Pollution of the Skadar Lake

Authors:

Dr Dr Danijela Šundić Branko Radujković

Podgorica, December 2012

Table of contents

1. INTRODUCTION ...... 4

2. THE MAIN CHARACTERISTICS OF LAKE SKADAR...... 5 2.1. Geographical position ...... 5 2.2. The depth of the lake ...... 5 2.3. Sublacustric springs (‘’oka’’, ‘’vrulje’’) ...... 5 2.4. Drainage basin of Lake Skadar ...... 5 2.5. Ground waters ...... 6 2.6. Water currents ...... 6 2.7. Water temperatures ...... 8 2.8. Transparency ...... 8 2.9. Electroconductivity ...... 8 2.10. Water balance of Lake Skadar ...... 8 2.10.1. Water level fluctuation of Lake Skadar ...... 8 2.10.2. Surface area and volume of Lake Skadar ...... 8 2.10.3. Flooded and wetland areas ...... 10

3. CLIMATE CHARACTERISTICS OF ZETA – BJELOPA PLAIN ...... 11 3.1. Air temeperature...... 11 3.2. Precipitation...... VLIĆI 12 3.3. Winds ...... 15

4. SOURCES OF POLLUTION OF LAKE SKADAR ...... 17 4.1. Point (concentrated) sources...... 17 4.1.1. Waste waters ...... 17 4.1.2. Air pollution ...... 21

4.2. Nonpoint (dispersed) sources ...... 25 4.2.1. KAP’s solid waste disposal site...... 25 4.2.2. “Red mud” disposal of KAP ...... 26 4.2.3. Contamination of ground waters under the solid waste and the “red mud” disposal site of KAP ...... 30 4.2.4. Nikšić Steelworks waste disposal site ...... 33 4.2.5. Illegal waste dumping ...... 34 4.2.6. Agricultural areas ...... 34 4.2.7. Other nonpoint sources of pollution ...... 36

5. WATER AND SEDIMENT POLLUTION OF LAKE SKADAR ...... 37 5.1. Physico-chemical characteristics of the lake ...... 37 5.2. Water pollution ...... 42 5.3. Ground water pollution ...... 50 5.4. Sediment pollution ...... 51

6. QUALITY, CLASSIFICATION AND CATEGORISATION OF WATER AND SEDIMENT OF LAKE SKADAR...... 56 6.1. Trophic status of the lake ...... 56 6.1.1. Phytoplankton as bioindicator of trophic level ...... 57 6.1.2. Aquatic oligochaetes as bioindicators of trophic level ...... 59

6.2. Saprobic status of the lake ...... 60 6.2.1. Phytoplankton as bioindicator of saprobity ...... 60 6.2.2. Aquatic oligochaetes as bioindicators of saprobity ...... 61

6.3. BMWP index ...... 63 6.4. ASPT index ...... 64 6.5. WQI index ...... 65 6.6. IOBL index ...... 67

7. POLLUTION IMPACT ON LIVING ORGANISMS OF THE LAKE AND EVOLUTION OF CHANGES70 7.1. Ichthyofauna ...... 70 7.2. Ornithofauna ...... 71 7.3. Phytoplankton ...... 73 7.4. Macrophytes...... 74 7.5. Macrozoobenthos ...... 76 7.5.1. Oligochaetes ...... 78

7.6. Bioaccumulation ...... 81 7.6.1. Bioaccumulation in macrophytes...... 81 7.6.2. Bioaccumulation in fish ...... 84

8. FACTORS AFFECTING THE IMPLEMENTATION OF IDEAL MANAGEMENT OBJECTIVES ...... 87

9. CONCLUSION AND RECOMMENDATIONS ...... 89

10. REFERENCES ...... 90

1. INTRODUCTION

This report is structured so that it summarizes available results on pollution research of Lake Skadar, pollution sources and pollution pathways, as well as the consequences for living organisms and humans. This issue is prepared within the frameworkof the cross-border project: ''Integrated Ecosystem Management of Lake Skadar–EMA-Plan''. The report was prepared for the NGO Green Home, who realizes this project in partnership with the Research Center for Rural Development in Albania. The project is supported by the Delegation of the European Commission to Montenegro and Albania under the IPA cross-border program Albania–Montenegro 2007-2013.

In this report the following aspects are elaborated:

• an analysis of the main characteristics of lake ecosystems (hydrological, hydrographic, climate),

• the identification of point (concentrated) and nonpoint (dispersed) sources of pollution in the lake's ecosystem,

• the characteristics of different types of waste water and waste, which generate most important pollutants are identified,

• an analysis of the general physical and chemical characteristics of the water and sediment over a long period,

• analysis of the chemistry of water and sediment as a result of various types of pollution,

• identification of quality, categorization and classification of water and sediment in the lake,

• the impact of pollution on living organisms and the evolution of the changes through a decade long period are presented,

• identification of factors influencing the implementation of ideal management objectives.

2. THE MAIN CHARACTERISTICS OF LAKE SKADAR

2.1. Geographical position

Lake Skadar is situated between Malo Blato in the north (42°21’54’’ N 19°09’52’’ E) and the source of the River Bojana in the south (42°03’15’’ N 19°30’00’’ E); the most westerly point is near Rijeka Crnojevica: 42°21’19’’ N 19°01’28’’ E; the most easterly point is 42°03’15’’ N 19°30’00’’ E, near Skadar It is the largest lake on southeastern Europe and its size varies with the season between 360 km2 and 500 km2 (according to some authors 530 km2, even 600 km2) (Beeton, 1981a). The lake is 50 km long, maximum 14 km wide, and the shore line is 207 km long, at average water-level. The correlation between the water level, size and volume of the lake is shown in the table 1.

Tabl e 1. Surface and volume of Lake Skadar, depending on water level (after Kneže 9; modified). vić, 200 Water level (masl) Size (km2) Volume (km3) 4.60 353.30 1.71 5.25 381.25 1.96 6.37 418.01 2.39 8.55 463.00 3.35 9.82 500.04 3.97

2.2. The depth of the lake

The lake is a cryptodepression; its minimal water level is about 5 m above the sea level. The maximal depth with this water level is 8.3 m, and 5.01 m on average. This does not refer to the depth of sublacustric springs (“oka”, “vrulje”) that can be as deep as 60 m. The depths of the lake depend on the water level.

2.3. Sublacustic springs (‘’oka’’, ‘’vrulje’’)

These springs appear at the bottom and around funnel depressions, of various depths. They are mostly found near the north, northwest and southwest shores of the lake. There are over 60 named ones, with known depths; numerous ‘’oka’’ are not named and their depths are not known. The deepest ‘’oka’’ are by the southwest edge of the lake: 10-60 (80!) m. The spring discharge of these ‘’oka’’ is not well known or not known at all. It varies seasonally and it is the biggest during autumn rains and the periods when snow melts in spring. It is estimated that the sublacustric springs bring on average 60 m3/s water to the lake (18% of the total inflow) (table 2).

2.4. Drainage basin of Lake Skadar

The drainage basin of Lake Skadar is part of the Adriatic Sea drainage basin and has a size of 5 490 km2; out of which 4 460 km2 are in Montenegro and 1 030 km2 belong to the territory of Albania (map 1). The two largest rivers of this basin are Zeta k, Bistrica, Glibovac, Moštanica,

(with its tributaries: Gračanica, Mrkošnica, Grabovi 5

(with its tributaries: Ratna, Požnja, Topli, Vrela, Ibrištica, Mrtvica, Melještak, Obeštica,Bogutovski, Smrdan, Zeta, artificial Sušica, Suvodol,canal Mareza, Morava, Sitnica, Rimanić, Javorski, Brestica Slatina, and Koštanica, Širalija) and Sjevernica, Morača

Kruševački, Mala rijeka, Ribnica and Cijevna). Table 2. Water balance of Lake Skadar (after Water balance (m3/s) Radulović, 1997). Water inflow Precipitation 30 river 210 9 OrahovšticaMorača river 5 CrmnicaRijeka Crnojevića river 4 Other watercourses 17 Sublacustric 60 springs Σ 335

Water outflow Bojana river –320 Evaporation –15 Σ 335

At the southern part of the Zeta Plain there are a range of smaller watercourses that flow directly into Lake Skadar: Rujela, Mala and Velika Mrka, Pjavnik, Zetica, Mala

Gostiljska river. Smaller and occasional watercourses from the Albanian side are: Proni i TMorača,at, Sica, Šegrtnica, Proni i Rjolit, Rijeka Proni Crnojevića, and Vraka. Orahovštica, Crmnica, Plavnica, Karatuna and the

2.5. Ground waters

The ground waters of this area lay from the plain north of Podgorica and mouth of Zeta river and extend to the Lake Skadar (map 1.). The size of the area is around 157.4 km2. The thickness, and valleys of theĆemovsko, aquifer Zagoričko,filled with Dinoško,water varies Tološko from and 20 Lješkoto 60 m and it is thinner in the northern part. Elevation of the water level in this area are at H=35 masl and at the southern at H=10 masl therefore, the direction of the groundwater flows is from north to south (to the lake).

2.6. Water currents

Water mass movement are either turbulent, caused by the influx of water from sublacustric springs and watercourses or they are surface, depending on the wind direction and strength.

Map 1. Drainage basin of Lake Skadar (after Royal Haskoning, 2006; modified): ground waters area.

2.7. Water temperature

Minimal average water temperature during the year varies from 7.3°C (February) and 25.4°C (August), whereas, the average maximal varies between 8.6°C

(February) and 30.1°C (August). Relatively high temperatures are measured during the whole period from May to September (22°C to 30°C) (table 22).

2.8. Transparency

Transparency is reduced in warmer months, due to increased density of plankton populations. Minimal transparency is only about 0.60 m in August, and maximal goes up to 4 m in the winter period (table 22.).

2.9. Electroconductivity

The values measured in the lake range from 179 to 415 s/cm and correspond to the values specified for the Category II of surface water. Seasonal variations of this parameter are not stated. μ

2.10. Water balance of Lake Sakadar

From the table 2 it is obvious that the overall, average water inflow to the lake is around 335 m3/s, and that it is the same as the outflow of the River Bojana plus the evaporation from the surface. Annually this amounts to over 10.2 km3, which shows that the water in the lake changes about 5 times per year (at normal water level of about 5.5 meters above sea level the lake volume is 1.96 km3 – table 1). The largest inflow is brought by the river (and tributaries) – 73%, and then sublacustric springs – over 17% and direct precipitation – about 9%. The inflow depends on the season, i.e. the amount of precipitationMorača (whose average, monthly values during the four summer months are below 50 mm).

2.10.1. Water level fluctuation of Lake Skadar

Water level of Lake Skadar, in the observed 40-year period (from 1961 to 2001) ranged from a minimum of 4.76 m above sea level (1985), to a maximum of 9.86 masl (1963). The average maximum, medium and minimum water level in this period is presented on graph 1. It is noticeable that the water level from 1981 to 2001 is lower than in the earlier period (with the exception in 1996). There is some opinion that this is due to anthropogenic factors, namely because of the construction of reservoirs on the rivers Zeta and Drim. The graph 2 shows the data of water levels measurements in the 40-year period. It is observed that the changes in water level correlated with precipitation, with a phase delay of approximately one month.

2.10.2. Surface area and volume of Lake Skadar

Surface area and volume of the lake are directly dependent on its water level. It is clear that both of them increase during the autumn and winter period, i.e. during

times of increased precipitation. Table 1. shows the relationship between the water level, the surface and lake volume. Thus, with the minimum water level of 4.60 meters above sea level, the surface is about 353 km2, and volume of 1.71 km3. At medium water level, 5.25 masl a surface is 381.25 km2, and volume of about 2 km3, and the highest water level, the lake surface exceeds 500 km2, and the volume is doubled (3.97 km3). 8

maximum medium minimum

6 (masl) level water

5 1961 1966 1971 1976 1981 1986 1991 1996 2001 year Graph 1. The average maximum, medium and minimum water level of Lake Skadar, measured at the station of Plavnica for the period: 1961- 2002 (according to Kneževi , 2009; modified).

ć 8.5

7.5

6.5 maximum medium 6 minimum 5.5 water level (masl) level water 5

4.5 4 I II III IV V VI VII VIII IX X XI XII

months

Graph 2. The average maximum, medium and minimum monthly water level of Lake Skadar, from the station of Plavnica for the period: 1961-2002 (according to Kneževi , 2009; modified).

ć 9

2.10.3. Flooded and wetland areas

This term encompasses the areas of the Zeta Plain, which are under the influence of periodic or continuous lake water inundation, in which the processes of swamping, marshing and soil erosion occur. Those areas can be divided into four zones (Kneževi , 2009). ć Zone I - constantly under water, it is a zone of wetlands and peat which extends when the water level is below 5.5 masl. It occupies also small areas spread along the northern edge of Malo Blato. Most of the year, zone I, is under water or the water is just below the soil surface (when the land is not flooded , ground waters are at a depth of less than 1 m, in the case of minimum water level of 4.6 masl). This zone is covered with marsh and swamp vegetation and has an area of 6 006 hectares (5 800 ha of Lake Skadar and 206 ha of Malo Blato).

Zone II - constantly flooded zone, with elevation between 5.5 and 8.0 masl; comprising the southern edge of Malo Blato. These lands are exposed to constant flooding during the year, mainly because the water level of Lake Skadar varies between these two elevations; the main soil type in this zone is alluvium, calcareous subtype. Alluvial depth depends on the depth of the groundwater level which is associated with changes in water level of Lake Skadar and the distance from it. Moving away from the lake, marsh vegetation changes to natural meadows, rarely to arable land. This zone has an area of 4 262 ha (4 005 ha of Lake Skadar and 257 ha of Malo Blato).

Zone III - the periodic inundation zone; this zone is continuation of zone II, with elevation of above 8 masl. Flooding in this area occurs seasonally (usually from November to February); the water table varies from a few tens of centimeters in the autumn and spring, up to 4-5 m during the summer. The dominant soil type in the area is loamy alluvium. The size of this zone is 1 475 ha. The watercourses that flow through this area often break their banks, especially the river, and additionally flood the surrounding are; smaller watercourses Gostiljska, Plavnik, Svinjiš, Velika and Mala Mrka, except Rujela), Moračaare located on the floodplain of Lake Skadar. (Plavnica, Mala Morača, Tara,

Zone IV - a zone flooded by the river; the surface of this zone is 567 ha; shallow groundwater is formed along this zone at the depth of less than 1 m. Many hydrographic changes have occurred in this areaMorača in the past, caused by changing the direction of the main flow watercourses.

Skadar Lake is one of the shallow sub-Mediterranean lakes, which trophogenic zone extends to the bottom, and tropholitic is absent or reduced to a small layer of water near the bottom. In these lakes trophic processes are much more dynamic than saprobic ones, so they are prone to eutrophication. During the warm months of the year, with water temperatures of 30°C or more, and when water exchange and flow are low, the process is even more drastic.

3. CLIMATE CHARACTERISTICS OF ZETA – BJELOPAVLIĆI PLAIN

It is often said this area has a submediterranean climate; however this term is not precise. So, it is better to use Köppen's classification, which is the most exact so far. It is based on the hydrothermal-analysis of precipitation and air temperatures, taking into account the average values and extreme deviations. According to this classification, the Zeta-Bje is defined as Csa subtype, which is characterized by hot, dry summers and mild and rainy winters. To some extent, this area differs from the true etesian (mediterranean)lopavlići Plain climate due to somewhat hotter summers and colder winters (Buri & Micev, 2008). The humid period starts in mid-September and ends in late April, whereas, in the typicalć adriatic-mediterranean area (also defined as Csa) extends from mid-October to early April. Arid and a drying period begin around the first of June and ends in early September.

3.1. The air temperature

Mean temperature ranges from 5°C (January) to 27°C (August), mean minimum of 2°C to 21°C (in the same months), and the mean maximum of 8°C to 33°C. The highest measured temperature was 44.8°C and the lowest -10°C. The number of days in an annual period with the temperature above 32°C is 58, and lower than 0°C is 26 (table 3).

Table 3. The air temperature in Podgorica for the period from 2001 to 2012 (after Weatherbase, 2012; modified).

Months Average Average Average Maximal Minimal t≥32°C t<0°C temperature maximal minimal temperature temperature (days) (days) (°C) temperature temperature (°C) (°C) (°C) (°C) Jan 5 8 2 16 -10 7 Feb 5 9 2 20 -7 9 Mar 10 14 6 26 -3 3 Apr 15 20 10 31 2 May 17 23 12 32 5 Jun 23 29 18 37 11 9 Jul 26 32 20 40 13 19 Aug 27 33 21 41 11 24 Sep 22 27 17 38 11 6 Oct 16 21 12 31 5 Nov 11 15 7 22 -5 1 Dec 7 11 3 17 -7 6

Average annual temperature (°C) 15 Average maximal annual temperature (°C) 20 Average minimal annual temperature (°C) 11 Average annual number of days with t≥32°C 60 Average annual number of days with t<0°C 29

3.2. Precipitation

In the area of Lake Skadar, the average annual amount of precipitation in the period from 1950 to 1984 was 1 664.50 mm (Kneževi , 2000). The maximum average annual amount of precipitation measured during this period was in 1979 (2 317.50 mm) and the minimum in 1953 (869.60 mm). ć

2500

2000

)

1500 1398

1000

Precipitation (mm Precipitation

500

Graph 3. Total annual precipitation (mm) in Podgorica, for the period from 1984 to 2011.

1800

1600

1400 1338

1200

1000

800 600

Precipitation (mm) Precipitation 400

200 0

Graph 4. Total annual precipitation (mm) in Podgorica, for the period from 1985 to 2001. 12

In the period from 1984 to 2011 the average annual rainfall amounted to 1 398 mm, which represents a statistically significant decrease compared to the first mentioned period (graph 3). If we look at separate periods from 1985 to 2001 and from 2002 to 2012 we will notice that the trend continues. The average rainfall in the first period was 1 338 mm, and the second 1 280 mm (graph 4 and 5).

1400 1280

1200

1000

mm) 800

600

recipitation ( recipitation

P 400

200 180 200 140 130 80 110 110 80 80 40 40 40

Graph 5. Average monthly and annual precipitation (mm) in Podgorica, for the period from 2002 to 2012 (according to Weatherbase, 2012; modified).

However, the lack of data can create the wrong image, therefore certain deficiency should be removed before making any conclusions. Total number of rainy days during the period of observation from 1961 to 2011 ranged from a minimum in 1993 (77 days; 1389 mm precipitation), up to the maximum in 1978 (156 days; 1 976 mm rainfall) (graph 6). The average number of rainy days during the same period amounted to 113.2. During the period of the last 11 years (2002 to 2012), the average number of rainy days has decreased to 78 (graph 7), although in 2010 there were 135 rainy days, with a maximum of 2 269 mm of rainfall. The highest average monthly precipitation was in November and December (graph 5 and 8). On the Albanian side, the average annual rainfall ranges from 1 750 to 2 500 mm. In the area of Skadar Lake's basin the extreme rainfall of 5 238 mm was recorded in 1958. The maximum amount of rainfall in one day – 420 mm was measured on December 15, 1963.

180

160

140

120

100

Number of rainy days rainy of Number 40

1961 1962 1973 1974 1975 1976 1977 1978 1979 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1994 1997 1998 2001 2003 2004 2006 2007 2008 2009 2010 2011 1993 Average

Graph 6. Total number of rainy days in the area of Podgorica, in the period from 1961 to 2011.

78 80

umber of rainy days rainy of umber

N 20

12 10 7 8 7 10 6 5 6 4 4 3 1 0

Graph 7. Average number of rainy days per month and year, in Podgorica, for the period from 2002 to 2012 (according to Weatherbase, 2012; modified).

350

300

250

200 1950-1984

150 2002-2010 100 (mm) Precipitation 50

0 I II III IV V VI VII VIII IX X XI XII months Graph 8. Average monthly values of rainfall in the area of Lake Skadar, for the periods: 1950-1984 and 2002-2010 (after HMZ-Montenegro; modified).

3.3. The winds

In the area of Lake Skadar there are numerous winds, from those blowing from northern directions (N, NNE and NNW) during the winter, to those from the south (S, SSE) during the warm period. One can see in the table 4 and graph 9 that the north wind (N) has the highest frequency of (18.7%) and maximum velocity (14.8 m/s). The next most frequent are SSE (11.5%) and NNW (10.4%), but their maximum speed differs (10.6 m/s and 14.3 m/s, respectively). The winds are important for life of the lake, because they cause movement and turbulance the water mass generating the aeration of deeper layers and saprobic and trophic processes.

Table 4. The frequency, maximum and average wind velocity with different directions (N-north, S-south, E- east, W-west) in the municipality of Golubovci in the period from 1993 to 2000 (according to , 2007; modified).

MarkovićN NNE NE ENE E ESE SE SSE S SSW SW WSW W WNW NW NNW Frequency 18.7 6.0 3.4 2.2 4.3 5.6 7.4 11.5 6.9 2.1 1.4 1.6 2.6 2.6 6.2 10.4 (%) velocity 4.3 1.9 1.5 1.5 2.3 3.2 2.8 2.8 2.9 2.3 1.6 1.7 1.6 2.1 3.0 3.5 (m/s) max velocity 14.8 8.3 4.0 5.3 11.2 10.6 10.0 6.7 9.0 10.1 4.4 4.8 6.6 7.8 10.0 14.3 (m/s)

Graph 9. The wind rose plot in the area of Golubovci in the period from 1993 to 2000 - 4.frequency SOURCES of OFwind POLLUTION (%), - average OF LAKE wind SKADAR velocity (m/s), - maximum wind velocity (m/s) (after Markovi , 2007).

