 -0.069 1.000 TABLE 3 - Pearson Correlation Analysis results of ecosystem components WATER SOIL 1.000 WATER 1.000 SOIL 0.752* 0.525 SEDIMENT 0.946** * BENTHOS 0.758 1.000** 0.398 MACROPHYTE 0.878** 0.449 0.105 FISH PLANKTON 0.943** 0.833* **. Correlation is significant at the 0.01 level (2-tailed). *. Correlation is significant at the 0.05 level (2-tailed). SEDIMENT BENTHOS MACROPHYTE FISH PLANKTON 1.000 0.945** 0.985** 0.069 0.609 1.000 0.878** 0.121 0.834* 1.000 0.086 0.468 1.000 0.131 1.000 FIGURE 4 - Dendrograms of the ecosystem components in respect to their heavy metal contents. (Method: Hierarchical Cluster Analysis, Furhest Neighbor, Measure: Euclidean distance). 184 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin HCA was used to create a hierarchical classification of the ecosystem components in respect to their heavy metal contents, and the groups with their containing subgroups were displayed as a dendrogram (Figure 4). Dendrograms of heavy metals showed how the cases (ecosystem components) were clustered together at each stage of the cluster analysis. In each dendrogram, the most similar ecosystem components were first joined to form the first cluster, which was then considered as a new object. All the subgroups were joined in the final cluster, containing all the ecosystem components (Figure 4). The lowest distance values indicated the closest ecosystem component similarity, while the greatest distance values suggested the least habitat resemblance of these components. Considering ecosystem components, behaviors of Al, Co, Cu, Fe, and Zn showed similar characteristics. Within this group, soil and sediment components established a cluster, while the other components constituded another cluster. However, Pb and Cd did not show any similarities neither to each other nor to the others. In Pb, soil, benthos and plankton formed the first cluster, while water, sediment, macrophyte, and fish formed the second cluster. In Cd, all components except benthos established one cluster (Figure 4). Conformity between HCA (Figure 4) and correlation (Table 2) results was observed. Close relationships among Al, Co, Cu, Fe, and Zn variables in both HCA and correlation analysis indicated that these heavy metals mostly accumulate in the soil and sediment. The exact correlation between soil and benthos (1.00) in Table 3 can be explained by HCA results of Pb (Figure 4). The HCA clearly displayed the Pb accumulation from soil to benthos or vice versa. High correlations of benthos-macrophyte (0.878) and benthos-plankton (0.834) pairs (Table 3) reflected to the HCA results of Cu (Figure 4). The HCA clearly delineated the accumulation of Cu from benthos to macrophyte and plankton. Similarly, Cd accumulation (from soil to plankton and macrophyte or from macrophyte and plankton to soil) and Cd and Pb accumulations (from sediment to macrophyte or from macrophyte to sediment) were detected. 4. DISCUSSION AND CONCLUSION Five fish species (Capoeta banarescui, Carassius auretus, Carassius carassius Carassius gibelio Squalius cephalus) and five macrophyte species (Myriophyllum spicatum, Nasturtium officinale, Phragmites australis, Potamogeton natans, Potamogeton pectunatus) were identified in the ecosystem of Zinav Lake Basin. Ecosystem was researched in seven main components including (1) fish, (2) macrophyte, (3) sediment, (4) water, (5) benthos, (6) plankton, and (7) soil. Within these components, the order of heavy metal concentrations was determined as Fe > Zn > Al = Cu = Pb = Co = Cd in water, Zn > Fe > Al > Pb > Co > Cu > Cd in fish species, Al > Fe > Zn > Cu > Pb > Co > Cd in macrophyte species, Fe > Cu > Pb > Al = Co = Zn = Cd in plank- ton, Fe > Al > Zn > Cu > Pb > Co > Cd in benthos, Al > Fe > Zn > Cu > Co > Pb > Cd in sediment, and Fe > Al > Zn > Cu > Co > Pb > Cd in soil. It was reported that the concentration of different metals in water, plankton, and fish tissues followed the same order (Zn > Cu > Pb > Cd) in Lake Manzala [20]. Consequently, our study produced similar results for fish and water components. The orders of heavy metal levels in the ecosystem components of Zinav Lake were also determined. Except Fe, the levels of all investigated heavy metals ordered as soil > sediment > macrophyte > fish = benthos > plankton. High levels of heavy metals in the sediments, up to 10 000 times higher than in water, were found in Lake Barato [21]. In general, metal content in sediments is indicative of the degree of pollution and serves as a source of precipitation or solubilization into water depending on the physico-chemical circumstances (pH, tempearture etc.) and the uptake by benthic organisms [22]. In this study, the presence of higher heavy metal in sediments was found consistent with other related studies. However, the Fe contents of lake sediments were found higher than some literature reports [2325]. Results of Zn, Cu and Pb at sediment were found as 78.08 mg/kg, 55.48 mg/kg and 0.048 mg/kg, respectively. Comparing these results to some literature [23], Zn and Cu levels of lake sediments were found higher, while lower Pb level was observed. Our results indicated that Pb level in soil (3.86 mg/kg) was found higher than sediment. Sekabira et al. [1] reported that the reason for accumulation of heavy metals in the Nakivubo stream sediments could be co-precipitation of Pb, Cd and Zn with Mn and Fe hydroxides along with scavenging of other metals. The reason of heavy metal accumulation in Zinav Lake sediment can be explained similarly because alkaline status of lake (pH>8) [26]. We found Fe, Al and Zn maximum in almost all ecosystem components, but plankton. On the contrary, Cd was determined as minimum. In a study conducted in the Anzali wetland of Iran, different accumulation (higher Pb and lower Cu) rates of heavy metals in smaller Mytilaster lineatus (bivalve molluscs) were observed [27]. It was also reported that the quantity of heavy metals in plankton usually depends on their concentration in water and partially on sediment [28]. These cases can explain the minimum detection levels of heavy metals in plankton. In a similar study, it was also reported that the organic matter, accumulated at the bottom of the lake and river, increase the concentration of the heavy metals in sediment [24]. These results confirmed our findings. We determined that Al showed strong positive correlations with Co (0.793), Cu (0.836), Fe (0.889) at 1% level. Moreover, we also observed strong positive correlations between Co and Cu (0.734); Co and Fe (0.827); Co and Zn (0.793); Cu and Fe (0.857); Fe and Zn (0.716) at 1% level. Relationships among heavy metals may signify that each paired elements has identical source or common sink in the lake sediments [1, 29, 30]. Good correlations among Co, Cu, Fe, Zn, and Th might be from the same source of contamination [31]. These kinds of correlations suggested that 185 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin contamination input is mainly due to atmospheric deposition, human settlement and agriculture activity [31]. Zinav lake and the lake basin are under the threats of household discharge, spoiled water quality, incorrect fish species modifications, unsound land management, and forest destruction at the present time [26]. Consequently, strong positive correlations between heavy metals in the Zinav lake ecosystem are compatible with above literature. We observed conformity between HCA and correlation indicating that Al, Co, Cu, Fe, and Zn mostly accumulated in the soil and sediment in the Zinav Lake Basin. Similarly, it was reported that the cluster trees can confirm correlations [32], and it was stated that metals are commonly found adsorbed in sediments [22]. These findings showed that organic matter plays an important role in heavy metal concentrations within sediment. Each biomonitor, such as benthic fauna, fish, bivalves and algae, responds differently to a particular metal fraction of an aquatic system [22]. Our results showed that heavy metals have different accumulation characteristics in the ecosystem components. The directions of accumulation were determined as; from soil to benthos or vice versa in Pb, from benthos to macrophyte and plankton or vice versa in Cu, from soil to macrophyte and plankton or vice versa in Cd, from sediment to macrophyte or vice versa in Cd and Pb. Accumulation of Pb and Cu in benthos was also reported in a research conducted in macro invertebrates of Anzali wetland [27]. Some kinds of toxic sediments kill benthic organisms, reducing the food available to larger animals such as fish [15]. We observed that Pb, Cd and Cu in benthos, macrophytes, soil and sediment have clear connection to the catchment area of Zinav lake. Consequently, the results of the present study supplied detailed information for understanding the threats focused on the lake basin. According to the FAO food standards for fish, levels of Zn, Cu, Fe and Al were found below the thresholds of concern, whereas Co was found slightly above the acceptable limits for human consumption (40, 30, 100 and 13.8 mg/kg wet weight for Zn, Cu, Fe and Al, respectively) [33, 34]. Among the heavy metals, Pb and Cd have been classified as toxic metals that cause chemical hazards and therefore maximum residual levels have been prescribed for human consumption by various agencies of food standards [35-37]. In this study, Cd contents (0.13 mg/kg) in the samples were found much less than the permitted level (0.50 mg/kg) [33]. However, we observed that Pb level in fish is higher than the permissible limits of FAO (0,50 mg/kg) [30]. Measures should be taken to reduce this amount. A study conducted in Gediz river showed that eutrophication due to the accumulation of organic matter at the bottom of the river caused an increase of metal concentrations [24]. Consequently, increasing heavy metal concentrations in the Zinav Lake may be related to lake's trophic status. Another study carried out in the river Laire estuary ecosystem illustrated that transfer of Cd, Pb, Cu and Zn through the trophic chain of the river estuary ecosystem caused bioaccumulation in fish [38]. However, fish had no correlations with the other ecosystem variables in this study. This can be explained by the feeding behavior of fish in the lake. Fish are different from the other components of Zinav Lake ecosystem. Feeding from the lake is limited for fish because of hypertrophic and anoxic conditions. For this reason, fish generally move on to the mouth of the rivers or rivers that are often cleaner for feeding. This situation causes low heavy metal accumulation in fish. Heavy metal pollution of lakes has a seriously detrimental impact on people and ecosystems. Ecosystem contamination by heavy metals is an important issue because of the potential accumulation in biosystems, through contaminated water. A better understanding of heavy metal sources and their behaviors in ecosystem components is extremely important in ongoing risk assessments and sustainable managements of lake ecosysytems. In this point of view, the results of this study supplied valuable detailed information. ACKNOWLEDGEMENTS The authors thank the Scientific and Technical Research Council of Turkey (TÜBİTAK) for project funding (Project No: ÇAYDAG- 1110Y117); and Saliha Dirim Buhan for her technical assistance as part of her Ph.D. thesis. 186 The authors have declared no conflict of interest. REFERENCES [1] Sekabira, K., Oryem Origa, H., Basamba, T.A., Mutumba, G., Kakudidi, E. (2010) Assessment of heavy metal pollution in the urban stream sediments and its tributaries. International Journal of Environmental Science and Technology, 7(3): 435-446. [2] Linnik, P.M. and Zubenko, I.B. (2000) Role of bottom sediments in the secondary pollution of aquatic environments by heavy metal compounds. Lakes and Reservoirs Management, 5(1): 11-21. [3] Campbell, L.M. (2001) Mercury in Lake Victoria (East Africa): Another Emerging Issue for a Beleaguered Lake? Ph.D. dissertation, University of Waterloo, Ontario, Canada. [4] Lwanga, M.S., Kansiime, F., Denny, P. and Scullion, J. (2003) Heavy metals in Lake George, Uganda with relation to metal concentrations in tissues of common fish species. Hydrobiologia, 499 (1-3), 83-93. [5] El Diwani, G. and El Rafie, S. (2008) Modification of thermal and oxidative properties of biodiesel produced from vegetable oils. International Journal of Environmental Science Technology, 5(3): 391-400. [6] Al-Momani, I.F. (2009) Assessment of trace metal distribution and contamination in surface soils of Amman. Jordan Journal of Chemistry, 4(1): 77-87. [7] Muwanga, A. (1997) Environmental Impacts of Copper Mining at Kilembe, Uganda: A Geochemical Investigation of Heavy Metal Pollution of Drainage Waters, Stream, Sediments and Soils in the Kilembe Valley in Relation to Mine Waste Disposal. Ph.D. dissertation, Universitat Braunschweig, Germany. [8] Zvinowanda, C.M., Okonkwo, J.O., Shabalala, P.N. and Agyei, N.M. (2009) A novel adsorbent for heavy metal remediation in aqueous environments. International Journal of Environmental Science and Technology, 6(3): 425-434. © by PSP Volume 24 – No 1a. 2015 [9] Fresenius Environmental Bulletin Okafor, E.C. and Opuene, K. (2007) Preliminary assessment of trace metals and polycyclic aromatic hydrocarbons in the sediments. International Journal of Environmental Science and Technology, 4(2): 233-240. [10] Mohiuddin, K.M., Zakir, H.M., Otomo, K., Sharmin, S. and Shikazono, N. (2010) Geochemical distribution of trace metal pollutants in water and sediments of downstream of an urban river. International Journal of Environmental Science and Technology, 7(1): 17-28. [11] Erdoğan, M. (2009) Monitoring and Statistical Assessment of Heavy Metal Pollution in Sediments Along İzmir Bay Using ICPMS. Ph.D. dissertation, The Graduate School of Engineering and Sciences of İzmir Institute of Technology, İzmir, Turkey. [12] Copat, C., Bella, F., Castaing, M., Fallico, R., Sciacca, S. and Ferrante, M. (2012) Heavy metals concentrations in fish from Sicily (Mediterranean Sea) and evaluation of possible health risks to consumers. Bulletin of Environmental Contamination and Toxicology, 88: 78-83. [13] Farombi, E.O., Adelowo, O.A. and Ajimoko, Y.R. (2007) Biomarkers of oxidative stress and heavy metal levels as indicators of environmental pollution in African Cat Fish (Clarias gariepinus) from Nigeria Ogun River. International Journal of Environmental Research and Public Health, 4(2): 158–165. [14] Begum, A., HariKrishna, S. and Khan, I. (2008) Chemical composition of rainwater in South Bangalore, Karnataka. Rasayan Journal of Chemistry, 1(4): 774-781. [15] Begum, A., HariKrishna, S. and Khan, I. (2009) Analysis of heavy metals in water, sediments and fish samples of Madivala Lakes of Bangalore, Karnataka. International Journal of Chemical Technology Research, 1(2): 245-249. [16] Tuncer, S. and Uysal, H. (1983) Etude des Metaux Lourds Chez les Mollusques Dans les Differentes Zones de la Baie d'Izmir (Turquie). VIes Journees D'etudes Sur les Pollutions Marines en Mediterranee, Cannes: pp. 307-313. [17] Anonymous (1984). Determination of total Cadmium, Zinc, Lead and Copper in Selected Marine Organisms by Flameless Atomic Absorption Spectrophotometry. Reference Methods for Marine Pollution Studies No. 11. United Nations Environment Programme (UNEP), Geneva: 18 pp. [18] Ragosta, M., Caggiano, R. and Macchiato, M. (2008) Trace elements in daily collected aerosol: level characterization and source identification in a four-year study. Atmospheric Research, 89(12): 206-217. [19] SPSS (2007) SPSS 16.0 for Windows. SPSS Inc.: Chicago. [20] Bahnasawy, M., Khidr, A.A. and Dheina, N. (2011) Assessment of heavy metal concentrations in water, plankton, and fish of Lake Manzala, Egypt. Turkish Journal of Zoology, 35(2): 271-280. [21] Jumbe, A.S. and Nandini, N. (2009) Heavy metals analysis and sediment quality values in Urban Lakes, American Journal of Environmental Sciences, 5 (6): 678-687, 2009. [22] Ogoyil, D.O., Mwita, C.J., Nguu, E.K. and Shiundu, P.M. (2011) Determination of heavy metal content in water, sediment and microalgae from Lake Victoria, East Africa. The Open Environmental Engineering Journal, 4: 156-161. [23] Mendil, D., Uluözlü, Ö.D. (2007) Determination of trace metal levels in sediment and five fish species from lakes in Tokat, Turkey. Food Chemistry, 101: 739-745. [24] Öner, Ö. and Çelik, A. (2011) Gediz Nehri Aşağı Gediz Havzası'ndan alınan su ve sediment örneklerinde bazı kirlilik parametrelerinin incelenmesi. Ekoloji, 78: 48-52. [25] Tariq, J., Jaffar, M., Ashraf, M. (1991) Trace metal concentration, distribution and correlation in water, sediments and fish from the Ravi river, Pakistan. Fisheries Research, 19:131-139. [26] Buhan, E., Doğan, H.M. and Polat, F. (2014) Zinav Gölü ve Havzasında Su Kalitesi ve Balık Topluluklarının Zamansal ve Alansal Değişimleriyle Ekolojik Risklerinin Belirlenmesi. TÜBİTAK, CAYDAG, Research Project (No: 110 Y 117) Final Report. 187 [27] Pourang, N. (1996) Heavy metal concentrations in surficial sediments and benthic macroinvertebrates from Anzali Wetland, Iran. Hydrobiologia, 331(1-3): 53-61. [28] Elmacı, A., Teksoy, A., Olcay Topac, F., Ozengin, N., Kurtoğlu, S. and Savaş Başkaya, H. (2007) Assessment of heavy metals in Lake Uluabat, Turkey. African Journal of Biotechnology, 6: 22362244. [29] Singh, M., Muller, G. and Singh, I.B. (2002) Heavy metals in Freshly deposited stream sediments of rivers associated with urbanization of the Ganga plain, India. Water, Air, and Soil Pollution, 141(1-4): 35-54. [30] Nyangababo, J.T., Henry, I. and Omutunge, E. (2005) Heavy metal contamination in plants, sediments and air precipitation of Katonga, Simiyu and Nyando wetlands of Lake Victoria Basin, East Africa. Bulletin of Environmental Contamination and Toxicology, 75(1): 189-196. [31] Hamzah, Z., Saat, A., Wood, A.K., Abu Bakar, Z. (2011) Sedimentation, Heavy Metals Profiles and Cluster Analysis of a Former Tin Mining Lake. International Journal of Environmental Science and Development, 2(6): 448-453. [32] Nguyen, H.L., Leermakers, M., Elskens, M., De Ridder, F., Doan, T.H. and Baeyens, W. (2005) Correlations, partitioning and bioaccumulation of heavy metals between different compartments of Lake Balaton. Science of the Total Environment, 341 (1-3): 211-226. [33] FAO, (1983) Compilation of legal limits for hazardous substances in fish and fishery products. Food and Agriculture Organisation (FAO) Fishery Circular, No. 464, pp. 5-100. [34] IAEA (2003) World-Wide İntercomparison Exercise For The Determination of Trace Elements and Methylmercury in Fish Homogenate International Atomic Energy Agency- 407 Report No IAEA/ AL/144 IAEA/MEL/72. [35] Rejomon, G., Nair, M. and Joseph, T. (2010) Trace metal dynamics in fishes from the southwest coast of India. Environmental Monitoring and Assessment, 167(1-4): 243-255. [36] Nauen, C.E. (1983) Compilation of Legal Limits for Hazardous Substance in Fish and Fishery Products. Food and Agricultural Organization of the United Nations, Rome: 102 pp. [37] EC. (2001) European Commision Regulation (EC) No. 466/2001 of 8 March 2001. Official Journal of the European Communities, 1.77/1. [38] Amirad, CA-T., Mateyaer, C. (1980) Marich J, Bio-accumulation of heavy metals in the trophic chain of the river Laire estuary. Water Res. 14: 665-72. Received: April 03, 2014 Revised: June 24, 2014; August 04, 2014 Accepted: August 04, 2014 CORRESPONDING AUTHOR Hakan Mete Dogan Gaziosmanpaşa University Agricultural Faculty Soil Science Department GIS&RS Unit Taşlıçiftlik, Tokat TURKEY Phone: + 90 356 252 16 16 (internal: 2280) Fax: + 90 356 252 14 88 E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 180 – 187 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin COMPARATIVE ANALYSIS OF BIOTIC INDICES FOR EVALUATION OF WATER QUALITY OF ESEN RIVER IN SOUTH-WEST ANATOLIA, TURKEY Bülent Yorulmaz1,*, Atakan Sukatar2 and Murat Barlas1 1 Muğla Sıtkı Koçman University Science Faculty Biology Department, 48000 Kötekli Muğla, Turkey 2 Ege University Science Faculty, Biology Department, 35100, Bornova, Izmir, Turkey Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey ABSTRACT Five biotic indices were used for the assessment of water quality of Eşen River in South-west of Turkey. The classification of water quality based on benthic macroinvertebrate and physical and chemical parameters were also done. Taxonomic composition of benthic macroinvertebrate fauna was used for calculation of the following biological indices; Saproby Index (SI), Biological Monitoring Working Party (BMWP), Average Score Per Taxon (ASPT), Family Biotic Index (FBI) and Belgian Biotic Index (BBI). Electrical conductivity, temperature, dissolved O2 content, pH, BOD5, Cl-, NH4-N, NO2-N, NO3-N, PO4-P were analyzed. According to the data obtained, the water quality of Eşen River varied from poor to high ecological status. The indices SI, BMWP, BBI and ASPT were the more adequate estimate of water quality in accordance with physicochemical characteristics of the examined watercourse. KEYWORDS: Biotic Indices, Benthic macroinvertebrates, Esen River, Water Quality. 1. INTRODUCTION Freshwater ecosystems, especially rivers are most threatened ecosystem in the world. Ideally, the quality of running waters should be assessed by the use of physical, chemical and biological parameters in order to provide a complete spectrum of information for appropriate water management [1]. The methods used now to determine the environmental state of a river or a river basin is mostly biological-control methods based on the assessment of the flora and fauna of water bodies. [2]. In the past decades, hundreds of biological monitoring approaches have been * Corresponding author developed to assess the water quality, about 60% of which are based on macroinvertebrate analysis [3-5]. Most of the biological approaches are particular to specific geographic regions. Various European countries use various indices with different levels of identification of organisms, and different assumptions of final interpretation of results [6]. For example the Saproby indices [7] in Germany, Biological Monitoring Working Party- BMWP and Average Score Per Taxon-ASPT [5] in England, Biotic Index for Pampean rivers and streams-IBPAMP [8] in Argentina, Belgian Biotic Index-BBI [9] in Belgium, seem to give the most reliable results specific to geographic regions. Unification of river classification and the use of a common biotic index are impossible due to different geographic distribution of macroinvertebrate species, and biotypological differences among the rivers [6]. Yet a biological water quality approach particular to Turkey has not been developed. Biological water quality classification studies started in the 1990’s in Turkey. Some researchers used a number of biotic indices such as BMWP, ASPT, FBI and SI for assessment of water quality of rivers [10-19]. According to the European Union water framework directive, all member states are obliged to evaluate environment status according to do criteria imposed by EU directives including river quality by the end of 2015 [20]. The objective of this study is to compare the results of five water quality approaches and to determine the most adequate estimate of water quality in accordance with physicochemical characteristics of the examined watercourse. 2. MATERIALS AND METHODS Eşen River is the largest river in West Mediterranean river basin of Turkey with the total length of 146 km. The most important pollution sources on Eşen River are overirrigation, gravel gathering, dams and extensive using of chemicals for farming in the surrounding. Benthic samples were collected from seven stations that represent the river. 188 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin Macroinvertebrate communities along the stream were sampled monthly between June 2003 and June 2005, using a bottom kick net (500 μm mesh). The samples were taken from an area of nearly 100 m2 in order to include all possible microhabitats at each station. In some areas with the presence of large stones, the collected macroinvertebrates were first picked out and washed into the kick net in order to remove pupae and other attached individuals. In addition, macroinvertebrate samples were separated from the macrophytes and the sediment using sieves (250 μm). Collected organisms were immediately fixed in formaldehyde (4%) in the field and then transferred to 70% ethyl alcohol. The macroinvertebrates were sorted, identified to the lowest possible taxon (species, genus or families) and counted under a stereomicroscope. Simultaneous with macroinvertebrate sampling, water samples were taken and analyzed for the following parameters, BOD5, Cl-, NH4-N, NO2-N, NO3-N, PO4-P. All analyses were done in accordance to national standards. Water temperature (ºC), pH, dissolved oxygen (DO mgL-1) and electrical conductivity (EC μScm-1) were measured in the field by portable equipments. Water quality assessment by physico-chemical parameters was done according to Klee (1991) and Water Pollution Control Regulation (WPCR) (1988) [21, 22]. 2.1 Biotic indices This study is restricted to indices focused on the determination of water quality. The following five indices were tested: Average Score Per Taxon (ASPT) [6], the Saproby Index (SI) [7], Belgian Biotic Index (BBI) [5], Biological Monitoring Working Party (BMWP) [4], Family Biotic Index [23]. Correlation analysis was based on Pearson’s and multiple regression analysis from SPSS version 11.5. 3. RESULTS AND DISCUSSION The results of physical and chemical parameters variables measured at the seven stations are presented in Table 1. The lowest EC value was measured in the first station while the highest value was found in the seventh station and ranges between 145 Scm-1 and 622 S cm-1. The water temperature varied from 9, 9 ºC to 25, 8 ºC. The highest DO was found at the third station and varied between 4, 7 mg L-1 and 13, 8 mg L-1. The highest biological oxygen demand was measured in sampling point six (5, 04 mg L-1). The average of pH values were similar among the sampling points and ranged between 7, 05 and 8, 64. The highest ammonium nitrogen (NH4-N) was measured in sampling point seven as 4, 35 mg L-1, but the highest average was measured in sampling point six as 1, 73 mg L-1. The average nitrite nitrogen (NO2N) was high in sampling points three, six and seven but the highest level was measured in sampling point three and six as 0, 0329 mg L-1. The highest average nitrate nitrogen (NO3-N) was found in sampling point six as 5, 97 mg L-1, but the highest nitrate nitrogen value was measured in sampling point seven. The highest level of phosphorus (PO4-P) was measured in sampling point three as 2, 32 mg L-1 (Table 1). In this study, 22061 individuals were collected. A total of 111 benthic macroinvertebrate taxa consisting of 48 genera and 63 species, which belong to classes Turbellaria, Gastropoda, Bivalvia, Hirudinea, Malacostraca and Insecta were identified. Of these, 86%, 84 (96 taxa) belong to Insecta (Fig. 2). It was determined that, Gammarus sp. was dominant on 1, 2, 4 and 5, while Chironomus sp. was dominant on 3, 6 and 7 sampling points. FIGURE 1 - Study area and the sampling points (■ Sampling points, Settlement Areas). The advantage of monitoring by the use of bioindicators is that biological communities reflect overall ecological quality. Moreover monitoring integrates the effects of different stressors providing a broad measure of their impact and an ecological measurement of fluctuating environmental conditions [1, 9, 24-27]. Biological water quality can be assessed by various kinds of organisms such as macrophytes, phytoplankton, diatoms, macroinvertebrates and fishes for regular observations. The use of benthic macroinvertebrates as biological indicators has been widely applied in river quality assessment, because these organisms are relatively sedentary and thus are unable to avoid deteriorating water/sediment quality. These organisms, having relatively long life-spans, reveal marked responses to stress depending on their species-specific sensitivity/tolerance levels and 189 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 1 – Maximum, minimum and mean levels of physicochemicals according to the sampling points 1 2 3 4 5 Min*. 145.0 224.0 268.0 146.0 344.0 Mean 277.2 321.4 340.6 234.6 427.1 EC μScm-1 Max. 400.0 425.0 458.0 387.0 590.0 Min. 10.8 12.4 10.0 9.9 13.1 ºC Mean 11.6 12.9 14.8 10.5 14.3 Max. 11.9 14.6 19.0 12.4 18.5 Min. 6.8 6.2 6.6 6.4 4.7 DO mgL-1 Mean 9.0 8.5 9.2 8.8 6.1 Max. 10.5 10.5 13.8 10.3 7.7 Min. 7.2 7.1 7.5 7.2 7.1 pH Mean 7.7 7.5 7.9 7.7 7.5 Max. 8.6 8.3 8.6 8.6 8.3 Min. 0.8 0.7 0.3 0.6 0.5 BOD5 mgL-1 Mean 2.4 2.5 2.7 2.5 1.4 Max. 3.9 4.3 4.3 4.5 2.5 Min. 0.2 0.2 0.2 0.2 0.3 Cl- mgL-1 Mean 1.7 1.7 1.5 1.5 2.1 Max. 4.0 2.5 2.0 2.5 4.0 Min. BDL BDL BDL BDL BDL NH4-N mgL-1 Mean 0.6 0.7 0.8 0.8 0.5 Max. 2.5 1.5 2.5 2.2 2.5 Min. BDL BDL BDL BDL BDL NO2 -N mgL-1 Mean 0.006 BDL 0.006 BDL BDL Max. 0.01 BDL 0.033 BDL BDL BDL BDL BDL BDL Min. BDL NO3 -N mgL-1 Mean 2.2 2.7 2.9 2.7 1.9 Max. 8.8 8.0 8.8 7.5 8.8 BDL BDL BDL BDL Min. BDL PO4 -P mgL-1 Mean 0.2 0.001 0.2 0.03 0.04 Max. 0.3 0.014 2.3 0.4 0.7 *minimum level as Min, average level as Mean and maximum level as Max were given. BDL: Below detection limits 6 345.0 487.0 590.0 13.4 19.3 25.8 6.3 8.4 11.3 7.3 7.7 8.3 0.8 2.6 5.0 0.2 2.5 6.0 0.2 1.7 3.6 BDL 0.003 0.033 0.6 6.0 12.5 BDL 0.05 0.8 7 289.0 416.1 622.0 13.7 19.8 24.7 6.1 8.3 10.6 7.5 7.9 8.6 0.5 2.4 4.8 1.5 2.7 4.0 BDL 1.4 4.4 BDL 0.002 0.02 N.A 4.9 15.0 BDL 0.005 0.04 Number of Taxa 30 25 20 15 10 5 0 FIGURE 2 - Distribution of Taxa on Order Base. TABLE 2 - Assessment of water quality according to applied indices. 1 2 3 4 WPCR VG VG VG VG Klee (1991) G G G G Sİ. G G M G FBI G G G G BMWP G G G G ASPT VG VG VG VG BBI G G G G Letters refer to water quality: Very Good: VG, Good: G, Moderate: M, Poor, and Very Poor: VP. 190 5 VG VG VG G G VG G 6 G M M M P M M 7 VG G P M P G M © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin play a vital role in cycling nutrients and materials between the underlying sediment and the overlying water column [3-7, 28, 29]. According to our study water quality varied from poor (according to BMWP and SI 7th and according to BMWP 6th) to very good. However there was a disagreement between the in-dices applied. The physical chemical parameters based indices showed higher results than the biological based indices. According to BMWP the 6th station was found “poor” water quality class while it was found “moderate” water quality class according to other biotic indices. The 7th station was found “poor” according to SI and BMWP indices and “moderate” according to FBI and BBI. However the 7th was found “good” water quality class according to ASPT (Table 2). Table 3 summarizes the correlations of both biological and physicochemical indices. It was found that two physicochemical indices have significant correlation value (r value 0,582, p<0.01). Among physicochemical indices and biotic indices, the significant correlation was found between Klee (1991) and SI (r value 0,224, p<0.05). Among biotic indices the highest significant correlation was found between BMWP and BBI (r value 0, 827, p<0.01) followed by BMWP and ASPT (r value 0, 708, p<0.01). The significant negative correlation was found between SI and BBI, BMWP, ASPT respectively. A negative correlation was found between physicochemical indices (WPCR and Klee) and BMWP, ASPT, BBI. However an increase in the results in BBI index and BMWP, ASPT scores systems shows good ecological quality while an increase in SI, FBI, and physicochemical based indices shows bad ecological quality. The highest ecological water quality was determined in the 5th station according to SI in winter season. The most effective physicochemical parameter on SI was temperature (Table 4). All biotic indices were in accordance between each other except FBI. According to correlation of between physical-chemical parameter and indices, significant correlation value was determined between NH4-N with both physicochemical indices (Klee (1991) and WPCR), followed by NO3-N. Among biotic indices the significant correlation was found between NO2-N and SI (r value 0,229, p<0.05), between BOD5 and SI (r value 0,188, p<0.05). The significant correlation was found between temperature and SI because sabroby value increases with temperature [7]. Benthic macroinvertebrate species are differentially sensitive to many biotic and abiotic factors in their environment [30, 31]. In many studies diversity indices are also used for assessing water quality but the biotic index and score systems are better for assessing organic pollution and eutrafication but poor for assessing toxic and physical pollution [3]. From the biotic indices and scores systems applied at Eşen river, SI BMWP, BBI and ASPT were adequate in assessing water quality while FBI was inadequate. Kantzaris et al. [29] applied nine biotic indices and scores at two rivers in Greece and BMWP, ASPT and LQI were determined inadequate in assessing water quality while BBI and IBE were suitable. Zeybek et al. [32] applied five versions of BMWP and three versions of ASPT indices in Değirmendere Stream and obtained different score values because, in their view, applied ver sions were based on the geological and ecological futures of their source countries. TABLE 3 - Correlation assessment between biotic indices and physicochemical indices. WPCR KLEE SI WPCR 1 ,582** ,128 KLEE 1 ,224* SI 1 FBI BMWP ASPT BBI ** and * Correlation is significant at the 0.01 and 0.05 levels (2-tailed). FBI ,152 ,157 ,349** 1 BMWP -,340** -,186* -,558** -,228* 1 ASPT -,222* -,112 -,535** -,317** ,708** 1 BBI -,273** -,173 -,571** -,241** ,827** ,681** 1 TABLE 4 - Assessment of Pearson correlation between physicochemical parameters and biotic indices WPCR KLEE SI BOD5 ,144 ,265** ,188* ** ** Temperature ,355 ,307 ,609** pH ,188* ,177 ,190* TH ,134 -,017 ,134 NH4-N ,747** ,827** ,182* NO3-N ,735** ,816** ,175 NO2-N -,032 ,055 ,229* PO4-N -,080 ,106 -,015 ** and * Correlation is significant at the 0.01 and 0.05 levels (2-tailed). FBI ,095 ,127 -,006 -,022 ,147 ,098 ,117 ,138 191 BMWP ,020 -,574** -,028 -,339** -,329** -,290** -,154 ,045 ASPT -,036 -,478** -,075 -,170 -,173 -,157 -,232* ,024 BBI -,088 -,587** -,023 -,332** -,226* -,200* -,183* ,076 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FIGURE 3 - The distribution of the results of the biological water quality according to seasons and stations. 