STUDY ON SURFACE WATER QUALITY IN DJERDAP/IRON GATE PROTECTED AREA
Francisc Popescu, Milan Trumić, Ioan Laza, Bogdana Vujić, Virgil Stoica, Maja Trumić, Nada Štrbać, Ion Dragos Uţu, Milan Antonijević, Dorin Lelea, Carmen Rădescu, Snežana Đoševska
The study is a result of “Academic Environmental Protection Studies on surface water quality in significant cross-border nature reservations Djerdap / Iron Gate national park and Carska Bara special nature reserve, with population awareness raising workshops”, financed thru the Interreg – IPA CBC Romania – Serbia Programme 2014 - 2020 Project acronym: AEPS Project eMS code: RORS-462 Project webpage: http://aeps.upt.ro
TIMIŞOARA, 2021 ISBN 978-973-0-33702-0
Contents Acknowledgment ...... 2 1. Danube. National Park Djerdap ...... 3 2. Danube. Iron Gates Natural Park ...... 7 3. Danube’s main tributaries in National Park Djerdap – Iron Gate Natural park area ...... 14 3.1. Nera River ...... 14 3.2. Berzasca River ...... 18 3.3. Porecka River ...... 20 3.4. Pek River ...... 22 3.5. Cerna River ...... 25 4. Cross-border legal framework in surface water quality ...... 27 5. Study target surface water pollutants fact sheets ...... 31 5.1. Oxygen regime. Dissolved Oxygen (DO), Biochemical (BOD) and Chemical Oxygen Demand (COD) ...... 31 + + - - 5.2. Nutrients and general ions. Sodium (Na ), Calcium (Ca2 ), Nitrates (NO3 ), Nitrites (NO2 ), - 3- 2- - Ammonium (NH4 ), Orthophosphate (P-PO4 ), Sulphates (SO4 ), Chloride (Cl ) and Total Nitrogen (TN)...... 32 + + 5.3. Heavy metals. Mercury (Hg), Arsenic (As3 ), Lead (Pb), Zinc (Zn2 ), Cadmium (Cd), Manganese (Mn) and Iron (Fe) ...... 34 6. Water quality assessment on Danube and its main tributaries in Interreg IPA-CBC Romania- Serbia programme eligible area...... 37 6.1. Sampling, methods and analytical equipment...... 37 6.2. Water quality on Danube, in Iron Gate / Djerdap cross-border natural parks...... 41 6.3. Water quality on Nera River...... 48 6.4. Water quality on Berzasca River...... 57 6.5. Water quality on Porecka River...... 64 6.6. Water quality on Pek River...... 68 6.7. Water quality on Cerna River...... 73 7. Conclusion and results analysis ...... 79 References ...... 86
1 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Acknowledgment
This study was conducted in the frame of research project “Academic Environmental Protection Studies on surface water quality in significant cross-border nature reservations Djerdap / Iron Gate national park and Carska Bara special nature reserve, with population awareness raising workshops.”, acronym AEPS, conducted in partnership of University Politehnica Timisoara (RO), University of Belgrade - Technical Faculty in Bor (SR), Pro Mehedinti Association (RO) and Citizen’s association “Village – Movement for Rural Development Zlot (SR).
The project was founded thru Interreg IPA Cross-border Cooperation Romania-Serbia Programme 2014-2020, Programme Priority: PA 2 Environmental protection and risk management / Specific Objective: 2.1 Environmental protection and sustainable use of natural resources.
As water is essential to life and is an indispensable resource for ecosystems and their services and for nearly all human activities, our project team experts focused project activities to reach 2 main objectives:
Evaluation of environmental current situation in cross border “sister” Danube banks nature reservation Djerdap (Serbia) and national parks Iron Gate (Romania)
Raising the awareness of young generations on both sides of the border on the immediate need to protect the region remarkable natural heritage
All project activities, outputs, photo gallery and visibility actions can be followed on project webpage: www.aeps.upt.ro
2 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
1. Danube. National Park Djerdap
Danube river, one of the longest rivers in Europe, along its flow makes natural border, and one of the remarkable areas, between Republic of Serbia and Romania - „Iron gate“, the pearl of the Danube river.
This area is proclaimed as protected areas on both, Serbian and Romanian, sides. Hence, on Romania side, there is National park „Parcul natural Portile de fier" that covers 115655 ha, in Caras-Severin and Mehedinti County, the second largest NP in Romania. National park „Djerdap” is one of the five national parks and the largest one in Serbia. For the first time it is proclaimed as protected area by the Low on NP „Djerdap“ (Official Gazette of RS, No. 39/1993, 44/1993-correction, 53/1993, 67/1993, 48/1994, 101/2005 and 36/2009). The boundaries of NP „Djerdap“ are established by the Law on National Parks (Official Gazette of RS, No. 84/2015 and 95/2018) where it is defined that it covers area of total 63 786,48 ha (45.454,87 hа is state property and 18.331,60 hа is private property).
Photo 1. View of the Danube.
3 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
The most impressive landmark of this area is certainly gorge “Iron gate” the biggest and one of a kind in Europe, consisting of four smallest gorges and three basins, covering 100km in length and reaching the maximum depth of 170m. It encompasses parts of the massifs of North Kucaj, Miroc and Strbac in the width of 2-10 km, as well as part of the Danube, which belongs to the Republic of Serbia.
Photo 2. View of the Danube’s gorges.
Additionally, this area is habitat of the over 1100 plant species (e.g.Corylus colurna, Juglans regia, Syringa vulgaris, Taxus baccata, Tilia argentea,Tilia caucasia, Acer intermedium,Quercus pubescens, Ilex aquifolium, etc). Also, this is the only habitat in the world of the Tulipa hungarica, the unique tulip flower.
Rich flora and forest ecosystems contributed to the variety of fauna. Hence, the NPs are home of the more than 150 bird’s species. Some of them are exceedingly rare and unique (Aquila chrysaetos, Circaetus gallicus, Haliaeetus albicilla, Ciconia nigra etc). The mammals are also remarkably diverse in this area. For example, this is habitat of otters (Lutra lutra), bears (Ursus arctos) lynx (Lynx lynx), golden jackal (Canis aureus), wild boar (Sus 4 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
scrofa), deer (Cervus elaphus), roe deer (Capreolus capreolus) and chamois (Rupicapra rupicapra).
Also, the uniqueness of national parks is also internationally recognised. Hence, NP “Iron gate” is included on the RAMSAR list of wetlands of international importance and this area is recently designated as UNESCO GLOBAL GEOPARKS, as one of the 15 unique geoparks in the world, as well.
The specificity, diversity and the importance of the terrain, flora and fauna is fulfilled throughout the “Lepenski vir” archaeological settlement from 7000 BC, that testify that this area was suitable habitat for prehistoric people, but also very important transit corridors of the Roman Empire (road ruins, Rex Decebal Statue and Tabula Traiana), as well as important defensive stronghold of medieval Serbian town Golubac.
Photo 3. View of the Golubac fortress guarding the Danube.
Throughout the history, different communities (Serbian, Czech, Hungarian, Turkish etc.) left ethnic mark on local habitants shaping its authenticity and contributing to the multiculturalism that is present until nowadays. This remarkable area connects people from both sides, either
5 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
throughout its history or culture, but the additional connection, we may say, is water. Although, we share and uses all the benefits of Danube river, unfortunately, this valuable area is endangered by the human activities. Hence, we are witnessing the mass and aggressive urbanisation in the areas that are very close to the protected zones, industry that releasing effluents directly into the Danube or into to its tributaries, uncontrolled landfills near water banks, intensive agriculture activities that use huge amounts of fertilizers and pesticides and water tourism are some of the crucial sources of pollution. The Djerdap gorge is the deepest and most beautiful gorge in Europe, which has unpolluted environment, favourable climate, and complex geological and geomorphological characteristics. As such, it represents a unique European reserve of tertiary flora and fauna with a distinctly endemic and relict character. Based on the Law on nature protection, three protection zones (Protection degree I, II, and III) were formed on the territory of the NP Djerdap, as can be seen on Figure 1.
Figure 1. National Park Djerdap – Protection degree zones [1] - 26 November 2020
The lack of intensive economic activities and traffic in the mountain belt of the Djerdap area has a favourable effect on the state of the environment. In the remaining area of Djerdap and outside the National Park, the environment is relatively preserved.
6 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
2. Danube. Iron Gates Natural Park
The Iron Gates Natural Park is an 115666 ha Natural Park located in southwestern Romania and bordered for 140 km by the Danube. It includes the Romanian part of the Iron Gate of the Danube River, and stretches along the left bank of the river in the counties of Caras-Severin and Mehedinti. Across the river is the Djerdap national park in Serbia.
The Iron Gates Natural Park is the second largest natural park in Romania. It stretches from Socol in the west, to Drobeta-Turnu Severin in the east; to the north are the Banat Mountains and the Mehedinti Mountains. The park contains 18 protected areas, the largest one being the wet zone Ostrov– Moldova Veche.
Table 1. Iron Gates Natural Park protected areas. [4] IUCN Surface Protected area (in Romanian) Type category [ha] Dealul Vărănic mixed IV 350 Cracul Găioarei botany IV 5 Valea Oglănicului botany IV 150 Cracul Crucii botany IV 2 Fața Virului botany IV 6 Gura Văii - Vârciorova mixed IV 305 Dealul Duhovnei forestry IV 50 Locul fosilifer Bahna paleontological III 10 Cazanele Mari și Cazanele Mici mixed IV 215 Locul fosilifer Svinița paleontological III 95 Zona umedă Ostrov - Moldova Veche avifauna IV 1627 Peștera cu apă din Valea Polevii mixed IV 3.2 Valea Mare botany IV 1179 Divici - Pojejena avifauna IV 498 Râpa cu lăstuni din Valea Divici mixed IV 5 Zona umedă Insula Calinovăț avifauna IV 24 Baziaș mixed IV 170.9 Balta Nera - Dunăre mixed IV 10
Out of these 18 areas, four are Special Protection Areas for birds and wetland conservation: Divici – Pojejena 498 ha (a succession of five ponds
7 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
and swamp areas along the Danube River), Calinovăţ Island of 24 ha (located on the Danube River between Baziaş and Divici), Ostrov ‒ Moldova Veche of 1,627 ha (a large island with many wetland areas) and Nera Marsh ‒ Danube a mixt reserve of 10 ha (situated in the western extremity of the park at the confluence of Nera River with the Danube). [2]
Photo 4. View of Danube’s gorges
Iron Gates Natural Park is an area of outstanding diversity of landscapes, which is the result of various interactions in time of natural elements (lithology, relief, climate, hydrography, vegetation and wildlife) and human activities. These interactions have contributed to shaping one of the most spectacular areas in Romania, from the scientific, cultural, recreational, and educational perspectives. Because of the human-nature relations that shaped a landscape of aesthetic, ecological and cultural values, the Iron Gates Natural Park has been declared as a protected area according to the IUCN category V. [3]
8 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 2. Physical map of the Iron Gates Natural Park [4]
Iron Gates Natural Park is mostly covered by forest that is interspersed with streams and freshwater pools. The variety of ecosystems as well as the diversity of species is very high. Many species of flora (about 3700) and fauna (more than 5200) are protected under international, European and national regulations. Such species include birds like the Imperial Eagle (Aquila heliacal), amphibians like the European Fire-bellied Toad (Bombina bombina), vulnerable fish species such as Acipenser ruthenus, and mammals like the Otter (Lutra lutra). Some plant species are endemic to the area. The large Iron Gates water reservoir serves multiple purposes, from hydropower production to fishing, navigation and leisure activities. It is especially important as a breeding, staging and wintering site for many bird species and regularly supports 20000 or more water birds. [5]
On the territory of this nature park, the Danube forms the longest gorges in Europe (134 km) and, in its narrowest sector, creates the Great and Small Danube Gorges where tall and abrupt rocky hills like Ciucarul Mic (313 meters) and Stirbatul Mic (626 meters) border the river. The Great Gorges are 3.8 km long and 200-350 meters wide while the Small Gorges narrow Europe’s second-largest river to just 150 meters in some areas.