4. SOURCES OF POLLUTION OF LAKE SKADAR

The sources of pollution are usually divided into point (concentrated) and nonpoint (dispersed). The point sources of pollution are mostly industrial and municipal sewage outflows, and waste water treatement plant outflow, also, depending on the degree of treatment and technology. These sources include the emissions of chimneys that contribute to air pollution. Point sources are, almost always, stationary. The nonpoint (dispersed) bring contaminated substances from larger surfaces, usually by runoff of atmospheric precipitation, although it may also be from other mechanisms, such as flooding, winds, leaching into the ground waters, agriculture, irrigation etc. The main nonpoint sources of pollution are washout from farming areas with fertilizers, pesticides, and biostimulators in integral form or in the form of residue. Similar pollution is present in water used for irrigation, which penetrates both surface and underground waters. A significant amount of nitrogen, phosphorous, ammonia and methane comes from livestock farms, where waste and excrements are disposed of, without being treated nor recycled. Those farms usually have only improvised surface drains for liquid waste that flows to the closest watercourse, rather than to a local sewerage system. Garbage dumps, illegal dumps (or “wild dumps’’), which can contain toxic and non-toxic waste are also sources of water pollution. Since they are unsecured, the storm waters washe out and carry them easily. The traffic is both stationary and non-stationary source of pollution. Stationary sources are traffic surfaces like roads, railways, and their construction and maintenance. Non stationary sources are aircrafts, road vehicles, river, lake and sea transport vessels, which release gases into the air and certain pollutants into soil and water. Illegal construction, with no connection to the sewerage system, with or without septic tanks, also threatens the environment (especially waters), sometimes more via biological than chemical agents (bacteria, parasites).

4.1. Point (concentrated) sources

4.1.1. Waste waters

Waste waters can be municipal, industrial, or mixed. Wastewaters are classified into point (concentrated) sources of pollution, because they are discharged into watercourses through specific sewage outflows. In the area without sewerage system, waste water is flowing through a number of surface drains or from sloping banks into the river, so that they can almost be classified as nonpoint (dispersed) sources. Huge amounts of waste waters reach the Skadar Lake from and Danilovgrad (through the Zeta river), Podgorica (through the river), Cetinje and Rijeka (through the river), Skadar and other smaller settlementsNikšić (by sewerage system, usually without any treatment, directly intoMorača the lake). Crnojevića Crnojevića

Each year, over 69 million tons of various waste waters flow into the lake (table 5 and table 7), which represent about 3.45% of its total volume at a water level of 5.25 masl. These waters are generally loaded with organic matter, with the exception of waste waters from Alumina Plant Podgorica (KAP), Steelworks Nikši , Steelworks waste disposal site and the reloading base of Bauxite in , loaded mostly with the inorganic matter. ć These amounts vary and can not be exactly determined,Nikšić since there is no data available on the volume of production in a number of industrial units, and entire companies. Podgorica’s municipal wastewater is treated to some extent. Only about 50% of the flow of an existing installation of waste water treatment plant (WWTP) is treated completely, about 35% have only primary treatment, and 15% is discharged without any treatment into the River .

Morača Table 5. The amount of municipal and industrial wastewater discharged into Lake Skadar (excluding Alumina Plant Podgorica) (according to the Master Plan for Sewerage and Wastewater, 2004; according to the Register of polluters, 1998; according to Royal Haskoning, 2006; modified).

Municipality Main source of waste waters Quantity Daily (m3) Annualy (m3) Podgorica Municipal waste waters, Dairy, 45 706 16 682 690 ‘’Plantaže’’, Tobacco industry, City Hospital and other industry. Danilovgrad Municipal waste waters, pig, 1 048 382 520 cattle and poultry farms, the production of marble and others. Municipal waste waters, 34 748 12 683 020 Steelworks , Brewery Nikšić ‘’Trebjesa’’, reloading base of Bauxite , City Hospital, Hospital Brezovik,Nikšić ŠIK "Javorak", Dairy, Slaughterhouse, etc. Cetinje and Rijeka Municipal wastewater, fish 1 516 553 610 processing plant Skadar (Albanija) Municipal and industrial 25 000 9 125 000 Crnojevića waste waters In total 108 018 39 426 840

It should be noted that about 55% of the population of the city of Podgorica is not connected to the sewerage system. It is important to note that the said plant is receiving a large amount of waste waters from the AD Plantaže wine cellar, with high content of organic matter (wine marc and sludge), so that the COD and BOD5 are several thousand times higher than maximal allowed concentration (MAC) (graph 10). This leads to the failure of the Podgorica WWTP and work delay.

The most important quantity of waste waters brought by Zeta river is that from Nikši Steelwork. It produces between 10 and 11 million tones of waste water per year, which are discharged into the rivers Bistrica and Gra anica and reach Zeta river. These watersć are heavily loaded with sulfides, phosphates (100 times higher than MAC), phenols (10 times higher than MAC), cationic detergents,č fats, oils and mineral oils. In addition, they have an increased amount of suspended matter and higher COD, but much lower oxygen concentration (Register of polluters of the Zeta Plain drainage basin, 1998).

10000

9000

8000

7000

6000 5000 COD (mg/l) MAC (COD) 4000 BOD5 (mg/l) 3000 MAC (BOD5) 2000 1000

Graph 10. Increased concentrations of COD and BOD5 (mg/l) in wastewater of “Plantaže” that led to the failure of the WWTP in Podgorica in 2006 and 2008 (according to WYG International, 2011; modified): MAC (COD) = 125 mg/l; MAC (BOD5) = 25 mg/l.

The Zeta river brings sewage from pig, cattle and poultry farms from Danilovgrad, loaded mostly with organic matter. The amount of waste waters today is probably higher than the data in table 5. The largest amount of industrial waste waters, 29,835,160 m3 per year (table 7), generated in KAP, Skadar Lake. The KAP started working in 1971, and by the year 1979 it was already producing 102 000 t of primaryflows aluminum directly perinto year. the Morača For that river amount and reachesof liquid aluminum, 516 000 t of bauxite is used, 1 806 000 liters of firing oil, 1 689 GWh of electricity and over 180 tons of other material per year, along with the 33 000 000 m3 of water (table 6). This kind of production leaves about 400 000 tones of “red mud” every year and the already mentioned amount of wastewater. Only in the second basin, a new pool of 220 000 m2, 4 000 000 tons of red mud has already been disposed. Also, throughout the whole production period about 325 000 m3 of solid waste was disposed, which, like the “red mud”, is mostly hazardous waste.

The quantities and characteristics of wastewater from different technological units of KAP are shown in table 7. These waters are loaded with heavy metals and their salts, nitrates and nitrites, fluorides, phenols, ammonia, detergents, fats, mineral and other oils. The city of Skadar with its surroundings generate more than 9 000 000 tons of waste water per year, loaded mostly with organic matter from municipal sewerage systems and discharge into the lake without treatment (table 5). Cetinje and Rijeka discharge together about 553 000 m3 of untreated

releases a small amount ofCrnojevića industrial waste water (from the fish processing plant). wastewater annually; Rijeka Crnojevića, in addition to municipal waste water, also Table 6. Quantities of raw materials and energy necessary for the total annual production of liquid aluminum of 102 000 tons (after Royal Haskoning, 2006; modified).

Raw materials and Quantity Unit of measure energy

Bauxite 515 775 tons/year Electric energy 1 689 GWh/year Gray iron 657 kg Firing oils 1 806 500 liters/year Clad plates 2 400 piece/year Steel stubs 20 363 piece/year Caustic soda 26 910 tons/year Fuel oils 86 771 tons/year Sodium-sulphide 2 915 tons/year Baked anodes 65 869 tons/year Aluminum-fluoride 3 451 tons/year Cryolite 460 tons/year Cathode blocks 1 056 tons/year Carbon paste 624 tons/year Calcium-fluoride 24 tons/year Water 33 000 000 m3/year

At this time in the Skadar Lake area there are three plants for waste water treatment:

· Podgorica - capacity 55 000 IE · Virpazar-capacity 1 000 and IE · River Crnojevica- capacity 500 IE · Plant in Nikšsi is not in use.

For none ćone of these WWTP is there a monitoring of function, except, to some extent, for the one in Podgorica.

Construction of four new WWTP is planned: · Podgorica and KAP-capacity 275 000 IE · -capacity 106 000 IE

Nikšić

· Cetinje and Rijeka Crnojevi a-capacity 30 500 IE and · Danilovgrad-capacity 38 000 IE. ć Table 7. The quantity and characteristics of waste waters from different technological units of KAP (after Royal Haskoning, 2006; et al., 2004 and the Register of polluters, 1998; modified). Kadović Technological Quantity of waste Characteristics of waste water units of water (m3/year) of KAP (Kadović et al., 2004; KAP (Royal Haskoning, Register of polluters, 1998) 2006) "Glinica"- Aluminium 14 400 000 sodium (Na), potassium (K) processing unit calcium (Ca), magnesium (Mg), "Elektroliza"- 1 056 000 chloride (Cl), nitrite (NO2), Electrolysis nitrate (NO3), sulfate (SO42-), "Anode"- Anode 3 801 500 phosphate (PO43-), fluoride (F), Factory iron (Fe), aluminum (Al ), tin "Livnica"- Foundry 3 696 000 (Sn), copper (Cu), zinc (Zn), "Silumini"- Cylumin 30 660 ammonia (NH3), phenols, factory detergents, fats and oils, Aluminium forge 1 877 000 mineral oils "Valjaonica"- Cold 528 000 rolling mill "Prerada" - Alminium 2 112 000 Processing Equipment 2 334 000 maintenance unit and other Total 29 835 160

It is thought that their functioning will lead to a significant decrease in the intensity of pollution of Lake Skadar, but the problem of sludge from the treatment process remain unresolved.

4.1.2. Air pollution

This type of pollution is not monitored in industrial plants in Nikši , but only in two places in the city. Here are the results of measurements in 2008 and 2009, only those compounds which concentrations were higher than MAC (in bracketsć for the air in the cities):

• NO2 - 80 g/m3 (40 g/m3) • Ozone (O3) - 130 g/m3 (120 g/m3) • Benzo (a) pyrene - 1 to 6 g/m3 (1 g/m3) • Smoke and soot - 140 to 200 g/m3 (60 g/m3) • Particulate matter - 220 g/m3 (110 g/m3)

Skadar Lake, but it can be transported via surface water and groundwater. Air pollutionpollution fromemissions Nikšić fromprobably the doesKAP notare greatlycalculated affect in the tons air perand yearwater for of successive years: 2005, 2006 and 2007 (table 8). The amount varied from 5 453.04 to 11 437.75 tons per year.

Table 8. Emissions of air pollutants from Alumina Plant Podgorica in 2005., 2006. and 2007. (according to Markovi , 2007; modified). Pollutants from KAP 2005 2006 2007 ć (t/year) (t/ year) (t/ year) Total nitrogen 498.98 421.96 468.23 oxides Carbon monoxide 1 140.23 7 981.42 2 880.03 Sulphur dioxide 3 699.46 2 645.53 5 997.62 Particulate matter 114.34 383.31 99.93 The sum of heavy 0.0028 0.0098 0.0098 metals Hydrogen chloride – 4.26 2.28 Hydrogen fluoride 0.03 1.26 0.30 Total 5 453.04 11 437.75 9 448.40

Deposition rate depends on the wind velocity and direction, the distance from the source, atmospheric stability and height of the chimney (Markovi , 2007). Deposition rate of SO2 at constant very unstable atmosphere, ranging from 1 to 80 g/m3, about 500 m from the source, depending on the wind velocity. At ać distance of about 1 500 m, those values range from 40 to 52 g/m3 (also depending on the wind velocityμ ), and at greater distances deposition was less and less dependent on the wind velocity (graph 11 and graph 12). μ

Graph 11. SO2 deposition rate changes with increasing distance from the source and with the change of wind velocity at a constant very unstable atmosphere (according to Markovi , 2007). 22 ć

Graph 12. SO2 deposition rate at a distance of 1 km (November 15, 2005) (according to Markovi , 2007).

ć In a very stable atmosphere the highest deposition rate is about 5 km from the source of pollution - 250 to 900 g/m3, depending on the wind velocity (graph 13). At greater distances (up to 11 km) deposition rate varies very little. μ

Graph 13. SO2 deposition rate changes with increasing distance from the source and with the change of wind velocity at a constant stable atmosphere (according to Markovi , 2007).

ć 23

Deposition rate of particulate matter at the very unstable atmosphere is maximal at about 500 m from the source, and ranges from 25 to 37 g/m3, depending on the wind velocity. μ

Graph 14. Change the deposition rate of particulate matter (PM) with increasing distance from the source and with the change of wind velocity at a constantly unstable atmosphere (according to Markovi , 2007). 3 Deposition rate then decreases rapidly with distanceć : 7 to 17 g/m at 1 500 m, and 3 to 8 g/m3 at 2 500 m, depending on wind velocity (Markovi , 2007). μ μ ć

Graph 15. Deposition rate of particulate matter (PM) at a distance of 1 km (November 15, 2005) (according to Markovi , 2007). 24 ć

Graph 16. PM deposition rate changes with increasing distance from the source and with the change of wind velocity at a constant stable atmosphere (according to Markovi , 2007). ć

At larger distances deposition rate decreases uniformly, regardless of the wind velocity (graph 14 and graph 15). In a stable atmosphere, the particulate matter deposition rate varies, depending on the wind velocity, at 500 m distance from the source, from 700 to 2 500 g/m3. With greater distances deposition rate uniformly decreases, but not below 100 to 300 g/m3 (at distances over 10 km from the source) (graph 16). μ These studies have shown that pollutants from industrial facility chimneysμ can be transmitted by air over long distances and to further endanger the Skadar Lake.

4.2. Non point (dispersed) sources of pollution

The most important sources of this type of pollution are wastes from KAP, the so-called ''red mud'' and solid waste disposal. Annual production of “red mud” is 278 300 t (according to et al., 2004), but CDM, 2012 estimates it to 400 000 t. So far, in the second basin only, about 4 000 000 t have been deposited. Kadović

4.2.1. KAP’s solid waste disposal site

Over a several decades, KAP created about 325 000 m3 of solid waste, deposited at the site and classified as a hazardous waste, because of high content of fluorides,

polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), phenols, and nickel, chromium, copper, cadmium, zinc, arsenic, mercury, cyanide, mineral oils and other (table 9). In the table 9 the results of measurements of the concentration of hazardous and toxic substances in the solid waste disposal site, directly below it and in deeper soil layers are presented. Of the 12 parameters, 10 of them in shallower or 6 in the deeper layers had a concentration of 1 to 30 times higher than MAC. Seven parameters exceeded even high- risk concentration (cyanides, PAHs, PCBs, mercury, chromium, copper and nickel).

Table 9. Maximum concentrations of hazardous and toxic substances (mg/kg) detected in the soil in the area of solid waste disposal sites in KAP (after COWI, 2012; modified): MAC-maximum allowable concentration; HRC-high-risk concentration.

Concentration Concentration Concentration MAC for MAC for HRC for on the waste in the soil in deeper soil hazardous hazardous hazardous disposal site directly below layers below and and and the waste the waste harmful harmful harmful substances substances substances in the soil in the soil in the soil (Offical (Dutch (Dutch Gazette, Standards, Standards, 18/97) 1 2000, 2009)3 2009)2 Fluorides 40494.001,2 10911.001,2 6226.001,2 300.0 500.0 – Cyanides 1302.003 73.103 3.87 – – 20.0 PAH 772.601,3 237.611,3 86.901,3 0.6 – 40.0 PCB 459.501,3 15.671,3 0.0451 – 1.0 0.004 Arsenic (As) 80.701,2,3 12.50 8.24 20.0 29.0 55.0 Cadmium 556.221,2,3 1.862 1.422 2.0 0.8 12.0 (Cd) Lead (Pb) 345.651,2 48.09 43.88 50.0 85.0 530.0 Mercury (Hg) 0.098 22.813 0.073 1.5 0.3 10.0 Chromium 494.393 404.883 33.18 50.0 100.0 380.0 (Cr) Nickel (Ni) 843.941,2,3 245.011,2,3 162.021,2,3 50.0 35.0 210.0 Copper (Cu) 1273.831,2,3 182.971,2 25.70 100.0 36.0 190.0 Zinc (Zn) 553.291,2 210.132 583.211,2 300.0 140.0 720.0

4.2.2. “Red mud” disposal of KAP

“Red mud” is also classified as hazardous waste due to the high presence of fluoride, arsenic, PAHs, cadmium, lead, iron, chromium, cobalt, nickel, copper and zinc exceeding the MAC (table 10). Quantity and characteristics of solid and hazardous waste generated by the different technological units of KAP are given in table 11. It can be seen that the pH is

about 11.5. However, direct measurement of pH in the basin of “red mud” indicates that

Table maximum 10. Concentrations value can reachof hazardous 13.85 (Kadović and toxic et substancesal., 2004). (mg/kg) detected in the soil in disposal site of “red mud”' in KAP (after CDM, 2012; modified): MAC-maximum allowable concentration; HRK-high-risk concentration. Drilling Samples from MAC for MAC for HRC for samples from the surface hazardous hazardous hazardous soil (dam+ and and and tailing dump) harmful harmful harmful substances substances substances in the soil in the soil in the soil (Offical (Dutch (Dutch Gazette, Standards, Standards, 18/97) 2000, 2009) 2009)

Fluorides 42-251 151-905 300.0 500.0 – PAH 0.01–2.66 0.2–14.4 0.6 – 40.0 PCB <0.002–0.17 <0.002–0.09 – 1.0 0.004 Arsenic (As) 1.1–75 1.5–12.6 20.0 29.0 55.0 Cadmium (Cd) <0.25–1.2 2.8–8 2.0 0.8 12.0 Lead (Pb) 2.5–37.5 19–65 50.0 85.0 530.0 Mercury (Hg) 0.02–0.07 0.01–0.07 1.5 0.3 10.0 Hrom (Cr) 7–83 39–143 50.0 100.0 380.0 Cobalt (Co) <2.5–28 10–27 50.0 9.0 240.0 Nickel (Ni) 6–79 54–90 50.0 35.0 210.0 Copper (Cu) 4–20 1–45 100.0 36.0 190.0 Zink (Zn) <1.25–186 40–141 300.0 140.0 720.0 Iron (Fe) – 40.6–80.3 2.0 – –

Table 11. The amount and characteristics of solid and hazardous waste from various

technological units of KAP (after Royal Haskoning, 2006; modified).

Technological The amount of solid and Characteristics of solid and units of KAP hazardous waste (t/year) hazardous waste from KAP Alumina processing -solid “red mud” 309 168 t unit , crude oil, fuel oil Electrolysis -carbonic foam: 620 t PAH, PCB, -used anodes and cathodes: 2 950 t , carbon foam, Al, phenols -PCB: 25 t

Anode factory - settling from the anodes: 17 600 t PAHs, phenols, Cd, Hg, As Foundry -slag: 1 800 t Morinit, asbestos -other: 80–120 t Cylumin factory -solid Al dust: 4 230 t Al, colours, salts Aluminium forge - cement with ammonia: 1 462 t NH3 Cold rolling mill - diatomaceous earth: 1 697 t Si, Al, Fe oxides, mineral oil Processing - diatomaceous earth: 2 274 t Si, Al, Fe oxides, mineral oil Equipment - electrolysis: 25 t oils, lubricants, transformer maintenance unit -PCR: 50 t oil, pyralene (Arachlor

and other 1260, 1254), THB, tires, etc. In total 342 091 t “Red mud”, which is deposited in the basins, has a liquid and a solid phase. Liquid phase is made by adding about 15% water into the dry mud, to ease transport through 3 km long pipe. Atmospheric precipitation and water used for “red mud” watering remain on the surface of the disposal site, so that the total volume of liquid phase is 732 898 m3. The composition of the liquid phase of “red mud” is given in tables 12 and 13.

Table 12. Physico-chemical characteristics of the liquid phase of KAP’s “red mud” disposal

site (after , 2004; modified).

Kadović at al. Min Max pH 12.53 11.59 13.85 EC (mS/cm) 9.54 7.64 12.14 Suspended matter (mg/l) 79.00 68.00 90.00 Na (mg/l) 1 118.70 925.50 1 488.80 K (mg/l) 25.35 19.11 31.59 Ca (mg/l) 15.70 6.41 34.83 Mg (mg/l) 64.80 51.98 83.14 Fe (mg/l) 0.51 0.18 0.94 Al (mg/l) 4.00 4.00 4.00 Cn (mg/l) 0.0026 0.0026 0.0026 Cu (mg/l) 0.0036 0.0036 0.0036 Pb (mg/l) 0.00 0.00 0.00 Zn (mg/l) 0.04 0.04 0.04 (mg/l) 39.70 25.99 65.17 SO4 (mg/l) 53.20 51.74 54.00 (mg/l) 0.689 0.3974 0.9845

Table 13. Concentrations of hazardous and toxic substances (mg/l) in wastewater samples from a basin of “red mud” in the KAP (CDM, 2012; modified): MAC- maximum allowed concentration of hazardous and toxic substances in the waste waters, which are allowed to be discharged into surface waters.