192 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin 4. CONCLUSION The results of this study verify the use of macroinvertebrates as bioindicators for the assessment of water quality in southwest of Turkey. In conclusion, the indices SI, BMWP, BBI and ASPT seem to be more suitable than FBI. The biotic indices and scores were also found consistent with the physicochemical parameters but FBI was the least sensitive to pollution. The biotic indices used in our research were designed in order to sample many sites, in many countries with minimal effort [29]. However there is a need for the establishment of a Turkish Biotic Index which takes into account regional macroinvertebrates, their abundance, biology and ecology. This proposed Index can more or less differ from those used in the development of the other biotic indices. ACKNOWLEDGEMENTS The authors are thankful for the financial support of the Unit of Scientific Research Projects of Mugla Sitki Kocman University (Project No: 2003/10). The authors have declared no conflict of interest. [8]. Capitulo, A.R., Tangorra, M., Ocon, C. (2001). Use of Benthic Macroinvertebrates to Assess the Biological Status of Panpean Streams in Argentina. Aquatic Ecology 35, 109-119. [9]. De Pauw, N. and Heylen, S. (2001) Biotic Index for Sediment Quality Assessment of Watercourses In Flanders, Belgium. Aquatic Ecology 35, 121-133. [10]. Kazancı, N., Izbırak, A., Çaglar, S.S., and Gökçe, D. (1992). Hydrobiological Investigation of the Aquatic Ecosystem of the Köycegiz-Dalyan Specially Protected Area, Özyurt Printinghouse, Ankara. [11]. Girgin, S., Kazancı,N., and Doğan, O. (1997). A New Approach to the Irrigation Water Quality Criteria in Turkey: Ankara Stream, International Conference on “Water Management, Salinity and Pollution Control Towards Sustainable Irrigation in The Mediterranean Region” Vol. II Water Quality and Pollution Control, Bari Italy, pp. 43-54. [12]. Kazancı, N. and Girgin, S. (2001) Physico-Chemical Characteristics of Thermal Springs in Köyceğiz Dalaman Basins In South-Western Turkey And Recommendations For Their Protection. Water Science and Technology 45 (5), 211-221. [13]. Barlas, M., İmamoğlu, Ö. and Yorulmaz, B. (2002). The Determination of Water Quality in Tersakan Stream (MuğlaDalaman). XVI. Biology Congress, Abstract Booklet, 4-7 September 2002, Malatya/Turkey. [14]. Girgin, S., Kazancı, N. and Dügel, M. (2003). Science and Technology Ordination and Classification of Macroinvertebrates and Environmental Data of a Stream in Turkey. Water Science and Technology 47 (7) 133–139. [15]. Duran, M., Tuzen, M. and Kayım, M. (2003). Exploration of Biological Richness and Water Quality of Stream Kelkit, Tokat-Turkey. Fresenius Environmental Bulletin 12(4), 368-375 REFERENCES [1]. Georgudaki, I., Kantzaris, J., Katharios, V., Georgiadis, P., and Montesantou, B. (2003). An Application of Different Bioindicators for Assessing Water Quality; A Case Study in The Rivers Alfeios and Pineios (Peloponnisos, Greece). Ecological Indicators 2, 345-360. [2]. Semenchenko, P. and Moroz, M. (2005). Comparative Analysis of Biotic Indices in the Monitoring System of Running Water in a Biospheric Reserve Water Quality And Protection: Environmental Aspects 32 (2), 223–226. [3]. Kalyoncu, H. and Zeybek, M. (2011). An Application of Different Biotic And Diversity Indices for Assessing Water Quality: A Case Study in The Rivers Çukurca and Isparta (Turkey). African Journal of Agricultural Research 6(1), 19-27. [4]. Armitage, P.D., Moss, D., Wright, J.F., Furse, M.T. (1983). The Performance of A New Biological Water Quality Score System Based on Macroinvertebrates Over a Wide Range of Unpolluted Running Water Sites. Water Research 17, 333347. [5]. De Pauw, N. and Hawkes, H.A. (1993). Biological Monitoring of River Water Quality. in: Walley, W.J., Judd, S. (Eds.), River Water Quality Monitoring and Control. Aston University, Birmingham, pp. 87–112. [6]. Korycińska, M. and Królak, E. (2006). The Use of Various Biotic Indices for Evaluationof Water Quality in the Lowland Rivers of Poland (Exemplified by the Liwiec River). Polish Journal of Environmental Studies 15 (3), 419-428. [7]. DIN 38410-2 (1990). Biological-Ecological Analysis of Water (Group M); Determination of the Saprobic Index (M2), German Standard Methods for the Examination of Water, Waste Water and Sludge, p. 10. 193 [16]. Dügel, M. and Kazancı, N. (2004). Assessment of Water Quality of the Büyük Menderes River (Turkey) by Using Ordination and Classification of Macroinvertebrates and Environmental Variables. J. Freshwater Ecology 19, 605-612. [17]. Duran, M. (2006). Monitoring Water Quality Using Benthic Macroinvertebrates and Physicochemical Parameters of the Behzat Stream (Tokat, TURKEY). Polish J. Environmental Studies 15(5), 709-717. [18]. Kazancı, N., Dügel, M., and Girgin, S. (2008). Determination of Indicator Genera of Benthic Mactoinvertebrate Communities in Running Waters in Western Turkey. International Review of Hydrobiology 1(1), 1-16. [19]. Kalyoncu, H., Akyıldırım, G.H. and Yorulmaz, B. (2009b). The Comparison of the Diversity and Biotic Indices With Physical-Chemical Analyses Applied to Macroinvertebrate Community to Determine the Water Quality. International Conference On Lakes and Nutrient Loads- Pocrades, Agricultural University of Tirana, Albania, 24-26. [20]. Water Framework Directive (WFD) (2000). Directive of the European Parliament and of the Council (establishing a framework for Community action in the field of water policy), Official Journal of the European Communities, 327/1, 72 p. [21]. Klee, O., (1991). Angewandte Hydrobiologie.- G. Theieme Verlag, 2. neubearbeitete und erweiterte Auflage, StuttgartNew York, 272 p. [22]. Water Pollution Control Regulation (WPCR) (1988). Official Gazette Ankara, Issue: 19919. [23]. Hilsenhoff, W. L. (1988) Rapid Field Assessment of Organic Pollution with a Family-Level Biotic Index. J. N. Am. North American Benthological Society 7(1), 65-68. © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin [24]. Metcalfe-Smith, J.L. (1994). Biological Water Quality Assessment of Rivers: Use of Macroinvertebrate Communities. In: The Rivers Handbook 2. (Calow, P. Petts, G.E. eds.), Blackwell Scientific Publications, Oxford, pp. 144-170 [25]. Knoben, R.A.E., Roos, C., Oirschot, M.C.M. (1995). Biological Assessment Methods for Watercourses. UN/ECE Task Force on Monitoring and Assessment 3, P.O. box 17, 8200 AA Lelystads, The Netherlands, p. 86. [26]. Ghetti, P.F. (1997). Application Manual: Extended Biotic Index – Macroinvertebates In Quality Control Of Running Water Environments, in Italian [Macroinvertebrati Nel Controllo Della Qualita Di Ambienti Di Acque Correnti. Indise Biotico Esteso (I.B.E). Manuale Di Applicazione. Provincia Autonoma Di Trento]. Trento Italy, 222 pp. [27]. Scuri, S., Torrisi, M., Cocchioni., Dell’Uomo. (2006). The European Water Framework Directive 2000/60/EC in the evaluation of the ecological status of watercourses. Case study: The River Chienti (Central Apennies, Italy). Acta Hydrochimica Hydrobiologica 34, 498-505. [28]. Jose Antonio de-la-Ossa-Carretero, Jean-Claude Dauvin (2010). A Comparison of Two Biotic Indices, AMBI and BOPA/BO2A, for assessing the Ecological Quality Status (EcoQS) of Benthic Macro-invertebrates, Transitional Waters Bulletin 1, 12-24. [29]. Kantzaris,V. Iliopoulou- Georgudaki, J., Katharios, P., Kaspiris, P. (2002). A Comparison Of Several Biotic Indices Used For Water Quality Assessment At The Greek Rivers, Fresenius Environmental Bulletin 11 (11), 1000 – 1007. [30]. Friberg, N., Sandin L., Furse, MT., Larsen, ES., Clarke, R.T, Haaese P (2006). Comparison of Macroinvertebrate Sampling Methods in Europe. Hydrobiologia 566, 365-378. [31]. Ortiz, J.D., and Puig, M.A. (2007). Point Source Effects on Density, Biomass and Diversity of Benthic Macroinvertebrates in a Mediterranean Stream. River Research and Applications 23, 155-170. [32]. Zeybek, M., Kalyoncu, H., Karakaş, B., Özgül, S. (2014). The Use of BMWP and ASPT Indices for Evaluation of Water Quality (According To Macroinvertebrates) in Değirmendere Stream (Isparta, Turkey). Turkish Journal of Zoology DOI: 10.3906/zoo-1310-9. Received: April 09, 2014 Revised: May 26, 2014 Accepted: June 25, 2014 CORRESPONDING AUTHOR Bülent YORULMAZ Muğla Sıtkı Koçman University Science Faculty Biology Department 48000 Kötekli, Muğla TURKEY E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 188 - 194 194 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin DETERMINING OF AREAS WITH HIGH EROSION RISK IN KÜÇÜK MENDERES RIVER BASIN (WEST ANATOLIA, TURKEY) BY USING MULTI-CRITERIA DECISION MAKING METHOD Ali Ekber Gülersoy1,* and Mehmet Ali Çelik2 1 Dokuz Eylul University, Buca Faculty of Education, Department of Primary Education, 35150, Buca, Izmir, Turkey 2 Kilis 7 Aralık University, Faculty of Arts and Sciences, Department of Geography, 79100, Kilis, Turkey Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey 1. INTRODUCTION ABSTRACT The objective of this study was to determine the current situation of erosion in Küçük Menderes River Basin which is a site rich in natural environment potential, and to semtinize possible dangers which the erosion would create in the future, from a geographical-ecological point of view. In the research, Landsat satellite images were utilized to determine the relationship of the current land use-erosion, and “Multi-criteria analysis method” was used in the process of these images. Beside this, parameters such as slope, exposure, lithology etc., which are influential in erosion, were created on GIS software. Finally, areas with high erosion risk in Küçük Menderes River Basin were determined by overlaying each parameter. There is an inconsistency between the land capability classes and their usage in the basin. While the area occupied by Ist, IInd, IIIrd and IVth class lands which should be used as agricultural fields covers 32%, the area occupied by the agricultural fields covers currently 40%. This situation shows that, in the area, lands have not been used according to their capability classes. In other words, 4% of IIIrd class lands is used as the agricultural area; 16% of IVth class lands as forest; 38% of VIth class lands as the agricultural; 44% as forest-maquis; 11% of VIIth class lands as the agricultural, and 46% of VIIIth class lands as settlement area. The said situation leads to aggravation exacerbation of erosion in the area. As a matter of fact, severe erosion being seen at 30% of the basin affects the lands that are inclined and devoid of vegetation cover. As a result of land degradation and erosion, the basin lands become unuseable losing their natural feature. To prevent this loss is possible by establishing a pattern of land use which is suitable for natural environment potentials of the lands (land capability classes). KEYWORDS: Küçük Menderes River Basin, Erosion, GIS-Remote sensing, Basin Planning. * Corresponding author Soil, pedogenesis of which has occurred over thousands of years, is in danger of disappearing in a lot of regions in the World today [1, 2]. Soil erosion is one of the most important environmental problems in arid and semi-arid regions especially. For this reason, we also confront with the erosion as an important problem in Turkey where arid and semi-arid regions cover a wide area. A great part of Turkey is faced with the danger of erosion [3-6]. Since Geographic Information Systems (GIS) technology has various skills such as storing, producing, analyzing and visualizing spatial data, it possesses a great potential to solve and manage spatial problems [7]. Importance of Geographic Information Systems in planning and in protecting natural landscape is increasing day by day. Estimation of erosion in an area is a very large and effective method in workings for soil protecting and planning, and more effective and more correct data are obtained by using GIS technology. Both in Turkey and abroad, erosion risk analyses of many areas are carried out by ensuring integration of CBS and remote sensing data [8-13]. Used within this technology, Multi-Criteria Decision Making Method has features such as evaluating alternatives in solving the problem in line with the decision maker's priorities and selecting the most satisfying one, etc. For this reason, it provides the user with considerable flexibility (offers choices) in creating risk and sensitivity maps at planning works and thus giving a better and flexible response to the user's determinations. Considering the erosion's emergence depending on numerous reasons, Multi-Criteria Decision Making Method seems highly suitable for evaluating the emerging differences locally by so many alternatives in creating erosion risk maps. Therefore, this method was used while erosion risk map was being created in this study. The objective of this study was to determine the current situation of erosion in Küçük Menderes River Basin which is a site rich in natural environment potential, and 195 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FIGURE 1 - Location map of study area. to semtinize possible dangers which erosion would create in the future, from a geographic-ecologic point of view. 2. MATERIALS AND METHODS Sometimes for economic purposes, different land-use policies within different administrative boundaries can be implemented, which causes different soil losses within the same ecosystems. In this study, Küçük Menderes River Basin was investigated. The objective of the study was to present erosion risk in Küçük Menderes River Basin and to emphasize factors (land cover, geology, topography etc.) having influence over spatial differences in soil loss. In this study, it was aimed to determine areas of potential and true erosion danger with the help of Geographic Information System (GIS) and Remote sensing methodologies. To determine erosion risk of the study area, parameters of slope, lithology, vegetation cover, rainfall and exposure were used. Topography maps of 1/25.000 belonging to the study area were digitized on ArcGIS 10.x programme for the purpose of producing slope and exposure maps which were used as a parameter in the study, and databases of these parameters were established. The similar method was also used to establish database of lithological features which is an-other parameter that was utilized in presenting the erosion risk of the study area. In determining lithological features, ''Geology and Lithology Map of Küçük Menderes River Basin'' prepared by Gozenc (1978) was used as underlay [14]. Another influential factor used in the study is rainfall. For establishing database related to this data, annual average precipitation data belonging to the study area were obtained from Turkish State Meteorological Service. Distri- bution map of precipitation for the area was created via Inverse Distance Weighted (IDW) method by considering altitude factor, as well. Beside this, MODIS satellite image dated August 23, 2012 was used to present land cover density of Küçük Menderes River Basin. NDVI (Normalized Difference Vegetation Index) image was created to measure closure status of land cover by utilizing from satellite image of the year 2012. Clearance or closure of the land in the study area in terms of vegetation cover was addressed within three different categories: a) Bare surfaces, b) Fewer vegetation cover, c) Areas with dense vegetation cover. 3. RESULTS AND DISCUSSION There is an inconsistency between the land capability classes and their usage in the basin. While the area occupied by Ist, IInd, IIIrd and IVth class lands which should be used as agricultural fields covers 32%, the area occupied by the agricultural fields covers currently 40%. This situation shows that, in the area, lands have not been used according to their capability classes. In other words, 4% of IIIrd class lands is used as the agricultural area; 16% of IVth class lands as forest; 38% of VIth class lands as the agricultural; %44 as forest-maquis; 11% of VIIth class lands as the agricultural, and %46 of VIIIth class lands as settlement area. The said situation increases erosion risk in the research area. 3.1. Slope In the research area, the erosion risk is high on the south slopes of Bozdağlar Mountains and the north slopes of Aydın Mountains, where the cleavage degree geomorphologically and the plain density have increased, and TABLE 1 - The Slope classes and reclassify values in the study area. Slope Classification Level-Very low slope (% 0-3) Moderate slope (% 3-12) Steep slope (% 12-25) Very steep slope (% 25-40) Sheer ( > % 40) Reclassify Value 20 40 60 80 100 196 GIS Value 10 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FIGURE 2 - The Slope map of the study area. TABLE 2 - Elevation zones and reclassify values in the study area. Elevation (m) 0-185 185-450 450-750 750-1150 > 1150 Reclassify Value 20 40 60 80 100 GIS Value 9 FIGURE 3 - DEM (Digital Elevation Model) map of the study area. which have the slope above 10-12%. It is moderate along the alluvial deposits, lower hilly areas and the erosional surfaces, where the slope is below 10-12%. The erosion risk is rather low on the basin bottom where the slope is less and the deposition is in the forefront. the areas which are at altitudes between 450-750 m. The erosion poses a serious threat on these areas, which are cleaved narrowly and deeply by rivers, and the basin densities of which are high. It is low on the areas with an elevation below 450 m. in the research area. 3.2. Elevation 3.3. Vegetation In the basin, the erosion risk is high on the areas that are inclined, the average elevation of which is above 750 m. and the vegetation cover density is low, while it is moderate on While, in Küçük Menderes River Basin, the erosion risk is high around residential areas where the vegetation cover has been destroyed, and on the areas which are de- 197 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 3 - NDVI classes and reclassify values in the study area. NDVI Dense vegetation Vegetation Non-vegetation Reclassify Value 25 50 100 GIS Value 7 FIGURE 4 - NDVI map of the study area TABLE 4 - Geological elements in the study area and their reclassify values Geology Alluvion Limestone-Conglomerate Rhyolite-Andesite-Granite-Quartzite Gneiss-Mica schist-Marble Reclassify Value 25 50 75 100 FIGURE 5 - Geology map of study area. 198 GIS Value 5 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin void of vegetation cover and where the slope is in excess of 10 %, it is moderate in the areas which are free from destruction, and the closure of vegetation cover of which is at an intermediate level. The erosion risk is low on the areas where there is a respectively high rainfall and density of vegetation cover. 3.4. Geology While, in the research area, the erosion risk is very high on slopes that are inclined and devoid of vegetation cover, which consist of metamorphic elements (gneiss, mica schist and marble), it is high on slopes which are inclined and consist of volcanic rocks (rhyolite, andesite, granite) and quartzites. The erosion risk is moderate over sedimentary elements (limestone, conglomerate) which show a spreading on a narrow area whereas it is rather low on the basin bottom and banks, which consist of alluvions. 3.5. Rainfall The research area receives an average rainfall around 724 mm. While north, northwest and west slopes of Aydın Mountains which are facing air masses coming from north, northwest and west receive higher rainfall (750-850 mm), the south and depression areas of Bozdağlar Mountains receive less rainfall (550-650 mm). Within this scope, erosion risk is high on the south of the basin on which the amount and density of precipitation are high (above 800 mm.) whereas it is moderate on the north of the basin receiving respectively less rainfall (below 750-800 mm.). The erosion risk is low on the areas receiving a rainfall below 700 mm. 3.6. Aspect In the basin, the erosion risk is generally high on the inclined slopes which consist of metamorphic and volcanic elements which face south, the vegetation cover of which has been destroyed, and which receive respectively less rain, while it is at a moderate level on slopes that face east-west, which receive rainfall on the basin average (724 mm), and which the closure of vegetation cover of is moderate. On the other hand, it is low on north-facing slopes, where the rainfall is more (750-780 mm.) than the basin average and of which the closure of vegetation cover is high. TABLE 5 - Rainfalls and reclassify values in the study area. Rainfall (mm) 650-700 700-750 750-800 800-850 > 850 Reclassify Value 20 40 60 80 100 GIS Value 3 FIGURE 6 - Rainfall map of the study area. TABLE 6 -Reclassify values according to the exposure in the study area. Aspect North East-West South Reclassify Value 25 50 100 199 GIS Value 2 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FIGURE 7 - Exposure map of the study area. 3.7. Erosion Risk Mapping Erosion risk maps were determined according to variables of geology, exposure, vegetation, slope, elevation and rainfall in Küçük Menderes River Basin. The erosion risk is high on the areas with high slope, rainfall and elevation, which are devoid of vegetation cover, with south-facing, and consisting of metamorphic-volcanic elements. It is moderate over the sedimentary-volcanic elements, with the intermediate degree of slope, which receive a rainfall on the basin average and which are at altitudes between 450750 m., with an intermediate degree of vegetation cover closure and with east-west-facing. The erosion risk is low on the areas consisting of alluvional-colluvial elements, with a low slope, which have an altitude below 450 m., where there is a respectively dense of vegetation cover, and with north-facing. FIGURE 8 - Erosion risk map of the study area. TABLE 7 - Areas (ha) and ratios (%) which are covered by erosion risk classes in the study area. Erosion Risk Low erosion Moderate erosion Moderately high erosion High erosion Extremely high erosion Area (ha) 140675,4 89826,9 47938,2 31620,9 16938,6 200 % 43,02 27,47 14,66 9,67 5,18 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FIGURE 9 - Agricultural activities which are done around Beydağ Dam are increasing the erosion and siltation, and consequently lifetime of the dam is getting shorter. FIGURE 10 - Agricultural activities being done over the inclined lands, in the north of D310 State Highway, in the south of Derebaşı Village, Tire County lead the fertile soil to erode. 201 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin 4. CONCLUSIONS In this study, the areas the erosion risk of which is high in the Küçük Menderes River Basin were determined by using the multi-criteria (geology, exposure, vegetation, slope, elevation and rainfall) decision making method. The areas where the erosion risk is high are sites with high slope, rainfall and elevation, which are devoid of vegetation cover, with south-facing, and which consist of metamorphic-volcanic elements. The areas with moderate erosion risk are the sites, which have intermediate level of slope, which are at altitudes of 450-750 m., which have a moderate closure of vegetation cover, receive rainfall on the basin average, with east-west facing, and which consist of sedimentary-volcanic elements. As for the areas with low erosion risk are sites, where the slope is low, which have an altitude below 450 m., where there is a respectively dense of vegetation cover, with north-facing, and which consist of alluvial-colluvial elements. In the research area, non-use of lands in a suitable way for their natural environment potential leads to the aggravation of erosion. As a matter of fact, severe erosion being seen at 30% of the basin affects lands that are inclined and devoid of vegetation cover. As a result of land degradation and erosion, the basin lands become unusable losing their natural feature. To prevent this loss is possible by establishing a pattern of land which is suitable for natural environment potentials (land capability classes) of the lands. [8] Ekinci, D. (2005). “Erosion Analysis of Kozlu River Basin with the GIS-Based a Modified a RUSLE Method”. Istanbul University Journal of Geography, Department of Geography, Faculty of Arts, 13, 109-119. [9] Kheira R.B., Abdallaha, C., Runnstromb, M. and Martenssonb U. (2008). Designing erosion management plans in Lebanon using remote sensing, GIS and decision-tree modeling. Landscape and Urban Planning 88, 54–63 [10] Karabulut, M. and Küçükönder, M. (2008). Detection of Erosion Areas around Kahramanmaraş City and its Plain by Using GIS. Kahramanmaraş Sütçü İmam University Journal of Physical and Engineering Sciences, 11, 14-22. [11] Sönmez, M. E., Çelik, M. A. and Seven, M. (2013). Detection of Erosion Risk Areas of Kilis Central District with the Help of Geographic Information Systems and Remote Sensing. Kahramanmaraş Sütçü İmam University Journal of Social Sciences, 1, 1-21. [12] Alexakis, D.D., Hadjimitsis, D.G. and Agapiou, A. (2013). Integrated Use of Remote Sensing, GIS and Precipitation Data for the Assessment of Soil Erosion Rate in the Catchment Area of “Yialias” in Cyprus. Atmospheric Research, 131, 108–124. [13] Conoscenti, C., Angileri, S., Cappadonia, C., Rotiglianoa, E., Agnesi, V and Märker, M., (2014). Gully Erosion Susceptibility Assessment by means of GIS-Based Logistic Regression: A Case of Sicily (Italy). Geomorphology, 204, 399–411. [14] Gözenç, S. (1978). The Use and Classification of the Land on Küçük Menderes River Basin. İ.Ü. (Istanbul University) Publishing House of Arts Faculty, Istanbul, Turkey (in Turkish). The authors have declared no conflict of interest. REFERENCES [1] Vrieling, A., Jong S.M., Sterk G. and Rodrigues S.C. (2008). Timing Of Erosion and Satellite Data: A Multi-Resolution Approach To Soil Erosion Risk Mapping. International Journal of Applied Earth Observation and Geo-information, 10, 267-281. [2] Nigel, R. and Rughooputh S.D.D.V. (2010). Soil Erosion Risk Mapping with New Datasets: An Improved Identification and Prioritisation of High Erosion Risk Areas. Catena, 82, 191-205. [3] Tağıl, Ş. (2009). Spatial Distribution and Affecting Factors of Soil Loss on Çakırdere and Yahu Dere Stream Basins (Balıkesir). Balıkesir University Journal of Institute of Social Sciences, 22, 23-39. Received: April 03, 2014 Revised: May 21, 2014 Accepted: June 25, 2014 [4] Gülersoy, A.E. (2008). Relationships between Natural Environment Conditions and Land Use in Bakırçay Basin. Institute of Educational Sciences, D.E.U., Unpublished Doctoral Dissertation, Izmir (in Turkish). CORRESPONDING AUTHOR [5] Doğan, O. (2011). Reasons, and Solution Suggestions of Erosion in Turkey. Education in the Light of Science and Intelligence, 134, 62-69. [6] Tunç, E. and Çelik, M. A. (2014). Monitoring The Effects of Rainfall Conditions on Wheat (Triticum Aestivum L.) Fields Using Modis Data in Araban/Gaziantep, Turkey. Fresenius Environmental Bulletin, 23 (3), 728-737. [7] Zhang, Y.J., Li, A.J. and Fung, T. (2012). Using GIS and Multi-Criteria Decision Analysis For Conflict Resolution in Land Use Planning Original Research Article. Procedia Environmental Sciences, 13, 2264-2273. 202 Ali Ekber Gülersoy Dokuz Eylul University Buca Faculty of Education Department of Primary Education Buca, Izmir TURKEY Phone: ++90 232 301 22 99 E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 195 – 202 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TROPHIC STATUS AND THREATS IN ZINAV LAKE (TOKAT/ TURKEY) Saliha Dirim Buhan1, Nihal Bektaş1, Mehmet Ali T. Koçer2,*, Hakan Mete Doğan3, Ekrem Buhan4 and Fatih Polat5 1 Gebze Institute of Technology, Faculty of Engineering, Environmental Engineering Department, Gebze/Kocaeli/Turkey 2 Mediterranean Fisheries Research Production and Training Institute, Antalya/Turkey, 3 Gaziosmanpaşa University, Agricultural Faculty, Soil Science Department, Tokat/Turkey 4 Gaziosmanpaşa University, Agricultural Faculty, Aquaculture and Fisheries Department, Tokat/Turkey 5 Gaziosmanpaşa University, Almus Vocational School, Tokat/Turkey Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey ABSTRACT This study was conducted to determine water quality and trophic state of Zinav Lake, which is located in the Central Black Sea Region of Turkey. Temperature, dissolved oxygen, pH, electrical conductivity, total suspended solids, Secchi disc transparency, ammonia, nitrite, nitrate, total nitrogen, soluble reactive phosphorus, total phosphorus and chlorophyll a were monitored in water column from January 2012 to June 2013. The study showed that Zinav Lake was a dimictic lake, which circulated in spring and fall, and thermally stratified in summer. Hypo-limnetic oxygen deficit and metalimnetic oxygen minima were the cases. Vertical distribution of dissolved oxygen and pH and ammonia accumulation in hypolimnion represented eutrophic/hypereutrophic conditions. The values and ratios of nutrients and chlorophyll a and Secchi disc transparency clearly classified Zinav Lake as eutrophic/hypereutrophic. Allochthonous loadings of organic matter and nutrients from the catchment and the changes in hydrological cycle by a power plant seem to be the most threatening factors controlling the water quality and trophic state in Zinav Lake. system and from terrestrial loadings from catchment area [1]. Many factors such as location, climate, vegetation and land cover/land use in the catchment area have significant influences on the water quality of small lakes [2, 3], considering they have the high hydrologic and nutrient processing rates [4]. Allochthonous organic matter, however, supplements primary production in small lakes, particularly in forested areas [5]. Therefore, organic matter and nutrient loadings from catchment area result in generally higher productivity of small lakes as compared with large ones [6]. Despite diminished characteristics, small lakes were neglected by ecologists partly due to presuming that ecosystems with a small areal extent cannot play a major role in global processes. However, recent analyses have shown that they play an unexpectedly significant role in global cycles [7]. Zinav Lake is a small lake with a surface area of 0.34 km2, located in the Central Black Sea Region of Turkey. There is a lack of data on the lake in spite of the biggest natural lake in Kelkit River Basin. In this context, this study aimed to investigate the vertical and seasonal fluctuations of physicochemical properties and trophic state of Zinav Lake. 2. MATERIAL AND METHODS KEYWORDS: Zinav Lake, water quality, nutrients, trophic state, threats Zinav Lake as abovementioned is located in the Central Black Sea Region of Turkey. The precise position of study area can be described as between the 37o13’-37o21’ North latitudes and 40o32’-40o23’ East longitudes (Figure 1). 1. INTRODUCTION Although the magnitude and proportion of the sources vary widely among different systems, aquatic ecosystems receive organic matter from primary production within * Corresponding author The study was carried out between January 2012 and June 2013. Surface water samples were collected from three areas of the lake representing inlet, outlet and mid-point, while vertical samples from 0, 5, 10 meters and deep water at the mid-point. Temperature, pH and electrical conductivity were measured in situ by using YSI-556 MPS multiparameter measurement instrument (YSI, USA). Total sus- 203 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin pended solids, ammonia, nitrite, nitrate, soluble reactive phosphorus, total nitrogen and phosphorus were determined with suitable methods and test kits using by DR2800 benchtop spectrophotometer (Hach-Lange Germany). Chlorophyll a concentrations were calculated by monochromatic method after extraction with 90% acetone solution and absorbance measurement by the spectrophotometer [8]. Normality was firstly tested for each variable using the Shapiro-Wilk test. Comparisons of sampling sites and nonnormally distributed water quality parameters were made using a signed rank test (Wilcoxon) and followed by post hoc test (Tukey’s HSD). Wilcoxon test did not detect significant differences between the three surface water sampling sites in terms of physicochemical variables (P > 0.05). Therefore, water quality of the lake was evaluated according to mid-point measurements. All statistical tests were carried out using JMP 8.0 software package. 3. RESULTS Vertical change of temperature was significantly different (P<0.01), with higher values at surface water than 10 meters and deep water (Table 1). Vertical temperature profile displayed a clear seasonal variation, revealing the periods of mixing and thermal stratification (Figure 2a). In summer, temperature sharply decreased from surface water to bottom, and the greatest thermal discontinuity was observed in July. Temperature of surface water gradually decreased in late summer, and thermal stratification was lost during the fall circulation. Measurements showed that the fall turnover was completed in November, and almost a thermal homogeneity in water column prevailed during winter. Dissolved oxygen sharply decreased in metalimnion during thermal stratification, and the hypolimnetic oxygen deficit was the case (Figure 2b). The large volume of anoxic hypolimnion which was expanded above 5 meters in July resulted in low dissolved oxygen concentrations in entire water column during the fall circulation. Despite low concentrations in deep water, high concentrations of dissolved oxygen in surface layers were observed during winter. FIGURE 1 - Location and topographic features of the study area TABLE 1 - Summary of monitored parameters in water column during the study period (parameters not connected by same letter in same line are significantly different; P < 0.05) Parameters 0m 5m a 10 m ab 7,7±2,7 20 m b 6,5±1,9b Temperature (°C) 13,7±7,1 10,5±4,6 Dissolved oxygen (mg/L) 9,4±2,9a 6,8±3,4ab 5,1±3,8bc 3,2±2,5c pH 8,4±0,4a 8,2±0,5ab 8,0±0,5bc 7,6±0,5c Electrical conductivity (µS/cm) 255±26 249±29 226±26 234±41 Total suspended solids (mg/L) 16±11 15±11 14±8 18±11 Ammonia (mg NH4 -N/L) 0,082±0,100 a 0,128±0,098 a 0,352±0,190 b 0,480±0,181b Nitrite (mg NO2--N/L) 0,009±0,007 0,009±0,007 0,014±0,011 0,023±0,023 0,165±0,108 0,218±0,143 0,266±0,163 0,279±0,227 2,2±1,4 2,2±1,3 2,3±1,0 4,0±1,8 Soluble reactive phosphorus (mg PO4 -P/L) 0,111±0,056 0,085±0,029 0,112±0,051 0,113±0,057 Total phosphorus (mg P/L) 0,125±0,140 0,109±0,069 0,127±0,010 0,201±0,193 + - Nitrate (mg NO3 -N/L) Total nitrogen (mg N/L) -3 Chlorophyll a (µg/L) Secchi disc transparency (cm) 27,4±22,5 105±38 204 a 15,3±11,1 ab 5,3±4,8 b 1,9±1,4b © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FIGURE 2 - Depth-time diagrams of (a) temperature (°C), (b) dissolved oxygen (mg/L), (c) pH and (d) chlorophyll a (µg/L). Vertical pH was measured between 7.1 and 9.2 and significantly higher (P<0.001) at surface water than 10 meters and deep water (Table 1). While it was homogenous in winter and spring, low values were observed in hypolimnion during thermal stratification and fall turnover (Figure 2c). Electrical conductivity was between 164 and 310 µS/cm, with higher values at surface layers than deep. However, differences of electrical conductivity among monitored depths were not significant (P>0.05). Although suspended solids was higher in deep water than the upper column (Table 1), there were no significant differences (P>0.05). Despite low pH values, ammonia nitrogen levels were clearly higher in deep water than surface layers (Table 1). It was determined at high concentrations in deep water with low dissolved oxygen concentrations during all the study period. Therefore, ammonia of 10 meters and deep water did significantly differ from surface water and 5 meters (P<0.001). Nitrite and nitrate nitrogen exhibited an increasing trend with depth (Table 1). Mean concentration of total dissolved inorganic nitrogen (NH4+NO2+NO3) represented only a small fraction of total nitrogen (12-27%) in water column. Indeed, total nitrogen in Zinav Lake was determined at high concentrations in a range of 0.7 and 6.1 mg/L. The ratio of soluble reactive phosphorus to total phosphorus was relatively high (56-89%). However, vertical changes of abovementioned nitrogen and phosphorus fractions were statistically insignificant (P>0.05). Chlorophyll a showed a clear decreasing trend with depth (Table 1). Chlorophyll a at surface water was significantly higher than 10 meters and deep water (P<0.001). In fact, chlorophyll a was observed at high concentrations in surface layers during thermal stratification and fall and spring turnover periods (Figure 2d). Secchi disc transparencies, measured between 40 and 180 centimeters, were not linearly related with chlorophyll a (r2=0.02; P>0.05). However, suspended solids at surface layers significantly affected Secchi disc transparency (r2=0.55; P<0.01). 