The Europaen Commission The Commission on the Protection of the Black Sea Against Pollution
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Report Contents

Preface Chapter 1A Chapter 1B Chapter 2 Chapter 3 Chapter 4 Chapter 5 Chapter 6 Chapter 7 Chapter 8 Chapter 9 Chapter 10 Chapter 11 Chapter 12
List of Tables List of Figures

State of Environment Report 2001 - 2006/7

Chief Editor, Prof. Dr. Temel Oguz, Institute of Marine Sciences, Middle East Technical University, Erdemli, Turkey

State of the Environment of the Black Sea - 2009

CHAPTER 3 THE STATE OF CHEMICAL POLLUTION (A. Korshenkoet al.)

This chapter describes the state of petroleum hydrocarbon (TPHs), organochlorine pesticide, and trace metal pollution in water and sediments in the Black Sea during the last ten years. The pathways of these anthropogenic pollutants into sea ecosystem are different. Many pollutants are restricted to rather narrow zone in the vicinity of large cities, estuarine areas of the large rivers and industrial places. The petroleum hydrocarbon pollution mostly originates from transportation activity over the sea and mainly confines to the surface.

The data used for the assessment of spatial and temporal variability of the pollutants came from three main sources. The last five years were mainly covered by the international monitoring data collected by Secretariat of the Black Sea Commission. Despite some restriction in the number parameters these data sets were rather well and allowed to compare the pollution level of coastal zones in different countries. The second important source was the international Screening Cruise 1995 (for bottom sediments), the IAEA Cruise (11-20 September 1998) (for water column), the IAEA Cruise (22.09-9.10.2000) (for water column),the IAEA Cruise (24.09-3.10.2003) (for bottom sediments), the BSERP Cruise (6-19.06.2006) (for bottom sediments of Romania and Georgia). The third source was the national scientific expeditions.

3.1. The State Of Total Petroleum Hydrocarbons (TPHs)

A. Korshenko

State Oceanographic Institute, Moscow, RUSSIA

Depending on the analytical procedures applied in different cruises [5], the petroleum hydrocarbons data are expressed either in total amount or in terms of relative contributions of Aliphatic, Aromatic and Polyaromatic groups in the oil.

3.1.1. Water

The most intensive spatial investigations of the TPHs distribution over the whole Black Sea were carried out during two IAEA Cruises ofRV "Professor Vodyanitskyi" during 11-20 September 1998 and 22.09-11.10 2000[1]. In 1998, 16 stations were visited in the western central basin, the Danube offshore area and Romanian shelf. The average concentration for all sampled area is 0.084 mg/l, the maximum reached 0.23 mg/l in the shallow waters off Romania coast south of Constanta where active ship traffic, oil refinery and harbor activities could be the main reason of very high level of TPHs concentration. TPHs concentrations in the Danube discharge region were not high as compared with the Constanta region. Lowest concentrations (0.03 mg/l) were recorded near the entrance of Bosporus Strait and near Odessa. In general, the spatial distribution of petroleum hydrocarbons in September 1998 was rather uniform and level was low (Fig. 3.1.1).

In the IAEA Cruise 2000, TPHs were measured at 32 stations in the Eastern and Central parts of the Sea. Its total concentration varied from negligibly low values to 0.73 mg/l with an average value of 0.097 mg/l. The anomalously high concentration of 3.27 mg/l was recorded in the surface layer of a shallow station near Feodosiya in Crimea. This level exceeded the Russian standard Maximum Allowed Concentration, MAC, (0.05 mg/l) for marine waters more then 65 times. The second high value (0.73 mg/l) measured close to this site in front of Yalta. Two other stations near Yalta also had quite high TPHs concentrations varied in different horizons from 0.13 to 0.19 mg/l. Such local patch of oil pollution in the Southern Coast of Crimea was the biggest at this time in the Black Sea waters and could be the result either of local spill or municipal discharge of large tourist centers (Table 3.1.1).

Table 3.1.1. The average concentration of TPHs (mg/l) in different part of the Black Sea measured during the September-October 2000 IAEA Cruise.

Region Central West Crimea Cost Kerch Strait Georgians waters Sinop polygon Central East Central open
Concentration 0.30 0.78 0.20 0.05 0.05 0.03 0.03

The waters at the Kerch transect was also relatively polluted by TPHs especially near the entrance of the Kerch Strait (Fig. 3.1.2) suggesting a discharge of oil pollution from the Kerch harbor and intensive ship traffic. On the contrary, the level of pollution in Georgian and Turkish waters was relatively low despite of a well-known center of oil processing in the Batumi area where the concentration of TPHs in surface and subsurface layers was lower than 0.09 mg/l and sometimes were under the detection limit of analytical procedure. In the Cape of Sinop region, the concentration varied from 0.02 to 0.12 mg/l. The Central part of the sea and the Eastern Basin showed only small concentrations of petroleum hydrocarbons which were often below the detection limit and never exceeded 0.05 mg/l.