Sample Sample MAC I II (Official Gazette 45/8; 9/10) Fluorides (mg/l) 9.0 3.2 2.0 Cyanides (mg/l) 0.0044 0.0053 0.005 Arsenic (As) (mg/l) 0.015 0.002 0.1 Cadmium (Cd) (mg/l) <0.0005 <0.0005 0.01 Lead (Pb) (mg/l) <0.001 0.002 0.5 Mercury (Hg) (mg/l) 0.0015 0.0019 0.005 Chromium (Cr) (mg/l) 0.002 0.004 0.1 Nickel (Ni) (mg/l) 0.007 0.002 1.25 Copper (Cu) (mg/l) 0.020 0.013 0.5 Zinc (Zn) (mg/l) 0.04 0.02 1.0 Total hydrocarbons (mg/l) 0.02 0.01 0.5

pH 8.2 10.0 6.5–8.5

Apart form the increased pH, elevated concentrations of fluorides, sodium, potassium and suspended matters are noted. et al. (2004) interpret it as the highly alkaline environment does not allow the present metals to dissolve in the liquid phase. This transition can, therefore, be expectedKadović if there is a dilution or change in pH (up to 7 or lower). In any case, neither the surface water, nor dry “red mud”, should be discharged into watercourses, or to get into the air, because it would threaten the health of humans, animals, plants and the environment.

Table 14. Minimum and maximum concentrations of PCB at sites within the KAP (B-17, B-18, B-19, AS-1, AS-2, AS-3) and in the immediate vicinity (Srpska, Botun, Mahala) in the period from 1990 to 1996 (after Royal Haskoning, 2006; modified).

Parameter PCB (μg/kg) Location min max Piezometar B-17 225 381 100 Piezometar B-18 51 17 310 Piezometar B-19 125 52 280 AS-1 10 490 245 400 AS-2 1 230 73 500 AS-3 14 390 144 900 Srpska 230 469 Botun 452 783 Mahala 125 234

It is believed that pollutants can penetrate into the soil and groundwater through leachate water. According to CDM (2012) this assumption is correct, because in drilling samples from the basin, below basin, as well as in the soil of the dam, significant concentrations of hazardous and toxic substances that reached the soil and ground water were found (table 10 and 14). The boreholes were drilled to less than 30 m below sea level, and reached the groundwater at different levels from 11.7 to 27.1 m below sea level. Concentrations of these substances were 2 to 20 times above the maximum allowed for the soil. . Concentrations of fluorides, PAHs, arsenic, cadmium, lead, chromium, cobalt, nickel, copper and iron were above the MAC prescribed by Montenegrin Directive for waters, and almost always above those of Dutch standards (table 10). Measurements of PCBs in the period since 1990 to 1996, in the soil within the KAP and the closest villages (Srpska, Botun and Mahala) showed increased concentration (17 to 381 times higher than MAC) within the plant, but in the surrounding soil it was below this value (table 14). Fine “red mud” dust, if it is dry, can be spread by wind over long distances. This happened and still happens sometimes. When deposited on farmland it enters the food chain through agricultural products that can endanger human and animal health. One of the measures to prevent air pollution with this dust is to regularly spray the water into the “red mud”, but it greatly increases the amount of water on their surface and allows the creation of leachates and their penetration into the soil and groundwater.

WYG International (2011) shows the contamination of soil in villages Botun and Srpska (table 15). Of the 14 measured parameters, only 4 (lead, mercury, nickel and PAHs), had a higher concentration than MAC: from 1.42 times (lead) to 36 times (PAHs). However, since these metals, their salts and polyaromatic hydrocarbons are highly toxic substances, these results are alarming.

Table 15. Soil pollution in villages Srpska and Botun in 2005 (after WYG International, 2011; modified). Location Srpska Botun–Velji brijeg MAC Pollutant cultivated uncultivated cultivated uncultivated Cadmium (mg/kg) 2 0.71 0.68 0.53 1.47 Lead (mg/kg) 50 38.97 35.62 34.19 71.22 Mercury (mg/kg) 1.5 3.28 2.31 5.28 7.1 Arsenic (mg/kg) 20 <2 <2 <2 <2 Chrome (mg/kg) 50 26.96 32.84 27.67 46.99 Nickel (mg/kg) 50 102.1 105.83 147.77 123.42 Flourine (mg/kg) 300 50.09 41.6 23.47 48.75 Zinc (mg/kg) 300 290.75 260.04 215.7 279.65 Copper (mg/kg) 100 39.33 40.88 35.9 39.56 Cobalt (mg/kg) 50 11.96 12.97 14.1 15.25 PAHs (mg/kg) 0.6 1.49 2.21 4.98 21.72 PCBs (mg/kg) 0.004 <0.003 <0.003 <0.003 <0.003 Congeners (mg/kg) 0.004 <0.002 <0.002 <0.002 <0.002 Mineral oils – 4.69 3.56 1.32 3.56 (mg/kg)

4.2.3. Contamination of ground waters under the solid waste and the “red mud” disposal site of KAP

The contamination of ground waters is very sensitive question, because they supply the wells in the near and distant surroundings of KAP. These wells are used for drinking water, but mostly for irrigation and livestock. Reference values of MAC and high-risk concentrations (Dutch standards) for groundwater are given in table 16. The results of the analysis of concentrations of hazardous and toxic substances in the groun dwaters under the “red mud” basin and solid waste disposal are presented in tables 17 and 18. As expected, there are significantly increased concentration of fluorides, cyanides, chlorides and mercury, whereas, other metals and salts, due to the still high pH values were not detected.

Table 16. Reference values for maximum allowable concentration (MAC) and high-risk concentrations (HRC) of hazardous and toxic substances in the ground waters given by the Directive on the classification and categorization of surface and ground waters of Montenegro (Official Gazette 2/07 of 10.29.2007) in comparison with Dutch Standards (2009).

MAC MAC MAC MAC MAC HRK A (Off. A1 ( Off. A2 (Off. A3 (Off. (Dutch (Dutch Parameters gazette gazette gazette gazette Standards, Standards, (mg/l) 2/07) 2/07) 2/07) 2/07) 2009) 2009) Fluorides 0.05 1.00 1.50 1.70 – – Cyanides

Table 17. Concentrations of hazardous and toxic substances in the groundwater in boreholes within the disposal site, in June and

November 2011 (after COWI, 2012): As–arsenic, Cu–copper, Hg–mercury, Cd–cadmium, Mg–magnesium, Ni–nickel,

Pb–lead, Zn–zinc, Cr–chromium, V–vanadium; PCB–polychlorinated biphenyls, PAH–polyaromatic hydrocarbons, EC–electroconductivity.

Locality

B275 B276 B277 B278 Parameter (mg/l) Jun Nov Jun Nov Jun Nov Jun Nov As (mg/l) <0.001 <0.001 0.029 0.019 0.002 0.007 <0.001 0.01 Cu (mg/l) 0.0027 0.007 0.0037 0.007 0.057 0.005 <0.0025 0.006 Hg (mg/l) 0.00014 0.0004 0.00014 <0.0001 0.00011 <0.0001 0.00016 <0.0001 Cd (mg/l) <0.00005 <0.0005 <0.00005 <0.0005 <0.0005 <0.0005 <0.0005 <0.0005 Mg (mg/l) 0.045 0.016 0.02 0.033 0.025 0.016 0.0278 0.02 Ni (mg/l) <0.001 0.0015 <0.001 0.0024 <0.001 0.001 <0.001 0.001 Pb (mg/l) <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 Zn (mg/l) <0.0025 0.008 <0.0025 0.014 0.007 0.008 0.003 0.0099 Cr (mg/l) 0.011 <0.001 0.004 <0.001 0.0027 0.001 0.003 0.002 V (mg/l) <0.001 0.0015 0.195 0.1 0.004 0.015 0.013 0.062 PCB (mg/l) <0.000002 <0.000002 <0.000002 <0.000002 <0.000002 <0.000002 <0.000002 <0.000002 PAH (mg/l) <0.000005 <0.000005 0.00046 <0.000005 0.00021 <0.000005 <0.000005 <0.000005 Fluorides 0.93 0.67 44 18.8 0.5 0.76 0.75 0.97 (mg/l) Cyanides 0.011 <0.001 0.112 0.147 <0.001 <0.001 <0.001 <0.001 (mg/l) Chlorides 3.51 3.51 62.12 21.4 5.6 4.5 5.95 4.56 (mg/l) pH 7.46 7.32 9.39 9.59 7.98 8.8 7.6 7.73 EC (μS/cm) 293 299 1447 781 310 272 378 363

Table 18. Concentrations of hazardous and toxic substances (mg/l) in the groundwater in the area of KAP : “red mud” basins (D1-D3), solid waste site (D4) and existing wells (after CDM, 2012 and COWI, 2012; modified).

Locality (KAP) D1 D2 D3 D4 Existing wells red red mud red waste disposal mud basin mud site basin basin Parameters (mg/l) Fluorides 80.00 0.16 4.00 108.00 0.062–1.42 Cyanide 0.0086 0.0028 0.0061 0.297 <0.001 PAH 0.00101 0.000285 <0.0000005 0.006042 <0.000005–0.00034 Arsenic (As) 0.0127 <0.001 0.0032 0.0042 <0.001–0.031 Cadmium Cd) <0.0005 <0.0005 <0.0005 0.0006 <0.0005 Lead (Pb) 0.0030 0.0040 0.0016 0.0030 <0.001–0.022 Mercury (Hg) 0.0012 0.0058 0.0064 0.0032 <0.0002–0.005 Chromium (Cr) <0.001 0.0019 0.0028 0.0028 <0.001–0.0082 Nickel (Ni) 0.0138 0.0080 0.0079 0.019 0.0015–0.0088 Copper (Cu) 0.0068 0.0017 0.0066 0.021 0.0033–0.0097 Zinc (Zn) 0.0033 0.0047 0.0012 0.068 0.016–0.147 Phenols — — — — <0.0005–0.0023 Total — — — — <0.00001–0.0040 hydrocarbons Nitrates — — — — 1.64–8.71 Nitrites — — — — <0.003–0.53

4.2.4. Nikšić Steelworks waste disposal site

The “'wild” (illegal) waste disposal site of Nikš Steelworks is a potential polluter of Lake Skadar. The quantity of 102 000 tons per year of non-metallic industrial waste is disposed annualy on this site. On the old site (D1)ić 600 000 m3 of all types of unsorted waste was disposed, thus its capacity is filled. Therefore, the second site (D2) was opened in 2006, with an estimated capacity of 825 000 m3. Table 19 shows the results of the analysis of the concentration of pollutants in 2006, 2007 and 2011 at the surface of both sites. Out of 13 parameters analyzed, 9 show, at least at one of the sites, the concentration higher than MAC (PCB–103 times higher than MAC, copper –39 times, PAHs–25 times, zinc–15 times and cadmium–over 13 times). In boreholes up to 10 m in the old landfill, 8 parameters exceeded the allowed levels. In the new disposal site, up to 10 m depth, 5 parameters exceeded the MAC, and over 10 m, only one parameter (chromium) (CDM, 2012). This shows that there is a slower process of penetration of leachate into the soil. At the time of rain and melting snow, there is a certain waste runoff into the river Gra anica, which belongs to the Zeta river drainage basin. So, there is a possibility that pollutants from this source reach Skadar Lake. č

Table 19. The concentration of pollutants on the surface of the Nikši Steelworks waste disposal site in 2006/2007 and 2011 (after CDM, 2012). ć 2006/2007 2011 MAC D1 (X) D2 (X) D1 (X) D2 (X) min max (Offical Gazette, no. Parameter 18/97) As (mg/kg) 12 12.9 7.6 14.5 5 28 20 Cu (mg/kg) 325 149 135 1 323 31 3 903 100 Zn (mg/kg) 4 500 383 1 566 1 869 267 3 170 300 Cr (mg/kg) 283 192 186 300 124 394 50 Co (mg/kg) 12.4 18 6.2 11.3 5.5 22.7 50 Ni (mg/kg) 124 110 60 172 23 299 50 Cd (mg/kg) 27.5 7 10 11.3 0.8 22 2 Pb (mg/kg) 1 772 303 487 1 314 51 2 615 50 Hg (mg/kg) 0.47 0.275 0.336 0.296 0.08 0.57 1.5 Cyanides - - 4.69 2.00 1.58 8.96 (mg/kg) Σ PAH (mg/kg) 2.39 0.34 6.15 4.22 0.6 14.9 0.6 Σ PCB (mg/kg) 0.81 <0.00 0.188 1.49 0.3 5.38 0.052 Hydrocarbons - - 1.33 0.21 <0.01 3.1 (mg/kg)

4.2.5. Illegal waste dumping

In the vicinity of Lake Skadar, in the municipalities of Golubovci and Tuzi, there are about fifteen illegal waste dumping, where construction waste, municipal solid waste and so called “garden waste” is disposed, with a total volume of 12 300 m3. In the “garden waste” there is often plastic, glass and paper packaging of toxic herbicides and pesticides, with the remains of the same (table 20 and 21). Although inspections in charge remove this waste, population creates new dumpings, with the same type of waste. Certain toxic and even hazardous substances can be washed out from the dumping site, and get into the lake. The total annual quantity of such waste is not known, and it is very difficult to assess it.

4.2.6. Agricultural areas

Flooding, washing out or irrigation of agricultural land, the most important, nonpoint source of pollution, leads to the introduction of fertilizers, pesticides,

herbicides, biostimulators, and other chemicals into water, by surface or underground watercourses. In the Zeta Plain, approximately 9 000 ha of land, is used for agricultural purposes: about 4 000 hectares of vineyards and orchards (mainly A.D. Plantaže) and about 5 000 hectares of other crops. There are no precise figures on the amount of fertilizer used, but we estimate that it is about 2 970 t per year. Agriculture uses about 80 tons per year of herbicides, insecticides, fungicides and pesticides. A good portion of these chemicals (some of which are poisons of category III and IV), migrate into the lake. The total flooded area of agricultural land is estimated at about 5 000 ha, and the amount of water used for irrigation is approximately 1 500 000 m3 per year.

Table 20. List of the most important Illegal dumpings in the area of Golubovci.

Locality Type of waste Site capacity (m3) –Tamnik Construction waste, bulky waste, 190 garden waste, municipal solid waste 1. Ljajkovići near Construction waste, municipal solid 1 100 – Botun waste, garden waste, bulky waste, 2. Morača bank rubber waste local road Ljajkovići – the mouth of the Construction waste, municipal solid 500 Cijevna river waste, garden waste, bulky waste, 3. Mitrovići rubber waste into Morača 4. Location on the left side of the Construction waste, garden waste, 2 000 road Cijevna – glass, solid waste, waste plastic, rubber waste, bulky waste 5. Golubovci –villageKuće Rakića Daljevac Construction waste, municipal solid 170 waste, garden waste, bulky waste

6. Balabani – Marmulja Construction waste, municipal solid 210 waste, garden waste, bulky waste

7. Korovi Construction waste, municipal solid 230 waste, garden waste, bulky waste ća murva 8. Mataguži – in the village Stari Construction waste, municipal solid 500 Viganj waste

9. Vukovci – next to bridge Vukovac Construction waste, municipal solid 1200 river waste In total 6 100 m3 on the Morača

Table 21. List of the most important Illegal dumpings in the area of Tuzi.

Locality Type of waste Site capacity (m3) 1. Municipality Tuzi, Construction debris, municipal 1100 solid waste, garden waste 2. Municipality Tuzi, Construction debris, municipal 250 Šipčanik, near the vineyard solid waste 3. Municipality Tuzi, Construction debris, municipal 750 Šipčanik solid waste, part of the waste is grown with plants 4.Elezovići, Municipality near the Tuzi, vineyard road Construction debris, municipal 3 000 Tuzi–Dinoša near the bridge solid waste, branches - homogenized 5. Municipality Tuzi, road Construction debris and tiles 500 Tuzi–Dinoša in front of private houses 6. Municipality Tuzi, road Construction debris in the length 500 Tuzi–Dinoša of about 200 m

7. Municipality Tuzi, Construction debris, municipal 100 solid waste, pits and bits of graden waste InSukuruć total 6 200 m3

4.2.7. Other nonpoint sources of pollution

The exhaust gases of vehicles, road runoff, septic tanks and storm sewer can be significant sources of water pollution. At this point we do not have precise data on these sources of pollution around Lake Skadar, but they should be obviously included in future management plans.

5. WATER AND SEDIMENT POLLUTION OF LAKE SKADAR

5.1. Physico–chemical characteristics of the lake

This chapter discusses the data obtained from different documents and studies such as ISML (2001), Rako

During 2001, 2005čević and (2006, 2010, 2012),besides Royal the Haskoningbasic ones (2006),, some Šundić of additional (2007), parametersHMZ (2010) concerning and Šundić chemistry & Radujković of the (2012). surface water were analysed. In December 2001 the water temperature in Skadar Lake ranged from 6°C at Plavnica to 8.9°C at the right mouth of the river (table 25). Transparency of the lake water during this period ranged from 1.5 m to 2.6 m. The pH (7.9 - 8.25) was within allowable limits for the water of A2CK2 class.Morača Oxygen concentration was the lowest at the right mouth of the (8.1 mg/l), and the highest in Virpazar (11.5 mg/l). Minimum oxygen saturation was stated at the right mouth of the (85%), while values of 147% andMorača 145%, riverstated at the localities Plavnica and Virpazar, were higher than maximum allowable ones. Electrical conductivity ranged fromMorača 240 to The concentration of total nitrogen at Virpazar was 0.7 mg/l, while at other localities was lower than 0.5 mg/l. The concentration of total phosphorus, at all sampling localities364 μS/cm. was lower than 0.05 mg/l (table 25). During the period 2003-2004 the measurements period of water temperature of Lake Skadar were conducted. Minimum water temperature was noted in December (4.4°C) and maximum in July (30.1°C). The highest average water temperature was measured in June (28.7°C) and the lowest average water temperature in December (6.48°C). The average temperature for the winter period was 8°C, and 24.5°C for the summer period (table 22). The minimum transparency value of 0.6 m was measured in August, and maximum of 4 m in May. Average values of this parameter were highest in the winter months in November (2.7m) and in December (2.87m). In the winter period the population density of phytoplankton is small (Rako evi , 2006) and increases transparency. Average transparency during the summer months of the’ 80-s was 2.5 m (Beeton, 1981b), which is significantly higher than the summerč ć average value for 2003 (0.8 m) (table 22). Minimum pH values ranged from 7.6 (May, August, October) to 8.0 (December), and maximum from 8.2 (April) to 8.9 (August). The average pH value , calculated from all sampling localities, ranged from 7.9 (February) to 8.4 (December). High concentrations of dissolved oxygen were stated in Lake Skadar in the period 2003-2004. Minimum oxygen concentrations ranged from 5.7 mg/l (August) to 10.39 mg/l (March), and maximum ranged from 9.08 mg/l (September) up to 14 mg/l (March). The average values of this parameter in the study period ranged from 8.19 mg/l (September) to 11.69 mg/l (March). Oxygen saturation ranged from 67% to 162%. Oxygen concentration and saturation were highest during the winter ( , 2006). Minimum electroconductivity values ranged from 179 to 255 s/cm, and a maximum from 285 to 404 s/cm. The averageRakočević values of this parameter were lowest in August (238 s/cm), and highest in December (298 s/cm). μ μ μ μ

Table 22. Physico-chemical characteristics of Lake Skadar water for the period 2003–2004 (after t–water temperature; Secchi–transparency; EC–electroconductivity; TN–total nitrogen; TP–total phosphorus). Rakočević, 2006; 2012) ( 2003 2004 May June July Aug Sep Oct Nov Dec Feb Mar Apr t (°C) 23.97 28.70 28.46 28.60 20.41 13.55 11.23 6.48 8.10 13.80 15.49 min 22.00 24.90 23.90 25.40 17.80 12.00 9.90 4.40 7.30 11.60 14.00 max 25.60 29.90 30.10 28.80 21.90 14.80 12.30 10.80 8.60 15.30 17.00

Secchi 2.37 1.67 1.34 1.23 1.72 2.10 2.70 2.87 2.13 2.73 2.46 (m) min 1.00 1.00 0.80 0.60 0.80 1.20 2.00 2.00 1.20 2.00 1.90 max 4.00 2.80 2.50 2.20 3.50 3.50 3.50 3.50 3.00 3.50 3.50 pH 8.2 8.1 8.2 8.3 8.1 8.0 8.00 8.4 7.9 8.3 8.2 min 7.6 7.7 7.8 7.6 7.8 7.6 7.7 8.0 7.8 7.9 7.8 max 8.4 8.4 8.4 8.9 8.3 8.4 8.3 8.7 8.0 8.6 8.2

O2 9.26 9.29 8.83 8.76 8.19 9.80 10.27 10.93 9.57 11.69 10.88 (mg/l) min 7.30 7.60 5.80 5.70 6.99 8.50 8.60 10.00 9.00 10.39 10.00 max 9.93 11.90 11.00 11.70 9.08 11.40 11.50 11.60 11.00 14.00 12.00

EC 249 260 251 238 257 263 288 298 258 248 250 (μS/cm) min 210 199 199 191 207 197 254 255 179 238 206 max 365 378 404 415 371 310 366 303 333 285 310

TN 0.18 0.66 0.62 0.48 0.36 0.18 0.28 0.15 0.15 0.16 0.16 (mg/l) min 0.15 0.16 0.16 0.15 0.15 0.15 0.20 0.15 0.15 0.15 0.15 max 0.34 1.32 1.10 0.85 0.70 0.33 0.60 0.15 0.15 0.20 0.20

TP 0.012 0.026 0.025 0.019 0.012 0.010 0.005 0.005 0.005 0.005 0.010 (mg/l) min 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 0.005 max 0.040 0.060 0.041 0.035 0.024 0.018 0.008 0.006 0.005 0.005 0.032

The concentration of total nitrogen ranged from 0.15 to 1.32 mg/l (table 22). The average values of this parameter was highest in June - 0.66 mg/l. The average annual concentration of nitrogen in the study period was 0.40 mg/l (according to Rako evi , 2006), which is twice the concentration measured during the 80's, when it was 0.20 mg/l (Beeton, 1981). č ć Total phosphorus concentrations ranged from 0.005 to 0.06 mg/l (table 22). The ording to OECD criteria (OECD, 1982), classifies Lake Skadar in the mesotrophic type of lakes (Rako 2006;annual 2012). average concentration was 0.012 mg/l (12 μg/l), which, acc The values of physico-chemical parameters monitored during the 2004č ević,are presented in table 23. All these parameters were within allowable limits for water of category II, i.e. A2 C K2 class, as Skadar Lake water is defined by Directive on classification and categorization of surface and ground waters (Official Gazette no. 2/07 from 29.10.