9 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 3. The hydrography of the “Iron Gates” Natural Park. [3]
The climate of the Iron Gates Natural Park is influenced by the circulation of warm air of Mediterranean origin, noticeable especially in the mountainous area where the air temperature registers higher values compared to other mountainous regions of the country. Near the Danube Gorge, the climate is close to the Mediterranean, the multiannual average being about 11 °C. In Orsova the average multiannual temperature is 11.2 °C, the value of the average temperatures of the coldest month oscillates between -1 and 1 °C, and that of the warmest month between 20-23 °C. The annual average values increase gradually from west to east, registering 11.2 °C in Moldova Noua, 11.4 °C in Berzasca, 11.5 °C in Svinita, 11.6 °C in Drobeta Turnu-Severin. Absolute minimum temperatures are related to the stagnation of cold air masses of eastern circulation. Under these conditions the air temperature can drop to -25 °C. The record values were -27.8 °C in January 1942, -24.6 °C in Drobeta Turnu-Severin in January 1947, -20 °C in January 1985 in Berzasca. The absolute maximum temperature registers values of 41 °C in Moldova Veche, 42.6 °C in Svinita, 42.5 °C in Orsova, 42.6 °C
10 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
in Drobeta Turnu-Severin. The snow layer reaches its highest value in February (20-35 cm), but does not last very long, about 30-40 days / year. [4]
The direct tributaries of the Danube have a mountainous character from the springs to the outflow. In addition to the main watercourses, there are also watercourses that have a temporary character, with small reception basins and torrential character: Stariste, Recita, Iuti, Liubotina, Povalina etc. The construction of the dam at Gura Văii and the formation of the Iron Gate I reservoir led to the flooding of all the mouths of the direct tributaries of the Danube and their transformation into bays of different sizes. The largest bays are those of Cerna, Bahna (near the Iron Gates I dam) and Mraconia. The tributaries of the Danube in the Iron Gate Natural Park are characterized by high waters, spring and winter floods, the winter runoff being higher due to the Mediterranean climate that determines the early melting of the snow.
Photo 5. View of Danube’s Iron Gate I hydropower dam.
The construction of the Gura Vaii Dam was carried out in partnership with Yugoslavia between 1964-1972, and produced significant changes in natural and human ecosystems. The Iron Gates I accumulation lake represents the largest hydrotechnical arrangement in Romania, but also
11 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
along the Danube. It was built behind the dam at Gura Vaii which has a height of 60.6 m. The lake has an area of 700 km² and a length of 130 km.
In the Iron Gates Natural Park, the railway transports are present on the Drobeta-Turnu Severin-Orsova-Toplet sector, which takes place in the Gura Vaii-Orsova sector on a single electrified line, on which numerous tunnels and viaducts have been built due to the rugged relief.
The main road transport routes in the park are the part of the E70 road between Drobeta Turnu-Severin-Orsova-Toplet, as well as the DN57 Orsova- Moldova Veche-Pojejena-Oravita road, built along the Danube and which is the main access road in many localities of the Iron Gates Natural Park.
Photo 6. Birds “siesta” on Danube.
From Moldova Veche starts a modernized road, through Moldova Noua, to Carbunari and Sasca Montană. Also, from Moldovita there is a road that passes through Garnic and descends through Sichevita in DN57. Access to the interior of the park is through forest and communal roads (to Ilovita and Bahna, branch of E70), Bigar (from Cozla 17 km) and to Eibenthal.
In the villages from the Iron Gates, Serbian, Czech, and Turkish communities left their mark on local culture, shaping its authenticity and cultural value. This is, in fact, the protected area with the highest ethnic diversity in Romania. A visit to the ethnographic museums from Eselnita, Gornea, or the
12 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Iron Gates I Hydroelectric Power Plant Museum is an excellent chance to learn more about the local multicultural diversity. Among the main attractions are the ruins of the medieval fortress Trikule, Mraconia Monastery, the water mills from Sichevita, the 14th-century Vodita Monastery, and the unconventional Catholic Cathedral from Orsova. Close to the Monastery of Mraconia, you’ll find the biggest rock sculpture in Europe, representing the ancient Dacian king, Decebal. Almost 55 meters tall, the sculpture required 10 years (1994-2004) of hard and often dangerous work as the rock is only accessible by water. On the opposing Serbian shore, you’ll see the symbol of the Roman Empire’s final attack over the Dacian Kingdom, the rock inscription Tabula Traiana, almost 2000 years old. [7]
Photo 7. View of Danube’s Iron Gate II hydropower dam.
One of the best attractions of the Iron Gates was, however, drowned by the Danube. The construction of the largest hydroelectric power plants on the Danube River, Iron Gates I and Iron Gates II, increased the water level by 35 meters. Together with other villages, the island of Ada Kaleh, inhabited for centuries by a Turkish community, was submerged and lost forever. [7]
Creating a unique landscape in Europe, crossing half of the continent and four capitals, the Danube parades in its full glory on the territory of Iron Gates Nature Park, one of Romania’s must-see natural attractions.
13 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
3. Danube’s main tributaries in National Park Djerdap – Iron Gate Natural park area
3.1. Nera River The near River flows thru Nera Gorge-Beusnita National Park (national park category II IUCN) is a protected area situated in Romania, in Caras- Severin County. The Natural Park is located at the south-west limit of the country, in the south of the Anina Mountains (group mountain included in Banat Mountains), on the middle course of Nera River and on the upper Beu River. [8]
Figure 4. Nera Gorges-Beuşniţa National Park and nearby areas. [9]
Nera Gorge-Beusnita National Park with an area of 36758 ha was declared natural protected area by the Law Number 5 of March 6, 2000
14 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
(published in Romanian Official Paper Number 152 on April 12, 2000) and represents a mountainous area (mountain peaks, cirques, crevasses, caves, valleys, canyons, waterfalls) what shelters a large variety of flora and fauna; some of the species are endemic or very rarely. Protected areas included in the park: Nera Gorge-Beusnita, Susara Gorge, Ducin, Izvorul Bigar, Izvoarele Nerei, Lisovacea and Valea Ciclovei-Ildia. [10]
Photo 8. View of “Ochiul Bei” lake, near Nera.
In the perimeter were identified 6 surface sites and 30 sites in the area adjacent to the park. Among these we notice the Socolari Fortress, the Calugara Monastery, the Roman construction from V. Boistea, the tunnels from Sasea, the Oravita Old Theater.
The underground sites are located in 24 caves in Cheile Nerei and represent traces of human habitation (ceramic fragments from the Neolithic to the present. The most important site is located in a cave in Cheile Minisului where human skeletal remains have been identified as the oldest in Europe.
15 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Climate is a temperate continental, with moderate winters, warm summers, low thermal amplitude, with rich rainfall, with Mediterranean influences. The minimum average temperature varies between -1 °C and -5 °C and the maximum average temperature between 15 °C and 20 °C. The absolute minimum and maximum temperature varies depending on altitude between -27 °C and 39 °C. The amount of precipitation is 700 - 1100 mm / m2 / year. The winds predominate in the southern and north-western sector, with speeds that can exceed 5 m/s in the high area.
Photo 9. View of “Beusnita” water fall, near Nera.
The population density is generally 10 inhabitants / km2, in certain areas (Poiana Lisovacea, Poiana Cuces, Poiana Roschii, Poiana Odobasnita) there are concentrations of dwellings, mostly inhabited only in spring – autumn. In the immediate vicinity of the park are the localities: Anina, Bozovici, Lapusnicu Mare, Moceris, Sopot, Carbunari, Sasea Romana, Sasea
16 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Montana, Potoc, Socolari, Ilidia, Ciclova Romana, Ciclova Montana, Oravita. [11]
On the territory of the protected area it has been identified several species of flora with European elements, Central European and Euro-Asian. The hydrological network includes Nera River and its tributaries: Coşava, Bănia, Beu, Ducin, Miniş, Nergana, Nerganiţa, Prigor, Rudăria, and Şopotu. Traditional activities are still carried out in non-forested areas and consist of animal husbandry, mowing and agriculture. [12]
Devil Lake is one of the fantastic tourist attractions in this area. Reflecting a blue-green or purple-black colour (depending on the propagation of the sun's rays) the karst lake was formed by the collapse of the ceiling of the adjacent cave. With a diameter of 20 m, the lake does not exceed a depth of 12 m. Beusnita waterfalls (of which the highest is over 5 m) were formed by the action of water on the calcareous soil, for millennia. Today they are a unique phenomenon, which has attracted the attention of both geologists and tourists. The Bei's Eye is a natural lake with an area of 284 m and a depth of 3.6 m in which the water never freezes as its temperature remains unchanged through the year, between 4 and 8 °C. Thus, in winter you can admire wild ducks and other migratory birds. [14]
Photo 10. Nera River, lower section. 17 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
3.2. Berzasca River The Berzasca River is a left tributary of the river Danube in Romania. It discharges into the Danube in the village Berzasca. Its length is 46 km and its drainage basin size is between 200 - 1500 km2, is a perennial river that never runs dry even in the hottest summer. [15, 16]
Based on water flow quantities, the Berzasca River can be considered as a big mountain river. The predominantly mountainous relief of the river basin areas induces high speed sediments flow, the majority being coarse dragged material (e.g. gravel and boulders) and a minority of sediments being in suspension. The brown trout (Salmo trutta fario) dominates in the upstream section until around 30 km sector and it is considered an indicator of a steady situation in the river over the last half of century in this section. Recent studies showed that Berzasca River experienced minor changes, a relatively stenotopic ichthyocenosis and smaller qualitative and quantitative changes over time, comparade to historical data. [16]
Photo 11. View of the mid-section of Berzasca River.
18 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
The main advantage of the Berzasca river is that the only human settlement (Berzasca village) is located at the river mouth, as it spills into Danube, and almost all of its 46 km length between Banat mountains is in total wilderness, banked by forest and mountains, and untouched by human activity. The only upstream industrial activity used to be forest logging, which was closed in early 90’s.
Photo 12. Historical photo of “Mocanita” logging steam train on Berzasca River banks. [17]
In present and past years, the Berzasca village municipality is trying to restore the historical 30 km steam train rails, but for touristic purposes, preservation of the wilderness of Berzasca river been a main priority for local authorities.
19 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
3.3. Porecka River
The Porecka River is a river in eastern Serbia, a 50 km-long right tributary to the Danube in the Djerdap gorge. It originates from two headstreams, the Saska and the Crnajka rivers, which meet at the village of Miloseva Kula.
The Crnajka river, the shorter but natural headstream, originates from the central west slopes of the Deli Jovan mountain, and flows to the north, next to the villages of Tanda and Crnajka, in the valley between the Deli Jovan to the east and Veliki Krs. The Saska river, the longer headstream (17 km), originates from the northern slopes of the Liskovac mountain, under the mountain's highest peak, Veliki Liskovac, east of the town of Majdanpek.
Photo 13. View of Veliki Krs mountains. [18]
20 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
The river flows to the south, curving around the western side of the Liskovac Mountain and the northern slopes of the Mali Krs mountain, next to the oldest copper mine in Europe and once prosperous mining village of Rudna Glava. It meets the Crnajka in the narrow valley between the southern Liskovac and northern Deli Jovan mountains, at the village of Miloseva Kula, forming the Poreska river. For the remaining 23 km the river flows under the name of Porecka river, diving in two the narrow valley and region of Porec (Serbian for land alongside the river or river valley). The river continues Crnajka northerly direction between the mountains of Liskovac (on the west) and Veliki Greben (on the east). The major settlements on the river are the villages of Klokocevac, Topolnica and Mosna, and the small town of Donji Milanovac near the river's mouth into the Danube in the Djerdap gorge. [18]
Photo 14. View of Donji Milanovac, the Porecka river flows to Danube. [19]
The Porecka river forms a small bay on Danube bank in the town of Donji Milanovac, a town that lies near the remains of an 8000-year-old Mesolithic settlement of the Lepenski Vir, an important archaeological site of the Mesolithic, thelatest radiocarbon and AMS data suggests that the chronology of Lepenski Vir spans between 9500 – 7200 BC. 21 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Photo 15. View of Lepenski Vir idol, 7000 BC, Vinča culture figurine. [20]
3.4. Pek River The Pek river springs near the Black Peak, and it flows into the Danube near Veliko Gradiste and it is among the biggest rivers of south- eastern Serbia. It is also known as the Golden Pek, and with a reason, since it has small pieces of gold. This area was famous for gold. Intensive diggings started when the Romans came to this area, especially during the reign of the king Hadrian, and in the Middle Ages, the Serbian kings continued. Only few people today know the traditional ways of searching for gold. In order to preserve this craft, every year at the shores of Pek, people demonstrate this skill during the celebration called “Motives of Homolje Mountains“. They show how to wash the sand with gold with a simple wooden dish called „ispitak“. This activity could be an unforgettable adventure and a challenge. [21]
22 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Photo 16. The confluence of the Pek river. [21]
The Pek River is a tributary of the Danube, and their confluence is at the City of Veliko Gradiste. The drainage area of the Pek River is about 1230 km2, with the mean annual temperature and precipitation are about 11.1 °C and 643 mm/y at V. Gradiste and 10.9 °C and 672 mm/y at Kucevo. [22]
Photo 17. View of the Pek river, in Branicevo area. [23]
The Pek originates from two major headwaters, Veliki Pek and Mali Pek. The Mali Pek comes down from the northern slopes of the Liskovac 23 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
mountain, flows to the southwest through the city of Majdanpek, one of the major mining centers of Serbia. After a short course, the Pek reaches the western side of the Homolje mountains and flows in into the river Lipa at the village of Debeli Lug. Measured from the Lipa source, Pek is 129 km long, measured from its own, 110 km. Near the confluence of the two rivers is the reservoir of Veliki Zaton (or Valja Fundata), artificial body of water used as a tailing pond for the nearby mines. The Lipa (or Veliki Pek) springs out on the western side of the Veliki Krs mountain, near the village of Lipa. It flows straight to the north, following the western side of the Mali Krs mountain, next to the villages of Vlaole, Jasikovo and Leskovo before it meets the Pek. In the Zvizd region the river course both begins and ends with a gorge. At the village of Rečica, the Pek enters the beautifully Kucevska klisura (Gorges of Kučevo). Branicevo is the lowest part of the Pek valley, so the river spills in several arms and passes next to many villages before it empties into the Danube east of the town of Veliko Gradiste. [24]
Photo 18. Historic photo of people mining gold on Pek river, with „ispitak“. [25]
24 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
3.5. Cerna River Cerna River flows thru The Domogled-Valea Cernei National Park is a protected area (national park category II IUCN) situated in Romania, on the administrative territory of counties Caras-Severin, Gorj and Mehedinti. The National Park stretches across over the Cerna Mountains and the Godeanu Mountains on the right side, and over the Valcan Mountains and the Medinti Mountains on the left side. It is located in the Retezat-Godeanu Mountains group, a group of mountains in the Southern Carpathians, in the Cerna River basin. Domogled-Valea Cernei National Park, with an area of 61211 ha was declared protected area by Law Number 5 of March 6, 2000 and represents a mountainous area what shelters a large variety of flora and fauna, some of the species very rarely or endemics. [26]
Photo 19. Cerna river, upper section.