4. DISCUSSION AND CONCLUSION Vertical temperature profile revealed that Zinav Lake was a dimictic lake which was entirely mixed by a combination of convection currents and wind-induced epilimnetic circulation in the spring and fall. The rise in thermal gradient, accepted as much more than 1 °C per meter [9], was maximum between 5 and 10 meters representing metalimnion depth during summer. Epilimnion narrowed to a depth of 34 meters in July. Distribution of dissolved oxygen in water column provided an evidence for trophic status of the lake. A hypolimnetic oxygen deficit observed during thermal stratification period was probably due to the oxidative consumption of organic matter as an indicator of eutrophic/hypereutrophic lakes [10]. Moreover, decomposition of settling material in the denser water of the metalimnion could evoke a metalimnetic oxygen decrease in the lake. Indeed, increasing eutrophication leads to an increase in hypolimnetic oxygen deficit [11]. This clinograde curve of dissolved oxygen during thermal stratification was suggested as an indicator of eutrophic conditions [9, 12]. In addition, the large volume of anoxic hypolimnion resulted in low concentrations of dissolved oxygen in water column during the fall turnover. It was reported that byproducts of anaerobic metabolism accumulated annually in the hypolimnion cause low dissolved oxygen concentrations in the upper waters during fall turnover [13]. Since dissolved oxygen and pH are mainly influenced by photosynthesis in epilimnion and the decomposition in 205 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin hypolimnion, they vary similarly in eutrophic lakes [14]. Therefore, a decrease in pH which was observed in hypolimnion during thermal stratification and fall turnover in Zinav Lake was probably due to an increase in carbon dioxide concentrations released from decomposition processes. In fact, eutrophic lakes with a clinograde pH curve possess a clinograde oxygen curve [9]. High amounts of organic matter together with distribution of dissolved oxygen and pH in water column seemed to be responsible for high concentrations of ammonia in deep water of Zinav Lake. An accelerated accumulation of ammonia in hypolimnion takes place under anoxic conditions and this condition cause a marked release of ammonia from the sediment because of reduced absorptive capacity [9]. Thus, it was suggested that the degree of development of the anoxic layer is the primary factor controlling the extent of hypolimnetic ammonia accumulation [15]. Although vertical pattern of ammonia evidently showed eutrophic conditions, higher concentrations of nitrate in deep water than surface were incompatible with these conditions [9]. This case might be due to nitrate assimilation by photosynthesis in surface layers of water column and prevailing low denitrification rate in deep layers of Zinav Lake. It is well known that dominant fraction of dissolved inorganic nitrogen in oxygen rich lakes is nitrate whereas in anoxic or oxygen fair conditions ammonia is dominant [16]. The concentrations of nutrients and chlorophyll a and Secchi disc transparency may be used to estimate trophic state. Ratio of nitrogen to phosphorus can also be used to indicate if a particular nutrient is limiting since they are major limiting nutrients in growth of primary production. Measurements of total nitrogen and total phosphorus are also useful for determining trophic state [16, 17]. Therefore, it is clear that Zinav Lake was classified as eutrohic/hypereutrophic based on mean Secchi disc transparency and average concentrations of total nitrogen, total phosphorus and chlorophyll a [9, 18-20]. The ratio of total nitrogen to total phosphorus in surface water (17:1 by mass) suggested that nitrogen was the limiting nutrient in Zinav Lake [21, 22]. In addition to above indicators, dissolved inorganic nutrients are also useful in trophic state determinations. If soluble reactive phosphorus are at high values (>0.1 mg/L), it indicates a phosphorus enriched system [17]. Soluble reactive phosphorus made up much of the total phosphorus in Zinav Lake. In conclusion, Zinav Lake was characterized as dimictic lake, mixed twice a year and stratified in summer. Although metalimnion was observed between 5 and 10 meters during summer, epilimnion narrowed to a depth of 3-4 meters in July. Vertical distribution of dissolved oxygen and pH and ammonia accumulation in hypolimnion represented eutrophic/hypereutrophic conditions. Hypolimnetic oxygen deficit and metalimnetic oxygen minima were the cases due to the oxidative consumption of organic matter. The values and ratios of nutrients and chlorophyll a and Secchi disc transparency clearly classified Zinav Lake as eutrophic/hypereutrophic. Nitrogen was the limiting nutrient. Water quality and trophic state in Zinav Lake are threatened by human activities by highly increasing terrestrial suspended solids and organic matter loadings as well as changing natural hydrological cycle. Streams flowing into the lake carrying rural and agricultural wastes from the towns and villages located upper parts of the basin are responsible for terrestrial loadings. As a common process in the basin, land clearing for agriculture also exacerbates erosion and accelerates sediment transport into the lake. But operation of a hydropower plant installed to outlet of the lake causes the changes in flow rates and ways of the currents in the lake. Therefore, terrestrial loadings from catchment, biological processes, stratification and circulation in water column seem to be the most important factors controlling the water quality and trophic state in Zinav Lake. ACKNOWLEDGEMENT The authors thank to The Scientific and Technical Research Council of Turkey for their grand (TUBITAK, Project No: ÇAYDAG-110Y117 ). The authors also thank staff of Mediterranean Fisheries Research Production and Training Institute for their invaluable help with data collection and laboratory analyses. This study is also a part of the doctoral thesis of Saliha Dirim Buhan. 206 The authors have declared no conflict of interest. REFERENCES [1] Carpenter, S.R., Kitchell, J. F. and Pace, M.L. (2002) Pathways of organic carbon utilization in small lakes: Results from a whole-lake 13C addition and coupled model. Limnology and Oceanography 47, 1664-1675. [2] Mallory, M.L., McNicol, D.K., Cluis, D.A. and Laberge, C. (1998) Chemical trends and status of small lakes near Sudbury, Ontario, 1983-1995: evidence of continued chemical recovery. Canadian Journal of Fisheries and Aquatic Sciences 55(1), 6375. [3] Müller, B., Lotter, A.F., Sturm, M. and Ammann, A. (1998) Influence of catchment quality and altitude on the water and sediment composition of 68 small lakes in Central Europe. Aquatic Sciences 60, 316-337. [4] Hanson, P.C., Carpenter, S.R., Cardille, J.A., Coe, M.T. and Winslow, L.A. (2007) Small lakes dominate a random sample of regional lake characteristics. Freshwater Biology 52(5), 814-822. [5] Sand-Jensen, K. and Staehr, P. (2007) Scaling of Pelagic Metabolism to Size, Trophy and Forest Cover in Small Danish Lakes. Ecosystems 10, 128-142. [6] Tilzer, M.M. (1990) Specific Properties of Large Lakes. In: Large Lakes (Tilzer, M. and Serruya, C., Eds.),. Springer Berlin Heidelberg,Germany, 39-43. [7] Downing, J.A. (2010) Emerging global role of small lakes and ponds: little things mean a lot. Limnetica 29(1), 9-24. © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin [8] APHA, AWWA and WEF (1998). Standard Methods for the Examination of Water and Wastewater. 20th edition. American Public Health Association, Washington, DC. [9] Wetzel, R.G. (2001) Limnology: Lake and River Ecosystems. 3rd edition. Academic Press, San Diego, CA. [10] Walker, W.W. (1979) Use of Hypolimnetic Oxygen Depletion Rate as a Trophic State Index for Lakes. Water Resources Research 15(6), 1463-1470. [11] Matzinger, A., Müller, B., Niederhauser, P., Schmid, M. and Wüest, A. (2010) Hypolimnetic oxygen consumption by sediment-based reduced substances in former eutrophic lakes. Limnology and Oceanography 55(5), 2073-2084. [12] Goldman, C.R. and Horne, A.J. (1983) Limnology. McGrawHill, New York. [13] Effler, S.W. and Matthews, D.A. (2008) Implications of redox processes for the rehabilitation of an urban lake, Onondaga Lake, New York. Lake and Reservoir Management 24, 122138. [14] Rogora, M., Garibaldi, L., Morabito, G., Arisci, S. and Mosello, R. (2002) Present trophic level of Lake Alserio (Northern Italy) and prospect for its recovery. Journal of Limnology 61(1), 27-40. [15] Satoh, Y., Ura, H., Kimura, T., Shiono, M. and Seo, S.K. (2002) Factors controlling hypolimnetic ammonia accumulation in a lake. Limnology 3, 43-46. [16] Dodds, W.K. (2002), Freshwater Ecology: Concepts and Environmental Applications. Academic Press, San Diego, CA. [17] Dodds, W.K. (2003) Misuse of inorganic N and soluble reactive P concentrations to indicate nutrient status of surface waters. Journal of the North American Benthological Society 22(2), 171-181. [18] OECD (1982) Eutrophication of waters: Monitoring, assessment and control. OECD Cooperative programme on monitoring of inland waters (Eutrophication control), Environment Directorate, OECD, Paris. [19] Hakanson, L. and Jansson, M. (1983) Principles of Lake Sedimentology. Springer, Berlin, Germany. [20] Nürnberg, G.K. (1996) Trophic state of clear and colored, soft and hardwater lakes with special consideration of nutrients, anoxia, phytoplankton and fish. Journal of Lake and Reservoir Management 12, 432-447. [21] Downing, J.A. and McCauley, E. (1992) The nitrogen: phosphorus relationship in lakes. Limnology and Oceanography 37(5), 936-945. [22] Guildford, S.J. and Hecky, R.E. (2000) Total nitrogen, total phosphorus, and nutrient limitation in lakes and oceans: Is there a common relationship? Limnology and Oceanography 45, 1213-1223. Received: April 03, 2014 Accepted: July 07, 2014 CORRESPONDING AUTHOR Mehmet Ali T. Koçer Mediterranean Fisheries Research Production and Training Institute Yeşilbayır Mah. Akdeniz Bul.No:2 Döşemealtı, Antalya TURKEY Phone: +90-242-251 05 85 Fax: +90-242-251 05 84 E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 203 – 207 207 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin APPLICATION OF MULTI-METAL BIOACCUMULATION INDEX AND BIOAVAILABILITY OF HEAVY METALS IN Unio sp. (UNIONIDAE) COLLECTED FROM TERSAKAN RIVER, MUĞLA, SOUTH-WEST TURKEY Tuncer Okan Genç*, Fevzi Yilmaz, Burak Evren İnanan, Bülent Yorulmaz and Gökhan Ütük Muğla Sıtkı Koçman University, Science Faculty, Biology Department 48000 Kötekli Muğla, Turkey Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey ABSTRACT In the present study, some heavy metals (Cd, Co, Cr, Cu, Fe, Mn, N, Pb and Zn ) were seasonally determined in some tissues of mussel Unio sp. from Tersakan River, which is an important agricultural, a visiting area and, a water source for irrigation. Generally, higher concentrations of the measured metals were found in the winter and autumn compared with those during spring and summer. High levels of heavy metals were found in shell samples, while low levels in muscle. The measured metal concentrations in tissues is not differed significantly for all metals except Fe between autumn and spring but significant differences for Cd, Co, Cr, Cu, Mn and Pb were observed between summer and autumn (p<0.05). Individual MultiMetal Bioaccumulation Index (MBI) values varied from 0.01 to 0.44, 0.00 to 0.47, and 0.00 to 0.43 in muscle, gill, and shell respectively. Generally, IMBI values calculated in muscle were higher than gill and shell. According to the acceptable values for human consumption designated by various health organizations, concentrations of some metals such as Cd and Pb were more than the designated limits, especially in summer. KEYWORDS: Bioaccumulation, heavy metals, multi-metal bioaccumulation index, Unio sp. 1. INTRODUCTION Effluents from textile, leather, tannery, electroplating, galvanizing, pigment and dyes, metallurgical and paint industries and other metal processing and refining operations contain considerable amounts of toxic heavy metal ions which are both potential hazards for human health and for other life forms. The river systems may be excessively contaminated with toxic heavy metals released from do* Corresponding author mestic, industrial, mining and agricultural effluents. The contamination of freshwaters with a wide range of pollutants has become a matter of great concern over the last few decades, not only because of the threat to public water supplies, but also with of the damage caused to the aquatic life [1-5]. Bivalves are well known for their biological features of concentrating some substances especially heavy metals in their tissues [6]. Because of their main characteristics such as being sedentary organisms, their longevity, their abundance and availability throughout the year, their environmental tolerance, they are often chosen for biomonitoring studies. Besides, bivalves have good net accumulation capacities. The importance of bivalves in pollution impact studies has been shown within the scope of the International Mussel Watch Programme [7-8]. Although all heavy metals are potentially harmful to most organisms at some level of exposure and absorption [9], some heavy metals such as Zn, Cu and Co are essential in trace amounts for normal growth and development. However, others such as Hg, Cd and Pb have no known biological role [10, 11]. Since it is edible and marketed commercially, the determination of contaminant levels in mussel species provides the assessment of possible toxicant risk to public health [12]. This study includes the metal bioaccumulation of Cd, Co, Cr, Cu, Fe, Mn, N, Pb and Zn in Unio sp. tissues and evaluating Individual Multi-Metal Bioaccumulation Index for influence of heavy metal pollution. 2. MATERIALS AND METHODS 2.1 Study Area In this study, heavy metals (Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn ) contents in Unio sp. were investigated. The mussels were collected from the Tersakan River polluted by agricultural and domestic wastes. The Tersakan River is a temperate stream (36°45'51"N, 28°49'20"E), which is im- 208 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin pacted by unpredictable environmental conditions associated with a Mediterranean climate. Its length is 30 km and this stream has temporal and spatial water flow variations throughout the water course (48–780 m3/s) [13]. The lower section of the stream was channelized by local authorities to prevent seasonal floods. The stream flows into Mediterranean Sea. Vegetation is usually abundant throughout the stream banks and depth varies between 0.5–2 m. The sampling site was characterized by muddy substrate, limited vegetation and slow flow velocity. It had recently been affected by heavy floods, which occur seasonally because of high annual precipitation [14]. (gradually increased) until all the materials were dissolved. After digestion, the digested samples were diluted with distilled water appropriately in the range of standards which were prepared from stock standard solution of the metals (Merck). The extraction procedure for the tissues included multi-acid digestion (HNO3-HClO4-HCl) and analysis for Cd, Co, Cr, Cu, Fe, Mn, N, Pb and Zn, by ICP-AES (Perkin-Elmer Corp., Nonvalk, CT, USA). Verification of the method was demonstrated by analysis of an independent standard reference material (DORM-2, certified dogfish muscle tissue, National Research Council, Ottowa, Ontario, Canada). 2.2 Collection of Mussel and Physical and Chemical Analyses 2.4 Data Analyses Freshwater mussels Unio sp. were caught by bucket. 20 freshwater mussels were selected from each caught in the Tersakan River in every season of 2010. Physico-chemical parameters (pH, temperature, conductivity and dissolved O2) of freshwater on sampling days were determined by a Hach Lange HQ40D model. The samples were brought to the laboratory at the same day, weighed, measured and dissected. During the sampling, physico-chemical parameters of the water were analyzed on the selected station using LCK cuvette test on Hach Lange DR 2800 model Spectrophotometer. LCK codes used were as follows: LCK 305 for (NH4N), LCK 339 for (NO3), LCK 342 for (NO2), LCK 348 for (PO4P), LCK 328 for (K), LCK 327 for (Ca) and (Mg). The analysis of each parameter was performed as described on standard cuvette tests. Kruskal-Wallis following Man-Whitney-U test were used to determine whether metal concentrations differ significantly between tissues and season at a level of a = 0.05. Paired relationships between environmental parameters and metal concentrations were revealed using Pearson’s correlation tests. These statistical calculations were performed with SPSS 20.0 for Windows. The individual mean (multi-metal) bioaccumulation index (IMBI) was calculated as [15]: IMBI ∑ 1 i/Cimax n With N the total member of metals, Ci the individual metal concentration of heavy metal i, Cimax the maximal observed concentration of heavy metal i and 0<IMBI<1. 2.3 Digestion and Heavy Metal Determination Tissues of the same species from the same station were pooled to make 20 subsamples. They were transferred to an oven set (120 °C) to dry. Drying continued until all the wet tissues reached a constant weight. Dry tissue samples were put into digestion flasks and 2 ml hydrogen peroxide and 8 ml nitric acid (Merck) were added. The digestion flasks were then put on a microwave digestion unit at 120 °C 3. RESULT AND DISCUSSION 3.1 Environmental Parameters and Shell Allometric Parameters Some physicochemical parameters of water in the study area and also shell allometric parameters of samples are presented in Table 1 and Table 2, respectively. TABLE 1 - Seasonally water parameters of Tersakan River (average±SEM, n=3) Autumun Winter Spring Ammonium (NH4N) mg/L 0.16±0.1 0.32±0.1 0.21±0.2 Summer 0.01±0.1 Nitrate (NO3) mg/L 0.55 ±0.2 1.85±0.2 0.27±0.1 0.71±0.1 Nitrite (NO2) mg/L 0.03±0.1 0.03±0.1 0.01±0.1 0.04±0.1 Orthophosphate (PO4P) mg/L 0.35±0.1 0.37±0.1 0.10±0.1 0.06±0.1 Potassium (K+) mg/L 0.35±0.1 1.71±0.2 3.30±0.1 0.23±0.1 Total hardness dH 21.80±0.1 40.20±0.3 49.4±0.3 22.80±0.2 Calcium (Ca) mg/L 54.40±0.2 41.10±0.3 31.70±0.2 46.20±0.2 Magnesium (Mg) mg/L 61.40±0.3 149±0.4 195±0.4 70.90±0.3 Dissolved Oxygen (mg/L) 8.50±0.1 6.83±0.2 10.24±0.3 9.54±0.2 Temperature T ºC 21.9±0.2 15.60±0.2 22.4±0.2 26.30±0.2 7.41±0.2 7.30±0.2 7.48±0.1 7.12±0.2 pH -1 Conductivity (µS cm ) 889±0.4 887±0.3 820±0.3 920±0.4 BOI5 4.02±0.2 0.96±0.1 2.50±0.2 4.14±0.2 209 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 2 – The seasonal averages of some allometric parameters in Unio sp. from Tersakan River (average±SEM, n=60) Autumn Winter Spring Summer Shell Length (mm) 66.30±0.2 66.51±0.3 55.97±0.6 54.08±0.6 Shell Width (mm) 26.63±0.1 26.61±0.1 20.35±0.1 20.36±0.2 It is well documented that salinity of waters is an important factor influencing concentrations of selected metals in the soft tissue of Unio sp. in the Tersakan River. The mean concentrations of Cd, Co, Cr, Mn, Ni, Pb and Zn are the higher in autumn and summer than winter and spring. Similarly, the values of conductivity, NO3, NO2 and Ca+2 in autumn and summer are also higher than the values in the other seasons. According to Broman et al. [16], the bioavailability of Cd in soft tissues of mussels is dependent on salinity of the adjacent water. The tissue Cd levels of Unio sp. collected from the Tersakan River in summer and winter were high when salinity levels were high. However Co, Cr, Mn, Ni, Pb and Zn concentration were determined higher in autumn and summer when salinity was high. Broman et al. [16] observed that there was no relationship between Zn levels and salinity. However, our results showed a positive relationship between Zn levels and salinity. Although some other environmental factors such as salinity, pH, hardness and temperature play significant roles in metal accumulation, other studies showed that accumulation of heavy metals in a tissue is mainly dependent upon water concentrations of metals and exposure period [17]. There were also seasonal differences between mussels of different size classes from the sampling site. The longest shell length of Unio sp. (70.58 mm) was measured in autumn while the shortest length (50.3 mm) was measured in summer. The longest shell width (40.35 mm) was in summer while the shortest shell width (24.3 mm) was in winter. The maximum mussel weight was determined in spring as 57 g and minimum weight of mussel also was determined in summer as 29 g. The longest shell height of mussel (43.82 mm) was measured in autumn while the shortest height (20.11mm) was measured in summer. Shell Height (mm) 42.33±0.1 42.24±0.1 34.04±0.5 33.53±0.5 Mussel Weight (g) 40.150±0.4 40.70±0.6 42.05±0.7 37.05±1.0 There was a statistically significant negative relationship between the metal content of the tissues and the mussel length, width, height and weight for all metals in autumn (p <0.05). Significantly positive relationships were found in winter between only Cr and weight (r < 0.509), while negative relationships were found between Pb-width and Cd-width (r < -0.511 and r < -0.598). Additionally in spring, almost all metals except Fe, Mn and Ni have negative correlation with length, width, height and weight (r < - 0.334). Finally, in summer Ni showed positive correlations with weight and length (respectively, r <0.287 and r <0.335). Other trace metals showed weak relationships. The amount of heavy metal bioaccumulation in the tissues may vary depending on length and weight of samples [18, 19]. Our data showed that almost all trace metals have negative relationships with mussel size in every season; only some of the metals such as Cr (in winter) and Ni (in summer) had positive correlations. 3.2 Seasonal Variations of Metal Accumulation Mean concentrations of all metal accumulation in autumn, winter, spring and summer is shown in Table 3. Investigated concentrations of heavy metals in tissues have shown seasonal variation and the following maximum concentrations were found: 2.660 µg/g dry weight (d.w.) for Cd, 4.786 µg/g d.w. for Co, 24.430 µg/g d.w. for Cr, 291.179 µg/g d.w. for Cu, 1921.090 µg/g d.w. for Fe, 752.840 µg/g d.w. for Mn, 112.440 µg/g d.w. for Ni, 15.960 µg/g d.w. for Pb and 460.330 µg/g d.w. for Zn. We have reported that almost all metals displayed the maximum values during the winter, except Fe, Cd and Co. The maximum metal concentration for Fe was determined in spring while the highest Cd and Co concentrations were found in summer. TABLE 3 - Mean concentrations (µg/g dry weight) of metal accumulation of Unio sp. on seasonally (average±SEM, n=60) Metals Autumn Winter Spring 0.131±0.01a 0.255±0.02b 0.081±0.03c Cd 0.501±0.08a 0.526±0.09a 0.488±0.07ab Co a a 4.274±0.56 5.618±0.74 2.891±0.40a Cr 6.973±0.83a 17.999±5.52a 6.084±0.94a Cu 533.804±66.73a 575.360±65.48a 373.690±47.43a Fe 490.940±183.84a 206.590±23.04a 179.472±24.22ab Mn 46,060±9.42a 12.937±2.35a 10.738±1.51a Ni 15.960±1.91a 5.870±1.98a 1.892±0.34a Pb a a 460.300±35.75 135.560±21.01 17.752±4.59a Zn The same superscript letters in the same row are not significantly different at p<0.05 210 Summer 1.075±0.07d 1.551±0.12b 8.404±0.33b 2.800±0.85b 352.141±38.92a 114.236±15.44b 10.910±1.54a 3.938±0.34b 17.907±4.11a © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 4 - Mean concentrations (µg/g dry weight) values of metals in tissues of Unio sp. in Tersakan River (average±SEM, n=240) Tissue Muscle Gill Shell Cd Co Cr Cu Fe Mn Ni 0.296±0.04a 0.284±0.06a 2.284±0.39a 3.070±1.97a 77.879±7.41a 12.975±6.26a 4.646±1.13a 0.478±0.05b 0.861±0.11b 6.206±0.41b 6.420±3.61b 627.184±38.887b 231.742±13.358b 7.536±0.77b 0.382±0.06a 1.155±0.08c 7.403±0.54b 15.902±1.24c 671.182±55.05b 268.291±18.24b 20.821±1.77c Result show that the highest accumulation of heavy metal for each season was Fe. Fe is generally the most abundant metal in all of the reservoirs because it is one of the most common elements in the earth’s crust [20]. According to Cabrera et al. [21] pyrite oxidation produces sulphate and the Fe2+ ion, which is oxidized to Fe3+ by microorganisms such as Thiobacillus ferrooxidans. Results shown that all metal concentrations decreased from winter to spring, but again increased from spring to summer. According to the correlations of heavy metal concentrations in Unio sp. from the Tersakan River, in autumn the data showed very high levels of correlation with mostly positive values for Cr and Fe (p <0.05, r<0.812). These two metals were in positive correlation with all metals. Additionally, Ni and Pb also showed positive correlations with all metals except for Cd and Zn in autumn (r<0.961). There are significant positive correlations between the tissues in winter and spring (r<0.642). In this season, Co and Cr are positively correlated with almost all metals. Significantly positive relationships were found in summer between CuFe, Cu-Ni, Mn-Cr, Mn-Zn (respectively, r<0.482, 0.459, 0.457, 0.535). On the other hand, in summer there was a significant high level correlation between Fe and Cr. (p < 0.05, r<0.943). The heavy metal accumulation of Cu, Mn, Ni, Pb and Zn in winter was found higher when comparing seasons. There were significant differences between the seasons and the tissues for each of the heavy metals (p<0.05). The concentrations of Fe, Ni and Zn in Unio sp. from the Tersakan River were not found to be statistically significant among all seasons (p<0.05). The heavy metal concentrations in tissues did not differed significantly for all metals except for Fe between autumn and spring (p<0.05) but significant differences for Cd, Co, Cr, Cu, Mn and Pb were observed between summer and autumn. All heavy metal elements were not significantly different in tissues between autumn and winter (p<0.05). In general, Cd and Pb have been found at higher levels in the tissues in Unio sp. in almost every season. A number of studies have shown that the concentrations of Cd and Pb in aquatic organisms depend mainly on their environmental levels [22-24]. The present study shows that levels of all metals were significantly higher in tissues in autumn and summer. High levels of metals in tissues on different season could be originated from different sources around the study area. These sources are motor oil and ballasts water for Pb and Cd in summer when tourist activities are increased. Also Cd could occur from phosphorus fertilizer used in agriculture in summer and autumn. Moreover, other heavy Pb 1.016±0.23a 2.123±0.3b 4.157±0.21c Zn 4.215±2.13a 56.627±7.28b 8.475±2.48c metals, such as Zn as composed fertilizer, Mn and Cu as micro elements fertilizer, are used in citrus fruits plantations and green-houses around the Tersakan River where agricultural activities become more intense especially in autumn and winter. 3.3 Metal Accumulations in Tissues The mean concentrations of all metals in the gill, shell and muscle of Unio sp. collected from Tersakan are given in Table 4. We determined that maximum metal concentration of Co, Cu, Mn, Pb and Zn were the highest in gill tissues but the mean metal concentration of these metal except Zn were highest in shell tissues. Maximum metal concentrations of Cr were observed in muscle while mean concentration for this metal were highest in shell tissues. The highest mean and the maximum concentration of Ni were determined in shell tissue. The maximum metal concentration for Cd was observed in shell tissues while the mean concentration of Cd was highest in gill tissues. The accumulation of investigated heavy metals in muscle tissue was in order as; Fe>Mn>Ni>Zn>Cu>Cr>Pb> Cd>Co. This order was as; Fe>Mn>Zn>Ni>Cu>Cr>Pb> Co>Cd in gill tissue while it was Fe>Mn>Ni>Zn>Cu> Cr>Pb>Co>Cd in shell tissues. The significant differences were not found for Cd between gill and muscle (p<0.05). The differences in Fe, Cr and Mn were not statistically significant between gill and shell (p<0.05) but significant differences were observed for other metals. Results show that the concentrations of Fe, Mn, Zn and Ni have shown high levels when their mean concentrations were compared with the mean concentration levels of other metals. The highest Co, Cr, Cu, Fe, Mn and Ni concentrations were found in shell tissues. General evaluation of the heavy metal accumulation in tissues could be ordered as shell>gill> muscle. The highest Co, Cr, Cu, Fe, Mn and Ni concentrations were found in shell tissues whereas the least metal concentrations were found in muscle tissues. These results are similar to those reported by Yilmaz [25] who indicated the heavy metal accumulations on economically important fish inhabiting nearly to Tersakan River. According to the results of Yilmaz [25], the lowest metal contents were determined in edible parts (muscle) of all species. Yap et al. [12] investigation regarding P. viridis at the west coast of Peninsular Malaysia revealed that P. viridis contained metal concentrations in the soft tissues which ranged from 0.68 to 1.25 µg/g d.w. for Cd, 7.76 to 20.1 d.w. µg/g for Cu, 2.51 to 8.76 d.w. µg/g for Pb and 75.1 to 129 d.w. µg/g for Zn. These metal concentrations were relatively higher for Cd, Cu, but less for Pb and Zn com- 211 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin pared to the concentrations in Unio sp. in the Tersakan River. Yarsan and Bilgili [26] measured heavy metal concentrations in tissues of Unio stevenianus of Van lake 1.43±0.81 µg/g d.w. for Pb, 0.09±0.02 µg/g d.w. for Cd, 5.83±0.73 µg/g d.w. for Cu, 15.93±3.26 µg/g d.w. for Zn. Our results were generally higher for all metals compared to their findings. Kır and Tuncay [27] investigated the accumulation of some heavy metals in muscle, liver and carapace tissues of crayfish (Astacus leptodactylus) inhabiting Kovada Lake. They showed that the metal concentrations found in the liver and carapace were higher than those in the muscle. These results were relatively similar with our results, but our results showed that mussels accumulate the heavy metals at a higher level than their surroundings. The studies on Cu and Zn in Crongon crongon [28] and Humarus americanus [29] present a marked ability on the part of crustaceans to regulate internal copper and zinc concentrations. In the present study, it has been shown that essential metals such as Zn, Cu, Mn and Fe were the most abundant metals in different tissues analyzed throughout the year, whereas Co was the least abundant in Unio sp. inhabiting Tersakan River. Zn and Fe play a role in the enzymatic and respiratory processes [30] and also Cu and Zn are apparently essential metals for crustaceans [31, 32]. The gill was also the main target organs for Pb and Zn accumulation which is in accordance with the findings of Manly and George [33] and VanBalogh [34]. Adams et al. [35] showed Zn was predominantly accumulated by the gill and the mantle in Amblema perplicata. Undoubtedly, the unionid gills play a distinct role in metal uptake and storage. As the gills serve also as breeding chambers, its involvement in metal storage may have harmful effects on the reproductive success of freshwater unionids [36]. Our result showed that some metals were found in higher concentration on shell tissue (Fig. 1). But as there is a lack of available information on shell metals for the adjacent regions of southwestern Turkey, concentration data related to other geographical zones were taken from literature and were compared with the data reported in the present study [37-40]. Yap [37] analyzed distributions of Cu and Zn in the shell lipped part periostracum and soft tissues of Perna viridis sampled from 17 geographical sites. The concentrations of Cu in the periostracum and the soft tissues of P. viridis were 7.41- 42.63 µg/g d.w. and 3.49-31.1 µg/g d.w., respectively. Meanwhile, the concentrations of Zn in the periostracum and soft tissues of P. viridis were 4.9039.79 µg/g d.w. and 65.75-144.9 µg/g d.w., respectively. General accumulations of Cu and Zn in the periostrcum in Perna viridis were higher than in shell tissue in our study. Yap et al. [38] measured distributions of Cu, Zn, and Pb concentrations in the selected soft tissues (foot, cephalic tentacle, mantle, muscle, gill, digestive caecum, and remaining soft tissues) and shells of the mud-flat snail Telescopium telescopium were determined in snails from eight geographical sites in the south-western intertidal area of Peninsular Malaysia. The shell demonstrated ten times higher concentrations of Pb (41.23± 1.20 digestive caecum) when compared to our result. Yap et al. [39] determined trace metals (Fe, Cu, and Ni) in the Mangrove Area of Peninsular Malaysia using different soft tissues of flat tree oyster Isognomon alatus. The mean concentrations of Fe, Cu and Ni in muscle were 797.43 µg/g d.w., 4.31 µg/g d.w. and 0.90 µg/g d.w., respectively. Their study show that highest Fe and Cu concentrations were found in the muscle but the concentrations of Ni in our study were higher than their findings. They also determined Fe, Cu and Ni (1129.71 µg/g d.w., 7.83 µg/g d.w. and 1.21 µg/g d.w., respectively) concentrations in mantle plus gill and these results were relatively similar with Fe concentrations but our study showed higher concentrations of Cu and Ni. Kraak et al. [40] made evident that the Cu regulation capacity of U. pictorum is organ-specific: gill, digestive gland and shell showed higher accumulation capacity for Cu than gonads and kidney. Bourgoin and Risk [41] found a considerably higher concentration of Pb in the recent shells of a bivalve Mya truncata than that in fossilized shells. This indicated a temporal increased concentration of Pb in the environment. They suggested that the bivalve shell could be used as a ‘benchmark’ to monitor the anthropogenic inputs of Pb to the environment. High degrees of heavy metal variability in the total shells of Unio sp. suggested it to be generally a more sensitive and precise biomonitoring material for heavy metals than the total soft tissues of Unio sp. Our study suggests that mussel shells can be used as a biomonitoring material as the metals directly absorb onto the shell surfaces of the mussels. This obviously could be due to the outer layer of the shell which is directly contacted with water. Levels of heavy metal accumulation found in all tissues of the analyzed mussel varied greatly. The distribution of total metal load IMBI values varied from 0.01 to 0.44, 0.00 to 0.47, and 0.00 to 0.43 in muscle, gill, and shell respectively. In summer, total metal load values in muscle and gill calculated high concentration when compared with other seasons. In contrast, the highest total metal loads were determined on winter for shell. Generally, IMBI values calculated in muscle were higher than gill and shell. IMBI concentrations were calculated in many articles for European eel Anguilla anguilla as a good monitoring tool [15, 42, 43]. However, the freshwater mussels are more useful in heavy metal studies to monitor polluted streams. Also, they are abundant and widely distributed along the Aegean coastal streams. This reason increases the importance of freshwater mussels. IMBI values were calculated for all tissues and were then compared with seasonally. It was shown that higher IMBI values were determined in muscle and summer. Our data showed that IMBI values can be successfully calculated for bivalves. Accumulation of heavy metals in mussels may be considered as an important warning signal for health and human consumption. Dietary standards and guidelines applicable for heavy metals in crustaceans are summarized by Turkish Food Codes (TFC) [44] and EU [45]. The limit values for human consumption of metals are shown Table 5. Consequently, it can be concluded that the levels of heavy metals in muscle are not at acceptable levels for all of the studied 212 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 5 - The limit values for human consumption of metals for Crustaceans (TFC [44] and EU [45]) Cadmium (Cd) EU (Max.limit) (µg/g) T.F.C (Max.limit) (µg/g) 0.50 6 Periodic Average (µg/g) 0.047±0.00 0.197±0.04 0.150±0.08 0.789±0.09 0.50 Tissue 5 muscle gill shell Lead (Pb) EU (Max.limit) (µg/g) T.F.C (Max.limit) (µg/g) 0.50 Periodic Average (µg/g) 0.151±0.08 1.031±0.32 0.149±0.06 2.734±0.73 0.50 Tissue 25 Tissue muscle gill shell muscle gill shell 5 4 20 3 15 3 Cr Co Cd 4 2 10 1 5 2 1 0 0 A 300 W SP 0 SU A Tissue 2000 W SP SU A Tissue 800 SP SU W SP SU W SP SU Tissue muscle gill shell muscle gill shell muscle gill shell W 250 1500 600 150 Mn Fe Cu 200 1000 400 100 200 500 50 0 0 A 120 W SP 0 A SU Tissue 20 muscle gill shell W SP SU A Tissue 500 Tissue muscle gill shell muscle gill shell 100 400 15 80 Zn Pb Ni 300 60 10 200 40 5 100 20 0 0 A W SP SU 0 A W SP SU A FIGURE 1 - Average heavy metal accumulation in tissues on seasonally (A:Autumn; W:Winter; Sp:Spring; Su:Summer). 