2007.) (Šundić, 2007; Šundić & Radujković, 2012).

Table 23. Physico-chemical characteristics of Lake Skadar water for the period 2004.– 2007; Sj2–Kamenik; Sj3– river); Sj5– middle of the Lake; Sj6–Plavnica; Sj12–Raduš; t–water temperatures; Secchi2005.–transparency; (after Šundić, EC– Šundić & Radujković, 2012)( Vranjina (right mouth of Morača electroconductivity; RP–redox potential; TN–total nitrogen; TP–total phosphorus).

2004 2005 Sj2 Sj3 Sj5 Sj6 Sj12 Sj2 Sj3 Sj5 Sj6 Sj12 t (°C) jun 29.8 29.1 29.3 30.5 29.6 24.9 19.7 25.9 26.0 26.2 aug 28.0 25.4 27.9 27.1 28.6 27.4 27.0 26.9 26.8 27.8 oct 16.0 13.3 18.5 19.7 16.9 16.8 15.8 19.0 19.4 18.3

Secchi jun 3.0 3.0 3.0 2.0 3.0 2.6 0.9 1.4 1.0 2.0 (m) aug 0.9 1.5 0.9 1.0 1.2 2.0 2.4 1.1 1.5 1.2 oct 1.8 3.0 1.8 1.6 2.5 2.0 2.2 1.6 1.6 2.0

pH jun 8.45 8.55 8.63 8.37 8.64 8.47 8.64 8.79 8.33 8.75 aug 8.6 8.08 8.60 7.62 8.79 8.28 8.54 8.72 8.36 8.55 oct 8.44 8.47 8.95 8.55 8.68 7.94 8.17 8.68 8.24 8.62

O2 jun 7.55 8.20 9.02 8.35 8.91 8.00 9.02 9.00 6.92 8.60 (mg/l) aug 9.88 10.05 9.62 8.05 10.50 8.05 9.54 7.95 7.80 8.65 oct 9.91 10.10 11.20 8.66 11.15 10.14 10.00 11.62 8.35 10.50

O2 (%) jun 97.0 88.0 118.0 111.0 116.0 95.0 99.3 101.0 86.3 103.0 aug 121.2 113.5 117.5 71.5 133.2 96.9 102.4 99.0 96.0 97.5 oct 102.9 95.9 117.6 93.6 116.0 106.5 97.8 124.4 92.2 110.1

EC jun 265 236 229 235 224 257 263 243 251 238 (μS/cm aug 232 299 206 229 155 270 269 259 205 229 ) oct 269 267 229 229 259 277 283 228 244 236

RP jun -87 -92 -96 -83 -97 -68 -76 -86 -62 -83 (mV) aug -104 -72 -107 -44 -116 -60 -74 -82 -64 -73 oct -60 -61 -87 -64 -80 -51 -63 -95 -70 -92

TP jun – – – – – 0.016 0.015 0.010 0.022 0.010 (mg/l) aug – – – – – 0.019 0.030 0.016 0.011 0.021 oct – – – – – 0.010 0.010 0.010 0.220 0.010

TN jun – – – – – 0.500 0.420 0.650 0.600 0.690 (mg/l) aug – – – – – 0.720 0.600 0.420 0.400 0.200 oct – – – – – 0.500 0.200 0.200 0.200 0.300

During the study period, the maximum water temperature of 30.5°C was stated in June at Plavnica (Sj6) and the minimum was found in October on the right mouth of the 3) (13.3°C). The temperature in June ranged from 29.1°C at location Sj3 to

Morača river (Sj 39

30.5°C at the locality Sj6. During August, the minimal temperature was measured at the locality Sj3 (25.4°C) and a maximal of 28.6°C at the locality Raduš (Sj12). In October 2004 the temperature ranged from 13.3°C at Sj3, to 19.7°C, at the sampling site Sj6. Transparency ranged from 0.9 m in August on localities: the middle of the lake (Sj5) and Kamenik (Sj2), up to 3 m in June at localities: Sj12, Sj5, Sj2 and Sj3, and in October at sampling site Sj3. During 2004, water of the lake showed a moderate alkaline reaction. The pH values ranged from 7.62 at location Sj6 in August, to 8.95 at location of Sj5 in October. The minimum value of the redox potential was determined at location Sj12 in August and was -116 mV, while the maximum at location Sj6 in the same month was -44 mV. The concentration of dissolved oxygen ranged from its minimum of 7.55 mg/l at location Sj2 in June, up to a maximum of 11.20 mg/l at location Sj5 in October. Oxygen saturation was lowest in August at the Sj6 and was 71.5%, whereas the highest of 133.2% was measured in the same month at location Sj12. Water electroconductivity at the studied sites, during 2004, ranged from 155 12 6. The basic physico-chemical parameters in the water of Lake Skadar in 2005 are alsoμS/cm shown at location in table Sj 23.in All August, parameters, up to 299 except μS/cm saturation in the same at one month and pHat location values at Sj several investigated locations, were within allowable limits. In June, the water temperature ranged from 19.7°C at location Sj3, up to 26.2°C, at location Sj12. Variations in temperature during August were not high from 26.8°C at location Sj6, up to 27.8°C at location Sj12. During October, temperatures ranged from 15.8°C at location Sj3 up to 19.4°C at Sj6. Maximum transparency was stated at location Sj2 in June (2.6 m) and the minimum of 0.9 m in the same month at sampling site Sj3. The maximum pH value of 8.79 was recorded at location Sj5 in June and minimum of 7.94 at location Sj2 in October, indicating that in 2005, water of the lake showed a moderate alkaline reaction. It should be noted that the pH value of locations Sj12 (June and October), Sj5 (June, August and October) and Sj3 (June) increased slightly compared to the maximal allowable value of 8.5 for water of A2 C K2 class, which is defined by Directive on the classification and categorization of water of Montenegro. The minimum value of the redox potential was recorded at location Sj5 in October (-95mV), and the maximum, of -51mV, at location Sj2 in October. The concentration of dissolved oxygen in the water ranged from 6.92 mg/l at location Sj6 in June, up to 11.62 mg/l at location Sj5 in October. Maximum oxygen saturation was recorded at location Sj5 in October and was 124.4%, which was slightly increased compared to the MAC for this parameter, while minimum value (92.2%) was stated at location Sj6 in October. Water electro 6, in August, to 3 in October. The concentrationconductivity of nitrate rangeds, in June from, ranged 205 μS/cm, from at0.42 location mg/l at Sj position Sj3, to 0.69283 μS/cm,mg/l at location position Sj Sj12. In August, the maximum concentration of this parameter was stated at sampling site Sj2 (0.72 mg/l), and the minimum at location Sj12 (0.20 mg/l). In October, the maximum nitrate concentration of 0.50 mg/l was measured at location Sj2, while the minimum concentration was 0.20 mg/l, at localities Sj5 and Sj6. In June, the maximum concentration of phosphates was recorded at location Sj6 and was 0.022 mg/l, while the minimum was 0.01 mg/l at the localities Sj12 and Sj5. In August, phosphates concentration ranged from 0.011 mg/l at location Sj6 up to 0.03

mg/l, at location Sj3. In October, at location Sj6, phosphates concentration of 0.22 mg/l was recorded while at the other four localities was 0.01 mg/l.

Table 24. Maximum allowable concentrations (MAC) for physical and chemical characteristics of the natural waters of classes A1 and A2 ("Official Gazette of Montenegro", no. 2/07 of 29.10.2007.) Parameter Units of MAC in water measure A1 class A2 class Water temperature °C 9-12 30 Water turbidity NTU 5 5 Electrical S/ cm 400 600 conductivity Suspended matter mg/l <10 20 pH - 6.8-8.5 6.5-8.5 Nitrates mg/l 20 25 Nitrite mg/l 0.003 0.005 Fluorides mg/l 1 1.5 Dissolved iron mg/l 0.1 0.3 Manganese mg/l 0.005 0.01 Copper mg/l 0.02 0.05 Zinc mg/l 0.05 1 Boron mg/l 1 1 Beryllium mg/l 0.001 0.005 Cobalt mg/l 0.001 0.010 Nickel mg/l 0.002 0.050 Arsenic mg/l 0.010 0.050 Cadmium mg/l 0.001 0.005 Total chromium mg/l 0.000 0.05 Lead mg/l 0.010 0.05 Mercury mg/l < od GD* 0.0005 Barium mg/l 0.1 0.7 Cyanides mg/l 0.001 0.005 Sulphates mg/l 20 50 Chlorides mg/l 20 40 Phosphates mg/l 0.02 0.05 Phenols mg/l 0.001 0.005 Total mineral oils mg/l 0.01 0.05 PAHs mg/l 0.0002 0.0002 Total pesticides mg/l < od GD* 0.001 COD mg/l 2 4 Saturation O2 % 80-110 80-120 BOD5 mg/l 3 4 Ammonium ion mg/l 0.02 0.05 TOC mg/l 1 2 Total coliforms 37˚C ind/1ml 10 500 Fecal coliforms ind/100ml 20 2000 Fecal streptococci ind/100ml 20 1000

According to data from CETI in 2005 (Royal Haskoning, 2006), it is noted that values of the basic physical and chemical parameters of the water were under the allowable limits for water of class II, according to the Directive on the classification and categorization of waters (table 24 and table 26). In the spring season during 2005, the lake water temperature ranged from 13.2°C

the lowest (7.63), while at the Kamenik the highest pH value (8.25) was recorded. Oxygen concentrationat Karuč up to ranged 23.2°C from at the 8.46 sampling up to 10.02 site Biševina. mg/l, and At sat theuration same from location 79.8% pH to value 115.4%. was

oxygen demand, which ranged from 1.22 to 3.57 mg/l and chemical oxygen demand whichElectroconductivity ranged from ranged0 to 3.2 from mg/l, 225 were to 240within μS/cm, allowable under limits, allowable since limit.the MAC . Biological for the water of category II is 4 mg/l. Table 27 shows values of physical and chemical characteristics of water in January 2010. Water temperature ranged from 5.5°C (Plavnica) to 7.5°C (middle of the lake). The pH value was similar at almost all localities, ranging from 8.0 to 8.2. According to these data, the concentration of oxygen was increased during the studied period and

ranged from 253 (middle of the lake) to 308 Biologicalranged from oxygen 12.7 mg/ldemand, in Plavnicawhich ranged to 14.5 from mg/l 1.5 in Starčevato 3.2 mg/l Gorica. and Electroconductivity chemical oxygen demand which rangedμS/cm from 1.1 to 2.9 mg/l, were withinμS/cm allowable (right mouth limits. of Morača river).

5.2. Water pollution

Besides general physico-chemical parameters (table 22 and table 23) in the water of Lake Skadar, concentrations of heavy metals, nitrates, nitrites, ammonium ions, chlorides, cyanides, phosphates, pesticides, detergents, polyaromatic hydrocarbons and polychlorinated biphenyls were monitored during 2001, 2005 and 2010. For the 2010 there are data on the presence of fecal and coliform bacteria. In 2001 all chemical parameters in the water ranged within allowable limits. The nitrites concentration was less than 0.005 mg/l, nitrates less than 0.1 mg/l, and ammonium ions less than 0.01 mg/l (table 25). Chlorides concentration was lowest at the right mouth of the (3 mg/l) and highest at Blato - 6.8 mg/l. The concentration of cyanides was less than 0.02 mg/l at all locations, and phenols less than 0.1mg/l. Aluminum concentrationMorača in the water ranged fromVučko 0.034 mg/l (Plavnica) to 0.063 mg/l (the right mouth of the river). Calcium concentrations ranged from 47.5 to 67.5 mg/l. The concentrations of copper, cadmium and zinc did not exceed the maximum allowable concentrations atMorača any of the sampling sites.

Table 25. Physico-chemical characteristics of Lake Skadar water during December 2001 (after IMSL, 2001; modified) (t–water temperature; Secchi–transparency; EC– electroconductivity; TP–total phosphorus; TN–total nitrogen; NO2-N–nitrites; NO3-N– nitrates; NH4+-ammonium ion; Cl––chlorides; CN–cyanides; Al–aluminum; Ca–calcium; Cu–copper; Si–silicon; K–potassium; Cd–cadmium; Zn–zinc). 2001 Locality Right mouth Raduš Vučko Plavnica Virpazar of the blato Morača river Parameter t (°C) 8.9 9 7.8 6 8.7

Secchi (m) 2 1.5 2.6 1.5 2

pH 8.1 8.2 8.2 7.9 8.25

O2 (mg/l) 8.1 9.2 11.1 11.2 11.5

O2 (%) 85 90 110 147 145

EC (μS/cm) 263 265 270 240 364

TN (mg/l) <0.5 <0.5 <0.5 <0.5 0.7

TP (mg/l) <0.05 <0.05 <0.05 <0.05 <0.05

NO2-N <0.005 <0.005 <0.005 <0.005 <0.005 (mg/l)

NO3-N <0.1 <0.1 <0.1 <0.1 <0.1 (mg/l)

+ NH4 (mg/l) <0.01 <0.01 <0.01 <0.01 <0.01

(mg/l) 3 4.3 6.8 3.4 6

CN (mg/l) <0.02 <0.02 <0.02 <0.02 <0.02

Phenols <0.1 <0.1 <0.1 <0.1 <0.1 (mg/l)

Al (mg/l) 0.063 0.048 0.052 0.034 0.035

Ca (mg/l) 67.5 56.5 47.5 54 75

Cu (mg/l) <0.02 <0.02 <0.02 <0.02 <0.02

2001 Locality Right mouth Raduš Vučko Plavnica Virpazar of the blato Morača river Parameter Si (mg/l) 1.1 1.1 1.1 1.98 1.65

K (mg/l) <5 <5 <5 <5 <5

Cd (mg/l) <0.025 <0.025 <0.025 <0.025 <0.025

Zn (mg/l) <0.2 <0.2 <0.2 <0.2 <0.2

he chemical parameters of the water did not exceed the maximum allowable concentration for water of category II even in 2005 (table 26). The nitrites concentration was belowТ the allowable limit of MAC for this parameter (0.005 mg/l). Nitrates concentrations ranged from 2.9 mg/l at Kamenik to 4.1 mg/l at . The concentration of ammonium ions ranged from 0.034 mg/l to 0.087 mg/l. Chlorides concentration was similar at all locations (4.1 – 4.59 mg/l) and was about ten timesKaruč lower than MAC (table 24). Concentrations of heavy metals ranged within allowable limits and did not exceed MAC. The concentration of mercury was not precisely detected, since it was found to be less than 0.002 mg/l at all locations and MAC for this metal is 0.0005 mg/l (table 24). The situation is similar with measurements of detergents and pesticides, as well as with some other parameters (table 26). The concentration of total carbon in the water was the lowest at sampling site Biševina - 0.9 mg/l, and the highest - 2.8 mg/l at Kamenik, where it exceeded MAC (2 mg/l).

Table 26. Physico-chemical water characteristics of Lake Skadar in spring, 2005 (after CETI,

2005; Royal Haskoning, 2006) (t–water temperature; EC–electroconductivity; BOD5–

biological oxygen demand; COD–chemical oxygen demand; NO2-N–nitrites; NO3-N– 3- nitrates; NH4+–ammonium ion; Cl––chlorides; CN –cyanides; SO42-–sulfates; PO4 – phosphates; – fluorides; Na– sodium; K–potassium; Ca–calcium; Mg– magnesium; As–arsenic; Cu–copper; B–boron; Zn–zinc, Pb–lead; Cr–chromium; F–iron; Mn– manganese, Cd-cadmium; Hg–mercury; Mo–molybdenum; Ba–barium; Ni–nickel; Se– selenium; PAH–polyaromatic hydrocarbons; PCB–polychlorinated biphenyls; TOC– total organic carbon. Locality 2005 Right mouth of Karuč Biševina Kamenik the Morača river Parameter t (°C) 20.5 13.2 23.2 21.9

pH 7.83 7.78 7.63 8.25

O2 (mg/l) 9.64 8.46 10.02 9.42

Locality 2005 Right mouth of Karuč Biševina Kamenik the Morača river Parameter

O2 (%) 105.1 79.8 115.4 106.7

EC (μS/cm) 239 225 240 237

BOD5 (mg/l) 3.57 1.22 1.71 2.29

COD (mg/l) 1.6 0 3.2 0.8

NO2-N (mg/l) <0.005 <0.005 <0.005 <0.005

NO3-N (mg/l) 3.4 4.1 3.3 2.9

NH4+ (mg/l) 0.05 0.087 0.034 0.076

(mg/l) 4.1 4.24 4.59 4.10

(mg/l) <0.005 <0.005 <0.005 <0.005

SO42- (mg/l) 6.31 8.22 6.95 13.29

3- PO4 (mg/l) <0.01 <0.01 <0.01 <0.01

Phenols <0.001 <0.001 <0.001 <0.001 (mg/l)

F (mg/l) 0.031 0.004 0.05 0.03

Na (mg/l) 1.40 1.63 1.90 2.51

K (mg/l) 0.34 0.27 0.2 0.197

Ca (mg/l) 38.88 37.81 36.8 37.7

Mg (mg/l) 4.28 4.98 8.32 8.77

As (mg/l) <0.001 <0.001 <0.001 <0.001

Cu (mg/l) <0.01 <0.01 <0.01 <0.01

B (mg/l) <0.05 <0.05 <0.05 <0.05

Zn (mg/l) <0.05 <0.05 <0.05 <0.05

Locality 2005 Right mouth of Karuč Biševina Kamenik the Morača river Parameter

Pb (mg/l) <0.001 <0.001 <0.001 <0.001

Cr (mg/l) <0.05 <0.05 <0.05 <0.05

Fe (mg/l) 0.07 0.07 0.07 0.06

Mn (mg/l) <0.01 <0.01 <0.01 <0.01

Cd (mg/l) <0.001 <0.001 <0.001 <0.001

Hg (mg/l) <0.002 <0.002 <0.002 <0.002

Mo (mg/l) <0.2 <0.2 <0.2 <0.2

Ba (mg/l) <0.01 <0.01 <0.01 <0.01

Ni (mg/l) <0.05 <0.05 <0.05 <0.05

Se (mg/l) <0.001 <0.001 <0.001 <0.001

Detergents <0.05 <0.05 <0.05 <0.05 (mg/l)

Pesticides <0.01 <0.01 <0.01 <0.01 (μg/l)

PAH (μg/l) <0.1 0.03 <0.01 <0.01

PCB (μg/l) <0.1 <0.1 <0.1 <0.1

TOC (mg/l) 1.03 1.9 0.9 2.8

In 2010 the water chemistry of Lake Skadar was also in accordance with the prescribed characteristics for the A2 class of surface waters. The concentrations of nitrates, nitrites, chlorides and sulphates were significantly lower than MAC (table 27 and table 24). The concentration of phenols and detergents, at almost all locations, was lower than 0.001 mg/l. The amount of total fecal coliforms ranged from 1 individual to 231 individuals per 100 ml of water, which is much less than the MAC (2 000 ind/100 ml). Volume quantities of coli bacteria ranged from 7 ind/100 ml at location Sj5, to 1 420 ind/100 ml at the right mouth of the Mo river. This value is about 3 times higher than MAC (table 24). rača

Table 27. Physico-chemical water characteristics of Lake Skadar in January 2010 (after HMZ, 2010) (Sj3–Vranjina; Vir–Virpazar; Sj6–Plavnica; Sj2–Kamenik; Sj5–Middle of the Lake; SG– eva Gorica; ŽC– t–water temperature; EC– electroconductivity; BOD5–biological oxygen demand; COD–chemical oxygen demand; NO2Starč-N–nitrites; NO3-N–nitratesŽabljak; NH4 +-ammonium Crnojevića; ion; Cl––chlorides; SO42-–sulfates; PO43-–phosphate; Na–sodium; K–potassium; Ca–calcium; Mg–magnesium; Fe–iron.