Within the Domogled – Valea Cernei national park, the local communities are represented by a locality (Cerna Sat), a few hamlets and the town of Baile Herculane, which although not included in the park as an
25 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
area, is surrounded by 95% of the park area, being directly related to the national park and consists of activities such as: exploitation of forest resources, animal husbandry, agriculture, spa tourism and exploitation of resources other than the forest. The local communities included inside the Domogled-Valea Cernei National Park contribute both to the attractiveness and to the value of the area protected by traditional customs, cultural richness and hospitality. Also, local communities have an important place in the development of sustainable tourism that without sustained cooperation and understanding from the locals could not be achieved in harmony with local spirituality. [27]
Photo 20. Cerna River, lower section.
Domogled is nationally and even internationally recognized, due to thermal caves found in this area: Adam’s Cave, where numerous colonies of bats live, steam grotto, hot steam coming out of cracks, with a strong smell of sulfur or Cave Ion Barzoni. The annual average temperature is around 10- 12°C even if we are in a mountain region. Due to its geographical position, the Cerna basin is predominantly subject to the western and southwestern atmospheric circulation. Thus, except for the northern sector of the area,
26 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
respectively the high sector of the Godeanu Mountains and partially of the Cerna Mountains, throughout the year, but especially in winter, there are invasions of humid and hot air mass of Mediterranean and oceanic origin, which determine higher air temperatures values than in the rest of the country. [28]
Domogled - Valea Cernei National Park is the area with the highest biodiversity in terms of lepidopterans, meeting almost 1500 species of butterflies (1463), 45% of the country's lepidopteran fauna being concentrated here. Among the vertebrates, the bird fauna, which is varied and rich in individuals, is still being studied in detail. Large wild mammals live in the heart of the forests, especially in the upper half of the Cerna basin, this area being characterized by a great wealth of important mammals in Europe. [29]
4. Cross-border legal framework in surface water quality
Water is essential for human life, nature and the economy. It is permanently renewed but it is also finite and cannot be made or replaced with other resources. Freshwater constitutes only about 2% of the water on the planet and competing demands may lead to an estimated 40% global water supply shortage by 2030. [30]
EU water policy has successfully contributed to water protection over the past three decades. Europeans can safely drink tap water and swim in thousands of coastal areas, rivers and lakes across the EU. Pollution from urban, industrial and agricultural sources is regulated and this has brought about significant improvements in the quality of European waters, particularly by reducing an excess of nutrients. As a result, iconic fish species such as salmon and sturgeon have, in some places, returned to European rivers. [31]
Our civilization has managed to pollute our water supplies to the point where we have to purify water for drinking. In the past, rain was nature’s way of providing freshwater; however, rain is usually contaminated 27 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
by various pollutants that we add to our atmosphere. The shortage of affordable pure water forces an estimated 1.2 billion people to drink unclean water. As a result, water-related diseases kill 5 million people a year, mostly children, around the world. The problem does not seem to be getting any better— the UN estimates that 2.7 billion people will face water shortages by 2025. [32]
As both Romania (EU member state) and Serbia (EU candidate state) have harmonized their national water quality legislation with EU legislation, since 2000, when the "Directive 2000/60/EC” of the European Parliament entered into force and established a framework for the Community action in the field of water policy, today, the limit values for main surface water and sediments pollutants are identical (or similar) in both countries.
Currently, the new European Union approach on water quality can be defined by the key words “River basin management”, with task of getting Europe's waters cleaner by managing water on a river basin scale. [33]
The Water Framework Directive has the following key aims:
expanding the scope of water protection to all waters, surface waters and groundwater achieving "good status" for all waters by a set deadline water management based on river basins "combined approach" of emission limit values and quality standards getting the prices right getting the citizen involved more closely streamlining legislation
There are a number of objectives in respect of which the quality of water is protected. The key ones at European level are general protection of the aquatic ecology, specific protection of unique and valuable habitats, protection of drinking water resources, and protection of bathing water. All these objectives must be integrated for each river basin. It is clear that the last three - special habitats, drinking water areas and bathing water - apply only to specific bodies of water (those supporting special wetlands; those identified for drinking water abstraction; those generally used as bathing 28 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
areas). In contrast, ecological protection should apply to all waters: the central requirement of the Treaty is that the environment be protected to a high level in its entirety. [33]
Based on the DIRECTIVE 2000/60/EC, annex V, the ecological status classification for the body of water shall be represented by the lower of the values for the biological and physico-chemical monitoring results for the relevant quality elements classified in 5 categories, as presented in next table.
Table 2. Classification of ecological status of water bodies, Directive 200/60/EC. [30] Ecological status classification Colour code
High Blue
Good Green
Moderate Yellow
Poor Orange
Bad Red
As no absolute standards for biological quality can be set which apply across the European Community, because of ecological variability, the controls are specified as allowing only a slight departure from the biological community which would be expected in conditions of minimal anthropogenic impact. A set of procedures for identifying that point for a given body of water, and establishing particular chemical or hydromorphological standards to achieve it, is provided, together with a system for ensuring that each Member State interprets the procedure in a consistent way (to ensure comparability). The system is somewhat complicated, but this is inevitable given the extent of ecological variability, and the large number of parameters, which must be dealt with. [33]
Regulation on limit values of polluting substances in surface and groundwater’s and deadlines for their achievement are imposed at national level in Romania by Ordinance no. 161/16.02.2006 for the approval of the Norm regarding the classification of surface water quality in order to establish the ecological status of water bodies [34] and in Serbia by Water
29 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Law [35, 36] and their subsequent legislative updates. In the next table, the limit values for all water quality parameters used in this study, in both countries is presented.
Table 3. Physicochemical quality elements and standards in surface waters, in Romania and Serbia [34, 35, 36] Limit values *, ** Parameter Unit I class II class III class IV class V class RO – (SR) RO – (SR) RO – (SR) RO – (SR) RO – (SR) pH - 6.5 – 8.5 (I-III: 6.5 – 8.5, IV-V: pH <6.5/ pH >8.5) ) Conductivity µS/cm -
Dissolved oxygen (DO) mgO2/l 9 (8.5) 7 (7) 5 (5) 4 (4) < 4 (<4) Biochemical oxygen 3 (Type 1=2) 5 (Type 1=5) mgO2/l 7 (7) 20 (25) > 20 (>25) demand (BOD – CBO5) (Type 2=1.8) (Type2=4.5) Chemical oxygen mgO2/l 10 (10) 25 (25) 50 (50) 125 (125) > 125 (>125) demand (COD – CCO-Cr) Chemical oxygen mgO2/l 5 (5) 10 (10) 20 (20) 50 (50) > 50 (>50) demand (COD – Mn) 0.4 0.8 - Ammonia (NH4 ) mg/l (Type 1=0.1) (Type 1=0.3) 1.2 (0.6) 3.2 (1.5) > 3.2 (>1.5) (Type 2=0.05) (Type 2=0.1)
- 1 (Type 1=1) Nitrates (NO3 ) mg/l 3 (3) 5.6 (6) 11.2 (15) > 11.2 (>15) (Type 2=1,5) - Nitrites (NO2 ) mg/l 0.01 (0.01) 0.03 (0.03) 0.12 (0.12) 0.3 (0.3) >0.3 (>0.3) Total Nitrogen (TN) mg/l 1.5 (1) 7 (2) 12 (8) 16 (15) > 16 (>15) 3- Orto phosphate (P-PO4 ) mg/l 0.1 (0.05) 0.2 (0.2) 0.4 (0.4) 0.9 (1) > 0.9 (>1) 2- Sulphates (SO4 ) mg/l 60 (50) 120 (100) 250 (200) 300 (300) >300 (>300) Chloride (Cl-) mg/l 25 (50) 50 (100) 250 (150) 300 (250) > 300 (>250) Sodium (Na+) mg/l 25 50 100 200 > 200 Calcium (Ca2+) mg/l 50 100 200 300 > 300 0.1 0.3 0.5 1 > 1 Mercury (Hg) µg/l 0.07 (Maximum Allowed Concentration) *** + Arsenic (As3 ) µg/l 10 (<5) 20 (10) 50 (50) 100 (100) > 100 (>100) 5 10 25 50 > 50 Lead (Pb) µg/l 14.0 (Maximum Allowed Concentration) *** + Zinc (Zn2 ) µg/l 100 (200) 200 (300) 500 (2000) 1000 (5000) > 1000 (>5000) 0.5 1 2 5 > 5 Cadmium (Cd) µg/l < 0.45 ÷ 1.5 (depending on total hardness of water body) **** Manganese (Mn - total) mg/l 0.05 (0.05) 0.1 (0.1) 0.3 (0.3) 1 (1) > 1 (>1) Iron (Fe – total) mg/l 0.3 (0.2) 0.5 (0.5) 1.0 (1.0) 2 (2) > 2 (>2) * the values in black are the limit values in Romania and in blue (in brackets) are the limit values in Serbia. ** limit values are variable by the type of the water body (in 6 classes, of interest Type 1 – large plain rivers; Type 2 - large rivers except for Pannonian plain rivers; Type 3 – small and medium water bodies at altitude up to 500 m, a.o.). Note: Danube is type 1 river and all other rivers in this study are type 2. *** Pb and Hg are regulated by MAC value (Maximum Allowed Concentration)
**** Cd is regulated by MAC that varies with water body total hardness: Cd MAC < 0.45 µg/l for class I (TH ≤ 40 mg CaCO3/l);
Cd MAC = 0.45 µg/l for class II (TH = 40 ÷ 50 mg CaCO3/l); Cd MAC = 0.60 µg/l for class III (TH = 50 ÷ 100 mg CaCO3/l);
Cd MAC = 0.90 µg/l for class IV (TH = 100 ÷ 200 mg CaCO3/l); Cd MAC = 1.50 µg/l for class V (TH ≥ 200 mg CaCO3/l);
30 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
5. Study target surface water pollutants fact sheets 5.1. Oxygen regime. Dissolved Oxygen (DO), Biochemical (BOD) and Chemical Oxygen Demand (COD) Dissolved oxygen (DO) is a measure of how much oxygen is dissolved in the water - the amount of oxygen available to living aquatic organisms. Although water molecules contain an oxygen atom, this oxygen is not what is needed by aquatic organisms living in natural waters. A small amount of oxygen, up to about ten molecules of oxygen per million of water, is actually dissolved in water. Oxygen enters a stream mainly from the atmosphere and, in areas where groundwater discharge into streams is a large portion of streamflow, from groundwater discharge. This dissolved oxygen is breathed by fish and zooplankton and is needed by them to survive. [37]
Chemical Oxygen Demand (COD) indicates all oxidable materials but provides no information on their biodegradability. Biological Oxygen Demand (BOD) indicates the amount of biodegradable matter of water body.
Certain environmental stresses (hot summer temperatures) and other human-induced factors (introduction of excess fertilizers to a water body) can lessen the amount of dissolved oxygen in a water body, resulting in stresses on the local aquatic life. One water analysis that is utilized in order to better understand the effect of bacteria and other microorganisms on the amount of oxygen they consume as they decompose organic matter under aerobic (oxygen is present) is the measure of biochemical oxygen demand (BOD).
Oxidation of biodegradable organic materials is closely linked to biochemical oxygen demand [38]
Biochemical oxygen demand (BOD) measures the amount of oxygen consumed by microorganisms in decomposing organic matter in stream water. BOD also measures the chemical oxidation of inorganic matter (i.e., the extraction of oxygen from water via chemical reaction). BOD directly affects the amount of dissolved oxygen in rivers and streams. The greater the BOD, the more rapidly oxygen is depleted in the stream. This means less oxygen is available to higher forms of aquatic life. The 31 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
consequences of high BOD are the same as those for low dissolved oxygen: aquatic organisms become stressed, suffocate, and die.