Table 3.1.2. The average and maximum concentrations of TPHs (mg/l) in Ukrainian part of the Black Sea, 2000-2005.

Region Kerch Strait Crimean towns Odessa Bay Odessa region [11] 1988-99 Harbour Yuzhny Harbour Illiechevsk Dnieper and South Bug Mouth 1992-99 [2]

(140 samples)

Average 0.05 0.01 0.01 0.03-0.07 0.01 0.01 0.025 0.05
Maximum 0.18 0.06 0.08 - 0.07 0.07 0.05 1.2

Table 3.1.3. Annual average (above) and maximum concentrations (below) of TPHs (mg/l) in Ukrainian coastal waters of the Black Sea, 2000-2004 [4].

Region 2000 2001 2002 2003 2004 2004 TPHs (tons)*

Danube Delta

0.05 0.05 0.05 0 0
0.09 0.1 0.09 0.08 0.07

Waterpasses in Danube Delta

0.06 0.06 0.04 0.05 0.01
0.10 0.12 0.08 0.08 0.07

Suhoi Liman

0.05 0.05 0 0 0
0.3 0.25 0.28 0 0

Harbour Illiechevsk**

0.05 0.05 0 0 0
0.08 0.16 0 0 0

Harbour Odessa

0.09 0.12 0.12 0.11 0.12

0.17 (with Suhoi Liman)

0.24 0.35 0.33 0.56 0.51

South Bug Estuary & Bug Liman

0.2 0.28 0.16 0.17 0.19

43.59 (Dniper and South Bug Mouth)

1.02 0.9 0.85 0.9 0.85

Balaklava Bay (Crimea)

0 0.05

6.9 (Sevastopol)

0.06 0.08

Harbour Yalta (Crimea)

0 0.05 0 0 0.02

1.8 (Large Yalta)

0 0.05 0.17 0.24 0.47

* - estimation of petroleum hydrocarbons (tonns) discharge to the Black Sea in 2004.

** - Harbor Illiechevsk, the Channel and waste-water purification plant.

More recent (2000-2005) monitoring data from the northern part of the sea[3] indicated a maximum 0.18 mg/l in vicinity of Kerch Strait in September 2004 and an average concentration of 0.05 mg/l suggesting that concentrations were often close to analytical limit (Table 3.1.2). The TPHs concentration was very low in the Crimean towns Sevastopol and Evpatoriya despite their dense ship traffic and harbor activities. The monitoring data from the Odessa Bay also showed very low average concentration and moderate maximum level of 0.08 mg/l during 2000-2005. In the Yuzhny harbour, among 37 samples over last 5 years the only five had the concentration above zero. Practically the same situation in the waters of Illiechevsk harbour. At stations in the Dniper and South Bug Mouth the water were also free of TPHs.

According the other Ukrainian monitoring data for 2004, the water pollution by TPHs in the Danube Delta was moderate in August-October: the average value was 0.06 mg/l and maximum reached only 0.07 mg/l both in surface and near-bottom layers [4]. The TPHs was absent in the water slightly north along the coast in Suhoi Liman and Illiechevsk harbor (Table 3.1.3). On the other hand, very high concentrations were noted for the Odessa harbor where the TPHs content in the surface waters varied from 0.11 to 0.51 mg/l. Maximum occurred in October and monthly average value was high as 0.31 mg/l and 2-3 times higher than in January-August. The annual mean value was 0.12 mg/l. Near-bottom layer waters were less polluted and maximum reached 0.34 mg/l. The Bug Liman and South Bug estuarine area were characterized by the TPHs concentrations from zero to 0.85 mg/l in 2004 and the level of pollution slightly increased over the last few years. Similar high concentrations were also recorded in the Dniepr Liman and for the Dniepr river where maxima reached 0.68 and 0.50 mg/l, measured in deep waters in July and at surface in September correspondingly. The pollution increased in whole water column about 1.3-1.8 times in these sites during the last few years. In the Crimean Balaklava Bay, the TPHs concentration varied from zero to 0.08 mg/l and mean value was 0.05 mg/l. Much higher mean values were recorded in the Yalta harbor where maximum in surface layer was as high as 0.47 mg/l in July and reached 0.17 mg/l near the bottom. The data for the 2004 were somehow higher than the average of the 5 years period (2000-2005). The difference could be high as 10 times, like in the Dnieper-South Bug area, Odessa Harbor or Crimean ports. The averaged data probably smoothed the real picks in the water.