213 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin samples in this region. Mean concentration of Cd and Pb levels in muscle were higher than the acceptable values for human consumption designated by various health organizations [44, 45]. The concentration of Cd was higher in summer and Pb concentration was determined higher in winter and summer. The means of heavy metal concentrations were beneath Turkish legal standards, which are 1.0 µg/g for Cd, 20.0 µg/g for Cu and 50.0 µg/g for Zn (wet weight) in bivalve mollusks [46]. 4. CONCLUSION When the data were compared with the acceptable values for human consumption designated by various health organizations, concentrations of some metals such as Cd and Pb were higher than the designated limits, especially in summer. In general, the measured heavy metals were found in higher concentrations in winter and autumn than the concentrations in spring and summer. No seasonal differences were found for the concentrations of Fe, Ni and Zn, while the concentrations of other heavy metals had seasonal differences, generally as a result of the measured concentrations in summer (p <0.05). On the other side, considering the tissues together, the highest levels of heavy metals were found in shell samples, while the lowest levels in muscle. It has been also shown that IMBI were useful for determining metal accumulations in Unio sp. ACKNOWLEDGMENTS The authors would like to thank financial support from The Scientific and Technological Research Council of Turkey (TÜBİTAK), Ministry of Agriculture and Muğla City Directorate for laboratory analysis. [6] Avelar, W.E.P., Mantelatto, F.L.M., Tomazelli, A.C., Silva, D.M.L., Shuhama, T. and Lopes, J.L.C. (2000) The marine mussel Perna perna (Mollusca, Bivalvia, Mytilidae) as an indicator of contamination by heavy metals in the Ubatuba bay, Sao Paula, Brazil. Water Air and Soil Pollution, 118, 65-72. [7] Goldberg, E. D. (1975) The Mussel Watch a first step in global marine monitoring. Marine Pollution Bulletin, 6, 111. [8] Kavun, V.Y., Shulkin, V. M. and Khristoforova, N. K. (2002) Metal accumulation in mussels of the Kuril Islands, north-west Pacific Ocean. Marine Environmental Research, 53, 219–226. [9] Larsson, A., Haux, C. and Sjöbeck, M. (1985) Fish pshysiology and metal pollution: results and experiences from laboratory and field studies. Ecotoxicology and Environmental Safety, 9, 250-281. [10] Kalay, M. and Canlı, M. (2000) Elimination of essential (Cu, Zn) and nonessential (Cd, Pb) metals from tissue of a freshwater fish Tilapia zilli. Turkish Journal of Zoology, 24, 429-436. [11] Nemesok, J.G. and Hughes, G.M. (1988) The effects of copper sulphate on some biochemical parameters of rainbow trout. Environmental Pollution, 49, 77-85. [12] Yap, C.K., Ismail A. and Tan, S.G. (2004) Heavy metal (Cd, Cu, Pb and Zn) concentrations in the green-lipped mussel Perna viridis (Linnaeus) collected from some wild and aquacultural sites in the west coast of Peninsular Malaysia. Food Chemistry, 84, 569–575. [13] Barlas, M., Dirican, S. and Özdemir, N. (2001), Fish fauna of Tersakan River. Proceedings of the National of XI. National Symposium on Fisheries-Hatay, Turkey, 309–318. [14] Önsoy, B., Filiz, H., Tarkan, A.S., Bilge, G. and Tarkan, A.N. (2011) Occurrence of non-native fishes in a small man-made lake (Lake Ula, Muğla): past, present, future perspectives. Turkish Journal of Fisheries and Aquatic Sciences, 11, 209–215. [15] Maes, J., Belpaire, C. and Goemans, G. (2008) Spatial variations and temporal trends between 1994 and 2005 in polychlorinated biphenyls, organochlorine pesticides and heavy metal in European eel (Anguilla anguilla) in Flanders-Belgium. Environmental Pollution. 153, 223-237 [16] Broman, D., Lindqvist, L. and Lundbergh, I. (1991) Cadmium and zinc in Mytilus edulis L. from the Bothnian Sea and the northern Baltic proper. Environmental Pollution, 74, 227–244 [17] Canlı, M. and Atlı, G. (2003) The relationships between heavy metal (Cd, Cr, Cu, Fe, Pb, Zn) levels and the size of six mediterranean fish species. Environmental Pollution, 121, 129–136. The authors have declared no conflict of interest. [18] Barghigiani, C. and Ranieri D,S. (1992) Mercury content in different size of important edible species of the northern Tyrrhenian sea. Marine Pollution Bulletin, 24, 114-116. REFERENCES [1] Malik, A. (2004) Metal bioremediation through growing cells. Environment International, 30, 261–278. [2] Leland, H.V., Luoma, S.N. and Wilkes, D.J. (1978) Heavy metals and related trace elements. Water Pollution Control Federation, 50, 1469-1514. [3] Corbett, R.G. (1977) Effects of coal mining on ground and surface water quality Monongalia County-West Virginia. Science of the Total Environment, 8, 21. [4] Mance, G. (1987) Pollution threat of heavy metals in aquatic environment. Elsevier- London, 363. [5] Langston, W.J. (1990) Toxic effects of metals and the incidance of marine ecosystems In: Furness, R.W. and Rainbow, P.S. (ed). Heavy Metals in the Marine Environment, CRC Press, New York, 256. 214 [19] Zyadah, M.A. (1999) Accumulation of some heavy metals in Tilapia zilli organs from lake Manzalah, Egypt. Turkish Journal of Zoology, 23, 365-372. [20] Usero, J., Izquierdo, C., Morillo, J. and Gracia, I. (2003) Heavy metals in fish (Solea vulgaris, Anguilla anguilla and Liza aurata) from salt marshes on the southern Atlantic Coast of Spain. Environmental International, 1069, 1–8. [21] Cabrera, F., Vlemente, L., Diaz Barrientos, E., Lŏpez, R. and Murillo, H. M. (1999) Heavy metal pollution of soil affected by the Guadiamar toxic Hood. Science of the Total Environment, 242, 117–129. [22] Amiard, J.C., Amiard-Triquet, C., Berhet, B. and Metayer, C. (1987) Comparative study of the patterns of bioaccumulation of essential (Cu-Zn) and non-essential (Cd-Pb) trace metals in various estuarine coastal organisms. Journal of Experimental Marine Biology and Ecology, 106, 73-79. © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin [23] Heath A.G. (1987) Water Pollution and Fish Physiology. CRC Press, Florida USA, 245. [24] Bryan G.W. and Langston, W.I. (1992) Bioavailability, accumulation and effects of heavy metals in sediments with special reference to United Kingdom estuaries, review. Environmental Pollution, 76, 89-131. [25] Yilmaz, F. (2009) The comparison of heavy metal concentrations (Cd, Cu, Mn, Pb, and Zn) in tissues of three economically important fish (Anguilla anguilla, Mugil cephalus and Oreochromis niloticus) Inhabiting Köycegiz Lake-Mugla (Turkey). Turkish Journal of Science & Technology, 4 (1), 7-15. [26] Yarsan, E. and Bilgili, A. (2000) Heavy Metal Levels in Mussels (Unio stevenianus Krynicki) Obtained from Van Lake. Turkish Journal of Veterinary & Animal Science, 24, 93-96. [27] Kır, İ. And Tuncay, Y. (2010) The Investigation of some Heavy Metals in Crayfish (Astacus leptodactylus) Inhabiting Kovada Lake, Sdu Journal of Science, 5 (2), 179-186. [28] Amiard J.C., Amiard-Triquet, C. and Metayer, C. (1985) Experimental study of bioaccumulation, toxicity and regulation of some trace metals in various estuarine and coastal organism. Symposia Biologica Hungarica, 29, 313-323. [29] Chou, C.C., Uthe, J.F., Castell, J.D., Kean, J.C. and Lores, E.M. (1987) Effect of dietary on growth survival and tissue concentration of cadmium, zinc, copper and silver injuvenile American lobester (Homarus americanus). Canadian Journal Of Fisheries & Aquatic Sciences, 44, 1443-1450. [30] Bryan, G.W. (1968) Concentration of zinc and copper in tissues of decapod crustacean. Journal of the Marine Biological Association of the United Kingdom, 48, 303-321. [40] Kraak, M.H.S., Toussaint, M., Bleeker, E.A.J. and Lavy, D. (1993) Metal regulation in two species of freshwater bivalves, Ecotoxicology of Metals in Invertebrates (SETAC Special Publications). Lewis, Chelsea, MI, 175-186. [41] Bourgoin, B. P. and Risk, M. J. (1987) Historical changes in lead in the eastern Canadian Arctic, determined from fossil and modern Mya truncata shells. Science of the Total Environment. 67, 287-291. [42] Esteve, C., Alcaide, E. and Urena, R. (2012) The effect of metals on condition and pathologies of European eel (Anguilla anguilla): In situ and laboratory experiments. Aquatic Toxicology, 109, 176-184. [43] Maes, G.E., Raeymaekers, J.A.M., Pampoulie, C., Seynaeve, A., Goemans, G., Belpaire, C. and Volckaert, F.A.M. (2005) The catadromous European eel Anguilla anguilla (L) as a model for fresh water evolutionary ecotoxicology: relationship between heavy metal bioaccumulation, condition and genetic variability. Aquatic Toxicology, 73, 99-114 [44] TFC. (2008) Turkish Food Codes, Official Gazette, Communique on Maximum Limits for Contaminants of Food Ingredients (Communique Number: 2008/26). [45] EU. (2006) Commission Regulation Directive, (EC) No 1881/2006 of 19 December. [46] Republic of Turkey, Ministry of Food, Agriculture and Livestock (1996) Guidebook of fisheries quality control services. General Directorate for Protection and Control, Ankara (in Turkish). [31] Voutsinou-Taliadouri, F. (1982) Monitoring of some metals in some marine organisms from the Saronikos Gulf. J. Etud. Pollut., 6, 329-333. [32] Rainbow, P.S. and White, S.L. (1989) Comparative strategies of heavy metal accumulation by crustaceans: zinc, copper and cadmium in a decapod, an amphipod and a barnacle. Hydrobiologia, 174, 245-262. [33] Manly, R. and George, W.O. (1977) the occurrence of some heavy metals in populations of the freshwater mussel Anodonta anatina (L.) from the River Thames. Environmental Pollution, 14, 139-154. [34] Van-Balogh, K. (1988) Heavy metal pollution from a point source demonstrated by mussel (Unio pictorum L.) at Lake Balaton, Hungary. Bulletin of Environmental Contamination and Toxicology, 41, 910-914. [35] Adams, T.G., Atchinson, G.J. and Vetter, R.J. (1981) the use of the three ridge clam (Amblema perplicata) to monitor trace metal contamination. Hydrobiologia, 69, 187-194. [36] Gundacker, C. (2000) Comparison of heavy metal bioaccumulation in freshwater molluscs of urban river habitats in Vienna. Environmental Pollution, 110, 61-71. [37] Yap, C.K. (2012) Distribution of Cu and Zn in the shell lipped part periostracum and soft tissues of Perna viridis: The potential of periostracum as a biomonitoring material for Cu. Pertanika Journal of Tropical Agricultural Science, 35 (3), 413–426. [38] Yap, C.K., Noorhaidah, A., Azlan, A., Nor Azwady, A.A., Ismail, A., Ismail, A.R., Siraj, S.S. and Tan, S.G. (2009) Telescopium telescopium as potential biomonitors of Cu, Zn, and Pb for the tropical intertidal area. Ecotoxicology and Environmental Safety, 72, 496–506. [39] Yap, C.K., Azmizan, A.R. and Hanif, M. S. (2011) Biomonitoring of trace metals (Fe, Cu and Ni) in the mangrove area of Peninsular Malaysia, using different soft tissues of flat-tree oyster Isognomon alatus. Water, Air and Soil Pollution, 218, 19-36. 215 Received: April 03, 2014 Revised: July 11, 2014; August 27, 2014 Accepted: September 09, 2014 CORRESPONDING AUTHOR Tuncer Okan Genç Muğla Sıtkı Koçman University Faculty of Science Department of Biology 48000 Kötekli TURKEY E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 208 - 215 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin HEAVY METAL ACCUMULATION IN BIOINDICATORS OF POLLUTION IN URBAN AREAS OF NORTHEASTERN POLAND Zbigniew Mazur1, Maja Radziemska2, Joanna Fronczyk2 and Jerzy Jeznach2,* 1 University of Warmia and Mazury in Olsztyn, Faculty of Environmental Management and Agriculture, Pl. Łódzki 4, 10-718 Olsztyn, Poland 2 Warsaw University of Life Sciences – SGGW, Faculty of Civil and Environmental Engineering, ul. Nowoursynowska 159, 02-776 Warszawa, Poland Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey ABSTRACT The aim of the study was to assess the contamination of the environment within the city of Olsztyn (northeastern Poland) by determining the level of lead, cadmium and zinc in Scots pine (Pinus silvestris L.) needles, the roots and leaves of broadleaf plantain (Plantago major L.), and the caps of fly agaric mushrooms (Amanita muscaria). The total content of: Zn, Pb, and Cd was assessed by means of the flame atomic absorption spectroscopy (FAAS) method. Plant samples for analysis were taken one month prior to the beginning of the heating season at ten different locations, including along busy transportation routes and residential neighborhoods. Significant differences in the content of cadmium, lead and zinc were found based on the place from which samples were collected as well as the plant species. The highest concentrations of cadmium, lead and zinc were noted in broadleaf plantain leaves, broadleaf plantain roots and fly agaric mushrooms, respectively, near a large subdivision of single-family houses. Low heavy metal contents in plants were noted in the City Forest, which is located far from sources of contamination. A significant correlation was confirmed between the amount of Pb in the leaves and roots of broadleaf plantain, whereas the correlation between the content of this element in the cap of the fly agaric mushroom and leaves as well as roots of broadleaf plantain was found to be high. KEYWORDS: heavy metals, Pinus sylvestris L., Plantago major L., Amanita muscaria, urban areas 1. INTRODUCTION One of the main kinds of environmental pollution in urban areas is heavy metal contamination [1-5]. The main * Corresponding author sources of these elements in air and soil are, above all, industry, transport and the burning of fuels for energy [69]. Soil as well as many species of plants (e.g., mosses, lichens, mushrooms, grasses and herbs, as well as tree bark, leaves and needles) are used to identify these con-taminants [3, 10-14]. Excessive soil and air contamination can pose a risk to human and animal health, and have a toxic effect on plants [15]. The effect of individual metals on living organisms is, however, varied [14, 16]. Lead is easily taken up by plants from contaminated soils and accumulated particularly in their mass [17]. Cadmium is an extremely significant pollutant due to its large solubility in water and high toxicity to most organisms, being the fourth most toxic element to vascular plants [18]. Zinc is characterized by a high mobility in soil and high uptake by plants, owing to the fast solubility of compounds in which it appears, especially in an acidic environment [19]. In many countries, hard coal is the cheapest and most common fuel used for heating houses. The burning of coal during heating season results in a considerable emission of gases, mainly ashes, into the atmosphere [20]. These ashes are a mixture of toxic substances, including aromatic hydrocarbons (AHC), heavy metals and dioxins [21-23]. In Poland, there are approximately 1 million furnaces (most often manufactured in the last century) in use, which run on hard coal. In 2010, the emission of ashes from the burning of hard coal in Poland amounted to 445.3 thousand Mg, including 142.7 thousand Mg released by households [24]. The percentage of heavy metal emissions connected with the burning of this fuel in individual household furnaces ranges from 10% in the case of Hg to 30% in the case of Pb, and as much as 40% for Cd. The aim of the study was to asses environmental pollution by determining lead, cadmium and zinc concentration in Scots pine needles, broadleaf plantain (Plantago major L.) roots and leaves and fly agaric mushrooms (Amanita muscaria) at 10 sampling points in Olsztyn (northeastern Poland) which varied in terms of their degree of urbanization. 216 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin 2. MATERIAL AND METHODS 2.1 Study area and Sample collection Olsztyn (Poland) and the areas around the city include mainly wooded, agricultural and tourist areas. There is no heavy industry which could influence the analyzed areas in terms of the emission of heavy metal contaminants. The city is home to 180,000 residents. In the northwestern part of the city, there is an automatic station for measuring the current levels of air pollution. Among others, the temperature and humidity of the air, air pressure, wind speed and direction, precipitation, sulfur dioxide, nitrogen oxides, particulate matter, and Pb, As, Ni, and Cd content in air are measured here. The average contents of lead, arsenic, nickel and cadmium for the year 2011 were found to be 0.006 ng·m-3, 0.82 ng·m-3, 0.75 ng·m-3, and 0.16 ng·m-3 respectively. These values did not exceed the permissible levels of these substances in air. The heating season in this region of Poland usually begins in the middle of September, thus the period of dry deposition (lack of rainfall at this time), which usually occurs near the source of pollution, lasted a few weeks. Plant samples and soils for analysis were taken from ten places located in various parts of the city, in the middle of October 2012 (Tab. 1, Fig. 1). Four samples of each plant were taken at each of these locations; samples from along roads were gathered at the same distance from the road and no further than 30 m apart from one another, with those collected from other places being no further than 15 m apart. The occurrence of all of the analyzed plant species in close proximity to each other determined the locations from which samples were collected. Heavy metals were analyzed in the 2-year-old pine needles. Only the caps of ripe mushroom fruiting bodies were analyzed. At each of the sampling points, 30 individual soil samples were taken using Egner's soil sampler from the 0-20 cm soil layer. These samples were combined into composite samples. 2.2 Laboratory and Statistical analysis Scots pine (Pinus silvestris L.) needles, caps of fly agaric mushrooms (Amanita muscaria) and the roots and leaves of broadleaf plantain (Plantago major L.), were washed with distilled water, cut into pieces and dried at 60oC to a constant weight. Soil samples were prepared for analysis by drying at room temperature and sifting them FIGURE 1 - Localization of sampling points, Olsztyn, Poland. 217 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 1 - Characteristics of sampling points. Sampling points 1 (53°44'20''N; 20°27'48''E) 2 (53°45'14'' N; 20°26'58''E) 3 (53°45'24'' N; 20°27'22''E) 4 (53°45'39'' N; 20°26'08''E) 5 (53°44'56'' N; 20°28'40''E) 6 (53°44'52'' N; 20°30'29''E) 7 (53°43'57'' N; 20°29'34''E) 8 (53°46'27'' N; 20°28'45''E) 9 (53°48'10'' N; 20°27'27''E) 10 (53°46'12'' N; 20°24'03''E) Characteristics National Road No. 51. Samples collected 5 m from the edge of the road. Traffic intensity of approx. 15,000 vehicles per 24-hour period. Northern part of the "Słoneczny Stok" subdivision (approx. 200 single-family houses), built mainly in the 60s80s of the past century. Many houses equipped with coal-burning furnaces. Very low traffic intensity. Park on campus of the University of Warmia and Mazury. 500 m radius characterized by low traffic intensity. Southeastern part of large subdivision - "Dajtki" (approx. 1,000 single-family houses) built mainly in the 70s80s of the past century. Many houses equipped with coal-burning furnaces. Very low traffic intensity. Middle of "Brzeziny" subdivision (approx. 200 single-family houses). Mostly newly built houses. Coal burnt sporadically. Low traffic intensity. Local road (samples collected 8 m from the edge of the road). Traffic intensity of a few thousand vehicles per 24-hour period (mainly passenger cars and buses). Road No. 598 (samples collected 15 m from the edge of the road). Traffic intensity of a few thousand vehicles per 24-hour period. Road in city center (samples collected 60 m from the edge of the road). Traffic intensity of a few tens of thousands of vehicles per 24-hour period. City Forest. Located 700 m away from the nearest buildings and 1,200 m away from the nearest busy road. National Road No. 16 (samples collected 10 m from the edge of the road). Traffic intensity of 15,000 vehicles per 24-hour period. through a 0.3-mm nylonscreen. The samples were kept at an ambient temperature until analysis. The total contents of lead (Pb), zinc (Zn) and cadmium (Cd) were determined by flame atomic absorption spectrophotometry in an air–acetylene flame on a SpectrAA 240FS spectrophotometer (VARIAN, Australia), using a Sample Introduction Pump System. The analysis was performed on extracts obtained after “wet” soil mineralization in nitric acid (analytically pure HNO3 at a concentration of 1.40 g cm−3), poured into Teflon™ vessels HP500 and placed in a MARS 5 microwave oven (Microwave Accelerated Reaction System, manufactured by CEM Corporation, USA). All reagents used in the research contained analytical high purity water (of 0.055 µS.cm-1) prepared by the double distillation of deionized water in a Crystal system (Adrona Laboratory Systems). All glass- and polyethylene flaskware had previously been treated for 24 hours in 5 mol . l-1 HNO3, and then rinsed with ultrapure water. Chemicals, purchased from Merck (Germany), were of analytical grade. The solutions of metals were prepared by the dilution of certified standard solutions (Fluka). The research results were subjected to statistical analyses, calculating average values, standard deviations and coefficients of variability. Pearson's simple correlation coefficients (r) were also calculated between the contents of the analyzed heavy metals in plant samples. 3. RESULTS AND DISCUSSION The contents of selected heavy metals at the individual analyzed locations within the city of Olsztyn (Poland) have been presented in Tables 2 and 3. Significant differences occurred in the concentration of cadmium (Cd), lead (Pb) an zinc (Zn), depending on the place from which the samples were collected as well as the plant species. The chemical composition of pine needles is a reflection of the abun- dance of nutrients in trees as well as environmental pollution, although climate conditions, such as the direction and strength of wind, temperature and amount of rainfall also play an important role [25]. In the presented studies, the concentration of cadmium (Cd) in pine needles (Pinus sylvestris L.) ranged from 0.08 mg·kg-1 in samples collected in the City Forest (sampling point 9), with the nearest buildings 700 m away and busy road 1200 m away from the sample collection point, to 1.10 mg·kg-1 in samples collected 5 m from the edge of National Road No. 51, where the road traffic intensity was approx. 15,000 vehicles per 24-hour period (point 1). Gworek et al. [26] found the maximum cadmium content in pine needles to be at a level of 0.62 mg·kg-1 dry mass at 5-10 m from a busy road. A high dependency of the content of microelements in pine needles on air pollution from different sources was confirmed by studies conducted by Lehndorff and Schwark [27]. Molski and Dmuchowski [28], on the other hand, recorded a maximum concentration of 0.17 mg·kg-1 dry mass in needles from pines near the northern border of Finland. Mushrooms, which are characterized by the ability to absorb nutrients from the substrate and gather numerous elements in their fruiting bodies at concentrations that are much higher than in the actual substrates on which they grew, can also be an indicator of environmental contamination with heavy metals [29-31]. Das [32] reported a high variability in the heavy metal content of various mushroom species depending on the level of environmental pollution. Similarity to Scots pine needles, the lowest content of cadmium in the cap of the fly agaric mushroom, i.e., 0.09 mg·kg-1 dry mass, was noted in samples derived from the City Forest (sampling point 9), with the highest content of 1.89 mg·kg-1 dry mass near a subdivision of single-family houses, where inhabitants burn hard coal to heat their homes. Broadleaf plantain Plantago major L., which is considered an herb, is a plant that is commonly used in environmental biomonitoring; analyses makes use of its above-ground (leaves, stems) as well as below- 218 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 2 - Cadmium (Cd), lead (Pb) and zinc (Zn) contents in plants (mg kg-1 d.m.). Sampling points 1 Type of sample Cd Pb Zn Needles of Pinus sylvestris L. Amanita muscaria Leaves of Plantago major L. Roots of Plantago major L. 1.10 1.11 2.22 1.23 8.07 2.82 15.1 23.4 85.2 37.3 45.5 75.8 2 Needles of Pinus sylvestris L. Amanita muscaria Leaves of Plantago major L. Roots of Plantago major L. 0.81 1.89 2.68 2.01 5.13 5.38 21.7 27.1 75.2 126.2 98.7 90.4 3 Needles of Pinus sylvestris L. Amanita muscaria Leaves of Plantago major L. Roots of Plantago major L. 0.69 0.19 0.31 0.31 5.96 0.92 4.95 7.43 29.9 19.6 51.1 56.4 4 Needles of Pinus sylvestris L. Amanita muscaria Leaves of Plantago major L. Roots of Plantago major L. 0.10 1.12 1.88 1.99 1.04 4.67 18.9 17.8 41.9 92.7 68.7 86.1 5 Needles of Pinus sylvestris L. Amanita muscaria Leaves of Plantago major L. Roots of Plantago major L. 0.40 0.49 0.60 0.52 1.87 1.04 5.09 4.67 90.1 24.7 33.0 39.1 6 Needles of Pinus sylvestris L. Amanita muscaria Leaves of Plantago major L. Roots of Plantago major L. 0.09 0.51 1.22 2.41 2.88 0.60 8.11 10.5 61.3 29.6 39.2 38.8 7 Needles of Pinus sylvestris L. Amanita muscaria Leaves of Plantago major L. Roots of Plantago major L. 0.91 0.43 1.10 1.05 2.53 0.82 5.78 5.49 28.9 22.5 32.6 28.9 8 Needles of Pinus sylvestris L. Amanita muscaria Leaves of Plantago major L. Roots of Plantago major L. 0.59 1.12 1.51 1.73 4.02 1.48 8.31 8.12 53.3 34.6 50.1 52.9 9 Needles of Pinus sylvestris L. Amanita muscaria Leaves of Plantago major L. Roots of Plantago major L. 0.08 0.09 0.19 0.37 0.49 0.52 3.78 4.89 22.8 19.6 38.4 31.3 10 Needles of Pinus sylvestris L. Amanita muscaria Leaves of Plantago major L. Roots of Plantago major L. 0.32 1.73 1.72 1.61 4.81 2.61 22.2 24.9 59.5 46.0 68.1 102.4 TABLE 3 - Cadmium (Cd), lead (Pb) and zinc (Zn) contents in soils (mg kg-1 d.m.). Sampling points Cd Pb Zn 1 2 3 4 5 6 7 8 9 10 1.04 1.29 0.35 0.99 0.25 0.59 0.38 0.29 0.16 0.83 40.1 69.8 5.8 41.2 17.7 5.7 35.2 22.6 5.97 62.3 110.2 119.5 39.8 99.4 17.6 40.2 65.8 45.1 29.7 141.2 219 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin ground (roots) parts [14, 33, 34]. In the above-ground parts of broadleaf plantain Plantago major L., the lowest concentration of cadmium, equal to 0.19 mg·kg-1 dry mass, occurred in samples taken from the City Forest (point 9), whereas roots of plant samples collected on the premises of the University of Warmia and Mazury in Olsztyn (sampling point 3) contained the lowest amount of this element, i.e., 0.31 mg·kg-1 dry mass. The highest concentration of this metal (2.68 mg·kg-1 dry mass) in leaves of the broadleaf plantain (Plantago major L.) were present in samples from the northern part of a subdivision of single-family houses, where most homes are equipped with coal-burning furnaces and traffic is minimal (point 2). In terms of the below-ground parts of the tested plant, the highest Cd content, equal to 2.41 mg·kg-1 dry mass, was present in samples collected 8 m from the edge of a local road with a traffic intensity of a few thousand vehicles in a 24-hour period, mainly passenger cars and buses (sampling point 6). Much higher cadmium contents in the leaves and roots of broadleaf plantain (Plantago major L.) were reported by FilipovićTrajković et al. [34] who analyzed contaminated soils of Serbia. Pearson's simple correlation coefficients (r) between the content of cadmium (Cd) in the analyzed plants and soil (Table 4) revealed a high correlation between the content of this element in the caps of Amanita muscaria and the above-ground parts of Plantago major L. A moderate correlation occurred between the cadmium contents of Plantago major L. roots and leaves, and in Amanita muscaria caps. The content of lead (Pb) in pine needles (Pinus sylvestris L.) was highest (8.07 mg·kg-1 dry mass) in samples collected 5 m from the edge of National Road No. 51, which is characterized by high traffic intensity (sampling point 1), and lowest in those samples derived from the City Forest (point 9). Similar dependencies were observed in research carried out by Gworek et al. [26], whereas Buszewski et al. [10] reported average Pb levels of 5.811.5 mg·kg-1 dry mass when analyzing its content in Pinus sylvestris L. needles in Toruń (Poland). An increased content of lead in Pinus Eldarica Medw. needles was confirmed near a highway in Teheran by Kord et al. [35]. As of 2000, lead concentration in Scots pine needles was 40 mg·kg-1 dry mass in the urbanized areas of Erzurum of northeastern Turkey, and 19 mg·kg-1 dry mass in the suburban areas of this region of the above-mentioned country [36]. Near subdivisions of single-family houses (sampling points 2 and 4), a high concentration of lead amounting to 5.38 and 4.67 mg·kg-1 dry mass respectively, was noted in Amanita muscaria caps; the reason behind this may be the burning of hard coal in this area. When analyzing mushrooms of the Amanita species in the province of Reggio Emilia (Italy), Cocchi et al. [37] determined lead content to be in the range of 0.32 - 4.43 mg·kg-1 dry mass. Lead (Pb) content in broadleaf plantain leaves (Plantago major L.) oscillated between the values of 3.78 in samples from the City Forest, where the nearest busy road was 1,200 m away from the point of sample collection (sampling point 9), to 22.2 mg·kg-1 dry mass in sampling point 10 - National Road No. 16, where samples were collected just 10 m from the edge of the road and traffic intensity was approx. 15,000 vehicles in a 24-hour period. In the roots of broadleaf plantain (Plantago major L.), the contents were slightly higher and ranged from 4.67 mg·kg-1 dry mass in samples taken from the middle of a subdivision of single-family houses where hard coal is burned only sporadically (sampling point 5), to 27.1 mg·kg-1 dry mass in sampling point no. 2. Malizia et al. [14], when analyzing the content of trace elements in samples of broadleaf plantain leaves and roots collected in the fall and grown on soils characterized by various levels of contamination, revealed the content of lead to be 0-8.0 mg·kg-1 dry mass in the leaves and 4.0-28.0 mg·kg-1 dry mass in the roots. Kurteva [38], when analyzing environmental pollution in various regions of Bulgaria in 2006-2008, determined the content of lead in the above ground parts of broadleaf plantain (Plantago major L.) to fall in the range of 2.22 to 7.09 mg·kg-1 dry mass. Table 5 presents the dependencies between the concentrations of lead in plants and soil. A very high correlation was noted between the amount of Pb in the leaves and roots of broadleaf plantain (Plantago major L.), with a high correlation between the content of this element in the cap of the fly agaric mushroom and the leaves as well as roots of broadleaf plantain. A high correlation between the amount of lead in the leaves and roots of Plantago major L. was confirmed in the research of Malizia et al. [14]. A moderate correlation was noted between the content of lead in Plantago major L. needles and roots. The concentration of zinc (Zn) in pine needles (Pinus sylvestris L.) ranged from 22.8 mg·kg-1 dry mass at sampling point 9 (in samples from the City Forest) to 90.1 mg·kg-1 dry mass in samples taken from the middle of a subdivision of single-family houses where hard coal is burned sporad- TABLE 4 - Correlation between cadmium (Cd) contents in analyzed samples. Type of sample Needles of Pinus Amanita muscaria Leaves of P. L. Roots of P. L. 0.90*** 0.62* 0.80** 0.73** 0.89*** 0.62** Amanita muscaria 0.19* Leaves of P. L. 0.33* Roots of P. L. -0.18* Soil 0,26* Significant at: *** p ≤ 0.001, ** p ≤ 0.01, * p ≤ 0.05. 220 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 5 - Correlations between lead (Pb) contents in analyzed samples Type of sample Needles of Pinus Amanita muscaria 0.22* Leaves of P. L. 0.33* Roots of P. L. 0.54* Soil 0.33* Significant at: *** p ≤ 0.001, ** p ≤ 0.01, * p ≤ 0.05. Amanita muscaria Leaves of P. L. Roots of P. L. 0.88*** 0.83*** 0.81** 0.95*** 0.89*** 0.85*** TABLE 6 - Correlation between zinc (Zn) contents in analyzed samples. Type of sample Needles of Pinus Amanita muscaria 0.47* Leaves of P. L. 0.53* Roots of P. L. 0.62* Soil 0.25* Significant at: *** p ≤ 0.001, ** p ≤ 0.01, * p ≤ 0.05. Amanita muscaria Leaves of P. L. Roots of P. L. 0.89*** 0.70** 0.64** 0.83*** 0.72** 0.89*** TABLE 7 - Average cadmium (Cd), lead (Pb) and zinc (Zn) content in analyzed plants (mg kg-1 d.m.). Type of sample Needles of Pinus sylvestris L. Caps of Amanita muscaria Leaves of Plantago major L. Roots of Plantago major L. Cd 0.51 ± 0.37 CV = 72.54% 0.87 ± 0.62 CV = 72.26% 1.34 ± 0.81 CV = 60.44% 1.32 ± 0.75 CV = 56.82% Pb 3.68 ± 2.36 CV = 64.13% 2.09 ± 1.83 CV = 87.56% 11.4 ± 7.6 CV = 66.67% 13.4 ± 8.9 CV = 66.42% Zn 54.8 ± 23.9 CV = 43.61% 45.3 ± 35.7 CV = 78.80% 52.8 ±21.8 CV = 41.29% 60.2 ± 26.7 CV = 44.35% ± standard deviation (SD) and coefficients of variation (CV) ically (sampling point 5). Similar values (20.1-94.9 mg·kg-1 dry mass) were reported by Gworek et al. [26] when analyzing lead concentration in pine needles near a busy road. Similar amounts of zinc, i.e., 48.72-79.60 mg·kg-1 dry mass in Pinus sylvestris L. needles were reported by Buszewski et al. [10]. The lowest content of zinc in the fly agaric mushroom (Amanita muscaria) was determined in sampling points 3 and 9, that is in the University park and the City Forest (19.6 mg·kg-1 dry mass), with the highest in the area of a large subdivision of single-family houses 126.2 dry mass (sampling point 2). Comparable Zn contents in mushrooms were reported by Das (2005). The concentration of this element in the above-ground parts of broadleaf plantain Plantago major L was found to be between 32.6 and 98.7 mg·kg-1 dry mass in samples collected in the proximity of road no. 598, where traffic intensity is equal to a few thousand vehicles in a 24-hour period, as well as in the area of a large subdivision of single-family houses (sampling points 7 and 2). The roots, on the other hand, were characterized by zinc contents of 31.3-102.4 mg·kg-1 dry mass in samples collected in the City Forest and 10 m from the edge of National Road No. 16 (sampling points 9 and 10). Greater differences between the concentration of zinc in the leaves and roots of broadleaf plantain were obtained by Kurteva [38], Malizia [14], and FilipovićTrajković et al. [34]. The dependencies between zinc contents in the analyzed plants and soil are presented in Table 6. A high correlation (r = 0.89) was noted between Zn content in the leaves and roots of broadleaf plantain and, similarity to cadmium, between the contents of this element in Amanita muscaria caps and Plantago major L. leaves. A moderate correlation occurred between lead content in Pinus sylvestris L. needles and Plantago major L. roots. A high dependency between the concentrations of Cd, Pb and Zn in broadleaf plantain leaves and roots was found in the research of Filipović-Trajković et al. [34]. The average cadmium (Cd), lead (Pb), and zinc (Zn) contents in Scots pine (Pinus sylvestris L.) needles, fly agaric mushroom (Amanita muscaria) caps, and broadleaf plantain (Plantago major L.) leaves and roots collected from 10 sampling location in Olsztyn (Poland) are presented in Table 7. The largest quantities of cadmium and lead accumulated in the leaves and roots of broadleaf plantain Plantago major L. The ability of broadleaf plantain leaves and roots to exhibit high concentrations of heavy metals was confirmed in the works of Siromly [39] and Filipović-Trajković et al. [34]. The lowest cadmium and lead contents were found in Pinus sylvestris L. needles and Amanita muscaria caps, respectively. Small differences between plants, not exceeding 33%, were noted in the case of zinc content. The highest variability was present in the lead content of fly agaric mushroom (Amanita muscaria) caps, 221 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin with the lowest in the zinc content of broadleaf plantain (Plantago major L.) leaves. 