Sources of BOD include leaves and woody debris; dead plants and animals, animal manure, effluents from pulp and paper mills, wastewater treatment plants, feedlots, and food-processing plants, failing septic systems and urban storm water runoff. [39]
BOD measures the amount of oxygen required by the aerobic organisms to decompose organic matter and COD measures the oxygen required to decompose organic and inorganic constituents present in the wastewater by chemical reaction. Subsequently, the concentrations of COD is greater than BOD.
+ + 5.2. Nutrients and general ions. Sodium (Na ), Calcium (Ca2 ), - - - Nitrates (NO3 ), Nitrites (NO2 ), Ammonium (NH4 ), 3- 2- - Orthophosphate (P-PO4 ), Sulphates (SO4 ), Chloride (Cl ) and Total Nitrogen (TN). As with organic pollution, nutrient pollution is mainly caused by emissions from agglomerations (cities and towns), industry and agriculture. Atmospheric deposition is also significant. Many industrial facilities, especially in the chemical sector, are significant sources. Nutrient pollution results from point sources and diffuse sources. Nutrient pollution from point sources is mainly caused by emissions from insufficiently or untreated wastewater into surface waters (from agglomerations, industry and agriculture). Emissions from the agricultural sector are a significant diffuse source of nutrient inputs, especially from mineral and organic fertilisers and livestock manure. Nitrates in particular leach easily into water from soils that have been fertilised with mineral fertilisers or treated with manure or slurry. Sources of nutrient pollution from atmospheric deposition include transport, the combustion of oil and derivate, agriculture (livestock farming) and industry. [40]
Sodium (Na+) in surface water are typically related to urbanization and population density and can have a significant impact on drinking water sources and the subsequent salinity of aquatic ecosystems.
32 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
The inorganic forms of Nitrogen that are “reactive”and therefore, potential pollutants, are likely to cause problems only when present in the wrong place, or in excess of local requirements. In the context of water
pollution, forms of reactive Nitrogen of known concern are NH3 (which + - - dissolves to form Ammonia NH4 ), Nitrites NO2 and Nitrates NO3 . [41]
Besides industrial agriculture, the major point sources of nitrate pollution are septic tanks. These tanks are mainly located in rural settlement areas where no central sewer systems exist. These sources cause the contamination of both surface water and groundwater. Wastewater treatment effluent, which is usually discharged to rivers, is the largest pollution threat to surface water in urban areas with central sewage systems. [42] Phosphorus (P) is one of the most important mineral nutrients for biological systems, yet it is also one of the most scarce nutrients in terms of its demand in both terrestrial and aquatic environments systems, phosphorus is tightly cycled through the plant–soil continuum, but in agricultural systems soil phosphorus is removed in the crop or animal products and must be replaced if phosphorus deficiency is to be avoided. 3- Therefore, mineral Orthophosphate (PO4 ) fertilizers and animal manures are applied to agricultural land to raise soil P levels and maintain crop yields. [41]
+ Ammonia (NH4 ) is a colourless, pungent gaseous compound of hydrogen and nitrogen that is highly soluble in water. It is a biologically active compound found in most waters as a normal biological degradation product of nitrogenous organic matter (protein). It also may find its way to ground and surface waters through discharge of industrial process wastes containing ammonia and fertilizers. Ammonia has been used in municipal treatment systems for more than 70 years to prolong the effectiveness of disinfection chlorine added to drinking water. [43]
Chloride (Cl-) occurs naturally in river waters. Some industrial and sewage treatment plant effluents may contain elevated chloride levels and changes in concentrations may be an indicator of pollution. Elevated levels may be seen occasionally in winter when salt is used to de-ice roads. Very high levels of chloride may be seen especially in the lower
33 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
reaches of rivers where a tidal influence exists. Its presence in lakes adjacent to coastal areas is generally due to saline deposition from 2- rainfall and is correlated with sodium concentrations. Sulphate (SO4 ) exists in nearly all natural waters, the concentrations varying according to the nature of the terrain through which they flow. They are often derived from the sulphides of heavy metals. Iron sulphides are present in sedimentary rocks from which they can be oxidised to sulphate in humid climates; the latter may then leach into watercourses so that groundwater are often excessively high in sulphates. Total Nitrogen (TN) is a measure of all forms of nitrogen (organic and inorganic). The importance of nitrogen in the aquatic environment varies according to the relative amounts of the forms of nitrogen present, be it ammonia, nitrite, nitrate, or organic nitrogen. [44]
+ 5.3. Heavy metals. Mercury (Hg), Arsenic (As3 ), Lead (Pb), Zinc + (Zn2 ), Cadmium (Cd), Manganese (Mn) and Iron (Fe) Metals are introduced in aquatic systems as a result of the weathering of soils and rocks, from volcanic eruptions, and from a variety of human activities involving the mining, processing, or use of metals and/or substances that contain metal pollutants. The most common heavy metal pollutants are zinc, arsenic, cadmium, chromium, copper, nickel, lead and mercury. The term “heavy metal” is somewhat imprecise, but includes most metals with an atomic number greater than 20, and excludes alkali metals, alkaline earths, lanthanides and actinides. Generally the ionic form of a metal is more toxic, because it can form toxic compounds with other ions. Electron transfer reactions that are connected with oxygen can lead to the production of toxic oxy-radicals, a toxicity mechanism now known to be of considerable importance in both animals and plants. Some oxy-radicals, - - such as superoxide anion (O2 ) and the hydroxyl radical (OH ), can cause serious cellular damage. [47]
Zinc (Zn) is widely distributed in nature and makes up 0.004 % of the Earth’s crust. It occurs only in the form of sulphide, carbonate and silicate ores, mainly as calamine, smithsonite, sphalerite and zincite. Zinc and its compounds are used in the manufacture of alloys, paints, pigments,
34 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
pharmaceuticals, cosmetics, crop protection products, wood preservatives, and also in the galvanization of metal surfaces. The large number of applications of this metal may thus pose a significant threat to the environment. In surface waters zinc is generally of secondary origin and + occurs in the divalent form (Zn2 ). Speciation studies have shown that sulphides and carbonates are the dominant forms in which zinc occurs in bottom sediments. In these sediments, zinc is also bound to Mn oxides and amphoteric Fe oxides. [45]
Cadmium (Cd) occurs naturally in zinc, in lead and copper ores, in coal and other fossil fuels, in shales and is released during volcanic action. These deposits can serve as sources to ground and surface waters, especially when in contact with low total dissolved solids and acidic waters. Cadmium has the chronic potential to cause kidney, liver, bone and blood damage from long-term exposure. Bacteria play a large part in binding cadmium in sediments, often causing the metal to precipitate as a sulphide. The most important Lead (Pb) mineral is galena PbS. Less common are cerussite, anglesite, crocoite, wulfenite and pyromorphite. The poor solubility of these minerals means that lead migrates into the environment far less intensively than cadmium or zinc. Even so, contamination by this element is unfortunately quite common. Lead can enter natural waters from industrial wastewaters, corrosion of tanks and piping, as well as materials made from lead or containing admixtures of the metal. [45]
+ Arsenic (As3 ) is potentially a very harmful, sometimes fatal, contaminant that can cause damage with immediate consumption or over the long term. In Romania, in many areas on the Wester plain (Arad and Bihor county) the Arsenic is so abundant in groundwater that the water exceed the maxim permissible limit for Arsenic concentration, for human use. The presence of arsenic (As) in nature is due mainly to natural deposits of metalloids in the earth’s crust and usually in ancient rock formations. Arsenic enters ground water through erosion or from man-made sources such as wood preservative, petroleum production, semi-conductor manufacture or due to misuse of animal feed additives and arsenic- containing pesticides.
35 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Mercury (Hg) is a naturally occurring metal that has several forms. The major source of mercury is from natural degassing of the earth's crust 30000 t/year, however, human activity adds another ~ 20000 t/year from combustion of fossil fuels and other industrial release. Often mercury from these sources can circulate in the global atmosphere for months from distant continents, across oceans and finally settle in inland rivers, lakes, and streams anywhere. Water borne pollution may originate in sewage and metal refining operations. The greatest concern for mercury poisoning comes from the food chain especially where fish is common in the diet. A build-up of mercury in the food chain presents a greater risk of mercury poisoning due to bioaccumulation and biomagnification, however this should not diminish the concern for mercury in water. [43]
Iron (Fe) is the most widespread heavy metal in nature, making up 5.08% of the Earth’s crust. All soils, rocks and natural waters contain compounds of iron (II) or iron (III). But in natural waters, this element is present in only low concentrations. Iron enters waters as a result of the weathering of rocks and soils, and also through leaching and infiltration in form of minerals containing iron in the form of oxides, hydroxides and sulphides. Elevated levels of iron can also result from the discharge of industrial effluents, the corrosion of tanks, piping and other equipment and installations containing iron. Iron is present in effluents from the smelting, dying, electroplating and tanning industries. Iron compounds are used as coagulants in the desulfurization of gases and in sewage treatment. [45]
Manganese (Mn) is particularly common due to its ubiquitous natural occurrence, ease of mobilization, and extensive association with industry. It + can occur in numerous oxidation states, with soluble Mn2 as the most + widely occurring form when reduced and insoluble Mn4 as the most common form when oxidized. Manganese occurs naturally in sediments and soils, primarily due to the weathering of the parent material. However, human activities such as mining, metal smelting, and the application of bio- solids and similar organic wastes to agricultural land have raised the Manganese content in many soils and sediments. [46]
36 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
6. Water quality assessment on Danube and its main tributaries in Interreg IPA-CBC Romania-Serbia programme eligible area. 6.1. Sampling, methods and analytical equipment. Sampling is a vital part of monitoring the quality of water. Every precaution must be taken to ensure that the sample collected is as representative as is feasible of the water source or process being examined.
The in-situ analysis (for pH, temp, total hardness and dissolved oxygen) were performed on site. All samples were preserved in-situ for
laboratory analysis with acids: HNO3 (nitric acid) for metal concentration
analysis on ZEEnit 700P, H3PO4 (phosphoric acid) for Total Nitrogen analysis
on Analytik Jena Multi N/C 3100 and H2SO4 (sulfuric acid) for Chemical Oxygen Demand analysis on Velp Eco6 and ammonia, phosphor, nitrite, nitrate, phosphate, a.o. on Analytik Jena Specord 250plus. All samples taken were analysed in-situ or at the end of the sampling day, at team accommodation location. On the large body of waters water sampling was done by kayak navigation.
Photo 21. Water sampling on Nera (N4) and in-situ analysis
Photo 22. Post sampling in-situ analysis in the same day, at accommodation. 37 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
In the next photos, an example of the sampling sheet used in-situ and a view of cooled stored samples are presented.
Photo 23. Sampling sheet, in-situ, example for Nera, N5 point.
38 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Photo 24. Preserved water samples stored in laboratory cooler, for AAS and UV- VIS analysis. International reference and recognized analytical methods were used for laboratory analysis, as seen in table below.
Table 4. Methods and analytical equipment’s used for parameter analysis in water samples. Sample preservation Parameters Addition Measurement methods Hold time acids to pH<2 pH Electrode - electric potential difference Conductivity In situ None Electrolytic probe Dissolved oxygen (DO) Galvanic probe Chemical oxygen 28 days H2SO4 Velp Eco6 thermo-reactor demand (COD – CCO-Cr) Biochemical oxygen 48 hours None demand (BOD – CBO5) - Ammonia (NH4 ) 28 days H2SO4 Analytik Jena Specord 250Plus, - UV-VIS photometric method Nitrates (NO3 ) 48 hours None
- Nitrites (NO2 ) 48 hours None HANNA HI 83200, 3- Orto phosphate P-PO4 48 hours None UV-VIS photometric method 2- Sulphates (SO4 ) 28 days None Chloride (Cl-) 28 days None Analytik Jena Multi N/C 3100. Corrosion-free Focus-Radiation NDIR Total Nitrogen (TN) 28 days H3PO4 detection and furnace technology of combustion. Sodium (Na+) Analytik Jena ZEEnit 700 P Calcium (Ca2+) Compact Tandem Spectrometer. Atomic Absorption Spectrometry – Iron (Fe – total) equipped with flame, hydride and + Arsenic (As3 ) graphite furnace, with Zeeman magnetic field control and Deuterium Lead (Pb) 6 months HNO3 and Zeeman background correction. + Zinc (Zn2 ) ICP-OES Perkin Elmer Optima 8300 Cadmium (Cd) Inductively Coupled Plasma Optical Manganese (Mn - total) Emission spectroscopy equipped with Segmented-array Charge-coupled Mercury (Hg) 28 days HNO3 Device. 39 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Surface water samples were collected in 2020, in 48 sampling locations, as marked in figure 5, from Danube and its main 5 tributary rivers in the Interreg IPA-CBC Romania-Serbia Programme eligibility area.
A minimum of 4 samples were collected for each sampling location, analysed in situ and preserved for laboratory analysis:
- Danube: 17 sampling location - Nera river: 12 sampling points and 3 sampling points on Bei river - Pek river: 1 sampling location [48] - Berzasca river: 8 sampling location - Porecka river: 1 sampling location [48] - Cerna river: 6 sampling location
Note: A compete study on surface water quality on Pek and Porecka Rivers can be analysed at http://aeps.upt.ro/downloads/, Study on the influence of the copper mining activities in Majdanpek on Danube River.