Locality 2010 Sj3 Vir Sj6 Sj2 Sj5 SG ŽC Parameter t (°C) 6.5 6.2 5.5 6.7 7.5 6.8 6.2 pH 8.0 8.0 8.0 8.0 8.2 8.1 8.0

O2 (mg/l) 14.1 12.9 12.7 13.7 14.5 14.5 14.0

O2 (%) 115 104 101 114 121 119 113

EC (μS/cm) 308 294 282 271 253 276 277

BOD5 (mg/l) 2.1 2.5 2.7 2.4 1.5 2.9 3.2

COD (mg/l) 1.1 1.6 2.9 2.0 1.2 2.0 2.5

NO2-N (mg/l) 0.004 0.008 0.006 0.003 0.003 0.002 0.004

NO3-N (mg/l) 1.25 <0.01 0.29 <0.01 0.17 0.14 <0.01

NH4+ (mg/l) 0.10 0.09 0.19 0.09 0.08 0.02 0.08

(mg/l) 5.3 5.4 6.9 5.5 7.2 5.6 4.1

SO42- (mg/l) 12.9 7.0 7.6 5.5 6.5 5.9 6.9

3- PO4 (mg/l) 0.04 0.01 0.02 0.02 0.02 0.03 0.04

Phenols (mg/l) <0.001 <0.001 <0.001 <0.001 <0.001 <0.001 <0.001

Na (mg/l) 2.2 2.4 3.4 2.1 2.4 2.3 2.1

K (mg/l) 0.6 0.6 1.1 0.5 0.6 0.6 0.7

Ca (mg/l) 49.6 45.3 43.4 40.8 39.4 42.6 43.2

Mg (mg/l) 7.5 9.1 8.8 9.0 7.4 8.4 8.1

Locality 2010 Sj3 Vir Sj6 Sj2 Sj5 SG ŽC Parameter Fe (mg/l) 0.07 0.08 0.05 0.06 0.06 0.08 0.20

Detergents (mg/l) <0.001 <0.001 <0.001 <0.001 0.05 <0.001 <0.001

Total fecal bacteria (ind/100 111 18 231 – – 1 28 ml H2O)

Total coliforms 1 420 90 416 – 7 10 79 (ind/100 ml H2O)

Aerobic bacteria 36 15 67 15 58 42 194 (ind/1 ml H2O)

The values of physical and chemical parameters in different study periods were under the allowable limits for water of A2 class. Chemical parameters which cause concern by their increased concentration and quantity are nitrogen and phosphorus, as these nutrients accelerate eutrophication process in the lake. During the ’80s-average annual concentration of nitrogen, as was already mentioned, was 0.20 mg/l, which is the half of the recentvalue. Estimated average amount of nitrogen that reached the lake, for a ten-year period (2001 - 2010) was 730 t. The lowest quantity was stated in 2010 - 176 t, and the highest in 2004 - 1 724 t 12). There are differencies in average nitrogen loading between localities. The lowest load was stated at Ckla - 389 t, and highest at Virpazar - 1 585 t annually (table(Đurašković, 28). 20

Table 28. Estimated load of Lake Skadar with inorganic nitrogen (IN), in period 2001- 2010, in tons , 2012).

Position (afterKamenik Đuraškovi Vranjinać Virpazar Middle Starčevo Ckla Mean Year of lake (annual) 2001 708 757 818 607 1053 482 737 2002 451 917 2303 528 365 464 838 2003 1048 624 862 676 653 560 737 2004 396 740 8119 519 342 229 1724 2005 1049 1263 1064 333 894 634 873 2006 733 1304 804 477 686 642 774 2007 1323 1310 1182 600 1032 608 1009 2008 206 398 435 107 117 194 243 2009 139 463 173 64 230 64 189 2010 93 636 92 171 56 9 176 Mean 615 841 1585 408 543 389 730

Concerning ortho-phosphorus, the estimated average annual load that reaches the lake was much lower than nitrogen load and amounts to 105 t (table 29). The lowest amount of ortho-phosphorus was detected in 2003 - 8 t, and the highest in 2004 - 594 t. The locations Ckla and the middle of the lake had lowest average load - 28 t, and Virpazar had the highest amount of phosphorus - 458 t.

Table 29. Estimated load of Lake Skadar with ortho-phosphorus (o-P) in tons, in period 2001- 2010, in , 2012).

Positiontons Kamenik (after to ĐuraškoviVranjinać Virpazar Middle of Starčevo Ckla Mean Year the lake (annual) 2001 17 57 83 77 36 84 59 2002 0 20 809 0 16 0 141 2003 7 23 14 0 3 0 8 2004 50 36 3366 53 36 24 594 2005 132 22 95 30 33 13 54 2006 22 46 33 30 35 30 33 2007 41 25 63 31 17 45 37 2008 28 36 90 29 57 57 49 2009 28 35 24 19 27 21 25 2010 17 15 6 8 213 11 45 Mean 34 31 458 28 47 28 105

The ratio nitrogen/phosphorus (TN/TP) is of high importance for determination of the lakes trophic status. t. When the TN/TP ratio > 15, the primary production in the lakes is limited by phosphorus concentration, when the TN/TP ratio < 7, the production is limited by nitrogen concentration, and when the TN/TP ratio is between 7 and 15, it is considered that the limiting factors can be either phosphorus or nitrogen or both of these nutrients (OECD, 1982). The ratio of total nitrogen to total phosphorus (TN/TP) in the Skadar Lake ranged from 22 to 26, in the warm period of the year, while the annual ratio of TN/TP was 33 (Rako evi , 2006). Such TN/TP ratio in this lake indicates that phosphorus is the limiting nutrient. During the ’80s, the TN/TP ratio was 6, indicating that there was a significant deficitč of nitrogenć in relation to the phosphorus concentration in the lake, which shows that nitrogen was the limiting factor in that period. If we consider the ratio of these nutrients through a ten-year period (2001 to 2010) we may conclude that there is no certain regularity or clear defined trend of their increase or decrease (table 30). The values of this ratio may vary depending on location and the year. Based on results shown in mentioned table, we may conclude that in most cases TN/TP ratio was higher than 15, which confirms that actual limiting nutrient in the Skadar Lake is phosphorus. The constant increase of the use of nitrogen fertilizers in the agriculture area of Zeta Plain increased the amount of this nutrient in the lake, and significantly influenced the trophic status of the lake.

Table 30. Ratio of average values of inorganic nitrogen and ortho-phosphorus (TIN/To-P) in Lake Skadar for the period 2001- 2010 (after , 2012).

Locality Rijeka Kamenik Vranjina ĐuraškoviVirpazarć Middle Starčevo Ckla Crnojevića of the Year lake 2001 3 41 13 10 9 29 6 2002 10 – 45 3 – 22 – 2003 8 151 28 62 – 188 – 2004 10 8 21 2 10 10 10 2005 9 8 57 11 11 27 49 2006 14 33 28 24 16 19 22 2007 10 32 53 19 19 63 14 2008 12 7 11 5 4 2 3 2009 13 5 13 7 3 9 3 2010 5 5 42 16 22 0.3 1

5.3. Groundwater pollution

The monitoring of physico-chemical characteristics and concentrations of pollutants in the Zeta Plain ground waters has not been continuous. It was done sporadically when needed. Table 31 shows average and maximal concentrations of various hazardous substances in the ground waters at different locations in this area, along with the values of MAC.

Table 31. Medium and maximum values of different chemical parameters in the Zeta Plain ground waters, at different sampling sites, in period from 1990–1996 (after Royal Haskoning, 2006; modified): MAC–maximum allowable concentration

according to Directive on classification and categorization of surface and ground waters (Official Gazette no. 2/07); *–MAC by Dutch Standards, 2009. Sampling site I II III IV MAC Parameter pH 7.30 8.24 7.20 7.46 6.5–8.5 max 7.70 12.31 7.50 7.55

F (mg/l) 0.125 1.44 0.26 0.329 1.5 max 1.10 51.56 1.07 2.660

PCB (μg/kg) 1.923 1.98 0.58 0.149 0.01* max 20.12 78.10 2.01 0.743

PAH (μg/kg) 1.386 4.23 2.91 0.425 0.2 max 9.46 198.10 11.90 1.730

Phenols (μg/kg) 0.50 2.90 1.20 0.75 5.0 max 2.10 12.60 2.30 1.55

Average values of pH ranged from 7.20 to 8.24, while maximum values ranged from 7.50 up to 12.31, which indicate an increase in accordance to MAC. The average concentration of fluorides ranged from 0.125 to 1.44 mg/l. Their maximum concentrations at locations II (51.56 mg/l) and IV (2.66 mg/l) were higher than the allowed concentration of 1.5 mg/l. Because the Montenegrin national regulation doesn’t prescribe the concentration of PCBs in ground waters, we used Dutch standards. The average and maximum concentrations of polychlorinated biphenyls exceeded the maximum allowable concentrations at all four locations, after these standards. Average times higher than MAC. When it comes to maximum concentrations, these differences concentrations ranged from 0.149 μg/kg (IV) to 1.98 μg/kg (II), which is about 200 810 times higher than MAC. are evenPolyaromatic more drastic. hydrocarbon Maximal s values concentration ranged froms ha ve 0.743 also μg/kg,been much which higher is 74 timesthan allowedhigher than at MAC, and up to 78.1 μg/kg, which is 7 is from 2 to 20 times higher than MAC. The maximum concentration of PAH ranged from all locations. Average concentrations allowableranged from value) 0.425. to 4.23 μg/kg, which The average concentrations of phenols ranged within allowable limits (0.5-2.9 1.73 to 198.1 μg/kg (990 times higher than the exception was stated at the locality II - table 31 and table 16). μg/kg). The highest concentration of this pollutant and the only 12.6 μg/kg (

5.4. Sediment pollution

Sediment plays an important role in the aquatic ecosystems, since it represents the source of organic and inorganic matter but, it is also a final spot for most of the pollutants of antropogenic origin (Hynes, 1983; Jones & Mulholland, 2000). In addition, beside current pollutants, sediment may contain residues of former pollutants (Danielopol, 1989; Gier, 1993; Lafont et al., 1996), so analysis of the sediment can detect a long-term pollution of an ecosystem (Lehman et al., 1997). In the period from 1993 to 1996 the concentrations of heavy metals, mineral oils, polyaromatic hydrocarbons and polychlorinated biphenyls in the sediment were monitored at different locations in Lake Skadar (table 32). Since Montenegro still has no national regulation on maximum allowable concentrations of various pollutants in the sediment, Dutch standards were used for evaluation (Dutch Standards, 2000, 2009). The concentration of copper (Cu) in the sediment ranged from 0.40 mg/kg at locality C the maximum allowable concentration (MAC). The concentration of cadmium (Cd) at all samplingrni sites Žar was to 19.40 above mg/kg the MAC at the (0.80 left mouthmg/kg). of The the concentrationMorača river and of chromium did not exceed (Cr) ranged fro exceed them MAC 4.60 of mg/kg 85.00 (rightmg/kg, mouth since of it theranged Morača from river) 12.40 to mg/kg 8.60 mg/kg (Crni (leftŽar) mouthto 30.00 of mg/kgthe Morača ( river), which is within allowable limits. Concentrations of lead (Pb) did not concentrationsleft mouth of this of metal the Morača were stated river). at The the highestlocations: concentration Crni Žar, Podhum of zinc and (Zn) Plavnica in the (sediment1.00 mg/kg). was foundConcentrations out at the of left nickel mouth (Ni) of andthe Moračaaluminum (14.60 (Al) mg/kg),ranged withinwhile the allowable lowest limits. Acidity of the sediment ranged from 6.67 at Plavnica to 7.54 at the right mouth of

the Morača. 51

Table 32. The concentration of different pollutants in the sediment samples from Lake Skadar for the period 1993-1996 (after Royal Haskoning, 2006). Locality Right Left mouth Crni Žar Podhum Raduš Plavnica Murići mouth of of the Parameter the Morača Morača Cu (mg/kg) 3.40 19.40 0.40 0.70 1.00 0.80 1.00 Cd (mg/kg) 0.92 1.66 1.06 1.30 1.30 1.06 1.20 Cr (mg/kg) 4.60 8.60 6.40 6.40 6.40 8.60 6.46 Pb (mg/kg) 14.90 30.00 12.40 12.80 13.20 14.00 14.40 Mn (mg/kg) 264.00 400.00 120.00 296.00 450.00 274.00 440.00 Fe (mg/kg) 1221.67 5738.93 12.00 16.00 294.00 60.59 144.00 Zn (mg/kg) 2.40 14.60 1.00 1.00 1.70 1.00 1.40 Ni (mg/kg) 7.00 4.00 4.00 5.60 2.00 5.20 6.00 Al (mg/kg) 1.28 0.44 1.87 8.02 2.80 1.86 5.62 F (mg/kg) 19.18 35.03 31.62 83.23 32.83 41.41 78.74 pH 7.54 7.17 7.35 6.87 6.86 6.67 6.81 SiO2 675.00 125.00 500.00 200.00 600.00 350.00 313.00 (mg/kg) Mineral oils 20.00 10.00 10.00 10.00 20.00 10.00 10.00 (mg/kg) PAH 0.30 0.50 1.00 0.20 0.00 0.90 0.10 (μg/kg) PCB (μg/kg) 0.80–17.89 1.76- 0.00 0.013 0.00 0.12- 0.00 100.70 1.90

Concentrations of polyaromatic hydrocarbons (PAHs) were significantly lower than MAC , as well as the concentration of polychlorinated biphenyls ( ). Althoughwhich there is 40 are 000 no μg/kgdefined values of maximum allowable concentrations for certain pollutantsMAC is (Mn, 1 000 Fe, μg/kg F, SiO2) detected in the lake sediment, but, their concentrations in the sediment being much higher (up to several hundred thousand times) from those in the water, are worning. Mn, Fe and SiO2 originate from bauxite, the main raw material in the Alumina Plant Podgorica (KAP). Annual quantity of this ore used for aluminium production amounts 515 775 t (table 6). The lowest concentration of manganese (Mn) was recorded at Crni Žar - 120.00 mg/kg, which is 30 000 times higher than its concentration in the water, and the highest at Raduš - 450.00 mg/kg (90 000 times higher than its concentration in the water). However, the greatest difference in the concentration of Mn in the sediment and that from the was more than 700 000 times higher, since only 0.0006 mg/kg was measured in the water (Royalwater Haskoning, was recorded 2006). at Murići. The situation At this locationis similar the concerning concentration iron in(Fe). the According sediment to data presented in table 32, concentration of the pollutant is much higher at the right (1 221.67 mg/kg) and at the left mouth of the river (5 738.93 mg/kg) then at other sampling sites. If we compare the iron concentrations in the sediment and water, it is evident that its concentration in the sedimentMorača is 375 times higher at Crni Žar and up to

163 969 times higher at the left mouth of the river. Fluori des concentrations in the sediment ranged from 19.18 mg/kg (right mouth of the ) to 83.23 mg/kg (Podhum) and at all positions were several thousandMorača times higher than those in the water. The lowest concentrations of silica (SiO2) in the sedimentMorača was recorded at the left mouth of the river - 125.00 mg/kg, which is about 60 times higher than the concentration in the water, while, the highest concentration was determined at the right mouth of the Morača - 675.00 mg/kg, which is about 300 times higher than the concentration in the water. This indicatesMorača that even small concentrations of pollutants which constantly arrive into the lake can cause serious problems, because their constant deposition in the sediment amplifies their concentration. Sediment analyses done in 2005 indicated the presence of heavy metals: Zn, Cu, Pb, Cd, Ni and Cr, which are considered to be the most significant pollutants in Lake Skadar (Filipovi , 1983, 1997, 2002). Various polyaromatic hydrocarbons were found out in the sediment of Lake Skadar, too (table 33). ć

Table 33. The concentration of heavy metals and polyaromatic hydrocarbons (PAHs) in the sediment samples from Lake Skadar in 2005 (after

2012). Šundić & Radujković, Lokality Sj2 Sj3 Sj5 Sj6 Sj12

HEAVY METALS Zn (mg/kg) 87.23 55.42 62.47 48.61 66.38 Cu (mg/kg) 10.36 25.52 27.71 17.96 27.03 Pb (mg/kg) 49.4 43.27 46.67 40.23 48.6 Cd (mg/kg) 1.01 0.1 0.1 0.12 0.14 Ni (mg/kg) 90.84 113.27 136.12 63.46 127.31 Cr (mg/kg) 86.02 64.66 60.53 43.82 52.39

PAHs Naphthalin [μg/kg] 57.0 19.7 16.5 21.2 - Acenaphthylen [μg/kg] 10.0 10.0 10.0 10.0 - Acenaphthene [μg/kg] 20.5 2.0 3.0 10.0 - Fluorene [μg/kg] 5.5 3.3 3.6 2.4 - Phenanthren [μg/kg] 42.5 23.9 28.1 15.2 - Anthracen [μg/kg] 10.0 2.3 2.8 10.0 - Fluoranthen[μg/kg] 26.5 22.3 32.2 8.8 - Pyren [μg/kg] 20.0 17.6 25.8 6.6 - Benzo(a)anthracen [μg/kg] 17.5 20.7 26.3 4.2 - Chrysen [μg/kg] 20.5 27.3 29.9 7.0 - Benzo(b)fluoranthen [μg/kg] 29.0 46.3 46.1 10.0 - Benzo(k)fluoranthen [μg/kg] 18.0 20.7 23.3 5.2 - Benzo(a)pyren [μg/kg] 17.0 27.2 32.2 5.2 - Indeno,1,2,3-cd pyren [μg/kg] 35.5 34.0 31.8 11.4 - Dibenz(ah)anthracen [μg/kg] 5550.0 2040.0 11.5 2780.0 - Benzo(ghi)perylen [μg/kg] 24.5 36.5 37.0 12.4 - Total concentration of PAHs 5904.0 2353.8 360.1 2919.6 -

The highest concentration of zinc (87.23 mg/kg) in the sediment was stated at the position Sj2 (table 33), within allowable limits, while the lowest concentration of this metal (48.61mg/kg) was stated at the position Sj6. Copper concentrations ranged within allowable limits and were consistent at almost all sampling sites, except at position Sj2, where the lowest concentration of this metal (10.36 mg/kg) was noted. The lea d concentrations ranged from 40.23 mg/kg at the position Sj6 to 49.4 mg/kg at the position Sj2. The concentration of cadmium (1.01 mg/kg) at the position Sj2 was slightly above the MAC, which is 0.8 mg/kg.. The concentrations of nickel at positions Sj12 (127.31 mg/kg), Sj5 (136.12 mg/kg) and Sj3 (113.27 mg/kg), exceed the MAC (35 mg/kg) by several times, which is, but are still below the high-risk concentration limit, according to Dutch standards. Chromium concentrations ranged from 43.82 mg/kg (Sj6) to 86.02 mg/kg (Sj2). At the positions Sj5, Sj2, Sj3 and Sj6 several different polyaromatic hydrocarbons were detected in the sediment, and were present in different concentrations. At position Sj5

dibenz(ah)anthracenethe benzo(b)fluoranthene at positions had highestSj2, Sj3, Sj concentration6 had concentrations (46.1 μg/kg), of 5 and anthracene 040 had the lowest concentration, which (2.8 are several μg/kg). times Polyaromatic higher than concentrations hydrocarbon of other PAHs at these positions. At the positions Sj2 and Sj6 fluorene550 had μg/kg, the lowest2 μg/kg and 2 780 μg/kg respectivelyand 2. y), while acenaphthen had the lowest 3 (table 33). At sampling site Raduš PAHs were notconcentration identified (5.5in the μg/kg sediment, 4 eitherμg/kg respectivelin the present or previous studies. The total concentration ofof 2polyaromatic μg/kg at the hydrocarbonsposition Sj in the sediment of Lake Skadar does not exceed the allowable limit of Polychlorinated biphenyls are classified into the most persistent pollutants. Time of their half-lifedecay, depending on the PCB’s class, ranges from 340 to 000 38 yeaμg/kgrs (Sinkkonen (40 mg/kg). & Paasivirta, 2000). In the six-year period (1990 - 1996), polyaromatic hydrocarbons were not detected in Skadar Lake sediment. The concentration of polychlorinated biphenyls in this study period did not exceed MAC which is 1 verage concentration of the maximum concentration ranged from table 34). 000 μg/kg. The a pollutant ranged from 0.004 to 11.76 μg/kg and 0.18 to 528.4 μg/kg ( Table 34. Concentrations of PCBs and PAHs in the sediment samples from Lake Skadar during 1990-1996 (after Royal Haskoning, 2006.) Parameter PCB (μg/kg) PAH (μg/kg) Locations max max Vranjina 0.004 0.18 0.00 0.00 Left mouth of Morača 1.76 100.70 0.00 0.00 river Plavnica 0.12 1.25 0.00 0.00 The middle of the lake 11.76 528.40 0.00 0.00

The concentrations of PAHs and PCBs were higher in ground waters than the MAC, which was not the case with their content in lake sediment. The most likely reason for the low concentrations of these pollutants in the sediment is the lake flow, since the lake water changes about 5 times during the year, which results in chemistry change of

surface sediment layer, from which samples for analysis are often taken while these pollutants remain and accumulate in deeper layers of sediment. Such a state of the sediment is probably the result of the large amounts of pollution that arrives with municipal and industrial wastewater into Skadar Lake (table 5 and table 7). The most important sources of Skadar Lake pollution are certainly waste waters from technological processes of Alumina Plant Podgorica (Filipovi , 1997, 2002; Radulovi materials (table 7), and their quantity is almost equal as the quantity ofć waste waters from all otherć, 1997; sources Šundić of &pollution. Radujković, 2012). These waters contain toxic and hazardous

6. QUALITY, CLASSIFICATION AND CATEGORISATION OF WATER AND SEDIMENT OF LAKE SKADAR

6.1. Trophic status of the lake

The Skadar Lake is a shallow lake in which the trophic zone is larger than tropholytic. Until the seventies, this lake was considered to be oligotrophic lake (Petkovi , 1971). In this period there was a balance between trophic and saprobic process. The measure of trophic processes is the relation between biomass and the fluctuationć of autotrophic organisms (the ability of aquatic ecosystem to produce organic matter). There are several trophic levels: oligotrophy, mesotrophy, eutrophy and hypertrophy. Saprobity is the relation between biomass and fluctuation of heterotrophic organisms (the ability of aquatic ecosystem to decompose organic matter). There are several saprobity levels: xenosaprobity, oligosaprobity, - mesosaprobity, -mesosaprobity and polysaprobity. If either of these two processes changes in favor of the other, the balance is immediately disturbed. The saprobity βin Skadar Lake hasα been changed in favor of trophic process, due to the high amount of nutrients, leading to eutrophication. The eutrophication is an increase in nutrients, primarily nitrogen and phosphorus in a water system, which increases primary production i.e. the amount of organic matter in it. The eutrophication is accompanied by an increase in algal and macrophytes biomass, as well as by decrease of oxygen and decreasing water transparency.