On the basis of these data sets, it can be suggested that, apart from accidental spills at localized areas, this part of the Black Sea did not show a chronic TPHs pollution. In general, it can be stated that large spatial and temporal variability of petroleum hydrocarbons distribution were encountered during the last years. It seems that patches of oil pollution were often local and short time visible, therefore the maximums better describes the real level of pollution.

In Romanian coastal waters during 2001-2005, the level of water petroleum hydrocarbons pollution is presented in Table 3.1.4 [3]. In 2005, the average concentration was 0.14 mg/l with the maximum 0.20 mg/l (Portita, October) in the Danube Delta. Along the coast to the south near Mamaia, the TPHs content in the surface waters was much higher and maximum reached level 0.47 mg/l. Almost the same situation with a small variation was noted for all Romanian coast up to Bulgarian border.

Table 3.1.4. The average and maximum concentration of TPHs (mg/l) in the surface coastal waters of Romanian part of the Black Sea, 2001-2005.

Region Year Danube Delta Mamaia Constanta Eforia Sud Costinesti Mangalia Vama Veche
Average 2005 0.14 0.21 0.23 0.18 0.23 0.25 0.28
Maximum 2005 0.20 0.47 0.37 0.26 0.41 0.41 0.43
Average 2001-2004 0.22 0.17 0.15 0.14 0.16 0.22 0.14
Maximum 2001-2004 1.28 0.75 0.76 0.71 0.67 2.27 0.40
number of observation 2001-2004 41 47 68 47 46 48 48

Typically, the average concentrations in all Romanian coastal waters were highest in 2003. Nevertheless, extremely high mean values were also noted in the previous years. The absolute maximum reached 2.27 mg/l in June 2003 in shallow waters near Mangalia of the Romanian coast. Another high level (1.28 mg/l) was marked in the Danube delta near Portita in April 2004. It is important to note that high concentration like 0.50 ? 0.70 mg/l was recorded many times in all regions of Romanian coast. In 2001, the average for 50 samples was 0.17 mg/l; a year later for 92 samples - 0.10 mg/l; in 2003 ? 68 samples and the mean was 0.14 mg/l; in 2004 ? 135 samples and the mean was 0.02 mg/l; in 2005 ? 74 samples and 0.21 mg/l. In general, among 344 records of TPHs concentrations in Romanian waters during 2001-2004 only 72 were less then 0.05 mg/l and the other mean values indicated a high level of petroleum hydrocarbon pollution along the Romanian coast.

The seasonal changes of TPHs did not show any clear trend during 2001-2004 measurements due to different number of observations in different months: The averages were 0.12 mg/l in 4 samples in March; 0.21 mg/l in 17 samples in April, 0.23 mg/l in 74 samples in May; 0.18 mg/l in 44 samples in June; 0.08 mg/l in 54 samples in July; 0.14 mg/l in 55 samples in August; 0.20 mg/l in 61 samples in September; 0.15 mg/l in 36 samples in October.

Bulgarian monitoring data did not include petroleum hydrocarbons measurements during 2001-2005.

Turkish coastal TPHs monitoring data covered 2003-2005. Near the outlet of the Bosporus Strait, the concentration at 3 shallow stations varied in the large range from 0.006 to 0.255 mg/l (exceeded 5 times the MAC according Russian legislation for marine waters) and the mean was 0.092 mg/l in January and February 2003. The general level of pollution of Turkish coastal waters was rather low and varied between 0.001 and 0.077 mg/l, the average was 0.011 mg/l next year mid-September. In August 2004 maximum (0.052 mg/l) was marked near the Sile to the east of the Bosporus exit section. All other concentrations fell inside the range of 0.001 ? 0.042 mg/l with heavier pollution levels observed in coastal waters near Samsun.

In April 2005, the average level of petroleum hydrocarbons content in 63 samples from the Turkish waters was 0.020 mg/l. Maximum was as high as 0.163 mg/l in Ordu area. Slightly lower pollution was recorded near Fatsa (eastern basin) and along the west coast. The situation however changed drastically by the end of September and beginning of October 2005. Some places could be considered as heavily polluted. The maximum concentration of TPHs reached incredible level of 25.466 mg/l at a station along the west coast characterized by surface waters of Danube origin; two other nearby stations had concentrations of 1.935 and 0.855 mg/l. Excluding these extreme values, the average of 60 samples was 0.199 mg/l. High values were spotted practically in all parts of the Turkish coast during October 2003: in Zonguldak, 1.279 mg/l, in Bartin, 0.573 mg/l, in Cide, 0.530 mg/l, in Akcaabat, 0.571 mg/l, in Sile, 0.900 mg/l. In general, very high water pollution was noted in the western part of the Black Sea where mean level for four stations occurred as high as 0.757 mg/l.