Figure 5. Sampling points for water quality analysis on target area.
40 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
6.2. Water quality on Danube, in Iron Gate / Djerdap cross- border natural parks.
Surface water sampling on Danube was conducted from 14 August to 19 October 2020, in 17 sampling points/locations, from Bazias (Banatska Palanka) down on Danube to Iron Gate II - Balta Verde (Dusanovac), practically on the Romanian – Serbian border formed by Danube. The sampling was performed with a kayak and samples were analysed in situ or preserved for laboratory analysis.
Photo 25. Surface water sampling on Danube, by kayak, near Berzasca.
41 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Photo 26. Surface water in-situ analysis on Danube, near Svinita.
In figure 6 and table 5 more detailed location of the sampling points is presented.
Figure 6. Sampling points for water quality analysis on Danube.
42 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Table 5. Results obtained for parameter analysis in samples of Danube, between 14 august 2020 and 19 October 2020 Legend: D1 – Bazias, D2 – Divic, D3 – Pojejena, D4 – Moldova-Noua, D5 – Coronini, D6 – Liborajdea, D7 – Liubcova, D8 – Berzasca, D9 – Cozla, D10 – Svinita, D11 – Dubova, D12 – Esalnita, D13 – Orsova, D14 – Iron Gate I, D15 – Drobeta Tr. Severin, D16 – Ostrovul Corbului, D17 – Iron Gate II Parameter Unit D1 D2 D3 D4 D5 D6 D7 D8 D9 D10 D11 D12 D13 D14 D15 D16 D17 Eco 24 - 27.09.2020 14 - 15.08.2020 18 - 19.10.2020 state pH - 6.9 7.1 7.5 6.5 7.1 7.2 7.3 7.5 7.5 7.4 7.2 7.3 7.1 7.5 7.0 6.7 6.7 - Conductivity µS/cm 399 402 408 411 411 405 408 409 405 402 403 405 399 389 394 388 404 - Oxygen concentration nd Dissolved oxygen (DO) mgO2/l 7.5 7.2 7.2 7.1 7.2 7.2 7.5 7.5 7.3 7.2 6.9 7.4 7.2 7.4 7.0 6.5 6.4 II
Biochemical oxygen nd mgO2/l 3.6 3.3 3.5 3.7 3.5 3.2 3.2 3.4 3.5 3.5 3.5 3.6 3.4 3.4 3.3 3.3 3.2 II demand (BOD – CBO5)
Chemical oxygen nd mgO2/l 26 22 20 24 25 22 20 22 24 26 27 25 24 20 20 18 18 II demand (COD – CCO-Cr) Nutrients and general ions concentrations Sodium (Na+) mg/l 2.1 3.4 4.1 1.9 2.5 3.4 2.9 3.3 3.4 2.8 2.2 2.7 3.5 3.3 4.1 3.8 2.9 Ist st Calcium (Ca2+) mg/l 4.5 5.8 6.5 5.1 6.5 6.8 7.2 7.1 6.1 5.8 4.7 5.6 5.3 4.9 5.8 5.1 3.9 I - st Ammonia (NH4 ) mg/l 0.11 0.21 0.22 0.16 0.18 0.28 0.31 0.24 0.18 0.16 0.14 0.21 0.16 0.18 0.28 0.31 0.33 I - st Nitrates (NO3 ) mg/l 0.77 0.84 0.85 0.81 0.99 0.92 0.88 0.78 0.81 0.79 0.72 0.80 0.84 0.72 0.72 0.68 0.66 I - nd Nitrites (NO2 ) mg/l 0.022 0.029 0.021 0.025 0.018 0.022 0.027 0.021 0.021 0.024 0.028 0.021 0.020 0.020 0.019 0.017 0.016 II
Orthophosphate rd 3- mg/l 0.31 0.28 0.29 0.35 0.31 0.18 0.24 0.25 0.30 0.27 0.32 0.30 0.27 0.22 0.25 0.21 0.22 III (P-PO4 ) 2- st Sulphates (SO4 ) mg/l 8.3 9.7 10.4 7.5 12.1 8.7 11.2 14.5 12.1 10.2 8.1 7.8 9.8 10.2 8.1 7.2 7.1 I Chloride (Cl-) mg/l 3.5 8.1 6.2 3.2 5.7 8.1 7.4 8.2 5.2 5.1 3.6 3.6 4.5 5.2 7.6 18.5 11.1 Ist Total Nitrogen (TN) mg/l 1.21 1.32 1.18 1.11 1.12 1.18 1.20 1.18 1.19 1.16 1.15 1.17 1.21 1.11 1.15 1.01 0.98 Ist Heavy Metals concentrations Mercury (Hg) µg/l 0.011 0.017 0.012 0.011 0.012 0.014 0.012 0.012 0.011 0.011 0.009 0.011 0.012 0.010 0.009 0.016 0.015 Ist + st Arsenic (As3 ) µg/l 0.09 0.12 0.09 0.11 0.12 0.14 0.09 0.10 0.12 0.10 0.11 0.14 0.11 0.09 0.11 0.14 0.14 I Lead (Pb) µg/l 0.21 0.24 0.21 0.25 0.28 0.21 0.22 0.18 0.20 0.21 0.22 0.21 0.24 0.22 0.22 0.28 0.31 Ist + st Zinc (Zn2 ) µg/l 21.1 18.5 14.5 17.8 20.1 18.5 18.4 20.1 20.2 17.9 19.1 21.0 20.8 19.7 19.4 23.3 18.1 I Cadmium (Cd) µg/l 0.004 0.009 0.007 0.005 0.008 0.012 0.005 0.008 0.011 0.014 0.008 0.011 0.018 0.011 0.042 0.107 0.088 Ist Manganese (Mn - total) mg/l 0.011 0.021 0.018 0.011 0.014 0.016 0.020 0.018 0.014 0.011 0.011 0.012 0.011 0.016 0.011 0.018 0.012 Ist Iron (Fe – total) mg/l 0.766 0.821 0.855 0.891 0.685 0.801 0.721 0.689 0.807 0.804 0.792 0.695 0.744 0.803 0.911 1.822 2.193 IIIrd
Note: Average ambient air conditions: 14 – 15.08.2020: t = 32.8 °C, RH = 48.5%, pb = 1004.9 mbar, Danube water temperature: 22.3 °C
24 – 27.09.2020: t = 21.9 °C, RH = 62.1 %, pb = 1010.5 mbar, Danube water temperature: 19.7 °C 18 – 19.10.2020: t = 16.2 °C, RH = 71.2 %, pb = 1012.7 mbar, Danube water temperature: 12.4 °C 43 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
In the next figures (7 to 12) graphical representation of results obtained on surface water analysis on Danube are presented.
Figure 7. Danube. Concentrations obtained for DO, COD and BOD5.
- + + Figure 8. Danube. Concentrations obtained for NH4 , Ca2 and Na . 44 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
3- - - Figure 9. Danube. Concentrations obtained for P-PO4 , NO2 and NO3 .
- 2- Figure 10. Danube. Concentrations obtained for TN, Cl and SO4 . 45 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 11. Danube. Concentrations obtained for Mn, Cd, Pb, As and Hg.
Figure 11. Danube. Concentrations obtained for Zinc. 46 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 12. Danube. Concentrations obtained for Iron.
On the basis of DIRECTIVE 2000/60/EC, annex V instructions and on the results obtained during the water quality assessment on Danube in the length of ~ 160 km (from Bazias to Iron Gate II) one can conclude that ESC – Ecological Status Classification varies from HIGH (quality) to GOOD on Danube.
More detailed, the Oxygen concentration parameters (DO, COD and nd + + - - BOD5) are all in II class, GOOD; most of the nutrients (Na , Ca2 , NH4 , NO3 , 2- st 3- SO4 , TN) fall into I class, HIGH quality while orthophosphates P-PO4 concentrations classifies Danube water quality in IIIrd class, MODERATE.
The heavy metals concentration in Danube surface waters in analysed area were all (Hg, As, Pb, Zn, Cd and Mn) very low, well into Ist class, HIGH quality. The only exception was found for Iron (Fe), whos values were constantly, to all length of analysed area, into IIIrd class, MODERATE water quality.
A more in-depth analysis is given in Conclusion chapter. 47 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
6.3. Water quality on Nera River. Surface water sampling on Nera River was conducted from 2-4 August in 12 sampling points/locations on Nera and 3 on Bei (a near tributary), from Socol (Banatska Palanka) up on Nera to Cantonul Damian. In the lower part, from Danube up to Zlatita (Kusic) Nera forms the Romanian – Serbian border. The sampling was performed with a kayak in lower part and by entering the river in the upper parts, samples were analysed in situ or preserved for laboratory analysis. In figure 13 and table 6 the sampling points coding and geographical identification by GPS coordinates can be observed.
Figure 13. Sampling points for water quality analysis on Nera River.
Photo 27. Surface water in-situ sampling and analysis on Nera, N5. 48 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Table 6. Sampling poits GPS coordinates for Nera River water quality analysis. Sample No Sampling site Protection zone Coordinates N1 N44°51’04.80” / E21°21’32.03” N2 N44°52’02.63” / E21°24’09.35” N3 N44°52’06.80” / E21°26’19.64” N4 N44°52’14.33” / E21°28’33.78” N5 N44°52’16.62” / E21°33’18.13” N6 The Nera Gorge- N44°55’09.94” / E21°42’30.51” N7 Beusnita National Park N44°54’03.04” / E21°44’17.01” N8 Nera N44°54’06.65” / E21°44’27.74” N9 II IUCN1 N44°54’06.42” / E21°44’50.05” N10 “National Park” N44°54’01.21” / E21°45’21.78” N11 N44°54’00.45” / E21°46’01.73” N12 N44°53’30.24” / E21°47’58.48” Bei1 N44°54’29.17” / E21°44’58.12” Bei2 N44°55’35.59” / E21°47’12.48” Bei3 N44°55’57.35” / E21°21’4718.59”
Table 7. Results obtained for parameter analysis in samples of Nera, on 3rd august 2020 (from Naidas downstream to Socol) Measured values – 3rd August 2020 Eco Parameter Unit N1 N2 N3 N4 N5 state pH - 7.94 7.88 8.05 7.92 7.98 - Conductivity µS/cm 293 302 296 299 308 - Oxygen concentration st Dissolved oxygen (DO) mgO2/l 10.4 9.9 10.1 9.7 10.9 I
Biochemical oxygen st nd mgO2/l 2.9 2.8 3.1 3.1 2.9 I -II demand (BOD – CBO5)
Chemical oxygen st nd mgO2/l 9.7 10.2 10.1 9.7 10.2 I -II demand (COD – CCO-Cr) Nutrients and general ions concentrations Sodium (Na+) mg/l 3.6 3.2 3.2 3.5 3.4 Ist Calcium (Ca2+) mg/l 38.5 37.4 33.5 36.7 38.1 Ist - st Ammonia (NH4 ) mg/l 0.38 0.41 0.35 0.39 0.40 I - st Nitrates (NO3 ) mg/l 0.53 0.61 0.56 0.55 0.54 I - nd Nitrites (NO2 ) mg/l 0.041 0.053 0.048 0.045 0.044 II
Orto phosphate nd 3- mg/l 0.16 0.17 0.16 0.15 0.16 II (P-PO4 ) 2- st Sulphates (SO4 ) mg/l 15.6 14.3 15.1 14.7 14.9 I Chloride (Cl-) mg/l 0.4 0.4 0.4 0.4 0.4 Ist Total Nitrogen (TN) mg/l 1.12 1.14 1.12 1.16 1.14 Ist Heavy Metals concentrations Mercury (Hg) µg/l 0.021 0.017 0.018 0.011 0.015 Ist + st Arsenic (As3 ) µg/l 0.33 0.14 0.21 0.17 0.11 I Lead (Pb) µg/l 0.088 0.094 0.091 0.081 0.085 Ist + st Zinc (Zn2 ) µg/l 12.7 14.1 13.7 12.9 13.5 I Cadmium (Cd) µg/l 0.007 0.007 0.010 0.008 0.007 Ist Manganese (Mn - total) mg/l 0.022 0.021 0.025 0.024 0.025 Ist Iron (Fe – total) mg/l 0.893 0.955 1.021 0.912 0.897 IIIrd
Note: ambient air conditions: t = 31 °C, RH = 58.4 %, pb = 1008.5 mbar Water temperature: 17.4 °C 49 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Table 8. Results obtained for parameter analysis in samples of Nera, on 2nd August 2020 (from Sasca Montana upstream ~ 1 km) Measured values – 2nd august 2020 Eco Parameter Unit N6 N7 N8 N9 N5 state pH - 7.76 7.78 7.91 7.82 7.80 - Conductivity µS/cm 301 312 308 310 305 - Oxygen concentration st Dissolved oxygen (DO) mgO2/l 10.8 10.9 10.8 11.1 10.9 I
Biochemical oxygen st mgO2/l 2.9 2.9 2.8 2.8 2.9 I demand (BOD – CBO5)