4. CONCLUSIONS Significant differences were found in the contents of cadmium, lead and zinc depending on the place of sample collection as well as plant species. The leaves and roots of broadleaf plantain Plantago major L. accumulated the most cadmium and lead. Small differences between plants were noted in the case of zinc contents. The highest Cd and Pb content in Scots pine (Pinus sylvestris L.) needles were found in samples collected 5 m from a very busy road. The amount of analyzed metals was highest in fly agaric mushroom (Amanita muscaria) caps and leaves of broadleaf plantain samples collected near a large subdivision of single-family houses, where hard coal is burned. The highest Cd, Pb and Zn contents in broadleaf plantain roots were observe near busy transportation routes. Low heavy metal content was noted in the City Forest, which is located far away from roads and residential neighborhoods. Cadmium content in the fly agaric mushroom was significantly correlated with the amount of this metal present in broadleaf plantain leaves. A very high correlation was established between the amount of Pb in the leaves and roots of broadleaf plantain, whereas the correlations between the content of this element in fly agaric mushroom caps and the leaves and roots of broadleaf plantain were found to be high. Zinc content in the leaves of broadleaf plantain was significantly correlated with the content of this element in the roots of this plant and in the fly agaric mushroom. The authors have declared no conflict of interest. REFERENCES [1] Grzebisz W., L. Cieśla L., Komisarek J., Potarzycki J. (2002). Geochemical assessment of heavy metals pollution of urban soils. Polish Journal of Environmental Studies, 11, 5, 493-499. [2] Yoon J., Cao X., Zhou Q., Ma L.Q. (2006). Accumulation of Pb, Cu, and Zn in native plants growing on a contaminated Florida site. Science of the Total Environment, 368, 456-464. [3] Uyar G., Ören M., Yildirim Y., Ince M. (2007). Mosses as indicators of atmospheric heavy metal deposition around a coalfired power plant in turkey. Fresenius Environmental Bulletin, 16, 182-192. [4] Taghipour H., Mosaferi M., Armanfar F., Gaemmagami S.J. (2013). Heavy metals pollution in the soils of suburban areas in big cities: a case study. International Journal of Environmental Science and Technology, 10, 243–250. [5] Sharma R.K., Agrawal M. (2013). Heavy metals pollution in the soils of suburban areas in big cities: a case study. International Journal of Environmental Science and Technology,10, 243-250. [6] Grigalavičienė I., Rutkovienė V., Marozas V. (2005). The Accumulation of Heavy Metals Pb, Cu and Cd at Roadside Forest Soil. Polish Journal of Environmental Studies, 14, 1, 109-115. 222 [7] Lammel G., Ghim Y.S., Broekaert J.A.C., Gao H.W. (2006). Heavy metals in air of an eastern china coastal urban area and the yellow sea. Fresenius Environmental Bulletin, 15, 15391548. [8] Kasassi A., Rakimbei P., Karagiannidis A., Zabaniotou A., Tsiouvaras K., Nastis A., Tzafeiropoulou K. (2008). Soil contamination by heavy metals: measurements from a closed unlined landfill. Bioresource Technology, 99, 8578–8584. [9] Kabala C., Chodak T., Szerszen L., Karczewska A., Szopka K., Fratczak U. (2009). Factors influencing the concentration of heavy metals in soils of allotment gardens in the city of Wroclaw, Poland. Fresenius Environmental Bulletin, 18, 1118-1124. [10] Buszewski B., Jastrzębska A., Kowalkowski T., Górna-Binkul A. (2000). Monitoring of selected heavy metals uptake by plants and soils in the area of Toruń, Poland. Polish Journal of Environmental Studies, 9, 6, 511-515. [11] Krawczyk J., Klink A., Wislocka M. (2009). Influence of tree canopies on concentration of some metals in throughfall, soil and moss Pleurozium schreberi (Bird.) Mitt. Fresenius Environmental Bulletin, 18, 1186-1191. [12] Yener S.H., Yarci C. (2010). Alcea pallida Waldst. et Kit. (Malvaceae) as a heavy metal biomonitor in Istanbul (Turkey). Fresenius Environmental Bulletin, 19, 1024-1030. [13] Sawidis T., Breuste J., Mitrovic M., Pavlovic P., Tsigaridas K. (2011). Trees as bioindicator of heavy metal pollution in three European cities. Environmental Pollution, 159, 12, 3560-70. [14] Malizia D., Giuliano A., Ortaggi G., Masotti A. (2010). Common plants as alternative analytical tools to monitor heavy metals in soil. Chemistry Central Journal, 6, (Suppl 2), S6. [15] Singh A, Sharma R.K., Agrawal M., Marshall F.M. (2010). Health risk assessment of heavy metals via dietary intake of foodstuffs from the wastewater irrigated site of a dry tropical area of India. Food and Chemical Toxicology, 48, 611-619. [16] Desplanque C., Rolland C., Schweingruber F.H. (1999). Influence of species and abiotic factors on extreme tree ring modulation: Picea abies and Abies alba in Tarentaise and Maurienne (French Alps). Trees, Structures and Function, 13, 218227. [17] Patra M., Bhowmik N., Bandopadhyay B., Sharma A. (2004). Comparison of mercury, lead and arsenic with respect to genotoxic effects on plant systems and the development of genetic tolerance. Environmental and Experimental Botany, 52, 199– 223. DOI: 10.1016/j.envexpbot.2004.02.009 [18] Pedro C.A, Santos M.S.S, Ferreira S.M.F, Gonçalves S.C. (2013). The influence of cadmium contamination and salinity on the survival, growth and phytoremediation capacity of the saltmarsh plant Salicornia ramosissima. Marine Environmental Research, 92, 197-205. [19] MacBride M.B. (1994). Environmental chemistry of soils. Oxford University Press, New York, Oxford, 406 pp. [20] Bond T.C., Bhardwaj E., Dong R., Jogani R., Jung S., Roden C., Streets D.G., Trautmann N.M. (2007). Historical emissions of black and organic carbon aerosol from energy-related combustion, 1850–2000. Global Biogeochemical Cycles, 21, GB2018. [21] Smołka-Danielowska D. (2006). Heavy metals in fly ash from a coal-fired power station in Poland. Polish Journal of Environmental Studies, 15, 6, 943-446. [22] Seshadri1 B., Bolan N.S., Naidu R., Brodie K. (2010). The role of coal combustion products in managing the bioavailability of nutrients and heavy metals in soils. Journal of Plant Nutrition and Soil Science, 10, 3, 378-398. © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin [23] Sitarz-Palczak E., Kalembkiewicz J. 2012. Study of Remediation of Soil Contamined with Heavy Metals by Coal Fly Ash. Journal of Environmental Protection, 3, 1373-1383. [39] Siromlya T. I. (2011). Influence of Traffic Pollution on Ecological State of Plantago major L. Contemporary Problems of Ecology, 4, 499-507. [24] Poland’s Informative Inventory Report. Submission under UN ECE Convention on Long-range Transboundary Air Pollution. (2012). Polish Ministry of the Environment – KOBiZE, Warsaw, Poland. [25] Pöykiö R., Perämäki P., Niemelä M. (2005). The use of Scots pine (Pinus sylvestris L.) bark as a bioindicator for environmental pollution monitoring along two industrial gradients in the Kemi-Tornio area, northern Finland. International Journal of Environmental and Analytical Chemistry, 85, 2, 127-139. [26] Gworek B., Dećkowska A., Pierścieniak M. (2011). Traffic pollutant indicators: Common Dandelion (Teraxacum officinale), Scots Pine (Pinus Silvestris), Small Leaved Lime (Tilia cordata). Polish Journal of Environmental Studies, 20, 1, 8792. [27] Lehndorff E., Schwark L. (2008). Accumulation histories of major and trace elements on pine needles in the Cologne Conurbation as function of air quality. Atmospheric Environment, 42, 833-845. [28] Molski B., Dmuchowski W. (1990). The comparison of environmental pollution in Northern Finland near Kevo and in Poland with the use of Pinus silvestris L. as bioindicator, Reports from the Kevo Subarctic Research Station, 21, 27–30. [29] Barcan V. SH., Kovnatsky E.F., Smetannikova M.S. (1998). Absorption of heavy metals in wild berries and edible mushrooms in an area affected by smelter emissions. Water Air and Soil Pollution, 103, 173-195. [30] Gast C.H., Jansen E., Bierling J. (1988). Heavy metals in mushrooms and their relationships with soil characteristics. Chemosphere, 17, 789-799. [31] Svoboda L., Zimmermannová K., Kalac P. (2000). Concentrations of mercury, cadmium, lead and copper in fruiting bodies of edible mushrooms in an emission area of a copper smelter and mercury smelter. Science of the Total Environment, 246, 61-67. [32] Das N. (2005). Heavy metals biosorption by mushrooms. Natural Product Radiance, 4, 6, 454-459. [33] Sowa I., Wójciak-Kosior M., Kocjan R. (2012). The content of some trace elements in selected medicinal plants collected in the province of Lublin. Acta Scientiarum Polonorum Horticulture, 11, 6, 15-22. [34] Filipović-Trajković R., Ilić Z.S., Šunić L., Andjelković S. (2012). The potential of different plant species for heavy metals accumulation and distribution. Journal of Food, Agriculture and Environment, 10, 1, 959-964. Received: April 03, 2014 Revised: May 06, 2014 Accepted: May 14, 2014 [35] Kord, B, Mataji, A., Babaie, S. (2010). Pine (Pinus Eldarica Medw.) needles as indicator for heavy metals pollution. International Journal of Environmental Science and Technology, 7, 1, 79-84. CORRESPONDING AUTHOR [36] Yilmaz S., Zengin M. (2004). Monitoring environmental pollution in Erzurum by chemical analysis of Scots pine (Pinus sylvestris L.) needles, Environment International, 29, 1041– 1047. [37] Cocchi L., Vescovi L., Petrini L.E. Petrini O. (2006). Heavy metals in edible mushrooms in Italy. Food Chemistry, 98, 277284. [38] Kurteva M.K. (2009). Comparative study on Plantago major and P. lanceolata (Plantaginaceae) as bioindicators of the pollution in the region of the Asarel Copper Dressing Works. Phytologia Balcanica, 15, 2, 261-271. 223 Jerzy Jeznach Warsaw University of Life Sciences – SGGW Faculty of Civil and Environmental Engineering Department of Environmental Improvement ul. Nowoursynowska 159 02-776 Warszawa POLAND E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 216 – 223 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin HEAVY METAL CONTAMINATION OF PLANT RAW MATERIAL INTENDED FOR FOOD Elvyra Jariene1,*, Honorata Danilcenko1 and Maria Jeznach2 1 Aleksandras Stulginskis University, Agronomy faculty, Agriculture and Food Sciences Institute, Kaunas-Akademija, Lithuania 2 Warsaw University of Life Sciences – SGGW, Faculty of Human Nutrition and Consumer Sciences, Department of Organization and Consumption Economics, Warsaw, Poland; Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey ABSTRACT Plants best absorb heavy metals by exchange. Most heavy metals get into plant roots and tubers from soil and into leaves from the atmosphere. The aim of this research was to determine the accumulation levels of heavy metals in organically grown pumpkin peel and flesh and in the tubers of Jerusalem artichoke. The following pumpkin and Jerusalem artichoke cultivars were selected for the investigations: Cucurbita maxima cv ‘Rouge vif d’Etampes’, Cucurbita moschata cv ‘Muscade de Provence’ and Helianthus tuberosus L. cvs ‘Rubik’, ‘Albik’, and ‘Sauliai’ and grown in a certified organic field. Heavy metal residues in all samples did not exceed the maximum permissible concentrations. Tubers of the investigated Jerusalem artichoke cvs are more sensitive to the effect of heavy metals than the over ground pumpkin fruits. KEYWORDS: Pumpkins, Jerusalem artichoke, Heavy metals. 1. INTRODUCTION In developing economy and social welfare, people are constantly concerned about food safety and quality. Food is routinely analyzed for a variety of elements to assess the possible nutritional or toxicological implications and to ensure its compliance with governmental regulations or product quality [1-3]. In order to eat safe food, firstly there is a need to grow high quality raw material. Consumers are exposed to a diversity of chemicals in all areas of life. Air, water, soil and food are unavoidable components of the human environment. Each of these elements influences the quality of human life and each of them may be contaminated [4-8]. Pumpkins and Jerusalem artichoke are known as vegetables that are nutritious and dietary. They contain a lot * Corresponding author of biologically active substances and are well valuable for their healing properties and simple cultivation technology. Recently, both plants are intensively grown in Lithuania. The aim of this research was to determine the accumulation levels of heavy metals (Cd, Pb, Cr, Ni, Cu, Zn) in organically grown pumpkin peel and flesh and in the tubers of Jerusalem artichoke. 2. MATERIALS AND METHODS The following pumpkins and Jerusalem artichoke cultivars were selected for the investigation: Cucurbita maxima cv ‘Rouge vif d’Etampes’, Cucurbita moschata cv ‘Muscade de Provence’ and Helianthus tuberosus L. cvs ‘Rubik’, ‘Albik’, and ‘Sauliai’. The experiments were carried out on limnoglacial loam on boulder clays, carbonate deeper gleyic luvisol (Calearie Luvisol) in the Sakiai region (Lithuania), on a certified organic field, whose soil richness was known and adequate for plant needs. Due to this, the plants were not fertilized additionally and pesticides were not used. The soil agrochemical characteristics were as follows: slightly neutral and neutral, medium humus content, phosphorusrich and potassium-rich. In the experimental area the soil was drained by drainage and the relief was artificially leveled. Heavy metal concentrations were determined in the soil [9, 10], their amounts were as follows: Cd – 0.23 mg kg-1, Cr – 11.76 mg kg-1, Ni – 9.27 mg kg-1, Pb – 11.67 mg kg-1, Zn – 153.67 mg kg-1, Cu - 24.50 mg kg-1 and did not exceed the maximum permissible concentrations (MPC) [11]. The experimental plants were grown in the following manner: pumpkins – interlinear – 2 m, with distance between the plants – 2 m, and Jerusalem artichokes – interlinear – 0.7 m, with distance between the plants 0.3 m in 4 repetitions. The repetition variants were distributed at random. Pumpkin fruits were harvested in the last decade of September and the Jerusalem artichoke tubers – in the first decade of November. For analysis of the heavy metal content, 5 kg of vegetables were collected from every rep- 224 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin etition. Jerusalem artichoke tubers and pumpkin fruit samples were washed with deionized water. The peel and flesh from pumpkin fruits were treated separately. Samples were weighed and air-dried for a day to reduce the water content. All samples were oven-dried at 70-80°C for 24 h. The dry samples were ground to fine powder using a stainless steel mill. Heavy metals (Cd, Pb, Cr, Ni, Cu, Zn) were determined using a mass spectrometer (Thermo Finnigan MAT, Bremen, Germany). Powdered samples of Jerusalem artichoke tubers and the peel and flesh of pumpkin fruits were transformed into solutions and analyzed. All analyzes were carried out in the Laboratory of Agricultural and Food Sciences, Institute of Aleksandras Stulginskis University and in the Agrochemical Laboratory of the Lithuanian Research Centre for Agriculture and Forestry. All analyses were conducted in three repetitions. The data was statistically treated using Anova data analysis and management module of the integrated system STATISTICA. For the evaluation of the analyses, one factor analysis of variance was carried out. Averages of separate treatments were calculated, the standard deviation and the least significant difference at a 95% probability level were estimated using the Fisher’s LSD test (P<0.05). 3. RESULTS AND DISCUSSION Table 1 shows the concentrations of heavy metals determined in the pumpkin fruits. The highest values of Cd and especially high Zn were determined in cv ‘Muscade de Provence’ pumpkin flesh at 0.011 mg kg-1 and 2.976 mg kg-1, respectively. The lowest value of Cd was determined in the peel of cv ‘Muscade de Provence’ and in the peel and flesh of cv ‘Rouge vif d’Etampes’ pumpkin at 0.002 mg kg-1, while the values of Zn in the flesh of cv ‘Rouge vif d’Etampes’ pumpkin reached 0.702 mg kg-1 (Table 1). Cadmium is known to be a principal toxic element, since it inhibits many life processes [12]. Some studies have found out close links between the low amount of zinc and increased risk of cancer. Zinc is an important element in numerous proteins and plays an essential role in several cell functions, e.g. the functioning of the immune system [6]. The results of the analysis have shown that Pb was determined only in cv ‘Muscade de Provence’ pumpkin flesh at 0.003 mg kg-1 and there were no traces of this metal in other pumpkin genotypes. The Pb content in the pumpkin flesh varied between 0.4 and 1.9 mg kg-1 as reported by other studies [13]. The highest values of Cr were determined in cv ‘Muscade de Provence’ and cv ‘Rouge vif d’Etampes’ pumpkin flesh at the level of 0.101 and 0.109 mg kg-1, respectively, while the lowest values were identified in peels of the above mentioned cvs. at 0.042 and 0.032 mg kg-1, respectively. There are no reports related to the accumulation of Cr in pumpkin peel and flesh, while in pumpkin seeds the Cr levels vary from 0.01 mg kg-1 to 0.28 mg kg-1 depending on the cultivars [14]. Nickel plays a role in body functions including enzymatic functions. It occurs naturally more commonly in plants rather than in animal flesh. It activates some enzyme systems in trace amounts but its toxicity at higher levels is more significant [15]. The highest amount of Ni was determined in cv ‘Muscade de Provence’ pumpkin flesh and the lowest one in cv ‘Rouge vif d’Etampes’ pumpkin peel at 0.221 mg kg-1 and 0.035 mg kg-1, respectively. Copper is an essential micronutrient which functions as a biocatalyst, in addition to iron is required for body pigmentation, maintains a healthy central nervous system, prevents anemia and is interrelated with the function of Zn and Fe in the body [16]. Cu concentrations in all tested samples were at very similar amounts and varied between 0.563 and 0.792 mg kg-1, with cv ‘Rouge vif d’Etampes’ pumpkin peel having the lowest and cv ‘Muscade de Provence’ pumpkin flesh having the highest values. The results obtained here for pumpkin flesh were similar compared to other published results [13]. Generally, the highest values of Cd, Cr, Ni, Cu and Zn in pumpkin fruits were detected in flesh of cv ‘Muscade de Provence’ and cv ‘Rouge vif d’Etampes’ (Table 1). They, however, do not exceed the maximum allowable concentrations recommended for vegetables by the EU [17]. Jerusalem artichoke tubers had a higher heavy metal content compared to the investigated pumpkin peels and flesh. Table 2 show the concentrations of heavy metals determined in Jerusalem artichoke cvs tubers. The results of the analysis have shown that the levels of the same heavy metals in samples from different cultivars showed no significant differences. Higher amounts of Cd, Pb, and Zn were deter- TABLE 1 - Heavy metals residue (mg kg-1 d.w.) in the peels and flesh of various pumpkin genotypes) Pumpkins genotype Cucurbita moschata Cucurbita maxima cv ‘Muscade de Provence’ pumpkin cv ‘Rouge vif d’Etampes’ pumpkin peel flesh peel flesh 0.002±0.00a 0.011±0.01b 0.002±0.00a 0.002±0.00a Cd a a a 0.000±0.00 0.003±0.00 0.000±0.00 0.000±0.00a Pb 0.042±0.02a 0.101±0.05b 0.032±0.01a 0.109±0.01b Cr 0.053±0.02b 0.221±0.03c 0.035±0.01a 0.064±0.01b Ni 0.605±0.19a 0.792±0.25a 0.563±0.01a 0.607±0.15a Cu 0.753±0.23a 2.976±0.21b 0.709±0.20a 0.702±0.15a Zn Note: The average values marked by the same letter in a row have no significant differences at P≤0.05 Heavy metals 225 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 2 - Heavy metals residue (mg kg-1 d.w.) in Jerusalem artichoke tubers (mean ± SD, n=12) Heavy metals Jerusalem artichoke cultivars ‘Albik’ ‘Rubik’ 0.04±0.01a 0.03±0.01a Cd 0.06±0.03a 0.04±0.00a Pb 3.27±0.35a 3.59±0.33a Cr 0.64±0.19a 0.70±0.02a Ni 3.29±0.35a 3.60±0.33a Cu a 9.27±2.93 8.60±1.09a Zn Note: The average values marked by the same letter in a row have no significant differences at P≤0.05 mined in cv ‘Albik’ tubers at 0.04 mg kg-1, 0.06 mg kg-1 and 9.27 mg kg-1, respectively; Ni – in cv ‘Rubik’ tubers at 0.70 mg kg-1; Cr and Cu – in cv ‘Sauliai’ tubers at 4.09 and 4.00 mg kg-1, respectively. Our results show that the residue of these metals in Jerusalem artichoke tubers does not exceed the MPC as recommended for vegetables by the EU [17]. However, particularly high zinc values (9.27 mg kg-1) have been detected in cv ‘Albik’ tubers (Table 2). High concentrations of lead and other heavy metals (Cd) have been occasionally reported [2]. Plants best absorb heavy metals by exchange. The concentration of heavy metals in plants increases in the following order: Cd>Pb>Zn>Cu, depending on their mobility and amount in soil; however, a reliable relationship between their amounts in soil and plants was not established. Most heavy metals get into plant roots from the soil and into leaves from the atmosphere. Roots are more sensitive to the effect of heavy metals than the over ground fruits [18] and the reason for these differences in our study could be explained by the different physiological activity of pumpkins and Jerusalem artichoke plants. Moreover, heavy metal bioavailability depends on the plant species and its ability to absorb metals. Up to a certain concentration, some higher plants may selfregulate the absorption of metals, e.g. in order to protect from the effect of Cd, plants can change the medium pH in the rhizosphere. Plants increase soil pH during the absorption of NO32- rather that NH4 + [19]. Plants commonly accumulate cadmium, to a lesser extent – zinc and copper, and lastly – manganese, nickel, and chromium. It has also been established that the content of heavy metals in Jerusalem artichoke tubers may increase the level of soil pollution with heavy metals [1,3] and the plant may be a promising crop for bioremediation in contaminated soils [19]. ‘Sauliai’ 0.03±0.02a 0.03±0.01a 4.09±0.97a 0.58±0.29a 4.00±0.97a 8.55±1.85a ACKNOWLEDGEMENT This publication is funded by European Social Fund and the Budget of the Republic of Lithuania (project „Eureka“E! 6855 – ECORAW „Higher functionality food products from organic vegetable raw materials“). The authors have declared no conflict of interest. REFERENCES [1] Antonkiewicz, J. and Jasiewicz, C. (2003). Assessment of Jerusalem artichoke usability for phytoremediation of soils contaminated with Cd, Pb, Ni, Cu and Zn. Pol. Archiwum Ochrony Środowiska, 29: 81-87. [2] Cieslik, E. and Baranowski, M. (1997). Minerals and lead content of Jerusalem artichoke new tubers. Brom. Chem. Toxicol., 30: 66-67. [3] Jasiewicz, C. and Antonkiewicz, J. (2002). Heavy metals extraction by Jerusalem artichoke (Helianthus tuberosus L.) from soils contaminated with heavy metals. Chemia i Inżynieria Ekologiczna, 9 (4): 379-386. [4] Orisakwe O.E., Kanayochukwu N. J., Nwadiuto A.C., Daniel D. and Onyinyechi O. (2012). Evaluation of Potential Dietary Toxicity of Heavy Metals of Vegetables. J Environment Analytic Toxicol, 2: 136. [5] Melø R., Gellein K., Evjea L., and Syversen T. (2008). Minerals and trace elements in commercial infant food. Food and Chemical Toxicology, 46:3339–3342. [6] Song Y., Leonard S.W., Traber M.G., and Ho E. (2009). Zinc deficiency affects DNA damage, oxidative stress, antioxidant defenses and DNA repair in rats. The Journal of Nutrition, 139 (9):1626-1631. [7] Jarienė, E.; Danilčenko, H.; Neverauskaitė, L.; Černiauskienė, J.; Mažeika, R.; and Staugaitis, G. (2013). Chemical Composition and Pollution Research in Pumpkin Fruit of Various Genotypes // Rural development 2013: proceedings. 6 (20): 115-118. Heavy metal residues in the peels and flesh of the analyzed pumpkin fruits and Jerusalem artichoke tubers did not exceed the maximum permissible concentrations (EU Commission Regulation (EC) No. 1881/2006). [8] Murphy, S.P. (2002). Dietary reference intakes for the U.S. and Canada: update on implications for nutrient databases, J. Food Compos. Anal., 15: 411-417. [9] ISO 11466:95. Soil quality - Extraction of trace elements soluble in aqua regia. Tubers of the investigated Jerusalem artichoke cultivars are more sensitive to the effect of heavy metals than the over ground pumpkin fruits. [10] ISO 11047:1998. Soil quality -- Determination of cadmium, chromium, cobalt, copper, lead, manganese, nickel and zinc -Flame and electrothermal atomic absorption spectrometric methods. 4. CONCLUSIONS 226 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin [11] Mazvila, J. (2001). Heavy metals in Lithuanian soils and plants. Monograph, 343 p. [12] Anonymous, (2000). International programme on chemical safety (IPCS INCHEM). Joint FAO/WHO expert committee on food additives (JECFA), Safety Evaluation of Certain Food Additives and Contaminants, Report No. TRS 44-JECFA 53/273, FAS 46- JECFA 55/247, WHO, Geneva. [13] Karanja, J. K., Mugendi, J. B.,. Fathiya, M. K. and. Muchugi, A. N. Comparative Study on the Nutritional Value of the Pumpkin, Cucurbita Maxima varieties from different Regions in Kenya (http://elearning.jkuat.ac.ke/journals/ojs/index.php/jscp/article/view/907). [14] Danilčenko, H.; Jarienė, E.; Gajewski, M.; Černiauskienė, J.; Kulaitienė, J.; Sawicka, B.; and Aleknavičienė, P. (2011). Accumulation of elements in some organically grown alternative horticultural crops in Lithuania // Acta Scientiarum Polonorum: Hortorum Cultus. Lublin, 10(2): 23-31. [15] Divrikli, U., Horzum, N., Soylak, M., Elci, L. (2006). Trace heavy metal contents of some spices and herbal plants from western Anatolia, Turkey. Int. J. Food Sci. Technol., 41: 712716. [16] Akinyele, I.O., Osibanjo, O. (1982). Levels of trace elements in hospital diet. Food Chem., 8: 247-251. [17] COMMISSION REGULATION (EC) No. 1881/2006. Setting maximum levels for certain contaminants in foodstuffs. [18] Öncel I., Keles, Y., Üstün, A. S. (2000). Interactive effects of temperature and heavy metal stress on the growth and some biochemical compounds in wheat seedlings. Environmental pollution, 107: 315 – 320. [19] Nyguist J., Greger M. (2009). Response of two wetland plant species to Cd exposure at low and neutral pH. Environmental and Experimental Botany, 65: 417 – 424. Received: April 10, 2014 Accepted: July 03, 2014 CORRESPONDING AUTHOR Elvyra Jariene Aleksandras Stulginskis University Agronomy Faculty Agriculture and Food Sciences Institute Kaunas – Akademija, LT-53361 LITHUANIA Phone: +37037 752326 E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 224 – 227 227 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin COPPER REMOVAL FROM CONTAMINATED GROUNDWATER USING NATURAL AND ENGINEERED LIMESTONE SAND IN PERMEABLE REACTIVE BARRIERS Joanna Fronczyk1*, Maja Radziemska1 and Zbigniew Mazur2 1 Warsaw University of Life Sciences - SGGW, Faculty of Civil and Environmental Engineering, Nowoursynowska 159, 02-776 Warsaw, Poland 2 University of Warmia and Mazury in Olsztyn, Faculty of Environmental Management and Agriculture, Pl. Łódzki 4, 10-727, Olsztyn, Poland Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey ABSTRACT NOMENCLATURE This work investigates the performance of natural and engineered limestone sand (thermally and chemically modified) with respect to copper removal from groundwater protected by permeable reactive barriers. The engineered sorbents (particle size 0.25 – 0.50 mm) were prepared using high temperature at 850ºC and solutions of 0.25M Fe(III), 1M NaOH and 1M HNO3. Batch tests were carried out using a constant mass of the sorbent (0.5 g) and 50 mL of numerous copper ion solutions at different pH values at a desired shaking time in order to analyze the mechanism of copper removal. At a final pH value above 6.3, natural and engineered limestone sand removed over 94% of Cu(II). Test data indicated that the mechanism of copper removal is significantly affected by the contact time and the final pH level. The main processes leading to the removal of copper ions included precipitation with calcite or carbonate solids, chemisorption and physisorption. The test data fitted well with the pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models (excluding data for Fe(III)modified limestone) as well as the linear Henry’s isotherm. The most suitable for further application as a reactive material in PRBs technology is NaOH-modified limestone, followed by thermally-modified, HNO3-modified, Fe(III)modified limestone, and limestone. KEYWORDS: groundwater contamination, limestone sand, natural and engineered sorbents, permeable reactive barriers * Corresponding author C0 is the initial concentration; Ct is the concentration after time t; KD is the partitioning coefficient of Henry’s law; KID is the intraparticle diffusion rate constant; KPFO is the equilibrium rate constant of the pseudo-first order model; KPSO is the equilibrium rate constant of the pseudo-second order model; qeq is the equilibrium adsorption capacity of the copper ions; qt is the adsorption capacity determined after time t; R is the removal ratio. 1. INTRODUCTION The occurrence of toxic inorganic (especially heavy metals, e.g. copper) and organic compounds in subsoil, caused by the development of civilization, is one of the most important environmental problems. Maintaining public health and biodiversity preservation require the development of new methods of soil and groundwater remediation. Permeable Reactive Barriers (PRBs) are an effective alternative to conventional remediation methods of contaminated groundwater such as pump and treat technology, soil flushing by surfactant solutions [1], biodegradation [2] and electrokinetic methods [3]. The technology is based on the use of materials (natural and synthetic) that react with the pollutants present in the subsoil system. The nature of the processes (i.e. natural attenuation processes) depends on the material used for PRB construction. The most common processes used in this technology include reduction, sorption and precipitation, while the most widely and successfully used reactive material is zerovalent iron [4-6], followed by activated carbon [7, 8], and natural sorbents e.g. zeolites [9, 10]. There are also reports that natural calcium carbonate may successfully be used in the PRB technology. 228 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin The application of limestone for pH neutralization of acid mine drainage has been reported by numerous researchers [11-13]. Moreover, the removal of numerous metals (e.g. Fe(II), Fe(III), Al(III), Mn(II)) [11, 14, 15], including heavy metals (Zn(II), Ni(II), Cu(II), Cr(III), Cd(II) and Pb(II)) was observed in limestone-based treatment systems [13, 16, 17]. Mechanisms of toxic metals removal by natural calcium carbonates include ion exchange of calcium and magnesium, sorption by carbonates, as well as precipitation. Recently, natural minerals and organic matter-based materials that were thermally or chemically modified are used in various water treatment technologies. As an example, the following materials may be mentioned: Fe(III)modified zeolite [18], Na-X zeolite [19], HCl-modified clays [20], oxidized granular activated carbon [21], montmorillonite/Trametes versicolor [22]. Thus, the impact of thermal and chemical pre-treatment of natural limestone on its removal efficiency of copper ions seems a valuable study project. In this regard, the presented studies have been carried out to determine the effect of contact time, initial pH level and initial concentration of copper ions on the sorption efficiency by natural limestone and its modified forms using 0.25M Fe(III), 1M HNO3, 1M NaOH at 850ºC. Additionally, the utility of natural and engineered limestone sand application as reactive materials in groundwater protection has been discussed. 2. MATERIALS AND METHODS 2.1 Material Natural Polish limestone from Czatkowice and its thermally and chemically modified forms were investigated in the research. The composition of natural limestone is very close to the formula CaCO3, with the chemical composition in oxide (wt.