Photo 1. ).

Skadar Lake overgrowth (photo: D. Šundić, 2008

The large amount of waste, municipal and industrial water (over 69 million m3 amount of organic matter. /year),Agricultural which Morača activity river in theand Zeta ground Plain waters includes bring the into use the of artificiallake, also fertilizers bring a large that also negatively affects and intensifies eutrophication of the lake.

Photo 2.

Biological quality ofSkadar the water Lake overgrowthand sediment (photo: of LakeD. Šundić, Skadar, 2008). specific impact of certain contaminants, and prediction of toxic pollutants risks are determinated by bioindicator methods. Bioindicator methods used the living organisms to define environmental conditions. Phytoplankton species, the first link in the food chain, sensitive to environmental changes and aquatic oligochaetes, benthic organisms, were used to determine the trophic level of the lake water and its quality.

6.1.1. Phytoplankton as bioindicator of trophic level

The trophic state index (TSI-Secchi) is based on water transparency (caused by density of phytoplankton). Its value indicates that Skadar Lake is eutrophic from June to September, while it is mesotrophic during the rest of the year. The average annual value of 50.34 indicates eutrophic conditions (table 35).

Table 35. The values of the trophic level of Lake Skadar in 2003 and 2004 obtained on the basis of

transparency, chlorophyll a 2006). concentration and concentration of total phosphorus (by Rakočević, 2003/2004 May June July Aug Sep Oct Nov Dec Feb Mar Apr TSI 48.63 53.36 56.55 58.06 53.72 46.89 45.83 47.69 49.49 45.9 47.37 50.34 (Secchi) TSI 52.50 54.60 58.04 65.24 51.77 51.00 49.49 44.91 40.41 44.49 54.82 52.16 (chl a) TSI 34.89 43.38 48.42 45.52 34.86 30.18 27.36 27.36 27.36 28.42 33.89 35.60 (TP)

The trophic state index based on the concentration of chlorophyll a (TSI-chl a) indicates mesotrophic conditions during the colder period of the year (November- March) and eutrophic conditions in the rest of the year, but in August the index value of 65.24 indicates extremly eutrophic condition (table 36). The annual mean of this index also indicates eutrophic conditions in Skadar Lake.

Table 36. Reference values of TSI with corresponding trophic degree. TSI (Trophic State Index) Trophic degree < 40 Olygotrophy 40-50 Mesotrophy 50-60 Eutrophy I 60-80 Eutrophy II > 80 Hypertrophy

The trophic state index values obtained from phosphorus concentration in the water (TSI-TP) indicate mesotrophic conditions from June to August and oligotrophic from September to May. The annual average of this index indicates oligotrophic conditions in the lake. These values are unlikely to reflect true trophic level in the lake since approximately 80% of the phosphorus present is in its bound form (in the form of phosphates) in the lake’s sediment (Karaman & Beeton, 1981). During the summer period, when water temperature increases, bacterial decay is intensified. Because of this process, oxygen concentration in the water reduces and stimulates the release of nutrients from the sediment, so the the values of this index was increases as well, indicating mesotrophy (table 35 and table 36). The annual average values of trophic state index (TSI-Secchi and TSI-chl a) are between mesotrophy and eutrophy, so perhaps it would be better to classify the lake as a meso-eutrophic type. To support this statement, we have to take into consideration the fact that the average concentration of chlorophyll a in Skadar Lake, during the research period, into the mesotrophic type - & Hollert, 2005). It was found out that values of all the three indices were highest in August, when waterwas level5.9 μg/l, was placingthe lowest it andthe water temperature(Rakočević was the Nedovićhighest. These conditions, with nutrients inflow, stimulated the phytoplankton to flourish.

6.1.2. Aquatic oligochaetes as bioindicators of trophic level

There are 22 oligochaete speciesin Lake Skadar a; 2011b), out of which 20 are indicator specie Depending on the trophic conditions in lakes,(Šundić oligochaete et al., 2011 populations can become extremely abundant, srare (Šundić or can& Radujković, completely 2012). disappear (Milbrink, 1983). Besides trophic level index, which takes into account the structure of oligochaete community and their abundance, presence and relationships of indicator groups of oligochaetes - oligotrophic, mesotrophic and eutrophic (Lang & Lang-Dobler, 1980) are important to define the trophic level. The analysis of benthic oligochaetes showed that the lake is at meso-eutrophic level, which depends on the season and sampling position. At the majority of examined locations (13), trophic condition index values indicated eutrophication. Seven localities indicated mesotrophy, and the remaining 6 indicated oligotrophic condition (graph 17).

2.5

1.5 oligotrophy 1 mesotrophy 0.5

eutrophy 0

Sj1 Sj4 Sj7 Sj8 Sj9 Sj2c Sj3c Sj5c Sj6c Sj2a Sj3a Sj5a Sj6a Sj10 Sj11 Sj2b Sj2d Sj3b Sj5b Sj6b Sj6d Sj12c Sj12a Sj13a Sj12b Sj12d Sj13b

Graph 17. Trophy level of Lake Skadar for the period 2004 - 2007, obtained by trophic

condition index (TC) using the aquatic oligochaetes as bioindicators (Šundić & Radujković, 2012). An increase in the trophic state index values has been noted at examined positions that are under the direct influence of the river that brings large amounts of wastewater, both municipal and industrial (table 5 and table 7). Benthic oligochaete populations are exposed to the negative impactMorača of hazardous substances, such as fluorides, mineral oils, polychlorinated biphenyls, polyaromatic hydrocarbons, and other organic and inorganic substances, that, due to inappropriate waste handling, river and the ground waters of the Zeta Plain and then from there into the lake. accidentsIncre orased intentional trophic spillsstate getindex into values the Morača were registered at the positions that are in the peat areas of the lake, which are rich with organic substance. At the examined pelagic sites, which are out of the influence of the rivers and sublacustic springs inflow, lower trophic state index values were determined, indicating mesotrophic condition.

6.2. Saprobic status of the lake

On the basis of the structures of phytoplankton and aquatic oligochaete communities’ saprobiological evaluation of Lake Skadar was done. Based on the indicator species, for the period 2003-2007, the saprobic index (Pantle & Buck, 1955), which represents quantification of saprobic condition of the lake, was calculated. According to this index, the saprobic level and category of the examined waters were stated, using the classification given by Liebmann, 1962. Parallel to these data, the official classification and categorization concerning saprobic level regulated by Directive was given (Official Gazette of Montenegro, no. 2/07 of 29.10.2007.). According to this Directive waters are classified into 3 groups: 1) drinking waters and water that can be used in food industry, 2) waters for fish and shellfish farming, and 3) water suitable for bathing. Within each of these three groups there are classes. Thus, the first group is divided into four classes: A - waters in natural state with eventual disinfection can be used for drinking, A1 - waters that can be used for drinking after a simple physical treatment and disinfection procedure, A2 - water that can be used for drinking after proper conditioning (coagulation, filtration and disinfection), A3 - water that can be used for drinking after treatment which requires intense physical, chemical and biological treatment with prolonged disinfection, chlorination, coagulation, flocculation, decantation, filtration, absorbing the activated carbon and disinfection with ozone or chlorine. Waters for fish and shellfish farming are divided into three classes: S - waters which can be used for farming of salmonid fish (Salmonidae), Š - water which may be used for shellfish farming and C - water which can be used for farming of cyprinid fish (Cyprinidae). Finally, a third group of water suitable for bathing is divided into two categories: K1 - very good and K2 - satisfactory. Besides the classes, Directive defines three categories of waters which meet the following requirements: 1) Category I refers to freshwaters belonging to classes A1, S, K1, but when sea water is considered it refers to class Š, 2) Category II refers to the water of class A2, C, K2 and 3) category III refers to waters of class A3, and and other non classified waters used for other purposes.

6.2.1. Phytoplankton as bioindicator of saprobity

The majority of the examined locations of Lake Skadar were classified - mesosaprobic, during all four seasons (spring, summer, autumn, winter) using the phytoplankton as bioindicator ( , 2006). Saprobic index values varied fromas 1.5 β to 2.4 (table 37). These values indicate that the lake is moderately loaded with organic matter i.e. that the lake waterRakočević is of category II. Even though almost all examined locations are of the -mesosaprobic level, at certain locations, slightly higher values of the index were determined during the year. β

Table 37. Seasonal average values of saprobic index of Lake Skadar during 2003 and 2004 T1-Raduš, T2-Middle of the lake I, T3- T4- Virpazar, T5- T6-Right mouth of T7-Petrova ponta, T8-Middle of

the(Rakočević, lake II, 2006) T9-Plavnica, ( T10- –oligosaprobicLeft (I),mouth of– oligosaprobicthe Morača, - - mesosaprobicVučko (I-II), blato, – -mesosaprobic (II),the Morača,– - -mesosaprobic (II-III)). Karuč; β β Saprobic Index (SIβ α) T1 T2 T3 T4 T5 T6 T7 T8 T9 T10 Spring 1.91 2.00 1.90 2.10 2.00 1.54 1.81 1.80 2.00 1.50 Summer 1.95 2.00 2.15 2.40 2.08 1.80 1.92 1.94 2.13 1.65 Autumn 1.81 1.91 2.10 2.20 2.05 1.70 1.80 1.81 2.00 1.51 Winter 1.80 1.90 1.50 2.00 2.00 1.50 1.81 1.83 1.80 1.42

The highest reference values have been recorded at sampling site Virpazar, - -mesosaprobity has been stated (II-III category of water) and indicated that the water was critically polluted. It is supposed that mentioned situation is caused by wherewaste watersβ α from Virpazar. The lowest values of saprobic index were stated on Kar throughout the year. It is evident that the values of this index slightly increase in spring and summer period and decrease in the fall and winter. uč

6.2.2. Aquatic oligochaetes as bioindicators of saprobity

3.5

2.5

1.5

0.5

Sj1 Sj4 Sj7 Sj8 Sj9 Sj2c Sj3c Sj5c Sj6c Sj2a Sj3a Sj5a Sj6a Sj2b Sj3b Sj5b Sj6b Sj10 Sj11 Sj2d Sj6d Sj12c Sj12a Sj13a Sj12b Sj13b Sj12d Graph 18. Saprobity level of Lake Skadar water for the period 2004 - 2007, obtained on the basis of values of saprobity index (SI), using aquatic oligochaetes as bioindicators (β-α— -mezosaprobity- –mezosaprobity; α— -mezosaprobity; α-p— –mezosaprobity-polisaprobity; p—polisaprobity; I, II, III, IV— water c β α α α ategory) (Šundić & Radujković, 2012).

The saprobiological status of aquatic ecosystems depends on qualitative structures of oligochaete communities, and their abundance (Uzunov et al., 1988). An increase in organic pollution may cause reduction of sensitive species and decrease in diversity. This kind of pollution can also cause an increase in species number that are tolerant to pollution, as well as an increase of entire community. In the same time, the abundance of other macrozoobenthic groups may decrease. Defferent saprobic levels were detected in Skadar Lake during the 2004-2007 on the basis of bioindicator species of aquatic oligochaetes (graph 18). - - mesosaprobity (locations Sj1, Sj7, Sj8, Sj9 and Sj12c) to polisaprobity (position Sj2b). On the most According to-mesosaprobic saprobic index level values, was thestated, saprobic and on level the varied few fromothers β α- mesosaprobity-polisaprobity was found out (table 38). locations,According to α the Directive on classification and categorization the water of Lakeα Skadar is classified as water of category II (A2 C K2). At the locations influenced by river, -mesosaprobity was recorded -mesosaprobity-polisaprobity -p) and polisaprobity (p). . It is important to note that, at those locations, an increaseMorača of populationα density of the(α) species which arealong indicators with α of high organic load, such as(α Limnodrilus hoffmeisteri and Potamothrix hammoniensis was evident ( , 2012). The population density of these species was different at other locations with different saprobic index values (2.31-3.68) (table 38). Šundić & Radujković

Table 38. Saprobic index values (Pantle & Buck, 1954), saprobic level, categorization (Liebmann, 1962) and classification of Lake Skadar waters according to Directive on categorization and classification of surface and ground waters ("Official Gazette of Montenegro", no. 2/07 from 29.10.2007.): SI (saprobic index), o (oligosaprobity), o------mesosaprobity- – – mes - –mesosaprobity- β (oligosaprobity β mesosaprobity), β (β mesosaprobity), β α (β α mesosaprobity), α (α Aquatic ecosystemosaprobity), Location α p (α SI Saprobicpolisaprobity), Water p (polisaprobity)Class (category) (Šundić of & Radujković, 2012; modified). level category water according to Regulation on Law on waters Skadar Lake Sj1 2.48 - II-III A2 C K2 (II) Sj2a 2.86 III Sj2b 3.68 βpα IV Sj2c 2.96 α III Sj2d 3.33 -p III-IV Sj3a 3.45 α-p III-IV Sj3b 3.20 α III Sj3c 3.15 α III Sj4 3.10 α III Sj5a 2.97 α III Sj5b 3.19 α III Sj5c 3.27 α-p III-IV Sj6a 3.02 α III Sj6b 2.99 α III Sj6c 2.72 α III Sj6d 3.30 α-p III-IV Sj7 2.59 α- II-III Sj8 2.70 α- II-III Sj9 2.31 β-α II-III β α β α 62

Aquatic ecosystem Location SI Saprobic Water Class (category) of level category water according to Regulation on Law on waters Skadar Lake Sj10 3.37 -p III-IV A2 C K2 (II) Sj11 3.45 -p III-IV Sj12a 3.36 α-p III-IV Sj12b 2.84 α III Sj12c 2.49 α- II-III Sj12d 3.47 α-p III-IV Sj13a 2.89 β α III Sj13b 2.80 α III α α

It can be seen that saprobic index values and thus saprobic degree values, obtained by oligochaete bioindicators, are higher than those obtained by phytoplankton bioindicators, and those from the official classification and categorization of water. Those differencies are expected since oligochaetes are benthic organisms, exposed to the higher concentrations of toxic substances.

6.3. BMWP index

Besides aquatic oligochaetes, there are also other benthic groups that inhabit Skadar Lake (Gastropoda, Bivalvia, Insecta, Crustacea, and Nematoda), which are also used as biological indicators of water and sediment quality. The BMWP (Biological Monitoring Working Party) index is a procedure for measuring water quality of an ecosystem, using various species of macroinvertebrates as biological indicators. These values in Skadar Lake varied from 8 to 47 (table 39), which indicates poor water quality and its contamination with organic matter (table 40).

Table 39. BMWP index values in the Skadar Lake during 2004, 2005 and 2007 (Sj13–Virpazar; Sj11– Petrovo).

BMWP index 2004 2005 2007 spring summer autumn spring summer autumn spring Sj12 31 32 28 28 41 43 18 Sj13 – – – – – – 33 Sj5 24 29 24 32 37 46 – Sj2 31 35 24 29 26 36 15 Sj3 11 32 21 34 8 29 23 Sj6 24 29 24 47 34 38 16 Sj11 – – – – – – 18

The lowest index values we river (Sj3) in spring 2004 (11) and in summer 2005 (8), indicating very polluted water (table re recorded at the right mouth of the Morača

40). Index values at other positions in the three-year period, indicated presence of organic pollution in the water.

Table 40. BMWP index reference values

BMWP index value Water quality > 151 very clean 100–150 clean 51–99 moderate 16–50 polluted 0–15 very polluted

6.4. ASPT index

The ASPT (Average Score per Taxon) index (Armitage et al., 1983) is also a procedure for measuring water quality by using the abundance of different species of macroinvertebrates. The index values varied from 2.66 to 4.00 (table 41) indicating that water quality of the lake ranges from poor to medium.

Table 41. The ASPT index values in the Skadar Lake during 2004, 2005 and 2007.

ASPT index 2004 2005 2007 spring summer autumn spring summer autumn spring Sj12 3.44 3.20 3.50 3.11 3.41 3.58 3.00 Sj13 – – – – – – 3.30 Sj5 3.00 3.62 3.00 4.00 3.36 3.83 – Sj2 3.44 3.50 3.00 3.22 2.88 3.27 3.00 Sj3 2.75 3.20 3.50 3.40 2.66 3.62 3.28 Sj6 3.42 3.22 3.00 3.61 3.77 3.80 3.20 Sj11 – – – – – – 3.00

During the spring in 2004, the lowest index value (2.75) was recorded at the right mouth of the river, which indicates poor water quality (table 42), while the highest value (3.62) was recorded in the summer period of the same year, which indicates a mediumMorača lake water quality at the location near Vranjina. In the autumn, poor water quality was stated at all positions.

Table 42. Reference values of ASPT index ASPT index value Biological water quality 4.81–5.40 very good 4.21–4.80 good 3.61–4.20 medium 3.01–3.60 poor

< 3 very poor

The values of this index were slightly different in 2005 and indicated different water quality. The lowest index values (2.66 and 2.88) were recorded in the summer at the right mouth of the river and near Kamenik, that indicated extremely poor water quality. In the same period, medium water quality was stated at Plavnica. In the autumn, medium water Moračaquality was found out at most localities. The highest ASPT index value (4.00) was found out during the spring season, near Vranjina. In spring 2007, poor water quality was stated at all sampling sites.

6.5. WQI index

In addition to mentioned biological indicators, water quality evaluation of Lake Skadar was made on the basis of physical and chemical indicators. Quantification of different physico-chemical parameters in water was performed by calculating the Water Quality Index - WQI.

70 Right mouth of Raduš Virpazar Plavnica 2001 91 91 Vučko91 blato 74 77 the Morača river Graph 19. Water Quality Index (WQI) of Lake Skadar in 2001.

91 90

89 88

87 86

85 84

83 Right mouth of the Biševina Kamenik

2005 89 Karuč84 90 89 Morača river Graph 20. Water Quality Index (WQI) of Lake Skadar in 2005.

Stated WQI values showed that lake water quality at most examined locations was very good in the period from 2001 to 2009. During 2001 the lowest index values were recorded at Virpazar and Plavnica (72 and 77) and indicated good water quality (graph 19). These values are also the lowest index values of the entire period. At other localities during 2001 index value was 91 and indicated excellent water quality (table 43). 92

84 82

78 Žabljak Kamenik Vranjina Virpazar Plavnica Middle

2010 89 80 85 79 90 Starčevo89 81 Crnojevića Graph 21. Water Quality Index (WQI) of Lake Skadar in 2010.

During 2005 the lowest index value (84) was highest index value (90) was recorded at Biševina and both indicated good to excellent water quality (graph 20). recorded at Karuč, while the

80 Kamenik Vranjina Virpazar Plavnica Podhum Middle Ckla 2005 86 92 87 88 89 92 87 90 90 Starčevo Moračnik 2006 85 90 86 86 88 91 89 89 89 2007 88 87 89 86 95 91 87 90 92 2008 91 91 89 92 83 93 94 93 92 2009 92 94 90 92 93 91 93 92 93 Graph 22. Water Quality Index (WQI) in the Skadar Lake in period between 2005 - 2009

(after Đurašković, 2010; modified).

stated, while at all other localities water quality was very good (graph 21). DuringComparative 2010 atanalyses Plavnica, of WQIŽabljak index Crnojevića for the five and year Vranjina period good (2005 water-2009) quality showed was that water quality for the entire period varied from very good to excellent at most examined locations (graph 22 and table 43). According to the data measured by the Environmental Protection Agency of Montenego, the average value of this index for 2011 was 85, which indicated a very good water quality of Lake Skadar.

Table 43. Water Quality Index (WQI) reference values.

WQI value Water quality

90–100 excellent

84–89 very good

72–83 good

39–71 poor

0–38 very poor

By using physico-chemical analyses and obtained index values we can only calculate current concentration of given pollutant, but not its toxic risk to the ecosystem, so we consider them unreliable indicators of the real condition of Skadar Lake water.

6.6. IOBL index

Biological quality of sediment in the Skadar Lake was determined by calculating IOBL index (Oligochaete Index of Sediment Bioindication in the Lakes) (AFNOR, 2005).