Chemical oxygen st mgO2/l 9.6 9.5 9.4 9.7 9.5 I demand (COD – CCO-Cr) Nutrients and general ions concentrations Sodium (Na+) mg/l 3.1 3.1 2.9 2.9 3.0 Ist Calcium (Ca2+) mg/l 42.2 51.1 38.9 44.1 40.8 Ist - st Ammonia (NH4 ) mg/l 0.33 0.28 0.25 0.27 0.27 I - st Nitrates (NO3 ) mg/l 0.48 0.48 0.51 0.39 0.46 I - nd Nitrites (NO2 ) mg/l 0.032 0.037 0.038 0.033 0.031 II
Orto phosphate nd 3- mg/l 0.12 0.12 0.11 0.11 0.12 II (P-PO4 ) 2- st Sulphates (SO4 ) mg/l 12.4 11.9 12.1 12.2 12.0 I Chloride (Cl-) mg/l 0.4 0.3 0.4 0.3 0.4 Ist Total Nitrogen (TN) mg/l 1.01 0.92 0.94 0.95 1.02 Ist Heavy Metals concentrations Mercury (Hg) µg/l 0.016 0.017 0.015 0.012 0.011 Ist + st Arsenic (As3 ) µg/l 0.21 0.19 0.18 0.16 0.16 I Lead (Pb) µg/l 0.081 0.090 0.088 0.084 0.087 Ist + st Zinc (Zn2 ) µg/l 13.1 13.2 12.8 13.1 12.9 I Cadmium (Cd) µg/l 0.008 0.007 0.008 0.008 0.009 Ist Manganese (Mn - total) mg/l 0.021 0.021 0.022 0.021 0.020 Ist Iron (Fe – total) mg/l 0.815 0.852 0.876 0.881 0.873 IIIrd
Note: ambient air conditions: t = 30.8 °C, RH = 55.7%, pb = 1004.3 mbar Water temperature: 17.1 °C
Photo 28. “Ochiul Bei” – on Nera Gorge – Beusnita National Park. 50 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Table 9. Results obtained for parameter analysis in samples of Nera, on 4th august 2020 (from Bei and Nera from “Tunele” upstream) Measured values – 4th August 2020 Eco Parameter Unit N11 N12 Bei1 Bei2 Bei3 state pH - 7.81 7.80 7.82 7.79 7.78 - Conductivity µS/cm 297 308 311 311 306 - Oxygen concentration st Dissolved oxygen (DO) mgO2/l 11.1 11.2 11.1 11.0 11.2 I
Biochemical oxygen st mgO2/l 2.7 2.8 1.9 1.7 1.8 I demand (BOD – CBO5)
Chemical oxygen st mgO2/l 9.4 9.3 7.5 7.1 7.2 I demand (COD – CCO-Cr) Nutrients and general ions Sodium (Na+) mg/l 3.0 3.0 11.2 10.8 11.6 Ist Calcium (Ca2+) mg/l 49.5 48.1 64.2 70.1 69.4 Ist - st Ammonia (NH4 ) mg/l 0.38 0.40 0.07 0.06 0.06 I - st Nitrates (NO3 ) mg/l 0.42 0.37 0.07 0.07 0.07 I - nd st Nitrites (NO2 ) mg/l 0.030 0.030 0.008 0.009 0.008 II (I )
Orto phosphate nd st 3- mg/l 0.12 0.10 0.02 0.02 0.02 II (I ) (P-PO4 ) 2- st Sulphates (SO4 ) mg/l 11.7 11.5 4.5 5.8 5.2 I Chloride (Cl-) mg/l 0.3 0.3 0.1 0.1 0.1 Ist Total Nitrogen (TN) mg/l 0.89 0.81 0.27 0.22 0.24 Ist Heavy Metals concentrations Mercury (Hg) µg/l 0.014 0.016 0.009 0.009 0.009 Ist + st Arsenic (As3 ) µg/l 0.18 0.17 0.16 0.16 0.17 I Lead (Pb) µg/l 0.082 0.084 0.014 0.016 0.011 Ist + st Zinc (Zn2 ) µg/l 13.2 13.0 4.7 4.8 4.5 I Cadmium (Cd) µg/l 0.010 0.009 < LD < LD < LD Ist Manganese (Mn - total) mg/l 0.020 0.021 0.007 0.009 0.007 Ist Iron (Fe – total) mg/l 0.849 0.844 0.142 0.131 0.137 IIIrd (Ist)
Note: ambient air conditions: t = 30.8 °C, RH = 58.6%, pb = 1002.3 mbar Water temperature: Nera = 17.2 °C / Bei = 10.5 °C
Photo 29. View of Nera River, upstream of “La tunele”. 51 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
In the next figures (14 to 21) graphical representation of results obtained on surface water analysis on Nera River are presented.
Figure 14. Nera River. Concentrations obtained for DO, COD and BOD5.
- + Figure 15. Nera River. Concentrations obtained for NH4 and Na . 52 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
+ Figure 16. Nera River. Concentrations obtained for Calcium, Ca2 .
3- - - Figure 17. Nera River. Concentrations obtained for P-PO4 , NO2 and NO3 .
53 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
- 2- Figure 18. Nera River. Concentrations obtained for TN, Cl and SO4 .
Figure 19. Nera River. Concentrations obtained for Mn, Cd, Pb, As and Hg. 54 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 20. Nera River. Concentrations obtained for Zinc.
Figure 21. Nera River. Concentrations obtained for Iron. 55 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Photo 30. Beusnita waterfall– on Nera Gorge – Beusnita National Park.
On the basis of DIRECTIVE 2000/60/EC, annex V instructions and on the results obtained during the water quality assessment on Nera one can conclude that ESC – Ecological Status Classification varies from HIGH (quality) to GOOD on Nera.
The Oxygen concentration parameters (DO, COD and BOD5) varied on the length of the Nera River, with a decay from HIGH to GOOD in the + + - - 2- lower part of the river. Most of the nutrients (Na , Ca2 , NH4 , NO3 , SO4 , TN) st - fall into I class, HIGH quality while nitrites NO2 and orthophosphates P- 3- nd PO4 concentrations are in II class, GOOD. All heavy metals concentration were (Hg, As, Pb, Zn, Cd and Mn) very low, well into Ist class, HIGH quality. The only exception was found for Iron (Fe), whos values were constantly, to all length of analysed area, into IIIrd class, MODERATE water quality.
56 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
6.4. Water quality on Berzasca River. Surface water sampling on Berzasca River was conducted in 12 and 13 August in 8 sampling points/locations upstream river. Samples were analysed in situ or preserved for laboratory analysis. In figure 22 and table 10 the sampling points coding and geographical identification by GPS coordinates can be observed.
Figure 22. Sampling points for water quality analysis on Berzasca River.
Table 10. Sampling points GPS coordinates for Berzasca River water quality analysis. Sample No Sampling site Date Protection zone Coordinates B1 N44°38’50.56” / E21°56’ 52.00” B2 N44°39’15.41” / E21°58’ 22.75” Vth IUCN B3 N44°39’47.31” / E21°58’ 31.90” 12- “Protected areas” B4 N44°40’14.48” / E21°58’ 59.32” Berzasca river 13.08.2 (part of Iron B5 N44°40’26.81” / E21°59’ 35.82” 020 Gates natural B6 N44°40’42.70” / E22°00’ 18.12” park) B7 N44°40’11.29” / E22°00’ 34.49” B8 N44°40’35.36” / E22°01’ 34.80” 57 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Table 11. Results obtained for parameter analysis in samples of Berzasca river, on 12th and 13th august 2020
Measured values – 12 - 13th August 2020 Eco Parameter Unit B1 B2 B3 B4 B5 B6 B7 B8 state pH - 8.11 8.11 8.07 8.10 8.07 8.07 8.07 8.08 - Conductivity µS/cm 288 284 284 287 289 291 290 289 - Oxygen concentration st Dissolved oxygen (DO) mgO2/l 14.5 14.9 14.1 14.7 14.7 14.8 14.5 14.6 I
Biochemical oxygen st mgO2/l 1.4 1.4 1.5 1.6 1.5 1.4 1.5 1.5 I demand (BOD – CBO5)
Chemical oxygen st mgO2/l 5.8 5.9 6.1 5.7 5.5 5.4 5.3 5.4 I demand (COD – CCO-Cr) Nutrients and general ions Sodium (Na+) mg/l 2.1 2.2 2.1 2.1 2.1 1.8 1.8 1.8 Ist Calcium (Ca2+) mg/l 2.7 3.1 2.8 2.7 2.7 3.0 2.8 2.7 Ist - st Ammonia (NH4 ) mg/l 0.07 0.06 0.07 0.05 0.05 0.05 0.06 0.06 I - st Nitrates (NO3 ) mg/l 0.22 0.14 0.11 0.09 0.10 0.09 0.08 0.08 I - st Nitrites (NO2 ) mg/l 0.011 0.009 0.007 0.006 0.006 0.006 0.005 0.006 I
Orto phosphate st 3- mg/l 0.06 0.03 0.03 0.02 0.02 0.03 0.02 0.02 I (P-PO4 ) 2- st Sulphates (SO4 ) mg/l 8.4 5.4 4.2 3.8 3.8 4.3 3.9 4.0 I Chloride (Cl-) mg/l 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Ist Total Nitrogen (TN) mg/l 0.78 0.51 0.47 0.42 0.43 0.42 0.38 0.38 Ist Heavy Metals concentrations Mercury (Hg) µg/l 0.008 0.007 0.007 0.006 0.007 0.006 0.006 0.007 Ist + st Arsenic (As3 ) µg/l 0.074 0.072 0.062 0.061 0.068 0.061 0.060 0.065 I Lead (Pb) µg/l 0.014 0.014 0.015 0.013 0.014 0.014 0.012 0.013 Ist + st Zinc (Zn2 ) µg/l 1.14 0.89 0.77 0.91 0.81 0.75 0.77 0.75 I Cadmium (Cd) µg/l 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 Ist Manganese (Mn - total) mg/l 0.018 0.012 0.014 0.013 0.015 0.012 0.014 0.014 Ist Iron (Fe – total) mg/l 0.087 0.068 0.071 0.070 0.068 0.069 0.065 0.066 Ist Note: ambient air conditions: t = 32.1 °C, RH = 51.3%, pb = 1005.1 mbar, Water temperature: 16.9 °C
Photo 31. Berzasca River. 58 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
In the next figures (23 to 29) graphical representation of results obtained on surface water analysis on Nera River are presented.
Figure 23. Berzasca River. Concentrations obtained for DO, COD and BOD5.
- + + Figure 24. Berzasca River. Concentrations obtained for NH4 , Ca2 and Na . 59 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
3- - - Figure 25. Berzasca River. Concentrations obtained for P-PO4 , NO2 and NO3 .
- 2- Figure 26. Berzasca River. Concentrations obtained for TN, Cl and SO4 .
60 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 27. Berzasca River. Concentrations obtained for Mn, Cd, Pb, As and Hg.
Figure 28. Berzasca River. Concentrations obtained for Zinc.
61 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 29. Berzasca River. Concentrations obtained for Iron.
Photo 32. “Emys orbicularis” – water turtle on Berzasca River. 62 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Photo 33. “Salamandra” on Berzasca River Valley.
Photo 34. Berzasca River, on Danube mouth.
From all Danube’s tributaries in the analysed area Berzasca River is by far of the highest ecological status, HIGH (quality). All measured parameters are well under Ist class of surface water quality, with values so low that we can talk about “ecological purity” of Berzasca River. Is not surprising that in the area of Berzasca River valley and Sirinia River valley is where we can find protected species as “Testudo hermanni boettgeri”, “Emys orbicularis” turtles (photo 32) and “salamandra” (photo 33). (Photos 32 & 33 shot in summer 2020) A more detailed analysis in Conclusion chapter. 63 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
6.5. Water quality on Porecka River. Surface water sampling on Porecka River was conducted in July, September and October 2020 in 1 sampling point/locations, near Donji Milanovac village, close to Porecka river mount to Danube. Samples were analysed in situ or preserved for laboratory analysis. In figure 30 and table 12 the sampling points coding and geographical identification by GPS coordinates can be observed.
In table 13 the results obtained for surface water quality analysis on Porecka River are presented.
Figure 30. Sampling point for water quality analysis on Porecka River.