%) C2O – 1.60%, N2O5 – 0.78%, MgO – 0.05%, Al2O5 – 0.49%, SiO2 – 1.34%, K2O – 0.48%, CaO – 87.4%, FeO3 – 7.80%. Moreover, studies on the sorption of nitrogen revealed that the natural limestone has a specific surface area of 0.91 m2/g, an average pore size of 133.4 Å, and is characterized by a non-porous structure. Figure 1 shows XRD spectra, SEM photographs and EDX mapping of the material. Before the pre-treatment stage, the natural limestone sand was sieved to obtain a uniform grain size of 0.25 – 0.50 mm. In the next step, the limestone was modified in four ways as follows: (1) 100 g of limestone was placed in a muffle furnace at 850ºC for 5 hours, then cooled down to room temperature; (2) 100 g of limestone was mixed with 200 mL of 0.25 M Fe(III) (Aldrich) solution at pH of 10.0 (adjusted with 1M NaOH in the beginning) for 7 days at room temperature; (3) 50 g of limestone was shaken with 500 mL 1M HNO3 solution for 7 days; (4) 50 g of limestone was shaken with 500 mL 1M NaOH solution for 7 days. After the reaction processes, the chemically treated samples were filtered and washed until the pH and the electrical conductivity values attained a constant level, dried at 60 ºC, and placed in plastic bags. 2.2 Sorption test A series of experiments were conducted to evaluate the effect of time, initial pH of the solution (pHi) and initial Cu(II) concentration on the copper removal efficiency of natural and engineered limestone sand. All sorption tests were conducted in a batch system at room temperature of 21±2ºC. 0.5 g of the sorbent and 50 mL of the copper ions solution were placed in a plastic bottle, then shaken for a desired period and centrifuged at 3000 rpm for 5 min. At the end of the experiments, the pH of each solution was measured with a standard pH-meter (Schott, Germany) and probe-calibrated with pH 4, 7, and 10 buffers. The concentration of copper (dissolved fraction) in both initial and equilibrium solutions was determined by atomic absorption spectroscopy – AAS (ICE-3000, Thermo Scientific, USA) with an air-acetylene flame and wavelength of 324.8 nm. The stock solutions for the sorption tests were made by dis- FIGURE 1 – XRD spectra, SEM image and energy dispersive X-ray mapping (EDX) of natural limestone 229 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin solving CuSO4•5H2O salts of analytical grade (Merck) in deionized water. The pH of the solution was adjusted using 1M HCl and 1M NaOH at the beginning of the tests (both analytical grade). Sorption kinetic tests were performed at an initial copper ion concentration of 50.0 mg/L and at an initial pH of 5.0. The desired shaking time was 10, 30 minutes and 1, 3, 5, 7, 24, 30, 50 and 75 hours. Sorption equilibrium tests were carried out with the solution of initial copper concentrations from 5.0 to 50.0 mg/L (in increments of 5.0 mg/L). The pH of the initial solutions was in the range of 5.0 – 5.5. Additionally, experiments of the pH effect (from 3.0 to 11.0 in increments of 1.0) were also performed. All experiments were conducted in duplicates and the average values were used in further calculations. The Cu(II) removal ratio R (%) was calculated from the formula: (1) and the sorption capacity was determined as follows: (2) where C0 and Ct are initial copper ion concentration and copper ion concentration after time t of the contact time (mg/L), respectively; R is the removal ratio of the copper ions by biosorbents (%); qt is the adsorption capacity of copper ions determined after time t of the contact time (mg/g); and V is the volume of the copper ions solution (L). The results of the sorption kinetic tests were analyzed using pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models with application of the following equations, respectively [23-25]: (3) 3. RESULTS AND DISSCUSION 3.1 Sorption kinetics In this study, the sorption processes are defined as adsorption, co-precipitation, and surface precipitation. Figure 2 shows the kinetics of copper ions removal as well as the variation of the final pH of the solution (pHf) depending on the shaking time. Analysis of the obtained test results allows to conclude that only the contact time exceeding 24 hours (for limestone, Fe(III)-modified limestone and NaOHmodified limestone) and 50 hours (for HNO3-modified limestone) caused an increase of the pHf to the value higher than 6.3, and thereby resulted in the precipitation of the copper ions in form of metal hydrooxides and metal carbonates in alkaline conditions [26, 27]. By contrast, regardless of the shaking time, in the case of thermally-modified limestone with a Cu(II) solution the measured pHf was higher than 12.0, which may be related to the dissolution of calcium carbonate. Because of the significant effect of the solution pH on the type of copper removal processes, further calculations using common adsorption kinetic models were performed for those samples, in which pHf was lower than 6.3. The time, after which equilibrium was attained, was determined as follows: less than 10 minutes for thermalmodified limestone, 3 hours for limestone, 7 hours for HNO3-modified limestone, and 24 hours for NaOH-modified limestone. Longer equilibration time may be related to physical adsorption, while a shorter to chemisorption [16, 17]. Based on the experimental results, the equilibrium time for Fe(III)-modified limestone was difficult to determine. Table 1 shows the critical parameters of the sorption kinetics. According to the coefficient of determination (R2), the pseudo-second order kinetic model is the most appropriate for Cu(II) sorption by limestone and thermallymodified limestone, the pseudo-first order and intraparticle diffusion models fit best the test data for NaOH-modified and HNO3-modified limestone, while data for Fe(III)-modified limestone could not be described using common kinetic models. Moreover, cop- (4) (5) where qeq is the equilibrium adsorption capacity of the copper ions (mg/g); qt is the adsorption capacity determined after time t (mg/g); KPFO and KPSO are the equilibrium rate constants of the pseudo-first order model (1/min) and pseudo-second order model (g/mg min); respectively; KID is the intraparticle diffusion rate constant (mg/g min1/2); C is the intercept (mg/g). Data from the equilibrium sorption tests were described using the linear sorption isotherm (Henry’s isotherm), which implies constant sorption in a solid-liquid system: (6) where KD is the Henry’s distribution coefficient (L/g). TABLE 1 - Kinetic constants of Cu(II) adsorption at pHf below 6.3 Kinetic model LS Pseudo first order kinetic model kPFO (1/min) qeq-cal (mg/g) R2 Pseudo second kinetic model kPSO (g mg-1 min-1) 2.584 qeq-cal (mg/g) 2.337 R2 0.999 Intraparticle diffusion kID (mg/g min1/2) 0.014 C (mg/g) 2.038 R2 0.354 T-LS NaOH-LS HNO3-LS - 0.001 1.329 0.967 0.005 0.817 0.909 1.002 4.990 0.999 - - 0.002 4.917 0.802 0.027 0.000 0.967 0.019 0.161 0.814 where LS is limestone; T-LS is thermally-modified limestone; NaOH-LS is NaOH-modified limestone; HNO3-LS is HNO3-modified limestone; qeq is the equilibrium adsorption capacity of the copper ions (mg/g); qt is the adsorption capacity determined after time t (mg/g); KPFO and KPSO are the equilibrium rate constants of the pseudo-first order model (1/min) and pseudo-second order model (g/mg min), respectively; KID is the intraparticle diffusion rate constant (mg/g min1/2); C is the intercept (mg/g). 230 Fresenius Environmental Bulletin 13 6 13 12 5.5 12 5 11 5 11 4.5 10 8 7 3 6 2.5 5 2 4 9 3.5 8 1 1 0.5 0 3500 0 1000 1500 2000 Time (min) 2500 3000 3 2 Thermally-modified limestone 0 500 1000 1500 2000 Time (min) 2500 3000 1 0 3500 13 6 13 12 5.5 12 5 11 5 11 4.5 10 4 9 3.5 8 7 3 6 2.5 5 2 4 1.5 3 1 0.5 0 500 1000 1500 2000 Time (min) 2500 3000 10 4.5 4 9 3.5 8 7 3 6 2.5 5 2 4 1.5 3 2 1 2 1 0.5 0 3500 0 NaOH-modified limestone 0 Adsorption capacity (mg/g) 6 5.5 Final pH Adsorption capacity (mg/g) 500 4 1.5 2 0 5 2 1 0 6 2.5 3 Limestone 7 3 1.5 0.5 Adsorption capacity (mg/g) 4 Final pH 3.5 10 4.5 6 13 5.5 12 5 11 Final pH 9 Final pH 4 Adsorption capacity (mg/g) 6 5.5 HNO3-modified limestone 0 500 1000 1500 2000 Time (min) 2500 3000 1 0 3500 10 4.5 4 9 3.5 8 7 3 6 2.5 5 2 Final pH Adsorption capacity (mg/g) © by PSP Volume 24 – No 1a. 2015 4 1.5 3 1 2 0.5 Fe(III)-modified limestone 0 0 500 1000 1500 2000 Time (min) 2500 3000 1 0 3500 FIGURE 2 – Effect of the contact time on the adsorption capacity and final pH per sorption by limestone did not follow the intraparticle diffusion model. This may indicate that surface sorption to a larger extent contributes to the rate-limiting step than intraparticle diffusion [28]. The agreement of experimental observation of Cu(II) sorption by limestone and NaOH-modified limestone with intraparticle diffusion kinetic model indicates two steps of the processes: (1) the initial surface adsorption, and (2) the final equilibrium stage with slower intraparticle diffusion due to low adsorbate concentration in the solution [29]. This is in agreement with other studies, which demonstrate that surface adsorption and intraparticle diffusion were involved in the adsorption of heavy metals [30, 31]. Furthermore, the calculated values of the sorption capacities at equilibrium (at pHf below 6.3) using the pseudo-first order and pseudo-second order kinetic models were similar to the experimental data. The calculated qeq for the desired test conditions (initial copper concentration of 50.0 mg/L and solid-to-solution ratio of 0.01 g/L) were 2.337 mg/g for limestone, 1.329 mg/g for NaOH-modified limestone and 0.817 mg/g for HNO3-modified limestone. 231 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin contaminated ground-water with the reactive material to ensure the occurrence of all the mechanisms of copper removal. 3.2 Equilibrium test Figure 3 shows the relationship of the adsorption capacity and copper concentration in the equilibrium solution. By contrast to previous reports [16], the data from the experimental equilibrium tests for Cu(II) did not fit the common sorption isotherms (Freundlich, Langmuir and Redlich-Peterson isotherms). The test results indicated that Henry’s isotherm, which shows a linear relationship, fits the data best with the values of the coefficient of determination above 0.8 for NaOH-modified (R2=0.808) and thermally-modified limestone (R2=0.831), and above 0.9 for limestone (R2=0.949), HNO3-modified (R2=0.927) and Fe(III)-modified limestone (R2=0.920). The slope of the sorption isotherm represents the Henry’s distribution coefficient (KD), which is presented together with the determined equations in Table 2. Comparing the calculated values of KD, the materials can be ranked with regard to their copper removal efficiency as follows: NaOH-modified, thermallymodified, HNO3-modified, Fe(III)-modified limestone, and finally limestone with the lowest removal efficiency. The measured sorption capacities of natural and engineered limestone sand (from 4.948 to 4.963 mg/g) were comparable to the values from the kinetic tests. It should be noted that apart from precipitation, a small amount of copper ions may be removed through ion exchange with Ca and chemisorption (although the pHf was higher than 6.3) and at higher pH levels through precipitation with calcite or carbonate solids [26, 32-34]. Moreover, according to Aziz et al. [16], both adsorption and precipitation mechanisms are expected to occur at low concentrations of heavy metals. TABLE 2 – Henry’s isotherm results Henry’s LS T-LS Fe(III)-LS NaOH-LS HNO3-LS isotherm KD (L/g) 8.954 11.074 10.123 11.476 10.867 Equaqeq=8.954 qeq=11.074 qeq=10.123 qeq=11.476 qeq=10.867 tions Ceq Ceq Ceq Ceq Ceq R2 0.949 0.831 0.920 0.808 0.814 3.3 Effect of initial pH FIGURE 3 – Adsorption isotherms of Cu(II) for natural and engineered limestone sand The sorption capacities determined for the contact time of 75 hours were similar for all materials (from 4.949 to 4.995 mg/g) and were the sum of the Cu(II) removed firstly due to the precipitation of copper oxides and carbonates, and secondly due to the sorption by mineral sorbents. The measured and calculated qeq for the tested materials correspond well with the values reported by Sdiri et al. [17] and Aziz et al. [16], who obtained sorption capacities for various limestones in the range from 0.784 to 1.845 mg/g and 2.915 mg/g, respectively. Finally, a PRB should be designed to provide a sufficiently long contact time of the The effect of initial pH of the solution on the copper removal ratio at a final pH of the solution is presented in Fig. 4. For natural limestone and all its chemically modified forms, the pHf of solution was substantially constant (from 7.4-7.9), irrespective of pHi in the range from 3.0 to 7.0. This may suggest the buffering capacity of the applied materials. Further increase of pHi led to the increase of the pHf to the maximum value of 10.7. By contrast, in the case of thermally modified limestone, the pHf was independent of the pHi values and reached 12.4. The increase of pHf may result from the presence of dissolved calcium carbonate in the solution. For all materials tested, after the shaking period the pH was above the solubility point of heavy metals, which led to their precipitation, therefore the 232 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin calculated removal ratio was higher than 94.29%. Sdiri et al. [17] reported that precipitation of metal carbonates occurs when the concentration product ([M2+1] [CO32-]) is higher than the corresponding solubility product constant (Ksp). Accordingly, the precipitation of copper as a metal hydroxide is expected at a pH of above 6. physisorption (by HNO3-modified and NaOH-modified limestone) and precipitation into insoluble hydroxide and carbonate forms in an alkaline environment (all tested materials). On the basis of equilibrium tests and the calculated Henry’s partitioning coefficients, the material with the highest removal efficiency was NaOH-modified limestone, followed by thermally-modified, HNO3-modified, Fe(III)modified limestone, and limestone. Finally, according to the obtained copper removal efficiency exceeding 94.29% it can be concluded that all materials may be recommended as low-cost reactive materials for the removal of Cu(II) from contaminated groundwater using PRBs technology. However, verification tests should be performed prior to the application of these materials in field conditions. ACKNOWLEDGMENTS This research was supported by Grant no. NN523 561638 obtained from the Ministry of Science and Higher Education of the Republic of Poland. The authors have declared no conflict of interest. REFERENCES FIGURE 4 - Variation of final pH and removal ratio at different values of the initial solution pH [1] Mulligan, C.N., Yong, R.N., Gibbs, B.F., James, S. and Bennett, H.P.J. (1999) Metal removal from contaminated soil and sediments by the biosurfactant surfactin. Environ. Sci. Technol. 33(21), 3812–3820. [2] Małachowska-Jutsz, A. and Kalka, J. (2010) Influence of mycorrhizal fungi on remediation of soil contaminated by petroleum hydrocarbons. Fresenius Environmental Bulletin 19(12b), 3217-3223. [3] Kim, S.H., Han, H.Y., Lee, Y.J., Kim, C.W. and Yang, J.W. (2010) Effect of electrokinetic remediation on indigenous microbial activity and community within diesel contaminated soil. Sci. Total Environ. 408, 3162–3168. [4] Permeable Reactive Barrier Technologies for Contaminant Remediation, (1998) EPA (U.S. Environmental Protection Agency). EPA/600/R-98/125. [5] Vogan, J.L., Focht, R.M., Clark, D.K. and Graham, S.L., 1999. Performance evaluation of a permeable reactive barrier for remediation of dissolved chlorinated solvents in groundwater. J. Hazard. Mater. 68, 97-108. [6] Farrell, J., Melitas, N., Kason, M. and Li, T. (2000) Electrochemical and column investigation of iron-mediated reductive dechlorination of trichloroethylene and percholoroethylene. Environ. Sci. Technol. 34, 2549-2556. [7] Lorbeer, H., Starke, S., Gozan, M., Tiehm, A. and Werner, P., 2002. Bioremediation of chlorobenzene-contaminated groundwater on granular activated carbon barriers. Water Air Soil Poll. Focus. 2, 183-193. [8] Bortone, I., Di Nardo, A., Di Natale, A. Erto, M., Musmarra, D., Santonastaso, G.F. (2013) Remediation of an aquifer polluted with dissolved tetrachloroethylene by an array of wells filled with activated carbon. J. Hazard. Mater. 260, 914-920. 4. CONCLUSIONS The results presented in this paper indicate that limestone as well as thermally and chemically modified limestone show high efficiency in copper ion removal. Moreover, the data signify that the contact time, pH, and initial metal concentrations play major roles in Cu(II) removal. The results (with the exception of data for Fe(III)-modified limestone) are consistent with the commonly used kinetic models such as the pseudo-first order, pseudo-second order and intraparticle diffusion kinetic models. Copper ions were removed mainly by chemisorption (by limestone), 233 © by PSP Volume 24 – No 1a. 2015 [9] Fresenius Environmental Bulletin Czurda, K.A. and Haus, R. (2002) Reactive barriers with fly ash zeolites for in situ groundwater remediation. Appl. Clay Sci. 1-2, 3-20 [10] Fronczyk, J. and Garbulewski, K. (2013) Evaluation of zeolitesand mixtures as reactive materials protecting groundwater at waste disposal sites. J. Environ. Sci. 25(9) 1764-1772. [11] Ziemkiewicz, P.F., Skousen, J.G., Brant, D.L., Sterner, P.L. and Lovett, R.J. (1997) Acidic mine drainage treatment with armored limestone in open limestone channels. J. Environ. Qual. 26, 1017-1024. [12] Watten, B.J., Sibrell, P.L. and Schwarz, M.F. (2004) Effect of acidity and elevated PCO2 on acid neutralization within pulsed limestone bed receiving coal mine drainage. Environ. Eng. Sci. 21, 786-802. [28] Georgescu, I., Mureşeanu, M., Cârjă, G., and Hulea, V. (2013) Adsorptive removal of cadmium and copper from water by mesoporous silica functionalized with N-(aminothioxomethyl)-2-thiophen carboxamide. J. Envirom. Eng.. 139(10), 1285-1296. [29] Örnek, A., Özacar, M. and Şengil, A.İ. (2007) Adsorption of lead onto formaldehyde or sulphuric acid treatment acorn waste: equilibrium and kinetic studies. Biochem. Eng. J., 37(2), 192-200. [30] Unuabonah, E.I., Adebowale, K.O. and Olu-OWolabi, B.I. (2007) Kinetic and thermodynamic studies of the adsorption of lead(II) ions onto phosphate-modified kaolinite clays. J. Hazard. Mater. 144(1-2), 386-395. [13] Miller, A., Figueroa, L. And Wildeman, T. (2011) Zinc and nickel removal in simulated limestone treatment of mining influenced water. Appl. Geochem. 26, 125-132. [31] Li, X., Yang, L., Li, Y., Ye, Z. and He, A. (2012) Efficient removal of Cd2+ from aqueous solutions by adsorption on PSEDTA resins: equilibrium, isotherms, and kinetic studies. J. Environ. Eng. 138(9), 940-948. [14] Aziz, H.A. and Smith, P.G. (1992) The influence of pH and coarse media on manganese precipitation from water. Water Res. 26, 853–855. [32] Papadopoulos, P. and Rowell, D.L. (1989) The reactions of copper and zinc with calcium carbonate surfaces. J. Soil Sci. 40, 39-48. [15] Santomarino, S. and Webb, J.A. (2007) Estimating longevity of limestone drains in treating acid mine drainage containing high concentrations of iron. Appl. Geochem. 22, 1244-2361. [33] Sdiri, A. and Higashi, T. (2013) Simultaneous removal of heavy metals by natural limestones. Appl. Water Sci. 3, 29-39. [16] Aziz, H.A., Adlan, M.N., Ariffin, K.S. (2008) Heavy metals (Cd, Pb, Zn, Ni, Cu and Cr(III)) removal from water in Malaysia: Post treatment by high quality limestone. Bioresour. Technol. 99, 1578–1583. [34] Sdiri, A., Higashi, T. and Jamoussi, F. (2014) Adsorption of copper and zinc onto natural clay in single and binary systems. Int. J. Environ. Sci. Tech. 11, 1081-1092. [17] Sdiri, A., Higashi, T., Jamoussi, F. And Bouaziz, S. (2012) Effects of impurities on the removal of heavy metals by natural limestones in aqueous systems. J. Environ. Manage. 93, 245253. [18] Kragović, M., Daković, A., Sekulić, Ž., Trgo, M., Ugrina, M., Perić, J. and Gatta, G.D. (2012) Removal of lead from aqueous solutions by using the natural and Fe(III)-modified Zeolite. Appl. Surf. Sci. 258, 3667-3673. [19] Derkowski, A., Franus, W. and Waniak-Nowicka, H. (2007) Textural properties vs. CEC and EGME retention of Na-X zeolite prepared from fly ash at room temperature. Int. J. Miner. Process. 82(2), 57-68. [20] Vengris, T., Binkiene, R. and Sveikauskaite, A. (2001) Nickel , copper and zinc removal from waste water by a modified clay sorbent. Appl. Clay Sci. 18, 183-190. [21] Huanq, X., Gao, N.Y. and Zhanq Q.L. (2007) Thermodynamics and kinetics of cadmium adsorption onto oxidized granular activated carbon. J.Environ. Sci. (China) 19(11), 1287-1292. [22] Akar, S.T., Akar, T., Kaynak, Z., Anilan, B., Cabuk, A., Tabak, Ö., Demir, T.A. and Gedikbey, T. (2009) Removal of copper(II) ions from synthetic solution and real wastewater by the combined action of dried Trametes versicolor cells and montmorillonite. Hydrometallurgy 97, 98-104. [23] Lagergren, S. (1898) Zur theorie der sogenannten adsorption geloster stoffe. Kungliga Svenska Vetanskapsakademines Handlingar 24, 1-39. [24] Ho, Y.S., and McKay, G. (1999) Pseudo-second order model for sorption processes, Process. Biochem. 34, 451–465. [25] Weber, W.J. and Morris, J.C. (1963) Kinetics of adsorption on carbon from solution. J. Sanit. Eng. Div. Am. Soc. Civ. Eng. 89, 31-60. [26] Petrovic, M., Macan, M.K. and Horvat, A.J.M. (1999) Interactive sorption of metal ions and humic acids onto mineral particles. Water Air Soil Poll. 34, 41-56. [27] Yong, R.N. and Mulligan C.N. (2004) Natural attenuation of contaminants in soils. Lewis Publication, Florida. 234 Received: April 10, 2014 Revised: May 12, 2014 Accepted: May 15, 2014 CORRESPONDING AUTHOR Joanna Fronczyk Warsaw University of Life Sciences – SGGW Faculty of Civil and Environmental Engineering Department of Geotechnical Engineering ul. Nowoursynowska 166 02-776 Warsaw POLAND E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 228 – 234 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin THE SALINITY PROBLEM AT YELKOMA LAGOON (YUMURTALIK-ADANA) AND ITS RESTORATION BY MIXING WITH FRESHWATER FROM CEYHAN RIVER Harun Aydin1,*, Hüseyin Karakuş2 and Osman Erdem3 1 2 Yüzüncü Yıl University, Department of Environmental Engineering, Van, Turkey Dumlupınar University, Department of Geological Engineering, Kütahya, Turkey 3 Nature Research Society, Ankara, Turkey Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey 1. INTRODUCTION ABSTRACT The Yelkoma Lagoon located at Ceyhan River Delta has been significantly deteriorated due to dam construction activities that cause lower freshwater inputs. Compared to the Mediterranean (~40 ppt), high salinity of the Yelkoma Lagoon (up to 116.0 ppt), has adversely affected the ecological life in the lagoon as evidenced by the number of fish deaths. In addition to less freshwater input, high evaporation rates and structure of the inlet channel between the lagoon and the Mediterranean are determined as major causes of high salinities. In this study, we applied EndMember Mixing Analysis to calculate the monthly amount of freshwater that should be contributed from the Ceyhan River to the Yelkoma Lagoon to decrease salinity and ensure sustainability of ecological life and fisheries. As a first stage of the study, a conceptual hydrological model of the Yelkoma Lagoon has been developed based on water volume and its salinity. A bathymetric map of the lagoon was produced allowing measurement of the area and volume of each sector in the lagoon. Monthly salinities were obtained from field surveys for all components of mixing equations. The optimum salinity of the lagoon water has been foreseen to be between the salinity of the Ceyhan River and the Mediterranean. Based on the conceptual model and using a mass balance equation, contributions of saline and freshwater end-members were calculated. As a result of mixing calculations, monthly required flow-rates of freshwater from the Ceyhan River to the Yelkoma Lagoon were determined to be in the range of 0.199 m3/s to 3.698 m3/s. The calculated freshwater has been given to the lagoon since March 2009, and positive developments have been observed in terms of ecological life. KEYWORDS: freshwater mixing, salinity, Yelkoma Lagoon, wetland restoration * Corresponding author Wetlands provide significantly essential environmental functions and products to us and to our economies, such as reed production, lagoon fishery, reduction of flooding, recharging of groundwater, treatment of wastewater, protection of shorelines, and support of a large biodiversity [1-7]. In general, the productivity and sustainability of wetlands are mainly depending on their hydrology and hydrochemistry including the amount of nutrients, water level fluctuations, evaporation, salinity, etc. However, over the last several decades, productivity and sustainability of wet-lands are threatened by various natural and artificial sources including climate change, industrialization, agricultural activities, uncontrolled construction, and unplanned hydrological activities in theirs watersheds. Among the wetlands, lagoons are known to be more sensitive to climate change and anthropogenic activities because of their shallow depth, limited sea connection, low freshwater input, etc. [6, 8-10]. One of the most important physical characteristics of coastal lagoons is the salinity [11]. According to the salinity, lagoons can be classified as fresh water (<3 ppt), hyposaline (3-30 ppt), marine (3035 ppt), and hypersaline (>35 ppt) ones [12]. The salinity of lagoons is mainly related to hydrological balance, freshwater input, and tidal effects [13]. Due to in-creasing evaporation rates, especially in dry summer seasons, hypersaline conditions may dominate in the lagoon at semi-arid regions. The negative impact of hypersaline con-ditions could be observed on productivity and diversity in the lagoons. Turkey has a total of 135 international important wetlands of which 14 are listed under the Ramsar Convention [14]. However, about 30% of the wetland area of Turkey has been deteriorated and/or drained over the last 60 years due to poor water management practices and water pollution. One of the Ramsar sites of Turkey is Yumurtalık Lagoons (Fig. 1), consisting of the whole of the alluvial delta formed by the Ceyhan River in the eastern Mediterranean, 235 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin with a complex of several lagoons as well as salt and freshwater marshes. The 2011 World Wildlife Fund report stated that dams constructed for energy production, flood protection, irrigation, and drinking water supply on the Ceyhan River have significantly affected freshwater input of the Yumurtalık Lagoons [15]. Also Tekelioğlu et al. [16] have reported that salinity is a vital problem at Yumurtalık Lagoons, especially in Yelkoma Lagoon. And previously published data indicate that the existence of hypersaline conditions in this lagoon could be related to lack of freshwater input and poor flushing similar to Ria Formosa lagoon in Portugal [6, 8]. To determine the contributions of mixing components in the hydrological budget [17-21], there is a widely used hydrochemical-mixing model known as End-Member Mixing Analysis (EMMA). As the first study related to rehabilitation of coastal wetlands in Turkey, we present the EMMA results applied to determine the monthly amount of fresh water that should be given to Yelkoma Lagoon from the Ceyhan River to decrease the salinity of lagoon waters, and to ensure the sustainability of fisheries and biodiversity. 2. MATERIALS AND METHODS 2.1 Description of the Study Area Yumurtalık Lagoons, consisting of a complex of lagoons, salt and freshwater marshes, are located at Yumurtalık district of Adana (Fig. 1a). These lagoons are situated on an area of about 164.3 km2 between the downstream of the Ceyhan River and İskenderun Bay on the shore of the eastern Mediterranean. Yelkoma Lagoon, one of the important fishery locations in Turkey, is located along the northeast-southwest direction at the southeast of Yumurtalık Lagoons with a 16.5 km2 lake area, and about 10.0 km length and 1.7 km width (Fig. 1b). The bathymetric map of the Yelkoma Lagoon was produced by a hydrographic survey carried out in August 2008, and the deepest point, average depth, and water volume were obtained as 70.0 cm asl, 35.0 cm asl and 5.18×106 m3, respectively (Fig. 2). The Yelkoma Lagoon is connected to the Mediterranean, at the east of the lagoon by communication channel or inlet, which has a narrow width (~10.0 m), shallow depth, and 4.0 km length. FIGURE 1 - (a) Location map of the study area and (b) sampling locations. The stars represent salinity observation stations 236 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin evaporation for the lagoon have been calculated as 818.4 mm and 1137.4 mm, respectively (Fig. 3). The highest and the lowest monthly average temperatures vary between 27.8 °C (August) and 10.2 °C (January), while long-term mean annual temperature was calculated to be 18.9 °C. According to the Thornthwaite climate classification, semi-arid and less humid climate conditions dominate the vicinity of the Yelkoma Lagoon [22]. FIGURE 2 - Bathymetric map of Yelkoma Lagoon (August 2008). 2.2 Climate and Hydrological Conditions The long-term (1975 to 2008) monthly meteorological parameters, such as air temperature, precipitation, and panevaporation rates, were obtained from the nearest meteorological stations that are operated by the State Meteorological Organization (DMİ) of Turkey. In order to calculate evaporation losses from the Yelkoma Lagoon, observed pan-evaporation readings were multiplied by a pan coefficient (0.7). The long-term average monthly meteorological parameters for Yelkoma Lagoon were generated by using the Thiessen Polygon Method in GIS environment. The long-term mean total annual precipitation and pan- As a result of changes in the Ceyhan riverbed, many lakes, lagoon, meanders, and marshes have been formed by floods in the Yumurtalık Lagoons. But the current stream-bed of the Ceyhan River along the Yumurtalık Lagoons was formed after a vast flood that occurred in 1932. However, flooding in Yumurtalık Lagoons was completely prevented after the construction of a series of dams on the Ceyhan River between the years of 1971 and 2003 [23]. Thus, Yumurtalık Lagoons was disconnected from the Ceyhan River and, therefore, receives freshwater input only from rainfalls. On the other hand, the connection of Yelkoma Lagoon with the Mediterranean Sea is provided by a narrow inlet channel having approximately 4.0 km in length, at the eastern part of the lagoon. We thought that the narrow shape of the inlet channel might be the cause of less mixing of lagoon waters with the Mediterranean sea waters by tidal effects. The flushing is good around inlet parts of the lagoon while remaining parts are poorly flushed. The low freshwater input and the restricted sea connection of the Yelkoma Lagoon result in increasing salinity during spring, summer, and autumn seasons. This situation is also supported by previously published studies for Yelkoma Lagoon [16, 23]. 2.3 Hydrochemistry A sampling campaign took place on July 2008, to measure hydrochemical parameters around the Yelkoma Lagoon. All sampling locations are shown in Fig. 1b and given in Table 1, along with field measurements of water 250 30 25 20 Temperature (C) Evaporation, Precipitation (mm) 200 150 15 E 100 P T 10 50 5 0 0 Jan Feb Mar Apr May Jun Jul Aug Set Oct Nov Dec FIGURE 3 - Long-term mean meteorological parameters for Yelkoma Lagoon (E: evaporation, T: temperature, P: precipitation). 237 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 1 - Some physicochemical parameters obtained from field work and literature for Yelkoma Lagoon. Coordinate (UTM Zone 36) T EC Sal pH Description X Y (C°) mS/cm (ppt) 1 738495 4065440 21.56 8.26 70.5 52.75 Station 1* 2 738495 4065440 22.25 8.26 81.4 61.12 Station 2* 3 738495 4065440 22.87 8.20 91.8 69.19 Station 3* 4 738495 4065440 22.27 8.16 94.0 71.16 Station 4* 5 738495 4065440 22.41 8.14 96.5 73.22 Station 5* CEY 729840 4058851 28.66 7.99 0.7 0.29 Ceyhan River DAL 739236 4065956 32.11 8.28 75.4 44.82 Fishery Shelter KOP 730975 4060844 31.43 8.48 0.7 0.29 Bridge MED 739098 4063584 32.68 8.29 69.4 40.29 Mediterranean ORB 735431 4063846 30.45 8.27 5.0 2.39 Old River Bed-Sea Connection SEA 735454 4063854 32.08 8.18 179.4 127.60 Sea-Old River Bed Connection YEL 731951 4060021 33.42 8.17 161.5 108.49 Yelkoma Lagoon * sign represents 12-month average values between 2007 and 2008 from [16] Code 30 120 25 80 20 60 15 40 10 20 5 Salinity (ppt) 100 1 2 3 4 5 Min Max Temperature 0 Dec 07 Jan 08 Feb 08 Mar 08 Apr 08 May 08 Jun 08 Jul 08 Aug 08 Sep 08 Oct 08 Nov 08 120 Temperature (C) a 0 0 b 20 100 Salinity (ppt) 80 60 80 60 Precipitation (mm) 40 100 40 120 20 140 Precipitation 1 2 3 4 5 Min Max 0 Dec 07 Jan 08 Feb 08 Mar 08 Apr 08 May 08 Jun 08 Jul 08 Aug 08 Sep 08 Oct 08 Nov 08 160 FIGURE 4 - The temporal variation of salinity with (a) temperature and (b) precipitation. Min and Max represent average minimum and maximum salinity of the Mediterranean, respectively [25]. The numbers represent salinity observation stations in Fig. 1b at Yelkoma Lagoon [16]. 238 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 2 - Some seasonal physicochemical parameters of Yelkoma Lagoon. Year Season 1998-1999 Spring Summer Autumn Winter 2007-2008 Spring Summer Autumn Winter pH T (°C) EC (mS/cm) S (ppt) 7.00 23.50 35.9 22.8 8.00 37.00 143.7 74.3 7.50 26.50 131.0 58.0 7.90 18.30 28.5 20.0 8.12 22.64 59.7 42.1 8.26 29.07 113.7 77.9 8.26 22.43 125.0 101.6 8.20 11.10 43.5 39.4 T: temperature; EC: electrical conductivity; S: salinity References [24] [16] FIGURE 5 - (a) Hydrological conceptual model of Yelkoma Lagoon and (b) divisions of the lagoon. phase pH, temperature (T), electrical conductivity (EC), and salinity (S) using a YSI 556 Multiprobe System with an accuracy of ±0.2 units, ±0.15 °C, ±1 µS/cm and ±1 ppt, respectively. Besides this, the same parameters were also obtained from previously published studies [16, 24]. Tekelioğlu et al. [16] also observed pH, T, EC, and S at five different stations on a monthly basis, between December 2007 and November 2008, in the Yelkoma Lagoon. The mean salinity of the Yelkoma Lagoon is calculated as 65.5 ppt while the highest and the lowest salinity are recorded as 25.6 ppt in February and 116.4 ppt in October, respectively. It is clearly seen from field measurements (Table 1) that salinity values at the entrance of the Yelkoma Lagoon (DAL) and the Mediterranean shore (MED) were measured around 40 ppt while this parameter was observed to be about 108 ppt in the lagoon’s remote parts from the sea. Salinity values that were observed at stations in the Yelkoma Lagoon show a gradual increase from the sea toward the hinterland (Table 1). The temporal variation of salinity with temperature and precipitation are given in Fig. 4. The salinity of Yelkoma Lagoon waters increases with rising temperatures, and also with the decrease of precipitation. We thought that this should be due to low freshwater input, high evaporation rate, and restricted sea connection that are all reducing flushing in the lagoon. Some previ- 239 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin ously published data on the seasonal variation of physicochemical parameters of the Yelkoma Lagoon are also given in Table 2. It is clearly seen from Table 2 that lagoon waters become more saline in the years between 1998 and 2008. Especially, except for the summer season, salinity values of lagoon water increased by about 85% as the rest of the year at this time interval. 2.4 Conceptual Model and Mixing Calculations In the scope of this study, based on water volume and salinity, a conceptual hydrological model of the Yelkoma Lagoon has been developed (Fig. 5a). This conceptual model consists of the required freshwater volume of the Ceyhan River, the volume of the Yelkoma Lagoon, and the volume of precipitation, and their salinities. Based on the conceptual model, monthly freshwater contributions from the Ceyhan River to the Yelkoma Lagoon were calculated by using three-component EMMA. Since the groundwater levels in close vicinity of the lagoon are generally less than 0.5 m asl, hydraulic gradient is assumed as 0; thus, the groundwater inflow to the lagoon was neglected from the conceptual model and also from the mixing calculations. Then, the lagoon was divided into four sectors that have known volume and salinity (Fig. 5b). Area and volume of each sector were acquired from the bathymetry map. The amounts of monthly total effective precipitations were calculated from monthly precipitation, and the corrected pan-evaporation data of the nearest meteorological stations (Karataş and Yumurtalık). The salinity of precipitation was accepted as 0 [26]. The monthly average salinity values of the Ceyhan River and the Yelkoma Lagoon were obtained from previously published data [16], and from field surveys (July 2008) (Table 1). We made the following assumptions: (1) final salinity of lagoon waters should be between the Ceyhan River (0.29 ppt) and the Mediterranean Sea (~38 ppt); (2) after mixing of freshwater, the final salinity of the lagoon water has been foreseen to be 20 ppt (in Jan, Feb, Dec), 25 ppt (in Mar), 30 ppt (in Apr), 35 ppt (in May) and 38 ppt (in Jun to Nov); (3) because of low tidal effect and flushing in the lagoon, it was accepted that there is not any change in the monthly salinity of each sector; (4) monthly average salinity of each sector was accepted that represents a whole month. Considering above statements and assumptions, the amount of freshwater for each month can be calculated from the following mass-balance equations: (Cf Vf ) = (Cc Vc) + (Cy Vy) + (Cp Vp) (1) Vf = Vc + Vy + Vp (2) Vc = [Vy (Cy - Cf) + Vp (Cp - Cf)] / (Cf - Cc) (3) where, the subscripts f, c, y and p represent the salinity (C) and volume of water (V) for final mixture, the Ceyhan River, the Yelkoma Lagoon and precipitation, respectively. 