IOBL

15.46 15.12 13.75 13.03

11.58 12.05 11.04 9.83 9.4 9.14 8.51 8.19 7.68 6.83

Sj2a Sj3a Sj5a Sj6a Sj12a Sj2b Sj3b Sj5b Sj6b Sj12b Sj2c Sj3c Sj5c Sj6c

Graph 23. IOBL values on researched sites in Skadar Lake during 2005 (a-spring, b- summer, c-autumn): –moderate quality of sediment; –poor quality of sediment, – bad quality of sediment

(Šundić & Radujković, 2012). 67

Since aquatic oligochaeta inhabit lake sediments and are in constant interaction with it, they react to any changes in their environment, caused by various pollutants. This was confirmed by IOBL index values, calculated after the data from different sampling sites in the Skadar Lake. On the basis of this index we identified three categories of sediment quality in the lake: moderate, poor and bad. The values of this index were different depending on the study period, as well as on the sampling position. The lowest IOBL index values characterize those positions that are exposed to the influence of the river, since it brings a large amount of both industrial and municipal waste waters into the lake, from the surrounding area (table 5 and table 7). The IOBL Moračaindex had the highest values in spring season – 15.46 at location Sj6 (Plavnica) and - 15.12, at location Sj3 (right mouth of the river) in the summer. These values indicate a moderate sediment quality at these locations. At the locations Sj12 and Sj5 poor sediment quality was stated in the springMorača period, since the IOBL index values were 11.04 and 13.75, respectively. Poor quality sediment was found out at the locations Sj2 (12.05) and Sj3 (13.03), in the autumn (graph 23). Besides IOBL index, sediment quality in Skadar Lake was assessed on the basis of three groups of oligochaeta indicator species, which are differently tolerant to pollution. At almost all sampling sites species from group 3 were dominant, which are indicators of high degree polluted sediment (graph 24).

100 90

70 60 Other species 50 Group 3 40 Group 2 30 20 Group 1

10 0

Sj2 Sj3 Sj5 Sj6 Sj2 Sj3 Sj5 Sj6 Sj2 Sj3 Sj5 Sj6 Sj12 Sj12 Sj12 spring summer autumn Graph 24. Participation of oligochaetes species (%) that differently tolerate sediment pollution: group 1 – sensitive species, intolerant to pollution; group 2 – species that are indicators of natural ecosystem distrophy; group 3 – species, tolerant to pollution, indicators of high level load by organic matter (after

Šundić & Radujković, 2012; modified). In the spring and summer period the dominance of species from group 3 is evident, but in the summer time, at location Sj12, species of the group 2 have a slightly higher share (37.50%), compared to those of group 3 (25.00%), while there are no species from group 1. At location Sj6 in the same period, the group 2 and group 3 were

equally represented, each with 22.22%. In autumn, species from groups 2 and 3 are also equally represented, each with 28.57% at location Sj5. Species from groups 1 and 3 at location Sj6 were also equally distributed. Their share in the sediment was 32%. The group 3 was present in all location during the autumn period, which is not the case with the species from other two groups (graph 24). According to the IOBL index values, during spring season it can be concluded the sediment quality of Lake Skadar was very poor at all locations (graph 23). At sampling sites where the IOBL index was lowest, species such as Limnodrilus hoffmeisteri and Potamothrix hammoniensis , because they are tolerant to the increased concentration of organic matter. The domination of species from group 3, throughout thedominated study period (Šundić at all & investigated Radujković, sampling 2012) sites indicates a high degree of pollution in the ecosystem (after Lafont, 2007). In the summer, extremely low values of the IOBL index were calculated indicating an extremely poor biological quality of the sediment (graph 23). The results of studies on the toxicity of the sediment of Lake Skadar obtained by using contact tests (bioassays) on macrophytes (Myriophyllum aquaticum test and Lemna test), confirmed that sediment quality was highly disturbed at the locations Sj2, Sj12 and Sj6. Application of the mentioned tests indicated that there was a 17% inhibition of growth of Myriophyllum aquaticum in the sediment at sampling site Sj12 and 21% in the sediment at Sj2, as well as an inhibition in growth of Lemna sp. of 20% in the sediment at Sj6

In autumn, the lowest values of IOBL index were found out at locations Sj5, Sj12 and(Stešević Sj6, indicatinget al., 2007) a very poor quality of the sediment, while the remaining two positions Sj2 and Sj3 indicated poor sediment quality. At most positions with poor sediment quality the dominant species were indicators of increased amounts of organic matter, and among them the most numerous was Psammoryctides barbatus, a frequent inhabitant of lakes where stratification is absent and which are rich in organic matter (Milbrink, 1973). It is important to note that sediment of Lake Skadar is still able to mineralize organic matter and thus keep the balance of the lake ecosystem, which is obviously exposed to negative anthropogenic pressures. This is confirmed by the IOBL index values that range from 6.83 to 15.46, and which, in addition to the ability to indicate current sediment quality, can define its metabolic potential. The moderate metabolic potential has the sediment with IOBL range from 6.1 to 10, the strong potential has the sediment with IOBL range 10.1 to 15, and sediment with very strong metabolic potential has IOBL value over 15 (Lafont et al., 2010).

7. POLLUTION IMPACT ON LIVING ORGANISMS AND EVOLUTION OF CHANGES

Within an aquatic system, the biocenosis is changing along with the change of environmental conditions in it. In the nineteenth century, it was observed that some species are less resistant than others to the pollution in the aquatic environment. The concept of bioindicators was then created and it is now largely applied. The toxicity of pollutants in water and sediments is impossible to determine simply by measuring their concentrations, but their availability for the living organisms, needs to be taken into account, regarding pollutants such as heavy metals and organic matter. Analyzing bioindicator organisms of Lake Skadar, structural and functional changes within their communities were determined, reflecting changing environmental conditions in the lake ecosystem.

7.1. Ichthyofauna

Table 44. Saprobic valence (S) of certain fish species from Skadar Lake and the characteristics of their population in 2001 compared to the results obtained 30 years ago (after 1995; 2001; modified). Marić, Fish species S Population characteristics Alburnoides ohridanus o rare species, population stable β very numerous population, but Alburnus scoranza (bleak) oscillating Alosa fallax (twaite shad) β population relatively stable β–α apparent decrease trend in Anguilla anguilla (eel) population abundance Barbus rebeli (western balkan barbel) β rare species, population stable β–α very numerous population with Carassius gibelio (Prussian carp) small oscillations o–β very rare species, because of Chondrostoma ohridanum (nase) overfishing Cobitis ohridana (ohridian loach) β rare species, population stable Ctenopharyngodon idella (grass carp) ? population number decreases β apparent decrease trend in Cyprinus carpio (carp) population abundance Gasterosteus gymnurus (stickleback) β rare species, population stable Gobio skadarensis (skadar gudgeon) β–α rare species, population stable ? apparent decrease trend in Hypophthalmichthys molitrix (silver carp) population abundance Hypophthalmichthys nobilis (bighead carp) ? population number decreases Liza ramada (thinlip grey mullet) ? migratory species Mugil cephalus (flathead grey mullet) ? migratory species o–β numerous species, population Pachychilon pictum ( roach) stable

Fish species S Population characteristics β numerous species, evident Perca fluviatilis (perch) increase in population Phoxinus lumaireul (italian minnow) o rare species, population stable Rhodeus amarus (bitterling) β–α rare species, population stable β numerous species, population Rutilus albus (white roach) stable or slightly increasing β numerous species, evident Rutilus prespensis (yellow roach) increase in population Salaria fluviatilis (freshwater blenny) β rare species, population stable Salmo farioides (brown trout) x–o rare population consistently o rare population, only few Salmo marmoratus (marbled trout) individuals present, reason- overfishing β numerous species, evident Scardinius erythrophthalmus ( rudd) increase in population β numerous species, population Squalius platyceps (chub) stable Telestes montenegrinus (riffle dace) β only few individuals present in sublacustric springs

Some 50 species of fish inhabit the Skadar Lake, according to the studies of

2007 and Kova variousDuring authors the (Knežević, investigations 1981; inMarić, 2001 1995; only Bianco29 of them & Kottelat, were recorded. 2005; Miller It is & e Šanda,vident that some fish čićpopulations & Šanda, 2007).of the lake have changed their characteristics over a thirty year period. The causes and dynamics of change within the fish populations varied for the different species (graph 44). Namely, the population of ten species had decreasing trend, while the four for of them increased in number. The twelve fish species had stable populations. For most of these species saprobic valance were analyzed, and their indicator potential was identified. The thirteen species were found to be an indicator of - mesosaprobity and four species as an indicator of – -mesosaprobic level. Saprobic β -mesosaprobic degree of Skadar Lake waterβ α , which corresponds to water ofindex cate gory value, II ( basedmoderate on pollution fish populations). as bioindicators was 1.93 (Marić, 2001), indicatingCertainly, a β these data are subject to change, if we take into account the fact that they are ten years old. The detailed and comprehensive study has to be conducted in order to assess exactly the fish stock.

7.2. Ornithofauna

The Skadar Lake is one of the five most important wintering areas for birds in Europe. From 1991 to 2009 an average number of 150 000 birds wintered there observed that in the period between 1991 and 1999, there was greater stability in the number of individuals in comparison with the earlier period, when (Saveljić, 2009). It is

the fluctuations were much more evident (table 45). The maximum number of individuals was determined in 1999, when 250 571 birds were counted in the lake area, and the lowest in 2006 – 32 918 individuals. Despite the evident decrease in the number of individuals, the criterion for the number of wintering birds in the wetlands (humid zones), which is prescribed by the Ramsar Convention, whose limit number is 000.

≥ 20

Tabela 45. The results of counting of wintering birds – IWC (International Water Census) on the Lake Skadar, in the periodfrom 1991 to

2009 (after

Saveljić, 2009). Year Number of individuals 1991 150 846 1992 178 765 1993 222 792 1994 160 119 1995 207 469 1996 192 190 1997 164 616 1998 244 313 1999 250 571 2000 96 977 2001 There was no counting 2002 There was no counting 2003 There was no counting 2004 85 727 2005 35 114 2006 32 918 2007 107 620 2008 148 697 2009 49 259

There are indications that the number of indicator species of birds in Lake Skadar reduced (Phalacrocorax pygmeus, Aythya nyroca, Aythya ferina, Pelecanus crispus and Ardea cinerea of abundance of their population does not have a certain regularity, it is impossible to surely determine what factors, and to) (Saveljić,what extent, 2009), cause but this since reduction. the fluctuations It is obvious that the overall environmental quality of the ecosystem, which is mostly a consequence of anthropogenic activities, affects very vulnerable groups, such as birds. The bigest negative anthropogenic influence was a very long hunting season, which lasted from mid-August to mid-March, although today’s Spatial Plan for Special Purposes for the National Park “Skadar Lake”, a document adopted in 2001 by the Parliament of the Republic of Montenegro, bans bird hunting in the National Park “Skadar Lake”. In addition to fishermen, hunters and poachers, tourism development is also affecting the birds by disturbance. Even some natural factors may adversely affect the ornithofauna. These are: climate change, which may affect the status of wintering populations, their arrival,

departure and birds staying on Skadar Lake (since 90% of its ornithofauna are migratory species) and the fluctuation of lake water level, which has a direct impact on the ecology of nesting.

7.3. Phytoplankton

In the phytoplankton community of Lake Skadar significant qualitative and quantitative changes have occurred during the last thirty years. The decreasing trend in the number of species in all phyla of algae in relation to previous studies has been stated.

Euglenophyta

Pyrrophyta

Chrysophyta

Bacillariophyta

Chlorophyta

Cyanophyta

0 50 100 150 200 250 300 350 400

Cyanophyta Chlorophyta Bacillariophyta Chrysophyta Pyrrophyta Euglenophyta 2006 20 51 87 3 4 2 1981 59 377 133 24 13 78

Graph 25. A comparative review of the number of species of different phytoplankton groups in Lake Skadar (after

Petković, 1981; Rakočević, 2006). 981), green algae (Chlorophyta), with 377 different species dominated in Lake Skadar (graph 25). Today, the population of mentionedAccording phylum to counts previous studies (Petković, 1 , compared to the previous period. The siliceous algae (Bacillariophyta) are now represented by 87 species,51 whereas species thirty (Rakočević, years ago 2006), this numberwhich is was a significant 133. Phenomenon decrease of reducing the number of species was stated within the phyla of Cyanophyta, Pyrrophyta, Chrysophyta and Euglenophyta. In contrast to the decreasing number of species, phytoplankton population density has increased comparing to the earlier period, from 3 up to 20 times at some sampling sites (table 46). In the past, population density was lowest at Raduš - 0.25 x 106 ind/l and highest at Middle of the lake II - 0.65 x 106 ind/l. According to recent data

(Rakočević, 73

2006), phytoplankton density was the lowest - 1.3 x 106 ind/l at the site left mouth of the river, whi le the highest at Raduš - 4.9 x 106 ind/l. The increase in abundance of algae in Lake Skadar is the result of increased inflow of nutrients in the lake. Morača

Table 46. Total abundance of phytoplankton of Lake Skadar (ind/l) in different periods of

research (by Rako evi , 2006).

čTotalć abundance of phytoplankton in the Lake Skadar (ind/l) LOCALITY , 1981) , 2006) Raduš 0.25 x 106 4.9 x 106 Middle of the lake I (Petković0.26 x 106 (Rakočević2.7 x 106 Left mouth of the 0.42 x 106 1.3 x 106 Morača river Petrovo 0.36 x 106 2.3 x 106 Middle of the lake II 0.65 x 106 3.4 x 106 Plavnica 0.32 x 106 1.7 x 106

7.4. Macrophytes

The communities of aquatic macrophytes in Lake Skadar are more developed in the northern part, since the lake bottom is flat there, gently sloping towards the south and south-west coast, which is steep. Macrophytes of Lake Skadar, especially submerged, have a significant role in the nutrients circulation. The macrophyte community of Lake Skadar, as other organisms in the lake, has been changed over the last thirty years. The surface area under macrophyte vegetation was 33.5 km2 approximately 56.52 km2 (graph 26). (Ristić & Vizi, 1981), while today is considerably larger and covers 60 56.52

33.5

30 1981 2012

0 Surface covered by macrophytes

Graph 26. Area under macrophytes (km2) in the Skadar Lake in 1981 and 2012.

These data were obtained on the basis of estimation, since there is no sufficient research, on the subject, and it is not possible to determine accurate qualitative and quantitative changes in the community.

30 29.26 29.42

21.68 20

10 RPM (%) 7 7.2 5

Graph 27. The relative plant quantity index (RPM, %) of macrophyte species in Lake Skadar (after ; modified).

Katnić, 2007 Today the Skadar Lake is known to have 164 species of macrophytes. During the research in 2006 (July-September), 17 species in eleven different positions were noted

of some species in the community (Kohler & Janauer, 1995), ranged from 0 to 29.42%. Ceratophylum(Katnić, 2007). demersum The RPM indexdominated value, inthat this indicates period theof research relative quantity,(29.42%). ie The dominance second most dominant species was Trapa natans (29.26%), followed by Nymphea alba with 21.68%, Nuphar luteum with 7.2% and Scripus lacustris with 7% (graph 27). Species that have dominated in macrophytes community: Ceratophylum demersum, Trapa natans, Nymphea alba, Nuphar luteum and Scripus lacustris are indicators of eutrophic condition Diversity index value ranged from 0, river, up to luka. A, tand this organic location, pressure the number (Stojanović of species et al., was 1998). highest - 12, while in the left mouth of the riverin onlythe left one mouth species of thewas Morača noted during the 1.35research at the period locality (graph of Mači 28). Morača

14 1.6 1.35 12 1.29 1.4

1.2 1.2 12 1.12 (H) index diversity 10 1.2 0.95 1.01 0.9 1 8 8 0.73 0.8 6 6 6 0.6 5 4 4 4 4 0.4 number of species 3 3 0.22 2 0.2 1 0 0 0

H Number of species

Graph 28. Diversity index (H) and number of species of macrophytes on the study sites of Lake Skadar (after Katni , 2007; modified).

ć 7.5. Macroinvertebrates

The benthic fauna of Lake Skadar contains different groups of organisms: Gastropoda (Bithynidae, Hydrobiidae, Lymnaeidae, Neritidae Physidae, Planorbiidae, Thiaridae, Valvatidae, and Viviparidae), Oligochaeta (Naidinae, Tubificinae, Lumbriculidae, Lumbricidae), Bivalvia (Dreissenidae, Sphaeridae, Unionidae), Insecta (Chaoboridae, Chironomidae, Coleoptera, Neuroptera, Plecoptera, Tabanidae, Trichoptera), Nematoda, Hirudinea, Crustacea (Amphipoda, Ostracoda) and Turbellaria. During the period from 2004 to 2007, qualitative and quantitative differences in the bottom fauna of Lake Skadar were recorded. Namely, in 2004, in all seasons, nearly all of the study sites were dominated by Gastropoda, from 30% up to 90%) (g The only river, in which, during the spring season, Oligochaeta dominated with over 70%. raph 29) (Šundić & Karaman, 2004). exceptionIt was was also the found right mouthout that of the the Gastropoda, Morača Oligochaeta and Chironomidae are the three dominant groups in the lake in 2004. They belong to the third group of macroinvertebrate organisms that tolerate organic pollution (Sharpe et al., 2002), and are considered to be its indicators. In 2005, in the benthic community, dominance of Oligochaeta, Gastropoda and Chironomidae was stated, but during this year, diversity of macroinvertebrates was higher than in 2004 (graph numerical abundance of insect groups, that belong to group I (macroinvertebrates sensitive to 30) (Šundić et al., 2005). It can be seen that the

pollution), was very low in the community. It is evident that there has been a reduction in the number of these indicators of clean waters in favour of the indicators from group III.

100% 90%

80% 70% Ostracoda

60% Plecoptera

50% Nematoda 40% Bivalvia Chironomidae 30% 20% Oligochaeta Gastropoda 10%

0% Sj12 Sj5 Sj2 Sj3 Sj6 Sj12 Sj5 Sj2 Sj3 Sj6 Sj12 Sj5 Sj2 Sj3 Sj6 spring 2004 summer 2004 autumn 2004

Graph 29. The numerical abundance (%) of different benthic groups in the sediments of Lake Skadar in 2004.

100% 90% Hirudinea 80% Neuroptera 70% Crustacea

60% Chaoboridae

50% Trichoptera 40% Plecoptera Nematoda 30% Bivalvia 20% Chironomidae 10% Oligochaeta 0% Gastropoda Sj12 Sj5 Sj2 Sj3 Sj6 Sj12 Sj5 Sj2 Sj3 Sj6 Sj12 Sj5 Sj2 Sj3 Sj6 spring 2005 summer 2005 autumn 2005

Graph 30. The numerical abundance (%) of different benthic groups in the sediments of Lake Skadar in 2005.

Similar qualitative and quantitative composition of the benthic community was stated in 2007. As shown in graph 31, Gastropoda and Oligochaeta were again dominating the community at almost all locations. Their numerical abundance ranged from 40% to 90%.

100%

90% Turbellaria 80% Coleoptera 70% Tabanidae 60% 50% Chaoboridae 40% Nematoda

30% Bivalvia 20% Chironomidae 10% Oligochaeta 0%

Sj12 Sj13 Sj2 Sj3 Sj6 Sj11 Gastropoda

summer 2007

Graph 31. The numerical abundance (%) of different benthic groups in the benthic sediments of Lake Skadar in 2007.

7.5.1. Oligochaetes

A comparative analysis of the number and biomass of aquatic oligochaetes in different seasons during 1975, 2004 and 2005 shows significant differences. Namely, where the number and biomass of these organisms is concerned, there is evident an increasing trend through the period of thirty years (graph 32). In the spring season of 1975, oligochaete abundance ranged from 0 (Sj6, Sj12) to 311.08 ind/m2 (Sj2, Sj3). In the same season, in 2004, the minimum population density was 311.08 ind/m2 (Sj12) and the maximum 2 547.0 ind/m2 (Sj3). In 2005, the number of oligochaete in the spring season, ranged from 1 288.83 ind/m2 (Sj3) to 1 955.49 ind/m2 (Sj5). In the summer season of 1975, oligochaetes were the most abundant at Sj5 (266.64 ind/m2), while the lowest number was recorded at Sj2 (44.44 ind/m2). In the same period in 2004, the number of oligochaetes ranged from 44.44 ind/m2 (Sj12) to 444.44 ind/m2 (Sj6). During 2005, significantly greater abundance were found than in previous years. It ranged from 444.44 ind/m2 (Sj12) to 2 577.67 ind/m2 (Sj3). In the autumn season of 1975, decreasing abundance was evident compared to the previous two seasons. At three sites, oligochaetes were not found, while on the remaining two, their abundance was very low: 44.44 ind/m2 (Sj12), and maximum 88.88

ind/m2 (Sj3). During the same period in 2004, minimum abundance was 44.44 ind/m2 (Sj12), and the maximum 1,244.44 ind/m2 (Sj2). In 2005, the abundance of oligochaetes ranged from 311.08 ind/m2 (Sj5) to 2 244.40 ind/m2 (Sj2).