Table 12. Sampling point GPS coordinates for Porecka River water quality analysis. Sample No Sampling site Protection zone Coordinates The Porecka river is located in National Park N44°24’40.49” / SS12 Porecka River Djerdap E22°10’20.45” II IUCN1 “National Park”
64 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Table 13. Results obtained for parameter analysis in samples of Porecka River, July, September and October 2020. (water quality classes according to Serbian regulations)
Measured values – SS12 eco Parameter Unit 21 July 2020 11 September 2020 7 October 2020 state pH - 8.17 7.77 7.72 Ist Conductivity µS/cm 613 496 455 - Oxygen concentration rd th Dissolved oxygen (DO) mgO2/l 4.6 5.5 4.5 III - IV
Biochemical oxygen st nd mgO2/l 1.3 2.0 3.5 I – II demand (BOD – CBO5)
Chemical oxygen st mgO2/l 2.78 1.8 2.38 I demand (COD – Mn) Nutrients and general ions - st rd Ammonia (NH4 ) mg/l 0.07 0.01 0.46 I – III - nd Nitrates (NO3 ) mg/l 1.97 0 4.8 II - st rd Nitrites (NO2 ) mg/l 0.03 0.01 0.11 I - III Orto phosphate 0.12 0 0.01 st nd 3- mg/l I – II (P-PO4 ) 2- nd th Sulphates (SO4 ) mg/l 90 50 400 II - V Heavy Metals concentrations + st Arsenic (As3 ) µg/l
Photo 35. Sampling surface for water quality analysis on Porecka River.
In the next figures (30 to 29) graphical representation of results obtained on surface water analysis on Porecka River are presented.
65 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 31. Porecka River. Concentrations obtained for DO, COD and BOD5.
3- - - Figure 32. Porecka River. Concentrations obtained for P-PO4 , NO2 and NH4 . 66 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
2- Figure 33. Porecka River. Concentrations obtained for SO4 .
Figure 34. Porecka River. Concentrations obtained for Mn.
Figure 35. Porecka River. Concentrations obtained for Zinc.
A detailed analysis of results can be found in Conclusion chapter and also in the study performed under the same project: Milan Trumić, Grozdanka Bogdanović, Maja Trumić, Bogdana Vujić, Zaklina Tasić, Ljubisa Andrić, Boban Spalović, Influence of the copper mining activities in Majdanpek on Danube river, AEPS, ISBN 978-973-0-33596-5, 2021, http://aeps.upt.ro/downloads/
67 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
6.6. Water quality on Pek River. Surface water sampling on Pek River (Veliki Pek, Mali Pek and Saski Potok) was conducted in July, September and October 2020 in 11 sampling point/locations. For this study, only one sampling point, SS10, will be used, near Branicevo village, close to Pek river mount to Danube. Samples were analysed in situ or preserved for laboratory analysis. In figure 36 and table 14 the sampling points coding and geographical identification by GPS coordinates can be observed.
Figure 36. Sampling point for water quality analysis on Pek River.
Table 14. Sampling point GPS coordinates for Pek River water quality analysis. Sample No Sampling site Protection zone Coordinates The Pek river is located in National Park SS10 Pek River Djerdap N44°42’12.51” / E21°32’14.48” II IUCN1 “National Park”
In table 15 the results obtained for surface water quality analysis on Pek River are presented.
68 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Table 15. Results obtained for parameter analysis in samples of Pek River, July, September and October 2020. (water quality classes according to Serbian regulations) Measured values – SS10 (Branicevo) eco Parameter Unit 21 July 2020 11 September 2020 7 October 2020 state pH - 7.79 7.79 7.77 Ist Conductivity µS/cm 698 795 786 - Oxygen concentration rd Dissolved oxygen (DO) mgO2/l 5.1 5.0 5.5 III
Biochemical oxygen st mgO2/l 1.9 1.4 4.0 I demand (BOD – CBO5)
Chemical oxygen demand st mgO2/l 2.95 1.8 4.13 I (COD – Mn) Nutrients and general ions - rd Ammonia (NH4 ) mg/l 0.42 0.01 0.08 III - nd Nitrates (NO3 ) mg/l 1.6 0 0 II - rd Nitrites (NO2 ) mg/l 0.09 0 0.05 III Orto phosphate 0.09 0 0.01 IIInd 3- mg/l (P-PO4 ) 2- nd th Sulphates (SO4 ) mg/l 150 367 250 III - V Heavy Metals concentrations + st Arsenic (As3 ) µg/l
Photo 36. Sampling for water quality analysis on Pek River. In the next figures (37 to 41) graphical representation of results obtained on surface water analysis on Porecka River are presented.
69 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 37. Pek River. Concentrations obtained for DO, COD and BOD5.
3- - - Figure 38. Pek River. Concentrations obtained for P-PO4 , NO2 and NH4 . 70 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
2- Figure 39. Pek River. Concentrations obtained for SO4 .
Figure 40. Pek River. Concentrations obtained for Mn.
Figure 41. Pek River. Concentrations obtained for Zinc.
71 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Photo 37. Sampling for water quality analysis on Pek River, upper side On the basis of DIRECTIVE 2000/60/EC, annex V instructions and on the results obtained during the water quality assessment on Pek River one can conclude that ESC – Ecological Status Classification varies from MODERATE to GOOD on Pek river.
The oxygen concentration parameters COD and BOD5 are in Ist class, but Dissolved Oxygen DO in on IIIrd class, showing a stress on Pek river water quality. As all nutrients (nitrates, nitrites, ammonia, orthophosphates and sulphates) fall into IIIst class, most probably the stress on river oxygen regime comes from high nutrients concentration.
The heavy metals concentration in Danube surface waters in analysed area were all (As, Pb, Zn, Cd and Mn) very low, well into Ist class, HIGH quality.
A detailed analysis of results can be found in Conclusion chapter and also in one of the studies performed under the AEPS project: Milan Trumić, Grozdanka Bogdanović, Maja Trumić, Bogdana Vujić, Zaklina Tasić, Ljubisa Andrić, Boban Spalović, Influence of the copper mining activities in Majdanpek on Danube river, AEPS, ISBN 978-973-0-33596-5, 2021, http://aeps.upt.ro/downloads/ 72 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
6.7. Water quality on Cerna River. Surface water sampling on Cerna River was conducted in 19 October 2020 in 6 sampling points/locations upstream river. Samples were analysed in situ or preserved for laboratory analysis. In figure 42 and table 16 the sampling points coding and geographical identification by GPS coordinates can be observed.
Figure 42. Sampling points for water quality analysis on Cerna River.
Table 16. Sampling point GPS coordinates for Cerna River water quality analysis. Sample No Sampling site Protection zone Coordinates C1 The Cerna river is N44°45’36.81” / E22°23’36.81” C2 located in National N44°52’00.13” / E22°24’26.29” C3 Park “Domogled – N44°53’02.37” / E22°25’18.86” Cerna river C4 Valea Cernei” N44°57’10.21” / E22°28’16.40” C5 II IUCN1 N45°08’10.16” / E22°43’32.89” C6 “National Park” N45°14’27.44” / E22°49’58.17”
73 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Table 17. Results obtained for parameter analysis in samples of Cerna, on 19th October 2020 Measured values – 19th October 2020 Eco Parameter Unit C1 C2 C3 C4 C5 C6 state pH - 7.34 7.33 7.38 7.42 7.38 7.31 - Conductivity µS/cm 372 394 388 389 378 377 - Oxygen concentration st nd Dissolved oxygen (DO) mgO2/l 5.7 6.8 9.9 10.1 10.5 10.2 I – II Biochemical oxygen Ist – mgO2/l 7.4 6.5 3.1 2.3 2.2 2.2 demand (BOD – CBO5) IIIrd
Chemical oxygen demand st nd mgO2/l 18.1 16.5 8.4 7.2 6.9 6.9 I – II (COD – CCO-Cr) Nutrients and general ions concentrations Sodium (Na+) mg/l 3.6 3.2 3.2 3.5 3.4 3.4 Ist Calcium (Ca2+) mg/l 41.2 38.9 39.1 29.8 33.4 27.9 Ist - st nd Ammonia (NH4 ) mg/l 0.74 0.65 0.11 0.09 0.07 0.09 I – II - st Nitrates (NO3 ) mg/l 0.34 0.33 0.22 0.14 0.12 0.12 I - st Nitrites (NO2 ) mg/l 0.028 0.028 0.017 0.012 0.014 0.014 I
Orto phosphate st 3- mg/l 0.09 0.08 0.06 0.06 0.06 0.05 I (P-PO4 ) 2- st Sulphates (SO4 ) mg/l 37.2 40.5 34.1 22.4 5.4 4.8 I Chloride (Cl-) mg/l 0.6 0.6 0.3 0.2 0.2 0.2 Ist Total Nitrogen (TN) mg/l 0.89 0.77 0.54 0.52 0.49 0.51 Ist Heavy Metals concentrations Mercury (Hg) µg/l 0.030 0.026 0.015 0.011 0.014 0.011 Ist + st Arsenic (As3 ) µg/l 0.088 0.087 0.087 0.088 0.086 0.079 I Lead (Pb) µg/l 0.054 0.016 0.018 0.014 0.016 0.017 Ist + st Zinc (Zn2 ) µg/l 12.1 12.8 10.1 8.9 8.8 7.5 I Cadmium (Cd) µg/l 0.007 0.005 0.006 0.005 0.005 0.006 Ist Manganese (Mn - total) mg/l 0.057 0.061 0.055 0.049 0.051 0.032 IInd Iron (Fe – total) mg/l 0.462 0.511 0.499 0.397 0.421 0.394 IInd
Note: ambient air conditions: t = 15.6 °C, RH = 68.7 %, pb = 1014.7 mbar, Water temperature: 12.2 °C In the next figures (43 to 50) graphical representation of results obtained on surface water analysis on Porecka River are presented.
Figure 43. Cerna River. Concentrations obtained for DO, COD and BOD5. 74 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
- + Figure 44. Cerna River. Concentrations obtained for NH4 and Na .
+ Figure 45. Cerna River. Concentrations obtained for Calcium, Ca2 .
75 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
3- - - Figure 46. Cerna River. Concentrations obtained for P-PO4 , NO2 and NO3 .
- 2- Figure 47. Cerna River. Concentrations obtained for TN, Cl and SO4 . 76 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 48. Cerna River. Concentrations obtained for Mn, Cd, Pb, As and Hg.
Figure 49. Cerna River. Concentrations obtained for Zinc.
77 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 50. Cerna River. Concentrations obtained for Iron.
Photo 38. Cerna River, upper part. In terms of water quality Cerna River can be considered a “text book” river. In its upper (wilder) part all analysed parameters (dissolved oxygen, biological oxygen demand, chemical oxygen demand, nitrites, nitrates, ammonia, phosphates, and total nitrogen) were all in Ist class, HIGH water quality. However, after Cerna passes first human settlements, Baile Herculane, Toplita and gets tributary from Belareca river, on its last ~20 km the water quality decreases dramatically, “transforming” itself into GOOD/MODERRATE quality river. A more detailed analysis of results can be found in Conclusion chapter.
78 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
7. Conclusion and results analysis
The Danube River Basin Management Plan is at European Union level managed by The International Commission for the Protection of the Danube River (ICPDR) that works to ensure the sustainable and equitable use of waters in the Danube River Basin. The work of the ICPDR is based on the Danube River Protection Convention (DRPC), the major legal instrument for cooperation and transboundary water management in the Danube River Basin. (https://www.icpdr.org/main/danube-basin)
In this frame and after analysing the results obtained by AEPS project team experts after sampling and analysis surface water on Danube, one can conclude that Ecological Status Classification varies from HIGH (quality) to GOOD on Danube, with oxygen concentration parameters (DO, COD and nd + + - - BOD5) are all in II class, GOOD; most of the nutrients (Na , Ca2 , NH4 , NO3 , 2- st 3- SO4 , TN) fall into I class, HIGH quality while orthophosphates P-PO4 concentrations classifies Danube water quality in IIIrd class, MODERATE.
The heavy metals concentration in Danube surface waters in analysed area were all (Hg, As, Pb, Zn, Cd and Mn) very low, well into Ist class, HIGH quality. The only exception was found for Iron (Fe), whose values were constantly, to all length of analysed area, into IIIrd class, MODERATE water quality. With the exception Berzasca river, all other investigated rivers (Cerna, Nera, Pek, Porecka) showed similar pattern for heavy metals, while all (Hg, As, Pb, Zn, Cd and Mn) showed concentration well under Ist class, iron (Fe) was constantly in IInd or IIIrd quality class. This would bring to our minds that this pattern may suggest that high iron (Fe) concentration in surface waters of Danube, Nera, Cerna, Pek and Porecka may be caused by regional geomorphic characteristics of surrounding mountains and that iron concentrations are given by washout of naturally occurred iron deposits. However, if we look closely on table 9 (chapter 6.3) where water quality was also analysed for one of Nera’s tributary, Bei river, the iron situation is completely different: while in Bei River (small, no human activity on banks) the iron concentration is ~ 0.14 mg/l, in Nera is ~0.85 mg/l, even if both Bei
79 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
and Nera springs from Semenic Mountains (part of Western Carpathians). So, one clear conclusion is not easy to draw on “Fe issue”.
Another issue observed was on nutrients concentrations (orthophosphates, ammonia, nitrates, nitrites and sulphates). The issues is found on Nera, as the rivers flows thru numerous villages, probably collects washouts (or direct dump) from villages/house-holds/farms septic tanks. As both summer and autumn of 2020 were extremely drought is unlikely that nutrients reaching Nera river came from agricultural land washout. Similar or worst situation was found on Pek and Porecka rivers. Danube on the other hand was in 1st class of water quality (High quality) in terms on nutrients, due to its volume and capacity of self-purification, with one exception, orthophosphates.