3. RESULTS AND DISCUSSION The restorations of coastal wetlands have been conducted worldwide to protect critical habitats for marine life, related freshwater aquatic life, stabilize beach erosion, etc. However, nowadays, there are many negative pressures on wetlands. One of the major stressors is the salinity that may directly affect plant growth and diversity of species in wetlands [27, 28]. The freshwater inflow to the lagoons occurs from rivers, runoff, groundwater, and precipitation. Also, freshwater input is an important source in diluting the salinity of these systems [29-32], and supplying nutrients and organic matter from upstream sources [33]. As in the Yelkoma Lagoon, lack of freshwater input to the wetlands has been found to adversely affect productivity and growth of wetland vegetation [34-36]. In addition, due to the hypersaline condition in the Yelkoma Lagoon, salt formation and fish deaths were observed on the shores of the lagoon at our field survey in July 2008 (Fig. 6a). Table 3 shows results of three-component EMMA calculations to achieve the estimated salinity values. Monthly amount of freshwater contributions were obtained as flowrates in the range of 0.199 m3/s to 3.698 m3/s with an average of 1.967 m3/s. The estimated freshwater contributions should be given from the Ceyhan River to the lagoon, increasing at the end of the rainy period. In order to attain an effective mixing, it has been recommended that the freshwater from the Ceyhan River should be given from three different points to the lagoon (Fig. 5b). Also, we suggested that the old riverbed of the Ceyhan River, which is located at the northwest of the lagoon, is a suitable flow path instead of constructing a new one. At the end of our study, a restoration plan aiming for freshwater supply from the Ceyhan River to the Yelkoma Lagoon was proposed on December 2008. With the collaboration of the Nature Research Society, General Directorate of Nature Conservation and National Parks (DKMP), General Directorate of State Hydraulic Works (DSİ), and local fishery cooperative, the improvement of the old riverbed was started at the end of December 2008. After the reclamation of the old riverbed, calculated freshwater has been conveyed to the lagoon since March 2009 and hydrologic restoration of the Yelkoma Lagoon wetland was successfully applied according to the proposed plan. Two major consequences have been observed after the implementation of the restoration plan. First, the reed growth has been noted around freshwater input points at the Yelkoma Lagoon (Fig. 6b). Second, after the application of the proposed plan, salinity of the lagoon water was measured as ~28 ppt on April 2009, which is a very close approximation to the estimated value (30 ppt) for April (Table 3). Thus, these results were interpreted as having achieved dilution of hypersaline lagoon waters. The presence of nutrient supply to the lagoon by the freshwater from the Ceyhan River is also supported by the reeds’ growth around the input points. Since then, the Yelkoma Lagoon started to regain its wetland ecosystem functions, and 240 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FIGURE 6 - (a) Before and (b) after freshwater input to Yelkoma Lagoon. TABLE 3 - The observed and estimated salinity values at Yelkoma Lagoon and the amount of freshwater required for lowering salinity. Jan Observed salinity (ppt) Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec 41.3 29.7 39.6 42.3 56.8 66.4 75.9 91.5 100.4 109.3 95.1 37.5 Estimated salinity (ppt) 20.0 20.0 25.0 30.0 35.0 38.0 38.0 38.0 38.0 38.0 38.0 20.0 3 Amount of freshwater (m /s) 1.431 0.199 0.858 0.729 1.419 2.140 3.042 3.411 3.555 3.698 2.519 0.605 positive developments have been observed in terms of ecology and productivity. 4. CONCLUSION This paper describes restoration of the Yelkoma Lagoon, at the eastern Mediterranean shore, which was disconnected from the Ceyhan River by a large flood in 1932 that formed the current stream-bed of the river. Also construction of a series of hydraulic structures has restricted natural flow of the Ceyhan River since 1971. Both of these natural and anthropogenic impacts led to alteration of natural conditions, such as hypersaline waters, less nutrient input, etc., which dominate the Yelkoma Lagoon. This is a first study about restoration of a deteriorated coastal wetland by freshwater supply in Turkey. Mixing calculations were made by End-Member Mixing Analysis (EMMA) to achieve natural salinity conditions in the Yelkoma Lagoon. The calculated freshwater was launched in March 2009, and hydrologic restoration of the Yelkoma Lagoon wetland was successfully applied. After supplying freshwater to the Yelkoma Lagoon, reed growth has been observed around freshwater input points and the salinity of the lagoon water was measured as 28 ppt in April 2009. Thus, this situation was interpreted as dilution of lagoon waters and nutrient input, and the lagoon started to regain its wetland ecosystem functions. The overall results of this study indicate that the Yelkoma Lagoon is a sensitive ecosystem to any artificial impact. Therefore, further hydrological studies and long-term hydrochemical monitoring programs are suggested for the Yelkoma Lagoon. 241 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin ACKNOWLEDGEMENTS This study is part of a project entitled “Management Plan of Yumurtalık Lagoon" conducted by the Turkish Nature Research Society on behalf of the General Directorate of Nature Conservation and National Parks (DKMP) and financially supported by Baku-Tbilisi-Ceyhan (BTC) Pipeline Company. The authors also thank Mr. Nazmi Tekelioğlu (Çukurova University) for providing the data. We also thank anonymous reviewers for their comments and suggestions, which improved the manuscript. REFERENCES Brinson, M., Lugo, A., and Brown, S. (1981) Primary productivity, decomposition and consumer activity in freshwater wetlands. Ann. Rev. Ecol. Evol. System, 12, 123–161. [2] Turner, K. (1991) Economics and wetland management. Ambio, 20, 59-63. [3] Whiting, G. and Chanton, J. (2001) Greenhouse carbon balance of wetlands: methane emission versus carbon sequestration, Tellus B, 53, 521–528. [4] LOICZ, 2005. Landeocean interactions in the coastal zone; science plan and implementation strategy. In: Kremer, H.H., Le Tissier, M.D.A., Burbridge, P.R., Talaue-McManus, L., Rabalais, N.N., Parslow, J., Crossland, C.J., Young, W. (Eds.), IGBP Report 51/IHDP Report 18, 68 pp. [5] Mitsch, W.J. and Gosselink, J.G. (2008) Wetlands, John Wiley th & Sons, 4 Edition, New York. [6] Mudge, S.M., Icely, J.D. and Newton, A. (2008) Residence time in a hypersaline lagoon: Using salinity as a tracer. Estuarine, Coastal and Shelf Science, 77, 278-284. [7] [8] [9] [14] RAMSAR (2013) The annotated Ramsar list of wetlands of international importance: Turkey. http://www.ramsar.org/cda/en/ramsar-pubs-annolist-annotated-ramsar15840/main/ramsar/1-30-168%5E15840_4000_0__ [last accessed December 4, 2013]. [15] World Wildlife Fund (2011) Protection of Wetlands of Turkey - Problems and Solutions. http://awsassets.wwftr.panda.org/downloads/2subat_bilginotu_1.pdf [in Turkish]. [16] Tekelioğlu, N., Çevik, F., Gökçe, G., Erçen, Z., Derici, O. B. and Erdoğan, E. (2009) Development of a modern fish barriers based on some parameters determined using the water and mud samples from Yelkoma Lagoon (KYF 2/9). UNDPBTC/KYF, Adana, 41 p [in Turkish]. The authors have declared no conflict of interest. [1] [13] Miller, J.M., Pietrafesa, L.J. and Smith, N.P. (1990) Principles of Hydraulic Management of Coastal Lagoons for Aquaculture and Fisheries. FAO Fisheries Technical Papers no. 314. Filho1, A.T.R., Furian, S., Victoria, R.L., Mascre, C., Valles, V. and Barbiero, L. (2012) Hydrochemical variability at the Upper Paraguay Basin and Pantanal wetland. Hydrol. Earth Syst. Sci., 16, 2723–2737. Newton, A. and Mudge, S.M. (2003). Temperature and salinity regimes in a shallow, mesotidal lagoon, the Ria Formosa, Portugal. Estuarine, Coastal and Shelf Science, 57, 73-85. Tett, P., Gilpin, L., Svendsen, H., Erlandsson, C.P., Larsson, U., Kratzer, S., Fouilland, E., Janzen, C., Lee, J., Grenz, C., Newton, A., Ferreira, J.G., Fernandes, T. and Scory, S. (2003) Eutrophication and some European waters of restricted exchange. Continental Shelf Research 23, 1635-1671. [10] Diamantopouloua, E., Dassenakisa, M., Kastritisa, A., Tomarab, V., Paraskevopouloua, V. and Poulosb, S. (2008) Seasonal fluctuations of nutrients in a hypersaline Mediterranean lagoon. Desalination, 224, 271–279. [11] Saunders,K.M., Mcminn, A., Roberts, D., Hodgson, D.A. and Heijnis, H. (2007) Recent human-induced salinity changes in Ramsar-listed Orielton Lagoon, south-east Tasmania, Australia: a new approach for coastal lagoon conservation and management. Aquatic Conserv: Mar. Freshw. Ecosyst., 17, 5170. [12] Kjerfve, B. (1994) Coastal lagoons. In Coastal Lagoon Processes, Kjerfve, B (ed.). Oceanography Series no. 60, Elsevier Science Publishers: Amsterdam; 1–8. 242 [17] Mulholland, P.J. (1993) Hydrometric and stream chemistry evidence of three storm flowpaths in Walker Branch Watershed. Journal of Hydrolology, 151(2-4), 291-316. [18] Petz, T.R. and Faure, G. (1997) Mixing of water in streams: Big Walnut Creek and its tributaries, Ohio. Ohio Journal of Science, 97(5), 113-115. [19] Tardy, Y., Bustillo, V. and Boeglin, J.L. (2004). Geochemistry applied to the watershed survey: hydrograph separation, erosion and soil dynamics. A case study: the basin of the Niger River, Africa. Applied Geochemistry, 19(4), 469-518. [20] Lieberman, J, Vulava, V, and Callahan, T. (2008) Application of geochemical end-member mixing analysis to delineate water sources to a forested riparian wetland. Southeastern Section, 57th Annual Meeting, Paper No: 31-20, April 10-11, 2008. [21] Vulava, V.M., Garrett, C.G., Ginn, C.L. and Callahan, T.J. (2008) Application of geochemical end-member mixing analysis to delineate water sources in a lowland watershed. Proceedings of the 2008 South Carolina Water Resources Conference, October 14-15, 2008. [22] Şensoy S, Demircan M, Ulupınar U. and Balta I. (2008) Climate of Turkey. State Meteorological Organization of Turkey (DMI); http://www.dmi.gov.tr/files/en-US/climateofturkey.pdf [last accessed December 4, 2013]. [23] Erdem, O. and Saraç, B. (2007) Management Plan of Yumurtalık Lagoon. General Directorate of Nature Conservation and National Parks (DKMP), Ankara, 208 p [in Turkish]. [24] ENCON (1999) Biological and ecological research project of wetlands of international importance - Sub-project II. General Directorate of Nature Conservation and National Parks (DKMP), Ankara, 529 p [in Turkish]. [25] Pinardi, N., Allen, I., Demirov, E., DeMey, P., Korres, G., Lascaratos, A., Le Traon, P.Y., Maillard, C., Manzella, G. and Tziavos, C. (2003) The Mediterranean Ocean forecasting system: first phase of implementation (1998–2001). Annales Geophysicae, 21, 3-20 pp. [26] Apello, C.A.J. and Postma, D. (2005) Geochemistry, Groundwater and Pollution. Balkema Publishers, Amsterdam, 649 p. [27] Greenway, H. and Munns, R. (1980) Mechanisms of salt tolerance in nonhalophytes. Ann. Rev. Plant Physiol., 31, 149190. [28] Kozlowski, T.T. (1984) Plant responses to flooding of soil. BioSci., 34, 162-167. [29] Gray, L.J. (1993) Response of insectivorous birds to emerging aquatic insects in riparian habitats of a tallgrass prairie stream. American Midland Naturalist, 129, 288-300. © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin [30] Shentsis, I. and Rosenthal, E. (2003) Recharge of aquifers by flood events in an arid region. Hydrological Processes, 17, 695-712. [31] Environmental Protection Agency (2013) Connectivity of Streams and Wetlands to Downstream Waters: A Review and Synthesis of the Scientific Evidence. EPA/600/R-11/098B. [32] Day, J., Ibáñez, C., Scarton, F., Pont, D., Hensel, P., Day, J. and Lane, R. (2011) Sustainability of Mediterranean deltaic and lagoon wetlands with sea-level rise: the importance of river input. Estuaries and Coasts, 34(3), 483-493. [33] Konstantinos, A.K., Nicolaidou, A. and Reizopoulou, S. (2001) Temporal variations of nutrients, chlorophyll a and particulate matter in three coastal lagoons of Amvrakikos Gulf (Ionian Sea, Greece). Marine Ecology, 22, 201-213. [34] Ingold, A. And Havill, D.C. (1984) The influence of sulphide on the distribution of higher plants in salt marshes. Journal Ecology, 72, 1043-1054. [35] Flynn, K.M., McKee, K.L. and Mendelssohn, I.A. (1995) Recovery of freshwater marsh vegetation after a saltwater intrusion event. Oecologia, 103, 63-72. [36] Baldwin, A.H. and Mendelssohn, I.A. (1998) Effects of salinity and water level on coastal marshes: an experimental test of disturbance as a catalyst for vegetation change. Aquatic Botany, 61, 255-268. Received: April 10, 2014 Revised: June 12, 2014 Accepted: June 25, 2014 CORRESPONDING AUTHOR Harun AYDIN Yüzüncü Yıl University Department of Environmental Engineering 65080, Tuşba, Van TURKEY E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 235 - 243 243 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin DETERMINING NATURAL AND CULTURAL CHANGES AROUND WETLANDS BY MEANS OF REMOTE SENSING TECHNIQUES: A CASE STUDY IN EGIRDIR LAKE Namık Kemal Sonmez1,*, Işın Onur2 and Sevda Altunbaş3 2 1 Akdeniz University, Faculty of Science, Space Science and Technology Department; 07059 Antalya, Turkey Akdeniz University, Faculty of Agriculture, Farm Structures and Irrigation Department; 07059 Antalya, Turkey 3 Akdeniz University, Remote Sensing Research and Application Center, 07059 Antalya, Turkey Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey ABSTRACT In wetlands, the land use/cover is under pressure of natural and human impacts and studies focus on changes of these areas are important. Turkey’s wetlands are under threat due to gain land for agricultural production. Not only restrict the wildlife habitat, causes pollution due to usage of herbicides, pesticides and fertilizers. Eğirdir Lake area and its surrounding in particular has been an important settlement region in the northeast Mediterranean. After 1960’s, the distinctive usage of the lake for agricultural irrigation increased the negative impact on it. The aim of this study is to examine the degree of the impact using Landsat satellite data dated 1987, 2002 and 2006, which are acquired and processed with remote sensing science and technology. Supervised classification was used in the research and land use/cover changes are presented. Class numbers and character names of the classes in the study area follow the CORINE methodology. According to the research results, the lake area decreased from 45,212 ha to 44,974 ha between 1987 to 2002 and then increased to 45,226 in 2006. With respect to specific cover types, the spread of Marshy and Reed Bed cover type expands from 1,345 ha to 2,903 ha between 1987 and 2002 and decreased to 2,625 ha in 2006. The Forest areas in the region decreased from 48,391 ha to 37,966 ha over the approximately 20 year study period. Furthermore scattered spread of Open Areas with Little or No Vegetation increased from 10,677 to 14,927 ha between 1987 to 2006. Perennial production patterns determined as Permanent Crops increased from 5,892 ha to 6,090 ha. Another land use class is annual agricultural production named as Arable Lands according to CORINE methodology, which expands from 4259 ha to 8585 ha. between 1987 to 2006. According to research findings, Urban Fabric land use class around Eğirdir Lake is determined to increase 1,066 ha to 1,422 ha. According to research results, some land use around Eğirdir Lake has * Corresponding author been detected as not appropriate, especially Forest land types are decreased significantly and convert to agricultural lands and urban structures. An increase in Marshy and Reed Bed cover is detected in approximately 20 years. KEYWORDS: Remote Sensing, Wetland, Supervised Classification, Monitoring, CORINE 1. INTRODUCTION Wetlands are the most important ecosystems of the world and like other ecosystems, they are subject to significant changes over time. These changes can be attributed to either natural or human factors. The negative effects caused by humans on wetlands mainly started during the last quarter of the twentieth century and continues until today. Xie et al. [1] stated that with decreasing water resources and increasing population pressures, dam construction, pollution, resource overuse, biologic influx, drainage, climate change and some inappropriate policies of governments, wetlands are decreasing in the world. Serious problems arise in and around wetlands as they are for the purpose of agricultural production. Other problems include being buried, burning of organic matter, salinization, drought, and deficiency of physical properties of the soil. Owing to these conditions increased the research on qualitative and quantitative changes and made them become more important [2]. Eğirdir Lake, Turkey’s second biggest fresh water resource and its surrounding areas form one of the most important wetland areas in Anatolia for centuries. The lake provides water for drinking by people living around the lake and habitat for animals like fishes and crayfishes which are used for commercial purposes [3]. Increase of the urban land cover in the region, insufficiency of infrastructure, overuse of herbicides, pesticides and fertilizers, as well as over hunting constitute some of the important negative changes in the lake ecology in recent years. These 244 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin changes and transformations occurred due to misuse of lands also caused important problems for people living in the region. For this reason, it is important to determine the land use types, as well as to detect their change over time. Monitoring and mediating the negative consequences of land use and land cover while sustaining the production of essential resources has therefore become a major priority of researchers and policymakers around the world [4]. In natural sciences, to examine land cover’s qualitative and quantitative changes, remote sensing science and technology has been used for many years [5]. Recently, land use/ cover change detection has become one of the most popular topics in remote sensing research and development [6]. Remote Sensing (RS) technologies have been used effectively in many different applications concerning land- use and land-cover change. This system is used for more detailed analysis of collected land-use information. This technology allows relatively accurate, fast and easy acquisition, analysis, and production of data on land cover and land use [7]. Studies carried out by using remote sensing science and technology; make it possible to monitor land use and land cover changes for long periods. Traditionally, Landsat MSS, Landsat TM, and SPOT satellite systems have been used to study wetlands [8]. As noted by researchers, the selection of an appropriate change detection algorithm is critical [9]. Supervised and unsupervised classification methods are the most commonly used digital classification to map wetlands. Rani et al. [10] carried out Wetland Assessment and Monitoring Using Image Processing Techniques for Ranchi city of Jharkhand state for the years 1996-2004. They reported that, the signatures of wetlands and associated land features were identified in an unsupervised classification approach based on their DN value using satellite data. They also found that there were drastic changes between 1996 and 2004. These studies carried out by means of satellite data, increases the effect of examining the change in water science and wetlands via remote sensing [11, 12]. In this study, land use class levels were determined according to the Coordination of Information on the Environment (CORINE) methodology [13]. One of the main purposes of this methodology is to standardize studies about environment and environmental change and it has been used over the years at different levels (international, within the European Union, national and regional) [14]. The CORINE system has a hierarchical level system ranging from one to three. It was established by the European Union as a land cover/use definition hierarchy. Sonmez and Sarı [15] carried out a study with remote sensing and GIS integration with visual analyses techniques. Researchers used land classification process with CORINE (Coordination of Information on the Environment) methodology [13]. This study is carried out by using remote sensing techniques on Landsat TM images of 1987, 2002 and 2006 for Eğirdir Lake wetland. Land cover and land use conditions were achieved by supervised classification technique and comparative analysis were made for each study period. 2. MATERIAL AND METHODS 2.1 Data The study aims to detect land cover and land use changes with Landsat satellite images by Maximum likelihood supervised classification in Eğirdir Lake district. In addition high resolution IKONOS satellite images, land use plans and 1:25 000 scaled topographic maps were used as ancillary data. 2.2 Study Area Eğirdir Lake and its surrounding area lies between the Mediterranean and terrestrial climate passage zone. The lake, which is 917 m higher than sea level, has an average depth of 10-12 m. and provides benefit for fisheries, agricultural irrigation, and for energy production. Besides sporting activities like climbing, wind surfing, cycling, it is also used for health tourism [16]. In the lake-basin, mountains are partly covered with forests, horticulture and other agricultural activities occur densely on plains. Lands surrounding the lake belong to the government, individuals and the municipality. Eğirdir Lake is designated on the stands in Wetlands List which has an international importance. This study, carried out in lake-district of Isparta, encompasses Eğirdir Lake and an adjacent 5 km surrounding it. The region is located between 37008’58” and 36041’08” north latitudes and 30018’31” and 30058’20” east longitudes and encompasses an area of 117000 ha. (Figure 1). 2.3 Methods 2.3.1 Determining Land Use Types and Levels Determining Land Use Types and Levels were conducted in several consecutive phases. Initially, satellite data were pre-processed. The pre-processing methods performed in this study include image enhancement and georeferencing. In this phase, histogram equalization, standard deviation stretch and necessary brightness/contrast adjustments were performed on each image in order to facilitate image interpretation. Furthermore, satellite images and aerial photographs georeferenced using topographic maps and resampled according to the second order polynomial transformation method and the frames of the data were mosaicked. In the second stages, studies were carried out in a region encompassesing important wetlands in the lake district. In this scope CORINE methodology was used as a base to determine types of land cover and land use. This methodology relies on the principle of generating land use classes hierarchically (from one to three) [13]. CORINE legend, which allows a minimum mapping unit of 1.56 ha at 1/25000 scale to be determined, was used as a base [14]. Assessments made in the region and resolution of Landsat satellite image is taken into consideration and according to CORINE hierarchical structure, distinguishable land use classes are determined and presented in Table 1. 245 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FIGURE 1 - Study Area Change detection and monitoring involve the use of multi-date images to evaluate differences in land use/ cover due to environmental conditions and human actions between the acquisition dates of images. Several authors have attempted to observe better and define change features using remotely sensed data. As noted by researchers, the selection of an appropriate change detection algorithm is critical. TABLE 1 - Land Cover Classes Level 1 Level 2 1. Artificial surfaces 1.1. Urban fabric 2. Agricultural areas 2.1. Permanent crops 2.2. Arable land 3. Forests and semi-natural areas 3.1. Forests 4. Water bodies 4.1. Inland waters 4.2. Marshy and reed bed cover 3.2. Open spaces with little or no vegetation 3. RESULTS AND DISCUSSIONS 2.3.2 Classification of the Study Area In the supervised classification process, first, pixel values are analyzed and statistical properties of the classes are determined. Then, samples of the classes are prepared and with the help of their digital properties, all images are classified. Sample pixels are collected from homogenous areas for every thematic class to form control pixels. Statistical information (mean, standard deviation, covariance matrix etc.) is formed primarily for these sets. Then, all pixels are examined statistically and every pixel is registered to the nearest control area that shows nearest statistical properties. Success of the supervised classification is mostly relies on the quality of the control set. Minimum Distance and Maximum Likelihood are most used supervised classification methods. Maximum likelihood method is used in this study. In this method, statistical concepts like mean vector, standard deviation, and covariance are used. When chosen bands are assessed, we detect which control class is similar to spectral model in which ratio. Similarity is mostly determined as percentage. Pixel is registered to a class that shows maximum similarity [17]. In the scope of remote sensing science and technology, classification results of remote sensing images are given in Figure 2. As can be seen in the figure, significant changes have occurred around wetlands. Supervised classification analyze results of three different years are presented in Figure 2. According to the classification results, urban fabric around the lake has spread from 1066 ha to 1422 ha between 1987 and 2006. In recent years, researchers have reported an increase in settlements around the lake [18]. Data obtained from Turkish Statistical Institute supports this finding. In addition to the regional enlargement, there has been a significant decrease in population density ac- cording to the results of census. Researchers reported that, due to the areal enlargement, there has been a decrease in population originating from migration [19]. According to the result of classification, lands having qualification of Permanent Crops which mainly has orchards were enlarged from 5892 ha to 6090 ha. Annual arable lands are detected between 1987 and 2006 increased from 4259 ha to 8585 ha. Hence there has been no industry 246 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin FIGURE 2 - Land use classes for years 1987, 2002 and 2006 and decrease in the fishery sector in years, the tendency of local people is on orchard and vegetable cultivation. In recent years, irrigated agriculture practices lead to the transformation of the fallow lands to agricultural production lands and there has been serious areal increase in vegetable cultivation. According to Balik et al. [20] dramatic changes have occurred in the lake in the past 50 years. Majority of the cover types in the region is Forested Areas. According to the results, these areas are decreased 48391 ha to 37966 ha between 1987 to 2006. In addition, Open Areas with Little or No Vegetation is enlarged from 10677 to 14927 ha between 1987 to 2006. Thus, forested areas, which have ecologically high ecosystem sensitivity, decreased due to human activities or natural pressure. In some regions, it is damaged and the land become barren and that can also be clearly seen from classified images. As a matter of fact, while Forested Lands are decreased Open Areas with Little or No Vegetation Lands are enlarged. In addition, the surrounding of the study area is mountainous and having high slope, has importantly rise the erosion risk. Erol [21] reported that Forest ecosystems are being rapidly and directly transformed by the land uses of the expanding human populations and economies. According to researcher, some forest sites in the watershed of Egirdir Lake have degraded. Eğirdir lake is one of the very important wetlands in Turkey and sheltering extremely important living things. Between 1987-2002 it has decreased from 45212 ha to 44974 ha and in 2006 it increased back to 45226 ha. Increase and decrease in the lake area also affected reed beds. Thus, Marshy and reed bed cover around the lake increased from 1345 ha to 2903 ha between 1987 to 2002 with in- verse ratio with the lake’s area decreased to 2625 ha in 2006 (Table 2). TABLE 2 - Land use results and areal extends Land Cover Classes Open spaces with little or no vegetation Forests Permanent Crops Arable land Urban fabric Marsh and reed bed cover Inland waters Total 1987 (ha) 2002 (ha) 2006 (ha) 10677 11153 14928 48391 5892 4260 1066 1346 45213 116845 42535 5970 7990 1319 2903 44975 116845 37966 6091 8585 1423 2625 45227 116845 4. CONCLUSIONS According to the study results, an important changes around Eğirdir Lake has been detected. The Lake that covers 39% of the study area, has important wetland property and has no significant change between 1987 to 2006. In addition, several researchers have stated that the lake water is used for energy production and agricultural irrigation. Thus, the lake water levels decreased in years and thereby negatively affected the lake’s ecological balance. Nowadays despite the water usage increases, lake water level remains stable due to the expansion valve. Researchers conducted by local and national agencies in study area shows that lake water is polluted with chemical herbicides, pesticides and fertilizers and eutrophication has started to develop. This phenomenon is also detected with 247 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin 1987(%) 2002(%) 2006(%) OpSp : Open spaces with little or no vegetation, For: Forests, PerC: Permanent Crops, ArbL: Arable land, UrbF: Urban fabric, MrsR: Marsh and reed bed cover, InlW: Inland waters FIGURE 3 - Land cover changes classification process. An important determined in the duration of 1987 to 2006 in Arable Land in this study. These areas correspond to 4% slice of the research area in 1987 and doubled in 2006 with 7%. The study area includes an important wetland, and an increase in Arable land has a negative effect in region’s economy (Figure 3). Another land cover change in the region is the decrease in forest cover (41% in 1987 decreasing to 32% in 2006). This finding shows that forests were transformed to Open Areas with Little or No Vegetation. According to research results, increase in Open Spaces with Little or No Vegetation is described as decrease in Forests. As a result, changes and transformations occurred in wetlands and its surrounding has to be done with plans which are susceptible to environment and ecology. Otherwise this area’s value will be lost non-recyclable and there will arise important environmental problems. ACKNOWLEDGEMENTS Authors would like to thank to the Scientific Studies Management Unit of Akdeniz University in Antalya, Turkey. The authors have declared no conflict of interest. [2] Baktır, I. and Sarı, M. (2002) Lake Avlan and Its Influences on Ecological Balance and Socio-Economic Status of Elmalı Country. Environmental Problems of The mediterranean Regıon EPMR-2002 International Conferance. 12-15 April 2002 NEU Nicosia-Northern Cyprus. [3] Altunbas, S. (2008) Eğirdir Gölü Yönetim Planı (2008-2012). Lake Management Plan Series: 1. Isparta. ISBN 978-975-585956-9. [4]. Ellis, E. and Pontius, R. (2007) Land-use and land-cover change. In Encyclopedia of Earth. http://www.eoearth.org/article/land-use_and_land-cover_change (14.09.2010).) [5]. Chou, T.Y., Lei, T.C., Wan, S., Yang, L.S. (2005) Spatial knowledge databases as applied to the detection of changes in urban land use. International Journal of Remote Sensing, 26, 3047–3068. [6]. Zhang, Y., Burbridge S. (2003) A neural network based approach to detecting urban land cover changes using Land- sat TM and IKONOS. Proceedings of the 2nd IEEE GRSS/ ISPRS Joint Workshop on Data Fusion and Remote Sensing over Urban Areas Imagery, Berlin, Germany. 157-161. [7]. Thongmanivong, S. (1999) Land use changes in the upper ca river basin, xiengkhuang provinces, Lao PDR 1995-97. Application of Resource Information Technologies (GIS/ GPS/ RS) in Forest Land & Resources Management Workshop. October 18-20, Hanoi, Vietnam. [8]. Shepherd, I., Wilkinson, G., Thompson, J. (1999) Monitoring surface water storage in the north Kent Marshes using Landsat TM Images, International Journal of Remote Sensing, 21:9, 1843-1865. [9] REFERENCES [1] Xie, Z., Xuegong, X., Lei, Y. (2010) Analzing Qalitative and Quantitative Changes in Coastal Wetland Associated to the Effects of Natural and Anthropogenic Factors in a part of Tianjin, China. Estuarine, Coastal and Shelf Science.86, 379-386. 248 Sonmez, N.K. and Onur, I. (2012) Monitoring of Land Use and land cover changes by using fuzzy supervised classification method: A case study of Antalya, Turkey.Journal of Food, agriculture &Environment. 10, 963-967. [10]. Rani, M., Kumar, P., Yadav, M., Hooda, R.S. (2011) Wetland Assessment and Monitoring Using Image Processing Techniques: A Case Study of Ranchi, India. Journal of Geographic Information System, 3, 345-350 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin [11] Seto, K.C., Woodcock, C.E., Song, C., Huang, X. (2002) Monitoring Land-Use Change in The Pearl River Delta Using Landsat TM. International Jornal of Remote Sensing 23, 19852004. [12] Vela, A., Pascualini, V., Djelouli, A., Langar,H., Pergent, G., Pergent_Martini, C., Ferrat, L., Ridha, M., Djabou, H. (2008) Use of Spot 5 and Ikonos Imagery for mapping Biocenoses In a Tunisian Coastal Lagoon (Mediterranean Sea). Estuarine, Coastal and Shelf Science 79, 591-598. [13] Ecsc-Eec-Eaec (1993) CORINE land cover technical guide ISBN 92-826-2578-8 ©ECSC - EEC - EAEC, Brussels, Belgium [14] Heymann, Y., Steenmans, C., Crosille, G. And Bossard, M. (1994) Corine Land Cover Technical Guide (Luxembourg: Office for Offical Publications of the European Communities). [15] Sonmez, N.K. and Sarı, M. (2007) Monitoring Of Land Use Changes In The West Mediterranean Region Of Turkey: A Case Study On Antalya-Turkey Coast. Fresenius Environmental Bulletin. 16, 1325-1330. [16] Basayigit, L., Dinc, U., (2010) Prediction of Soil Loss in Lake Watershed Using GIS: A Case Study of Egirdir Lake, Turkey. Natural&Environmetal Sciences. 1, 1-11. [17] Onur, I., (2007) Monitoring and Analysing of Land Use and Land Cover Change by Means of Remote Sensing and Geographic Information Systems: A Case Study of Antalya-Kemer. MSc Thesis, Istanbul Technical University, Turkey. [18] Bulut, C., Atay, R., Uysal, K. (2009) Seasonal Variation of Physico-Chemical Parameters in Egirdir Lake and It’s Limnological Evaluations. Anadolu University Journal of Science and Technology. 