3000

2500 ) 2 2000

1500

1000

500 (ind/m abundance 0 Sj2 Sj3 Sj5 Sj6 Sj12 Sj2 Sj3 Sj5 Sj6 Sj12 Sj2 Sj3 Sj5 Sj6 Sj12 spring summer autumn

1975 2004 2005

Graph 32. Total abundance of oligohetes (ind/m2) at the sampling sites in Lake Skadar, during 1975, 2004 and 2005 (according to Nedi & Karaman, 19 ; modified). ć 81; Šundić, 2007; Šundić & Radujković, 2012 The results of studies on the number of species and of oligochaete abundance in the Lake Skadar do not indicate the regularity of seasonal changes. This refers to the possible impact of hydrological and meteorological factors, as well as pollution, to the dynamics of population density of oligohetes. Parallely with the increase in density during thirty-year period an increase of total biomass of the oligochaete population was detected, too.

2.5

) 2 2

1975 1.5 2004

2005 1 biomass (gr/m

0.5

0 spring summer autumn winter

Graph 33. Oligohetes total biomass (gr/m2) in Lake Skadar, during 1975, 2004 and 2005 (after Nedi ; modified).

ć & Karaman, 1981; Šundić, 200779

In 1975, biomass of oligochaetes in Lake Skadar ranged from 0.086 g/m2 in the fall up to 1.301 g/m2 during the winter period. For years the 2004 and 2005, there is a lack of data for the winter season, because there was no research. In 2004 biomass was the lowest in the fall - 0.194 g/m2, and highest during the spring (2.456 g/m2). During 2005, biomass of oligochaetes was the highest, also in the spring - 1.684 g/m2, and the lowest during summer months – 1.002 g/m2.

Analysis of the oligochaete communities of Lake Skadar shows a presence of 20 indicator species. In addition of being a trophic and saprobic indicators (chapter 6), some of the species (12 of them) have shown a certain, new indicator capacities for the physical and chemical characteristics of water and sediment of the lake (table 47). Since living organisms react to the changes in the ecosystem and register permanent, long-term effects of pollution by changing of their abundance, biomass and/or species composition, , they can be considered as indicators of the environment capacity to receive certain pollution loads. Living organisms of the aquatic ecosystem are integrators of all events in the ecosystem, whether they are natural or man-made changes.

Table 47. The oligochaete species with evident indicator characteristics of water and sediment physical or chemical changes modified): (+)=positive cocorrelation, (–)=negative correlation. (after Šundić & Radujković, 2012; NAIDIDAE The physical and chemical parameters of water Naidinae and sediment 1. Dero obtusa (+): pH, O2 (mg/l), O2 (%) (in water) (–): acenaphthene, Cd and Zn (in sediment) 2. Nais barbata (–): Hg and phenols (in water)

3. N. communis (+): NH4+, Mn, dissolved Fe, nitrites (in water); total concentration of PAHs (in sediment) (–): F (in sediment) 4. N. elinguis (+):electroconductivity, redox potential (in water) (–): O2 (mg/l), O2 (%) (in water); acenaphthene, Cd and Zn (in sediment) Tubificinae 5. Aulodrilus pluriseta (+):electroconductivity in water, water temperature, redox potential (–): O2 (mg/l), O2 (%) (in water) 6. Ilyodrilus templetoni (+): HRC, turbidity, suspended matter, Mn, dissolved Fe, temperature and redox potential (in water); Cd and mineral oils (in sediment) (–): O2 (mg/l), O2 (%) (in water); acenaphthene, Cd and Zn (in sediment) 7. Isochaetides michaelseni (–): Hg and phenols (in water)

8. Limnodrilus hoffmeisteri (+): nitrogen, NH4+ (in water); acenaphthylen, benzo(ghi)-perylene (in sediment) (–): dibenz(ah)-anthracene (in sediment) 9. L. udekemianus (+): HRC, turbidity, suspended matter, Mn, dissolved Fe (u vodi); Cd and mineral oils (in sediment)

NAIDIDAE The physical and chemical parameters of water Naidinae and sediment (–): O2 (mg/l), O2 (%) (in water) 10. Potamothrix hammoniensis (+): temperature, nitrates, electrical conductivity (in water); Zn, Cu, acenaphthylen, benzo(ghi)- perylene (in sediment) (–): dibenz(ah)-anthracene (in sediment) 11. Psammoryctides albicola (+): COD, turbidity, suspended matter, Mn, dissolved Fe, nitrites (in water); Cd and mineral oils (in sediment) (–): O2 (mg/l), O2 (%) (in water) 12. Tubifex tubifex (+): temperature, redox potential, NH4+ (in water); Hg, benzo(k)-fluoranthene, benzo(a)pyren, pyren, fluoranthene (in sediment) (–): O2 (mg/l), O2 (%) (in water)

Based on the above, it can be concluded that some oligochaetes and macroinvertebrates species, as well as other living organisms of Lake Skadar, which were discussed in this chapter, are good indicators of the environmental condition.

7.6. Bioaccumulation

One of the ways to determine and quantify the impact of pollutants on certain ecosystem is monitoring of its effects on living organisms through the processes of bioaccumulation and bioconcentration. Bioaccumulation refers to the accumulation of toxic and hazardous substances from the water and sediment of an ecosystem in living individuals. Bioconcentration represents an increase in concentration of the pollutant accumulated through the food chain. If the organism is on a higher level in the food chain, the concentration of pollutants accumulated in it is much higher. Concentration of pollutants in the water or sediment can be seemingly low and not to exceed MAC, but after accumulation in the living organisms due to these processes, the pollutants become harmful for organisms and aquatic ecosystems in general.

7.6.1. Bioaccumulation in macrophytes

The concentrations of heavy metals, PAHs, PCBs, mineral oils, fats in macrophytes of Lake Skadar were measured between 1990 and 2005. In the period from 1990 to 1996, minimum concentrations of PCBs in samples of g/kg in the a river, while its maximum ranged from 0.225 g/kg in the Vranjina,macrophytes to 11 ranged.04 g/k fromg in 0.007 the μg/kg, in Plavnica and Grmožur,river (table up to 48). 1.22 It μ can be seen thatright the mouth concentrations of the Morač of this pollutant were the highest in the macrophytesμ samples from the right mouthμ right mouthriver. On of thethe Moračasampling site is the left mouth of the river, minimum concentration of PCBs was about 9 times higher compared to the same concentrationof ofthe pollutants Morača in the water, and the maximum up to 427 times higherMorača than in the water. At the sampling site Plavnica, an increase of the concentration

of this pollutant in macrophytes was also recorded, up to 78 times higher than in the water. Analysis of macrophytes in the right mouth of the river showed the largest increase in the concentration of pollutants in relation to its concentration in water (from 135 up to 1 226 times). Morača

Table 48. Accumulation of PCBs ( /kg) in samples of macrophytes from Lake Skadar from 1990 to 1996 (after Royal Haskoning, 2006.). Parameter μg PCB (μg/kg) Locality min max Vranjina 0.005 0.225 Left mouth of the river Morača 0.038 1.710 Right mouth of the river Morača 1.220 11.040 Plavnica 0.007 0.315 Middle of the lake 0.025 1.125 Raduš 0.019 0.855 Grmožur 0.007 0.315

From 1993 to 1996, a large number of pollutant concentrations in macrophytes of Lake Skadar in several different positions were stated. One can see, from the table 49 stated that the concentration of fluorides ranged from 105 mg/kg in Raduš to 1 206 mg/kg at the locality of Crni Žar. The concentration of silica was also significant and ranged from 66.67 mg/kg (left mouth river

Ta ble 49. Accumulation of polutants (mg/ofkg )the in mMoračaacrophytes of) toLake 203.04 Skada mg/kgr from 1993 (Murići). to 1996 (after Royal Haskoning, 2006).

Locality Right Left Crni Žar Podhum Raduš Plavnica Murići mouth of mouth of Parameter the the Morača Morača river river Cu (mg/kg) 0.37 0.34 0.05 0.05 0.38 0.17 0.01 Cd (mg/kg) 2.65 1.49 0.92 1.05 2.49 1.12 2.76 Cr (mg/kg) 1.15 0.67 0.26 0.19 0.89 0.43 0.64 Pb (mg/kg) 110.15 27.59 25.71 28.92 82.46 52.51 56.44 Mn (mg/kg) 1.32 1.49 0.00 0.00 1.27 0.00 0.21 Fe (mg/kg) 0.22 0.09 0.29 0.23 0.63 0.15 0.25 Zn (mg/kg) 24.40 17.60 25.30 12.90 34.30 34.20 23.90 Ni (mg/kg) 1.76 0.87 0.09 0.21 0.13 0.00 0.21 Al (mg/kg) 0.00 0.00 0.00 0.00 0.00 0.00 0.00 F (mg/kg) 176.00 675.00 1 206.00 360.00 105.00 441.00 318.00 SiO2 (mg/kg) 110.84 66.67 128.94 165.85 79.60 128.78 203.04 PAH (μg/kg) 0.00 0.00 0.00 0.00 0.00 0.00 0.01 PCB (μg/kg) 1.22–11.04 0.04–1.71 0.00 0.007-0.313 0.02–0.855 0.07–0.315 0.00 Oils and fats 64.00 375.00 91.00 160.00 39.00 331.00 102.00 (mg/kg) Mineral oils 88.26 80.25 40.59 0.00 221.10 77.27 42.71 (mg/kg)

Concentrations of lead ranged from 25.71 mg/kg (Crni Žar) to 110.15 mg/kg river), and zinc from 12.90 mg/kg (Podhum) to 34.3 mg/kg (Raduš). Oils and fats are detected also in higher concentrations (39 mg/kg - Raduš to 375(right mg/kg mouth – of the Morača river). The concentration of mineral oils is also important: 40.59 mg/kg (Crni Žar) to 221.1 mg/kg (Raduš). Other pollutants were present in muchleft lomouth of the the Morača concentration of 0.01 g/kg. Concentrationswer of concentrations, pollutants that whileare found PAHs in were the macrophytes detected only of in Lake Murići Skadar at a are given in comparisonμ to their concentration in water. Table 50 shows that the concentrations of some pollutants were up to several tens of thousands of times higher than the concentrations in the water. Increasing of the concentrations of cadmium

10 307 times (Raduš). ranged Thefrom concentration 836 (Crni Žar) of tozinc 13 in800 macrophytes times (Murići), in relation and lead to from its concentration 2 142 (Crni Žar) in the to water is significantly increased (7 166 times in Podhum to an incredible 57 000 times in Plavnica). The largest amplification of the concentration in macrophytes in relation to water refers to fluorides (concentration was increased at the site Crni Žar 80 400 times).

Table 50. Increase in the concentration of pollutants in the Skadar Lake macrophytes in relation to their concentration in the water, from 1993 to 1996 (after Royal Haskoning, 2006; modified): - pollutant was not detected in macrophytes, * pollutant was not detected in water.

Locality Right Left Crni Podhum Raduš Plavnica Murići mouth of mouth of Žar the the Parameter Morača Morača river river Cu 246 226 50 100 380 283 100 Cd 2 944 1 354 836 10 500 2 766 1 120 13 800 Cr 287 74 43 38 148 71 1 280 Pb 10 013 2 299 2 142 4 131 10 307 7 501 8 062 Mn 136 160 – – 254 – 350 Fe 6 2 9 115 25 94 11 Zn 9 760 11 000 19 461 7 166 22 357 57 000 18 384 Ni 293 174 18 210 130 – 105 Al F 11 733 45 000 80 400 21 176 7 000 17 640 21 200 SiO2 51 32 143 123 76 54 101 PAH – – – – – – * PCB 610–1 227 40–427 – * * 70–79 – Oils and fats 29 163 151 100 18 165 12 Mineral oils 240 184 123 – * 264 67

In 2005, the concentration of pollutants in several macrophytes was monitored. The concentration of mercury, which ranged from 0.25 mg/kg (Biševina) to 0.33 mg/kg river) was 130 to 250 times higher compared to the

(right mouth of the the Morača 83

concentrations measured in the water at the same locations (table 51). The concentration of PAHs in macrophytes, in the same period ranged from 0.003 to 0.006 mg/kg. Since PAH levels were not measured in water at these locations, during that period, the concentrations in macrophytes were compared with the MAC for this pollutant in water. Concentrations were 15 to 30 times higher in the macrophytes.

Table 51. Accumulation of different pollutants (mg/kg) in macrophytes samples from Skadar Lake in 2005 (after Royal Haskoning, 2006). Locations 2005 Biševina Karuč Right moth of the Parameters (mg/kg) Morača river

Mercury (Hg) 0.25 0.26 0.33

PAH 0.006 0.003 0.003

PCB + congeners <0.005 <0.005 <0.005 PCB <0.001 <0.001 <0.001

7.6.2. Bioaccumulation in fish

During 2001 and 2005, in fish samples from Lake Skadar, the content of heavy metals (Pb, Cd, As, Cr, Ni, Al and Mn) and polychlorinated biphenyls was analyzed. The levels of mentioned polutants were different in different species of fish. The concentrations of heavy metals detected in tissue from Skadar Lake fish are given in table 52. It can be seen that lead, cadmium and arsenic concentrations were the lowest in all studied fish species. In these fish samples slightly higher concentrations of manganese, aluminum and iron were found. The lowest concentration of manganese (0.07 mg/kg) was detected in the tissue of the carp, and the highest in eel tissue (3.1 mg/kg). The tissue of the Prussian carp had the lowest concentrations of aluminum (0.8 mg/kg), while the largest concentration of 4 mg/kg was detected in tissue of yellow roach. Iron concentrations ranged from 0.03 mg/kg (eel) to 5.3 mg/kg (yellow roach).

Table 52. Accumulation of heavy metals (mg/kg) in samples of Skadar Lake fish in 2001 (after Royal Haskoning, 2006). Heavy MAC for Cyprinus Carassius Perca Rutilus Anguilla metals heavy metals carpio gibelio fluviatilis prespensis anguilla (mg/kg) in fish tissue (carp) (Prussian (perch) ( yellow (eel) (Wyse et al., carp) roach) 2003) Pb 0.12 0.00 0.00 0.00 0.042 0.03 Cd 0.18 0.00 0.00 0.00 0.00 – As 12.60 <0.10 <0.10 <0.10 <0.10 – Cr 0.73 0.21 0.12 0.11 0.02 <0.10 Ni 0.60 2.70 0.05 0.09 0.00 0.01 Fe 146.00 2.75 4.50 2.25 5.30 0.03 Al 13.80 1.01 0.80 3.50 4.00 2.80 Mn 3.52 0.07 0.15 0.75 1.55 3.10

Concentrations of other pollutants were relatively low, with the exception of nickel, which is found in the tissue of carp at a concentration of 2.7 mg/kg, which is 4.5 times higher than the concentration allowed. It can be concluded that none of the heavy metals, detected in the fish samples, exceeded the dose limits prescribed by the International Atomic Energy Agency (Wyse et al., 2003). In addition to heavy metals in Skadar Lake fish tissue polychlorinated biphenyls were detected in different concentrations, depending on the fish species. The lowest concentration of this pollutant was found out in the tissue of perch - 35.45 g/kg, and the largest in the tissue of rudd fish - 200.4 g/kg (table 53). μ Table 53. μ compared to MAC (after Rastall et al., 2004). Concentration of PCBs (μg/kg) in tissue of different Skadar Lake fish species and Species PCB Ratio: concentration of (μg/kg) PCB in fish/MAC of PCB in water (times) Cyprinus carpio–carp 44.80 149 Carassius gibelio–Prussian carp 39.80 132 Perca fluviatilis–perch 35.45 118 Rutilus prespensis–yellow roach 50.20 167 Rutilus rutilus–roach 80.10 267 Alburnus scoranza–bleak 103.5 345 Scardinius erythrophtalmus–rudd fish 200.4 668

To perform the quantification of these concentrations, we compared them with the MAC for PCBs in water (ANZECC & ARMCANZ, 2000), which is 0.3 g/kg. Through the processes of bioaccumulation and bioconcentration, the amount of these pollutants in fish tissue increased up to several hundreds of times (from 118 timesμ – perch up to 668 times - rudd fish). Analyzing the PCB bioaccumulation of Skadar Lake fish for a longer period, from 1978 to 2005, one cannot determine a clear trend of increase or decrease in their concentration, due to scarcity of data. As shown in table 54, in only 5 fish species out of the nine studied, PCBs were detected in the tissue. It can be seen that the highest concentrations of this pollutant were measured in 1996, when the tissue of the bleak contained 498 g/kg of PCBs, carp 713 g/kg and eel even 2 200 g/kg. In 2001 this pollutant was not detected. In 2004, after the accident in KAP, concentrations of PCBs of 0.656 g/kg andμ 0.744 g/kg were foundμ in the tissue of rudd andμ trout. The concentrations of these pollutants in 2005 were lower than the MAC (0.3 g/kg) for polychlorinated biphenylsμ in lake water.μ Some pollutants were detected in different biological material, originated from the villages of Lake Skadar (tableμ 55). Their concentrations generally did not exceed the

(Official Gazette of RS 28/11, 2012). Polyaromatic MAC,hydrocarbons except for were eggs, detected in which only were in the found beef. out a PCB’s concentrations of 451.8 μg/kg, and the MAC was 300 μg/kg

Table 54. Concentration of PCBs ( g/kg) in tissues of different Skadar Lake fish species from 1978 to 2005 (after Royal Haskoning, 2006; modified; *– concentrations measured afterμ accident in APP, 2004). Year 1978 1990 1992 1996 1998 2001 2004 2005

Booke CETI, 2005 Species et al., 1981 0.019 Cyprinus carpio 3.00 0.138 6.21 713.00 2.68 0.00 – <0.01 (carp) <0.01 Carassius gibelio – – – – – 0.00 – – (Prussian carp) Perca fluviatilis – – – – – – – <0.01 (perch) 0.015 Anguilla anguilla – 0.092 41.00 2 200.00 1.30 – – 0.022 (eel) 0.068 Alburnus 0.007 scoranza – 0.912 4.14 498.00 5.40 0.00 – <0.001 (bleak) Scardinius <0.001 knezevici – – – – – – 0.656* 0.009 (rudd) 0.037 Squalius cephalus – – – – – – – 0.014 (chub) 0.016 Rutilus prespensis – – – – – – – 0.01 (yellow roach) Salmo sp. – – – – – – 0.744* – (trout)

Table 55. Accumulation of PCBs and PAHs material within Skadar Lake area from 1990 to 1996 (after Royal Haskoning, 2006). (μg/kg) in different biological PCB (μg/kg) PAH (μg/kg) BIOLOGICAL max max MATERIAL Human milk 0.001 0.006 – – Cow milk 3.89 69.9 – – Eggs 207.60 451.8 – – Carp 2.68 713.0 – – Eel 1.30 2200.0 – – Bleak 5.40 498.6 – – Beef 2.89 18.6 0.12 0.45

8. FACTORS AFFECTING THE IMPLEMENTATION OF IDEAL MANAGEMENT OBJECTIVES

The Implementation of Management Plan depends on a number of conditions and factors, mostly at the state level. This applies to the whole system of institutions, where the intersectoral collaboration is of essential importance. Therefore, it is needed to specify factors that are depending mostly on political will: · Government policy in the field of environment, · Institutional capacities, · Application of law and accountability in their implementation, · Intersectoral collaboration, · Financial support, · Involvement of interested institutions, communities and individuals (stakeholders) in all phases of development and implementation of the plan.

8.1. Natural factors of internal origin a. Natural eutrophication b. Fluctuations in populations of phytoplankton, zooplankton and bacteria c. Vegetation overgrowth of the lake d. Erosion e. Fluctuations of water regime.

8.2. Artificial factors of internal origin a. Impact of hydrological interventions on populations of fish, birds and other living organisms b. Impact of other human activities on pollution and eutrophication c. Impact of human activities in the lake (traffic, winter ports, exploitation of water and peat, tourism) d. Overfishing, illegal fishing e. Deforestation of flooded forests f. Invasive alien species g. Overconstruction on the coast.

8.3. Natural factors of external origin a. Coast and drainage basin erosion b. Floods c. Earthquakes d. Climate change and its impact on the lake and the living organisms e. Dynamics of coastal vegetation and forests f. Fires in coastal forests.

8.4. Artificial factors of external origin

a. Pollution – Waste waters

– Solid waste – Erosion of agricultural land – Washout from roads – Infrastructure construction (roads, railroads) – Traffic b. Exploitation of minerals, peat, gravel and stone c. Unplanned construction, overconstruction and occupation of the coast d. Changing of the landscape.

8.5. Factors arising from legislation or tradition

Existing legislation covers the most important areas to be treated by the management and monitoring plan for Skadar Lake. However, the application of the law in practice is not effective enough, which is a matter for inspection services and raising public awareness on the importance of joint efforts on a sustainable approach to conservation and exploitation of the lake. Most certainly, it will be necessary to bring in incentives for the development of organic agriculture, sustainable tourism, sustainable construction and so on.

9. CONCLUSIONS AND RECOMMENDATIONS

This document clearly shows the very high pressures, that municipal and industrial sources of pollution are putting on the ecosystem of Lake Skadar, and therefore the inhabitants of its shores and hinterland and their social and economic status. Since this is a cross-border phenomenon, firmer connection with both institutions and the civil society in both countries is needed with the aim of conservation and sustainable management of this unique and important resource for both countries. The integrated management plan should be developed in accordance with the principles of sustainable development and the legal frameworks of Montenegro, Albania and the European Union. In addition to pollution management and its monitoring, the Plan should include the protection of all water resources, water regime and balance, biodiversity and economic activities. The plan should include the control of illegal construction, illegal dumping sites, overall traffic and roads, management of cultural heritage and education of the population. It should also ensure close cooperation of the institutions of both countries.

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