One significant cause for high content of nutrients in Serbian river bodies can be deducted from figure 51 that shows the technological status of urban waste treatment plants in Europe, in correlation with population that benefits from centralized urban waste water collection systems. The most performant waste water treatment plants are so called “tertiary”, meaning that provide phosphorus and nitrogen reduction before dumping.
Figure 51. Urban waste water collection and treatment in Europe, 2017. [49]
80 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
The “secondary” waste water treatment plants provide only biological treatment, “primary” means that the system is only equipped with settling tanks and “collected without treatment” that the urban waste water system only collects the waste waters from population and dumps it without any treatment in natural water bodies.
In order to solve this issues the Urban Waste Water Treatment (UWWT) Directive (91/271/EEC) was enforced, and equivalent national legislation for non-EU countries, and is intended to protect surface waters from the adverse effects of waste water discharges such as oxygen consuming organic pollution, which degrades aquatic life but also prevent pollution thru microbiological contamination with pathogens.
Unfortunately, in Serbian case, only a handful of urban waste water systems are in the “tertiary” zone, while more that 50% of the Serbian population that benefit from waste water systems are serviced by “collected without treatment”, bringing a significant stress onto ecological status of Serbia rivers.
Figure 52. Urban waste water treatment in Europe, reference situation 2015. [50]
Up to 2007 Romania was in a similar situation with Serbia, in terms of waste water systems, the situation improved significantly (as seen in figures 51 and 52) with entrance into European Union Community when 81 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
enforcement of EU directives become effective with significant financial support thru EU cohesion policy. However, even with significant progress in urban waste water treatment systems (such as in western Romania: Timisoara, Arad, Oradea) in other areas the progress is slow, as an example in Bucharest (with over 3 million inhabitants) the waste water system spills into Dimbovita river (and subsequent into Danube) about 50% of its waste waters without any treatment.
At European level, the stress on surface waters quality has constantly decreased in the last 2 decades, with main water quality parameters such as Biological Oxygen demand, Ammonia, Phosphates and Nitrates following a significant decrease in concentration.
Note: Concentrations are expressed as annual mean concentrations. Figure 53. Trends in Biochemical Oxygen demand, nitrate, phosphates and ammonium in European rivers. [51] 82 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
The decrease in BOD and ammonium concentrations is mainly because of a general improvement in waste water treatment throughout Europe. The decrease in phosphorus concentration is likely related to improvements in waste water treatment and the reduction of phosphorus in detergents. The decrease of nitrates is likely related to effects of measures to reduce agricultural inputs of nitrate and improvements in waste water treatment. In Central and Eastern European countries, the economic decline of the 1990s also contributed to a decrease in pollution from manufacturing industries.
In terms of chemical status of surface waters in Interreg IPA-CBC Romania-Serbia programme eligibility area, all surface waters investigated, Danube, Nera, Pek, Cerna, Porecka and Berzasca rivers showed HIGH (quality) or GOOD (quality) chemical status. Chemical status is defined by concentrations of priority substances (such as heavy metals) defined in Environmental Quality Standards Directive 2008/105/EC amended by Priority Substances Directive 2013/39/EU). Our findings are consistent with the Water Information System for Europe (WISE) in the frame of Water Framework Directive map contains information from the 2nd River Basin Management Plans (RBMPs) reported by EU Members States, as seen in figure 54.
Figure 54. EU surface water bodies – Chemical status by country (2nd River Basin Management Plan) [52]
83 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
In conclusion, in the area analysed by us, in Interreg IPA-CBC Romania-Serbia programme eligibility area, the surface water quality of Danube and its main tributaries in the area, Nera, Porecka, Berzasca, Pek and Cerna rivers can be classified as HIGH -quality (all over its length for Berzasca river), GOOD and MODERATE, on various segments of water bodies.
The main stresses identified in the area are from waste water treatment systems (or lack of them), agricultural land washouts - contributing to pollution of surface waters with ammonia, phosphates and nitrites; and industrial activity with an emphasis on mining activity impact in Majdanpek on water quality of Pek river.
In our Romania-Serbia cross-border area, especially as is one of the most beautiful and wild part of entire Danube’s course to Black see, we must give a more focused attention to prevent 0rganic pollution from waste water as well as diffuse runoff from agriculture, as they negatively affect aquatic ecosystems, causing loss of oxygen and changes in species composition (i.e. deterioration of ecological status).
However, during the work on present study, in literature research we noted, besides more local/regional stress given by organic pollution of our waters, 2 new threats on our waters, with a significant impact in near future: increase in Danube’s water temperature (yearly average) and decrease of river flows in our region, due to global climate change with a significant impact in Balkan region in terms of increase incidents of droughts.
Figure 55. EU surface water bodies – Chemical status by country (2nd River Basin Management Plan) [53] 84 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
Figure 56. Model-based estimate of past change in annual river flows [54]
According to Europe flow data inventory and scientific estimates for near future trends [54], run-off showed positive trends in western and northern Europe and negative trends in southern and parts of Eastern Europe, meaning that our region decision making actors should already focus not only on nutrients and chemical pollution of our rivers but also on actions for long term measures for fresh water supply security and assurance for the future!
85 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
References
[1] Nacionalni park Đerdap (https://npdjerdap.rs/en/) [2] www.pnportiledefier.ro/ [3] C. Tetelea, Morphometric analysis to extrapolate geo-ecological potential of the rivers in the “Iron Gates” natural park (Banat, Romania), Transylvanian Review of Systematical and Ecological Research, Vol. 16(3), pp. 29-46, 2014, DOI: 10.1515/trser-2015-0031 [4] www.wikiwand.com/en/Iron_Gates [5] www.wikipedia.org/wiki/Iron_Gates_Natural_Park [6] https://rsis.ramsar.org/ [7] www.uncover-romania.com [8] https://en.wikipedia.org/wiki/Nera_Gorge-Beusnita_National_Park [9] Ianas A.N., Germain D., Quantifying landscape changes and fragmentation in a national park in the Romanian Carpathians. Carpathian Journal of Earth and Environmental Sciences, Vol. 13, No. 1, (2018) [10] www.wikiwand.com/en/Nera_Gorge-Beușnița_National_Park [11] http://turism.cjcs.ro/ro/parcul-national-cheile-nerei.php [12] https://cheilenerei.usab-tm.ro/descriere_ap.html [13] https://www.edusoft.ro/parcul-national-cheile-nerei-beusnita-un-loc-binecuvantat/ [14] https://www.edusoft.ro/parcul-national-cheile-nerei-beusnita-un-loc-binecuvantat/ [15] https://en.wikipedia.org/wiki/Berzasca_(river) [16] Banaduc D., Curtean-Banaduc A., The “Porţile de fier/Iron Gates” nature park (Romania) some Danube northern tributaries fish fauna, Transylvanian Review of Systematical and Ecological Research, Vol. 16(3), pp. 165-170, 2014, DOI: 10.1515/trser-2015-0040 [17] https://business24.ro/turism/destinatii-turistice-romania/o-comuna-saraca-din-clisura- dunarii-devine-paradis-turistic-1534837 [18] https://wikivisually.com/wiki/Pore%C4%8Dka_River [19] https://wikivisually.com/wiki/File:Panorama_Donjeg_Milanovca_1.jpg [20] https://wikivisually.com/wiki/Lepenski_Vir [21] https://en.srebrnojezero.com/okolina/the-confluence-of-the-pek-river/ [22] Dejan Dimkic, Stevan Prohaska, Bojan Stankovic and Predrag Pajic, Alluvial Water Source Capacity under the Climate Change and Other Impacts—Case Study of the Pek River in Serbia, Proceedings, 2018, 2, 596; doi:10.3390/proceedings2110596 [23] https://tamoiovde.wordpress.com/2015/05/16/zlatonosna-reka-pek/ [24] https://en.wikipedia.org/wiki/Pek_(river) [25] http://www.tokucevo.org/reka-pek/ [26] https://en.wikipedia.org/wiki/Domogled-Valea_Cernei_National_Park [27] www.romaniaturistica.ro/parcul-national-domogled-valea-cernei [28] https://hereihike.com/visit-domogled-valea-cernei-national/ [29] www.domogled-cerna.ro
86 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
[30] Charting our water future, a report of the 2030 Water Resources Group, http://www.mckinsey.com/client_service/sustainability/latest_thinking/charting_our_w ater_future [31] COM 673/2012, Communication from the Commission to the European Parliament, the Council, the European economic and social committee and the Committee of the regions - A Blueprint to Safeguard Europe's Water Resources [32] Ahuja S., (ed.) Monitoring Water Quality: Pollution Assessment, Analysis, and Remediation, Elsevier, ISBN: 978-0-444-59395-5, 2013 [33] EU Water Framework Directive - https://ec.europa.eu/environment/water/water- framework/ [34] Ordinance no. 161/16.02.2006 for the approval of the Norm regarding the classification of surface water quality in order to establish the ecological status of water bodies, Ministry of Environment and Water Management, Official Gazette 511` in 13.06.2006. [35] The Law on Waters - “Official Gazette of the RS“, No.30/2010 [36] Regulation on emission limit values of polluting substances in surface and groundwater’s and deadlines for their achievement (“Official Gazette of the RS”, No. 50/12) [37] U.S. Geological Survey, Dissolved Oxygen and Water, Water Science School, https://www.usgs.gov/special-topic/water-science-school/science/ [38] Togue F.K., Kuate. G.L.O., Oben L.M., Physico-Chemical characterization of the surface water of Nkam River using the Principal Component Analysis, Journal of Materials and Environmental Sciences, V.8 (6), pp. 1910-1920, 2017 [39] U.S.EPA, Water: Monitoring & Assessment, 5.2 Dissolved Oxygen and Biochemical Oxygen Demand, https://archive.epa.gov/water/archive/web/html/vms52.html [40] ICPDR, Joint Danube Survey, Significant Water Management Issue 2 – Nutrient Pollution, https://www.icpdr.org/main/ [41] Haygarth P., Jarvis S., Agriculture, Hydrology and Water Quality, CABI Publishing, New York, ISBN 0-85199-545-4, 2001 [42] Gorski J., Dragon K., Kaczmarek P., Nitrate pollution in the Warta River (Poland) between 1958 and 2016: trends and causes, Environmental Science and Pollution Research, Vol.26, pp. 2038–2046, 2019, https://doi.org/10.1007/s11356-017-9798-3 [43] Water Quality Association (WQA), Learn about water: Water Common Contaminants, https://www.wqa.org/ [44] Ireland Environmental Protection Agency, Integrated Water Quality Report 2012, Appendix 7: information on water quality parameters, http://www.epa.ie/ [45] Namiesnik J., Rabajczyk A., The speciation and physico-chemical forms of metals in surface waters and sediments, Chemical Speciation & Bioavailability, Vol. 22(1), pp. 1- 24, 2010, https://doi.org/10.3184/095422910X12632119406391 [46] Li P., Qian H., Howard K., Wu J., Lyu X., Anthropogenic pollution and variability of manganese in alluvial sediments of the Yellow River, Ningxia, northwest China, Environmental Monitoring and Assessment, Vol. 186, pp. 1385–1398, 2014, https://doi.org/10.1007/s10661-013-3461-3 [47] Lenntech, Metals in aquatic freshwater, https://www.lenntech.com/aquatic/metals.htm 87 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
[48] Milan Trumić, Grozdanka Bogdanović, Maja Trumić, Bogdana Vujić, Zaklina Tasić, Ljubisa Andrić, Boban Spalović, Influence of the copper mining activities in Majdanpek on Danube river, AEPS, ISBN 978-973-0-33596-5, 2021, http://aeps.upt.ro/downloads/ [49] European Environmental Agency, 2017, https://www.eea.europa.eu/data-and- maps/indicators/urban-waste-water-treatment/ [50] ICPDR, DanubeGIS platform, built on basis of Danube River Basin Management Plan 2015, https://www.danubegis.org/ [51] European Environmental Agency, 2020, Indicator Assessment: Nutrient trends in European water bodies; Trends in Biochemical Oxygen demand and ammonium in European rivers, https://www.eea.europa.eu/data-and-maps/indicators/ [52] European Environmental Agency, 2018, Chemical status of surface water bodies, https://www.eea.europa.eu/themes/water/european-waters/water-quality-and-water- assessment/ [53] EIONET, European Environment Information and Observation Network, EEA Report No 1/2017, ISBN: 978-92-9213-835-6 [54] Stahl K., Tallaksen L. M., Hannaford J., van Lanen H. A. J., 2012, Filling the white space on maps of European runoff trends: estimates from a multi-model ensemble, Hydrology and Earth System Sciences, Vol. 16(7), pp.2035–2047 (DOI: 10.5194/hess-16-2035-2012)
88 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.
89 Cooperation beyond borders. Interreg-IPA Cross-border Cooperation Romania-Serbia Programme is financed by the European Union under the Instrument for Pre-accession Assistance (IPA II) and co- financed by the partner states in the Programme.