10:2, 447-454. [19] Alkan, H., Korkmaz, M., Altunbaş, S. (2009) Interactions Between Local People and Lakes: An Example From Turkey. Journal of Environmental Engineering and Lanscape Management, 3, 17. [20] Balık, I., Cubuk, H., Cınar, S. (2008) Spatial and Seasonal Variations in Catch of Silver Crucian, Carp Carassius gibelio (Bloch, 1782) in Lake Eğirdir, Turkey. Turkish Journal of Fisheries and Aquatic Sciences. 8:347-353. [21] Erol, A. (2012) Climate Change Assessments for Lakes Region of Turkey. Ecologia Balkanica. 4:1, 87-93. Received: April 03, 2014 Revised: May 12, 2014 Accepted: June 12, 2014 CORRESPONDING AUTHOR Namık Kemal SONMEZ Akdeniz University Faculty of Science Space Science and Technology Department 07059 Antalya TURKEY Phone: +90 242 3102285 Fax: +90 242 2276581 E-mail: [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 244 – 249 249 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin ECOTOURISM, PROTECTED AREAS AND NATURE CONSERVATION Nihan Yenilmez Arpa1,* and Yusuf Ceran2 1 Ministry of Forestry and Water Affairs General Directorate of Nature Conservation and National Parks, National Parks Department-Division Director, Ankara, Turkey 2 Ministry of Forestry and Water Affairs General Directorate of Nature Conservation and National Parks, Nature Conservation Department-Department Director Ankara, Turkey Presented at the 7th International Symposium on Ecology and Environmental Problems (ISEEP2013), December 18-21, 2013, Antalya, Turkey ABSTRACT 1. INTRODUCTION The authors of this paper have conducted a series of interviews with local administrative staff through questionnaires, one to one meetings with visitors and national parks managers, and field studies to assess the general state of ecotourism in Turkey’s national parks. The existing official data on national parks, ecotourism and visitor management were also used in the assessment process. Results indicate that national parks of Turkey have unique values to support ecotourism. However, the authors believe that the willingness for ecotourism is high yet the know-how is low amongst the park managers and local people. These stakeholders have minimal experience on ecotourism and the infrastructure to support development of ecotourism is also limited. Currently, the visitors of the protected areas are mainly domestic, and they are interested more in recreational activities in the national parks rather than in their natural-cultural values. Approximately only 5 percent of the visitors are naturalists and interested in the nature and ecotourism activities such as trekking, bird watching, biodiversity observation and conservation, and camping. This study is focusing if ecotourism could be supported by Plan, Policy and Engagement of the Target Stakeholders to certainly perform as an important tool for biodiversity conservation. Besides conservation of the biodiversity ecotourism could contribute to the economic development and strengthens the institutional capacity of local people and preserves the local culture and traditional lifestyle in the protected areas. KEYWORDS: ecotourism, protected areas, assessment, biodiversity conservation, national parks * Corresponding author “The concept of Ecological Tourism or popularly known as Ecotourism is a new dimension of the global tourism industry in which selected sites and locations and sometimes entire geographical zones are preserved for people to visit and appreciate them in their pristine natural beauty” [1]. Ecotourism is defined as "responsible travel to natural areas that conserves the environment and improves the well-being of local people" [2]. It supports biological conservation, increases the local development and offers interpretation opportunities for both visitors and local community. Ecotourism could provide the economic resources necessary for the preservation of the protected areas; however successful case studies are still rare in Turkey. Nature based tourism and ecotourism in protected areas is becoming a particularly important component of government policy in many countries. It is one of the most powerful tools for protecting the environment and natural resources and generating income for local communities in and around the protected areas [3]. The development of the ecotourism in Turkey started in 2000s, and over the years it has become a buzzword. The explosion of interest in ecotourism led to the emergence of a lively debate among academics, governmental institutions, non-governmental organizations and tourism industry regarding its merits and importance. Many ecotourism workshops, meetings and training activities were held during the past few years and many successful case studies of the existing ecotourism sites were presented. The Ministry of Culture and Tourism (MoCT) prepared a tourism strategy and ecotourism has been incorporated as an important segment of the strategy [4]. The Ministry of Forestry and Water Affairs (MoFWA) also identified eco-tourism as an important tool and focused to develop it in the protected areas [5]. In addition, a planning disposition has been developed by General Directorate of Nature Conservation and National Parks (GDoNCNP) to identify eco-tourism plan- 250 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin ning stages and planning approach [6]. Although there is some progress on ecotourism in the protected areas, the authors observe that there are still no definite results emerged from these efforts. On the other hand, the potential value of the protected areas in relation to ecotourism is still not known adequately in Turkey. In this study the existing attractions and activities in the national parks were reviewed to understand the current practice and the requirements for managing ecotourism successfully and increasing its positive effects. In the process, the attractions for ecotourism in the protected areas were identified as core (natural) and supporting (manmade). Core attractions include natural and/or cultural and heritage attractions, while supporting attractions are manmade infrastructures and materials [7]. Results indicate that most of the activities are spontaneous without specific planned and developed products and targeting the visitors. There has been not enough investment in advertising, researching the market and technologies serving ecotourism. On the other hand all kind of nature based activities that have been implemented in the protected areas are labeled as ecotourism. The major differences between ecotourism and nature-based tourism are not known by ecotourism business operators, protected areas manager and other stakeholders. 2. MATERIALS AND METHODS The main source of data for this study is gathered from “40 national parks” in Turkey which were declared under article 2873 of National Parks Law and managed by GDNCNP under the MoFWA. A list of Turkey’s national parks is given in Table 1. TABLE 1 - National Parks of Turkey No 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 Name YozgatÇamlığı Karatepe-Aslantaş Soğuksu ManyasKuşcenneti Uludağ Yedigöller DilekYarımadası-Büyük Menderes Deltası SpilDağı Kızıldağ GüllükDağı-Termessos KovadaGölü MunzurVadisi Beydağları GeliboluYarımadası Historical NP Köprülü Canyon Ilgaz Mountain Başkomutan Historical Göreme Historical Altındere Valley Boğazköy-Alacahöyük Nemrut Mountain Beyşehir Lake Kazdağı Altınbeşik Cave Hatilla Valley Kaçkar Mountains Karagöl-Sahara Aladağlar Marmaris Saklıkent Troya Historical NP. Honazdağı Küre Mountains Sarıkamış-Allahuekber Mountains Ağrı Mountain Gala Lake Sultan Sazlığı TekTek Mountains İğneadaLongos Forest Nenehatun Historical NP Space (ha) 267 4.145 1.187 17.058 13.024 1.623 27.598 6.867 55.106 6.700 6.551 42.674 31.018 33.439 35.719 1.118 40.948 9.614 4.648 2.600 13.827 86.855 20.935 1.147 16.944 52.970 3.251 55.064 29.206 1.643 13.517 9.429 37.753 22.519 88.014 6.087 24.357 19.335 3.155 387 848.119 http://www.milliparklar.gov.tr/mp/index.htm 2013 [8] 251 Declaration time 05.02.1958 29.05.1958 19.02.1959 22.07.1959 20.09.1961 29.04.1965 19.05.1966 22.04.1968 09.05.1966 03.11.1970 03.11.1970 21.12.1971 16.03.1971 22.11.1973 12.12.1973 02.06.1975 08.11.1981 25.11.1986 09.09.1987 21.09.1988 07.12.1988 11.01.1993 17.04.1994 31.08.1994 31.08.1994 31.08.1994 31.08.1994 21.04.1995 08.03.1996 06.06.1996 07.11.1996 21.04.1998 07.07.2000 19.10.2004 17.11.2004 05.03.2005 17.03.2006 29.05.2007 13.11.2007 06.06.2009 Province Yozgat Osmaniye Ankara Balıkesir Bursa Bolu Aydın Manisa Isparta Antalya Isparta Tunceli Antalya Çanakkale Antalya Kastamonu-Çankırı Afyonkarahisar-Kütahya-Uşak Nevşehir Trabzon Çorum Adıyaman-Malatya Konya Balıkesir Antalya Artvin Rize-Artvin Artvin Niğde-Adana-Kayseri Muğla Muğla-Antalya Çanakkale Denizli Kastamonu-Bartın Kars-Erzurum Ağrı-Iğdır Edirne Kayseri Şanlıurfa Kırklareli Erzurum © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 2 - Inventory sheet of ecotourism attractions in national parks. Name of the National Park Natural attractions Cultural Heritage Attractions Geological/ geomorphological features (valleys, plains, canyons, cliffs, caves, beaches, bays, etc.) Hydrological resources (rivers, lakes, springs, waterfalls etc.) Biological resources (flora, fauna) Detailed inventory of ecotourism attractions is crucial to understanding of ecotourism values and to managing visitors in the protected areas. Therefore, n inventory sheet and a questionnaire were used to survey visitors and park managers and note their opinions The inventory sheet has been adapted from Ceballos-Lascurain study [8] on inventory of ecotourism attraction. The sample inventory sheet is given in Table 2. The questionnaire included open ended questions that were used to identify visitor profile, ecotourism activities in the parks and to gauge visitor expectation on ecotourism. The main headlines were related to the profile of visitors, joining activities, needs and requirements. 3. RESULTS AND DISCUSSION The assessment of ecotourism attractions, activities and types of the visitors was focused on park managers and visitors. The results indicate that there are six types of visitors. The first group is domestic and picnic group who live in and around the protected areas. This group generally is not interested in the protected area and its values. They prefer to spend their time outside their living areas for pic- Archeological features Support Attractions and Physical Facilities Interpretive facilities and services Local folklore, traditional lifestyle Visitor center Historical and architectural landmarks Nature trails nic and recreation. The second group includes students and short time training groups who come from high schools, universities, the army and other organized groups. They visit the protected areas with their teachers, guides and leaders within their study tour program and they spend maximum a day in the protected areas. The third group consists of daily international visitors. They visit the protected areas as a part of their vacation. Their main program is in the hotels. They spend generally a day to join organized activities such as rafting, trekking, canoeing, jeep safari, etc. The fourth group includes domestic visitors who are naturalists and adventures. They enjoy being in nature, prefer trekking, camping, bird watching, wildlife observation, climbing and they enjoy consuming local foods and meals. They move with a small group by professional guides and they spend 3-5 days depending on the activities and program. The last group is international visitors who want to get benefit and enjoy of the nature and protected areas. The common properties of the visitors in the last two groups are experience, higher education, higher income bracket, middle age to elderly, ask and tell their friends and colleagues about trips and they enjoy spend time not closed areas but in nature. They would like to get familiar with local culture and traditional lifestyle. They are real ecotourists. TABLE 3 - Visitor profile for national parks of Turkey 1 Type of Visitors Domestic picnic group-family group Main interest Recreation and picnic To see main attractions of the national park. They join short term training on national park’s values. They are interested in adventure activities such as rafting, safari, canoeing, 2 Students and short time training group 3 International daily group 4 Domestic naturalist and adventure-ecotourists To join many of the natural activities such as trekking, camping, bird watching, wildlife observation, climbing, botanic tours 5 International visitors-trekkers and naturalists-ecotourists To join many of the natural activities such as trekking, camping, bird watching, wildlife observation, climbing, botanic tours 6 Volunteer and individual visitors Doing holiday with small budget and get experience with learning by doing. 252 General specifications They spend limited time in the national park. They live around the areas. Generally more than 20 students and/or staff are joining the activities. This travel is a part of the study visit for the group. They travel with their family and/or friends with a small group. They travel with a group who is interested in nature based activities. They are responsible travelers. They support conservation of natural values and social-cultural values together. They learn and they teach others. Many of the activities have been done with local people. Local knowledge and traditional lifestyle is important for them. They can spend time and money for the areas and local people. They travel with a group who is interested in nature based activities. They are responsible travelers. They support conservation of natural values and social-cultural values together. They learn and they teach others. Many of the activities have been done with local people. Local knowledge and traditional lifestyle is important for them. They can spend time and money for the areas and local people. They visit with local transports. One or two people trip together. They spend limited budget for their travel. © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin Protected areas visitor numbers 10.145.972 11.053.158 5.958.963 2.773.544 2009 2.203.229 2010 2011 2012 2013 FIGURE 2 - Visitor numbers of protected areas between 2009-2013 [8]. National Park visitor numbers 5.342.785 4.209.685 2.983.963 1.182.364 2009 1.067.743 2010 2011 2012 2013 FIGURE 3 - Visitor numbers of national parks between 2009-2013 [9]. The assessment process shows that there is another group that they generally want to live with the family, local houses and in the camping tents; and they would like to join daily activities in the village and farms. They are volunteers and travel alone and/or sometimes with two friends together. However, they do not prefer spending money for conservation of protected areas or for the local people. But this group is not the main interested group for protected areas. The visitor profile is given Table 3. The number of visitors of the protected areas (national parks, nature parks, natural monuments and nature reserve) between 2009 and 2013 are given in Figure 2 and 3. The other output of our analyses is the connection between ecotourism values and attractions. The attractions in the protected areas were divided into two categories: core attractions and supporting attractions [8]. At the same time main ecotourism activities were identified for each national park. The results related with ecotourism values and attractions for each national park are given in Table 4. The visitors who come to understand and spend valuable time in the national parks mainly enjoyed and were impressed by the unique and natural habitat, monumental mountains, amazing landscapes, charming waterfalls, rivers and natural beauties and living culture and living in the intact nature. Besides their enjoyment they want to see nature-friendly facilities such as visitor and interpretation centers, path network and boards, guiding services, cycle paths and renting cycle, information points and local level small business to eat, buy and accommodate. Good prepared maps, books, booklets and other informative publications are preferred by visitors. On the other hand they mentioned that they do not want to see too much roads and motor cars, buildings everywhere and recreational facilities and waste in the nature. 253 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin TABLE 4 - Values and activities of national parks of Turkey [9]. No Name Values Core attractions/values (Natural-Cultural heritage) Black pine forests and rare species of steppe ecosystem which are the latest remainders of natural old forests in Central Anatolia steppes Archeological features, The arts of Late Hittite, Roman and Byzantine periods, calabrian pine forests, oak forests, maquis groves and flora and fauna species of Mediterranean Region Pine forests, steppe ecosystems, black Walter, wildlife The fossils of trees known as stoned forest or silicified tree fossils and belonged to miocene age that is 15 million years ago 1 YozgatÇamlığı 2 Karatepe-Aslantaş 3 Soğuksu 4 Manyas Kuşcenneti Wetland, water birds, avifauna 5 Uludağ 6 Yedigöller Forest species especially abies species, Uluadağ,one of 6 sacred mountains called as Olympus in Anatolia, has a very rich habitat such as forest lands, maquis areas, peatlands, sub-alpine mors, alpine steeps and open areas Wetland, lakes (7 landslide lakes), mixed deciduous forest, aquaculture, wildlife 7 DilekYarımadası-Büyük Menderes Deltası 8 Spil Dağı 9 Kızıldağ 10 GüllükDağı-Termessos 11 Kovada Gölü 12 MunzurVadisi Scrub (natural and unweathered Mediterranean habitats), forests, sea mammals, aqua species, wildlife, flora-fauna, wetland-fish trap, sand dunes, hills, valleys, bays and canyons within its morphological structure,Panionion, the sacred meeting center of Ion city in 9th century BC, antique Thebai city, Ayayorgi Monastery and Karine, HagiosAntonios Monasteries and Zeus Cave, historical Doğanbey Village (Domatia) many endemic flora and fauna species. Pine forest, mountain, plant species, geomorphological structure, rich flora and fauna, endemic plant species, historical and mythological ruins Cedar and pine forests (oxygen-rich forests), mountain, flora-fauna species, Mediterranean Forest belt is located in the transition zone to the steppes of Central Anatolia Region, geological and morphological characteristics consisted of interesting calcereous and karstic geographical formations Archeological ad historical values, Mediterranean forest and shrub species, wild life (mountain goat), rich biological diversity, epic and geomorphological formation (Mecene Canyon) and Termessos antique city Wetland, lake, forest, Mediterranean forest species, bird species Wetland, lake, grassland, forest, river, endemic plant species and fauna species, rich vegetation wildlife 254 Activities Supporting attractions/values (man-made) Recreational facilities such as table, WC, car park,etc. Camping, trekking, photography/photo safari - Trekking, photo safari, Visitor center, trails, wildlife observation cottage, information and sign boards, recreational facilities such as table, WC, car park, etc. restaurants, ways, path network Visitor center, trails, bird watching tower information and sign boards Camping, trekking, photography/ photo safari, black walter observation Tourism infrastructures as hotels and bungalows, New visitor center, entrance point, ski center, recreational facilities such as table, WC, car park, etc. Bungalows, entrance points, guest houses, bungalows, recreational facilities such as table, WC, car park, etc. trails, boards Visitor centers, old ancient settlement (Eski Doğan Bey Köyü), natural marine, small fish houses, local pensions, visitor centers, entrance points, recreational facilities (especially for swimming), boards , trails photography/ Camping, trekking, photography/ photo safari, bird watching, other avifauna activities as bird banding, Camping, trekking, photography/ photo safari, kayaking, skiing, wildlife observation Camping, trekking, photography/ photo safari (autumn colors), handline fishing, wildlife observation Camping, trekking, Birdwatching, photography/ photo safari, fishing, trekking, camping, diving, cycling, riding boat-cano, seal observation Recreation facilities, visitor center (still construction step), boards Camping, trekking, photography/ photo safari Trails, recreational bungalow, facilities, Camping, trekking, photography /photo safari, Visitor and training center, information and entrance point, boards, trails, Camping, trekking, photography/photo safari, wildlife observation Trails, viewpoints, recreational facilities such as table, WC, car park, etc. - Camping, trekking, bird watching, photography/photo safari Trekking, photography/photo safari © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin 13 Beydağları Mountains, dunes and sea side, forest, Mediterranean forest species, wildlife, cultural values as Çıralı. Olympus, Phaselis, Idyros antique cities , Beldibi Cave used 9 thousand years ago, rich biological diversity, epic and geomorphological formation, Göynük Canyon, defile folds of Kesmeboğazı and, step walls of Beldibi Channel and Tahtalı Mountain History on Çanakkale War. 14 Gelibolu Yarımadası Historical NP 15 Köprülü Canyon 16 Ilgaz Mountain 17 Başkomutan Historical 18 Göreme Historical Geological and geomorphological features. natural and cultural values 19 Altındere Valley 20 Boğazköy-Alacahöyük 21 Nemrut Mountain 22 Beyşehir Lake 23 Kazdağı 24 Altınbeşik Cave 25 Hatilla Valley 26 Kaçkar Mountains Rich vegetation, geological and geomorphological structures, Sümela Monastery and small monasteries in the region, European-Siberian phyto-geographical region origin plant species planted in humid warm and humid cold weather and unique samples of forest and alpine ecosystems, wildlife various historical arts in Hattuşaş (Boğazköy), the capital city of Hittites, one of the most oldest civilization of Anatolia, and surrounding of Hattuşaş, step vegetation Cultural and archeological ruins, Kommagene archeological ruins, Antiochos tumulus and huge monuments on Mount Nemrut and Eskikale, Yenikale, KarakuşTepe and Cendere Bridges, step vegetation and species, sunrise wetland areas, islands, forests, different ecosystems, cultural resource values, sundown oxygen store, endemic kazdağı abies, endemic species, waterfalls, valleys, sociacultural values and traditional festival Curtain travertines, stalactites, dickites and columns, Damlataş pools and cave pearls due to the hydrological conditions, Mediterranean forest ecosystem rich plant and wildlife diversity and variable landscaping values, Hatilla Valley and small valleys Rich biodiversity, flora and fauna species, glaciers of Pleistocene epoch, actual glaciation, glacial lakes, glacial valleys, cirque glaciers, moraines and rich fauna due to the land characteristics and variety Mediterranian species and maquis species, specific and unique cypress forest purely spread in the region, Selge Antique city and terrace fields, landscape values, historical bridge and settlements, valley formed with Köprü River, the geological structure formed of clay, sandstone and conglomerate rocks and karstic geographical formations, historical, archeological and cultural values, Pine forest, mountain, topographical structure, rich forest and vegetation, high wildlife potential, unique scenery, rich recreation resources, winter tourism opportunities and atmosphere useful for human health History on Independence War 255 Trails, viewpoints, Entrance points, Recreational facilities such as table, WC, car park, etc. tent camping, Camping, hiking, trekking, photography/ photo safari, canyoning Visitor centers, roads, cemeteries and martyrdoms, ınformation and simulation centres, recreational facilities such as table, WC, car park, etc. - Camping, trekking, photography/photo safari, visitation of historical places Ski facilities such as hotels, teleferic, accommodation units, entrance gate, ways, path network, boards, recreational facilities such as table, WC, car park, etc. Visitor centers, roads, cemeteries and martyrdoms, ınformation and simulation centres Paths, museum, visitor cente Camping, hiking, trekking Camping, hiking, trekking, photography/ photo safari, canyoning Trekking, photography/ photo safari, visitation of historical places Trekking, photography/ photo safari Entrance gate, recreational facilities, restaurants and buffets Camping, hiking, trekking, photography/photo safari, visitation to the historical places Entrance gate, paths and way, boards Trekking, photography/ photo safari, visitation to the historical places Entrance gate, paths and way, boards Trekking, raphy/photo safari, Way, bird watching tower Camping, trekking, bird watching, photography/ photo safari, boat tours, Camping, trekking, photography/ photo safari Visitor centre, local guide unit, entrance gate, boards, path network path Trekking, photo safari photog- photography/ Road, path Camping, hiking, trekking Entrance gate, visitor center, recreational facilities such as table, WC, car park, etc. Camping, climbing hiking, trekking, photography/photo safari © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin 27 Karagöl-Sahara lake, forest, plateau, rich landscape values and scenery integration, pin and abies mixed forests geological and geomorphological structures such as deep valleys, unique hills, step glacial rocks, caves and great canyons high plateaus; the unique characteristic examples of natural landscape, natural living spaces, plateaus and rich biological diversity unique landscape and natural, cultural and recreational values 1000-1100 m height with very high valley slopes cultural treasuries of east and west meet, feed with antique epics and reach at truth natural and cultural values 28 Aladağlar 29 Marmaris 30 Saklıkent 31 Troya Historical NP. 32 Honazdağı 33 Küre Mountains Canyons, channels, caves and dolines included in West Black Sea Karst Belt 34 S History on Sarıkamış Operation 35 Sarıkamış-AllahuekberMountains Ağrı Mountain 36 Gala Lake 37 Sultan Sazlığı 38 Tek Tek Mountains 39 İğneada Longos Forest 40 Nenehatun Historical NP Highest volcanic mountain of Turkey and Europe and the second highest volcanic mountain of the world and it also includes the greatest glacier of Turkey, step ecosystem and step species. Migrant birds visit between Europe and Africa, wetland, flora and fauna unique fresh water and salt water ecosystems in steppe ecosystem, rich biological diversity and two main migration routes used by migrant birds between Africa and Europe are intersected here and it is also one of the most important wetlands of the country Şuayb City (Özkent) ruins and caves, rock tombs of Assyria and Roma periods in Soğmatar (Yağmurlu) historical city, The castle ruins from Assyria period and Senem Caves abdstepe ecosystem species aka Lake, Mert Lake and marshy lands, Deniz Lake, Hamam Lake, Pedina Lake, deep spot forests and deciduous forests, Erikli Lake and surrounding marshy lands and deep spot forests in the north History bastions and historical and cultural values But other groups who are coming for outdoor activities such as recreation, picnic and adventure they want to see many of the facilities such as outdoor sport arenas, restaurants and barbeque facilities, good design roads and car parks, local product selling units, bungalows, other accommodation units in the national parks. 4. CONCLUSIONS For effective site management, visitor management and development ecotourism in the parks, the park systems require a sustainable tourism policy and strategy. It needs strong links between private tourism businesses, and protected area systems. Representatives from all sectors need Accommodation unit, recreational facilities such as table, WC, car park, etc. Entrance building, recreational facilities such as table, WC, car park, etc. paths, trails, camping Entrance gate, bards, trails Camping, trekking, photography/ photo safari Trekking, , photography/ photo safari Trekking, photography/ photo safari Camping, hiking, photography/ photo safari Entrance building, path network Entrance building, path network Entrance building, recreational facilities such as table, WC, car park, etc. paths, trails, Symbolic entrance gates, path network, accommodation opportunity, boards - recreational facilities such as table, WC, car park, etc. paths, trails, Visitor centre, boards - Camping, hiking, climbing, trekking, photography/photo safari Camping, hiking, photography/photo safari, canyoning, Trekking, photography/ photo safari trekking, photography/photo safari Trekking, bird watching, photography/photo safari, boat tours, Trekking, bird watching, photography/photo safari, boat tours, Trekking, /photo safari photography boards Camping, bird watching, photography/ photo safari, boat tours, Fence around the park, historical Photography, visit of the historical places to work together to develop sustainable forms of tourism for protected areas. It should integrate environmental concerns into national and regional tourism policies. Furthermore, sustainable nature-based tourism needs to be made a fundamental part of government policies relating to tourism. The strategy should be based on careful consultation and be approved and understood by local stakeholders. The quality of the natural environment is increasingly regarded as a major attraction by visitors. Protected areas in Turkey provide an amazingly rich resource for visitors. It is a strong force for conservation and sustainable development, generating income for parks and their local communities and awareness and support from visitors and within a wider public arena. 256 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin Ecotourism is experiencing rapid growth. There is a high level of expectation among ecotourism managers about what ecotourism can produce, but there is also a great deal of concern about the challenges it creates. It is clear that without planning and management, ecotourism will not succeed. It should be well managed and well understand by protected areas managers, staff and other related parts. [10] Anonymous (2013). Official Archives, Dossiers and Files of General Directorate of Nature Conservation and National Parks under the Ministry of Forestry and Water Affair, Ankara, Turkey Activities related with ecotourism, needs to consider visitor infrastructures and services based on existing values and attractions, because, protected areas offer rich opportunities for environmental education. They are an outdoor classroom for visitors and young generation. Interpretive trails, visitor centers, and other interpretive facilities should design and implement based on nature-friendly and core management objectives of the protected areas. Current ecotourism activities in Turkey may provide benefits for conservation and local people, but there is no regular and systematic structure to get benefits and how to manage it. The benefit sharing methodology and financial mechanism should be identified and through the process a systematic benefit structures should be established. The authors have declared no conflict of interest. REFERENCES [1] Eagles, P.F.J., Browman, M.E. and Tao, T. (2001) Guidelines for tourism in parks and protected areas of East Asia, IUCN – The World Conservation Union 2001, pp. 24-34 [2] The Ecotourism Society-TIES (1990). http://www.ecotourism.org/what-is-ecotourism, March 2013. [3] Lindberg, K., Furze, B., Staff, M. and Black, R. (2010). Ecotourism and other services derived from forests in the AsiaPacific Region: Outlook. Forestry Policy and Planning Division, Rome, Regional Office for Asia and the Pacific, Bangkok, pp. 1-12 [4] Ministry of Culture and Tourism (MoCT) Turkey Tourism Strategy 2023, Action Plan 2007-2013, Ankara [5] Ministry of Forestry and Water Affairs (MoFWA) 1st Forest and Water Council, Council Decisions, 21-23 March 2013, Ankara p [6] General Directorate of Nature Conservation and National Parks (GDoNCNP), Technical Specification on Ecotourism Planning in the Protected Areas Case on Beyşehir Lake National Park and Ilgaz Mountains National Park 2013, 2014 Ankara [7] Ceballos-Lascuráin, H. (1996). Tourism, ecotourism, and protected areas. The state of nature-based tourism around the world and guidelines for its development. IUCN, Gland, Switzerland, and Cambridge, UK , pp. 157-164 [8] Ministry of Forestry and Water Affairs, General Directorate of Nature Conservation and National Parks (MoFWA, GDNCNP), List of Protected Areas of Turkey, http://www.milliparklar.gov.tr/mp/index.htm 2013 [9] Anonymous (2013). Visitor Monitoring Sheets of General Directorate of Nature Conservation and National Parks under the Ministry of Forestry and Water Affair, Ankara, Turkey 257 Received: April 03, 2014 Revised: July 31, 2014 Accepted: August 04, 2014 CORRESPONDING AUTHOR Nihan YENİLMEZ ARPA Ministry of Forestry and Water Affairs General Directorate of Nature Conservation and National Parks Ankara TURKEY Phone: + 90 312 207 6008 Mobile: 90 533 399 90 98 Fax: + 90 312 207 6710 E-mail: [email protected] [email protected] FEB/ Vol 24/ No 1a/ 2015 – pages 250 - 257 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin SUBJECT INDEX A L Amanita muscaria assessment 216 250 195 163 188 208 250 188 163 163 228 modelling monitoring program monitoring multi-metal bioaccumulation index 172 163 244 208 national parks natural and engineered sorbents nutrients 250 228 203 permeable reactive barriers Pinus sylvestris L. Plantago major L. protected areas pumpkins 228 216 216 250 224 Remote Sensing 244 salinity soil accumulation Supervised Classification 235 172 244 threats trophic state 203 203 Unio sp. urban areas 208 216 Water Quality water quality wetland restoration Wetland wind energy wind turbines 188 203 235 244 163 163 Yelkoma Lagoon 235 Zinav Lake Basin 180 M B basin planning bat deaths benthic macroinvertebrates bioaccumulation biodiversity conservation biotic indices bird deaths bird migration limestone sand N P C CORINE 244 ecosystem ecotourism EIONET-SOIL erosion erosion Esen River 180 250 172 172 195 188 E R S F freshwater mixing 235 Geographic Information Systems GIS-Remote sensing groundwater contamination 172 195 228 G T U H heavy metal heavy metals heavy metals heavy metals hierarchical clustering analysis 180 208 216 224 180 Jerusalem artichoke 224 K-factor Küçük Menderes River Basin 172 195 LANDSAT-7 ETM+ 172 W J K L Y Z 258 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin AUTHOR INDEX Z A Zinav Lake Zinav Lake 172 203 Altunbaş, Sevda Aydin, Harun 244 235 Barlas, Murat Bektaş, Nihal Buhan, Ekrem Buhan, Ekrem Buhan, Ekrem 188 203 172 180 203 Çelik, Mehmet Ali Ceran, Yusuf 195 250 Danilcenk, Honorata Dirim Buhan, Saliha Dirim Buhan, Saliha Dirim Buhan, Saliha 224 172 180 203 Erdem, Osman Erdoğan, Ali Evren İnanan, Burak 235 163 208 Fronczyk, Joanna Fronczyk, Joanna 216 228 Gülersoy, Ali Ekber 195 Jariene, Elvyra Jeznach, Jerzy Jeznach, Maria 224 216 224 Karakuş, Hüseyin Kiziroğlu, İlhami Koçer, Mehmet Ali T. 235 163 203 Mazur, Zbigniew Mazur, Zbigniew Mete Doğan, Hakan Mete Doğan, Hakan Mete Doğan, Hakan Mete Kılıç, Hakan 216 228 172 180 203 172 B C D E F G J K M 259 © by PSP Volume 24 – No 1a. 2015 Fresenius Environmental Bulletin M Mete Kılıç, Orhan 180 Okan Genç, Tuncer Onur, Işın 208 244 Polat, Fatih Polat, Fatih Polat, Fatih 172 180 203 Radziemska, Maja Radziemska, Maja 216 228 Sencer Yılmaz, Doğaç Sencer Yılmaz, Doğaç Sonmez, Namık Kemal Sukatar, Atakan 172 180 244 188 Ütük, Gökhan 208 Yenilmez Arpa, Nihan Yilmaz, Fevzi Yorulmaz, Bülent Yorulmaz, Bülent 250 208 188 208 O P R S U Y 260