During the screening cruise in the Georgian waters in October 2000, the concentration of petroleum hydrocarbons was less than the detection limit of method used (0.04 mg/l) at 5 m depth as well as the near bottom layer at 114 samples out of 140. The overall average was 0.130 mg/l. In twenty four water samples, the TPHs content exceeded 1 MAC (0.05 mg/l) and reached the level of 1.13 mg/l, in average ? 0.23 mg/l. But the concentration of petroleum hydrocarbons at two coastal stations on the 5 m horizon reached 4.72 and 6.81 mg/l (more then 136 MAC). The reason of such amount of oil products in the water is unknown, probably it was a slick.

The extensive monitoring investigations along Russian coastal waters showed a moderate level of petroleum hydrocarbons pollution in 1988-1996 that was in general characterized by 0.1-0.2 mg/l, e.g. 2-4 MAC according to the Russian regulation for marine waters [12, 13]. At the same time, concentrations at some sites were as high as 1.10 ? 1.20 mg/l, 22-24 MAC. The maximum was recorded in Sochi area in 1990. The content of TPHs then decreased gradually.

Based on the topographical and hydrological conditions along the Russian coast, the shallow waters were divided into several zones (Fig. 3.1.3). To some extend the environmental parameters are uniform within each zone. The monitoring data from the each zone allowed estimation the magnitudes and local pollution sources.

The monitoring in these coastal waters over the last 5 years (2002-2006) provided 868 measurements with an average value of 0.073 mg/l. This level exceeds the Maximum Allowed Concentration (MAC) 0.05 mg/l according Russian regulation. At the same time the range of variation was extremely large and varied between analytical zeros (e.g. less then detection limit 0.002 mg/l) to 3.200 mg/l. The maximum was marked in 27 September 2003 in surface waters at the shallow station (8 m depth) in the vicinity of village Novaja Matsesta close to city Sochi. At the same time, the concentration of TPHs reached second maximum of 1.971 mg/l in the near-bottom layer. The other TPHs concentrations higher than 1.0 mg/l occurred two days earlier at the rather deep station (51 m depth) near the village Loo close to Lazarevskoe where it reached 1,380 and 1.548 mg/l in surface and bottom waters, respectively.

In general the high content of TPHs exceeded 1 MAC was measured in 421 cases, e.g. approximately in half of the samples. The mean was 0.131 mg/l. The mean concentration in other parts was 0.019 mg/l. The vertical distribution was rather uniform as well (Table 3.1.5) since almost 60% of measurement sites were less 20 m depth. In deep waters, the petroleum content in the water column was only occasionally studied, and the mean for the some measurements at the horizons between 50 m and bottom was 0.020 mg/l.

Table 3.1.5. TPHs concentrations in different water layers along the Russian coast in 2002-2006.

Layer Number of measures Mean, mg/l Maximum, mg/l
Surface 371 0.083 3.200
Intermediate 176 0.033 0.200
Near bottom 321 0.084 1.971

Geographical pattern of TPHs distribution demonstrate increasing level of TPHs pollution in the coastal waters close to the towns Novorossiysk and Gelendzhik (Table 3.1.6). The most peculiar values were measured during September-October 2003-2005 and therefore could not be completely compared with the other data. The abundant samples from the southern part of the Russian coast and rather low sampling from the northern part showed concentrations in excess of 1 MAC in the surface and bottom waters. Relatively high values were recorded in all regions in September 2003 and October 2004. On the other hand, high TPHs were recorded only in waters between Inal Bight and village Divnomorskoe in July 2005. Interannual variations are not evident for such a short period of measurements (Table 3.1.7). One could suggest that TPHs concentration is slightly increased during the last years but the trend have to be confirmed with other data sets, if available. Seasonal variations are also not evident from this set of data (Table 3.1.8). The only conclusion which could be drawn by these data sets is higher TPHs pollution in the second part of the year with the mean value of 0.078 as compared to 0.050 mg/l for the first half of the year.

Summary: The mean concentration of petroleum hydrocarbons in the Black Sea in general were rather high and usually exceed standard Maximum Allowed Concentration (0.05 mg/l) almost everywhere in the sea (Table 3.1.9). The petroleum pollution appears a major problem for the whole sea during the last two decades. The same situation was in the previous period of 1980-th when the average of TPHs concentration for almost 4 thousands water samples exceeded the threshold of Maximum Allowed Concentration about 2 times [10]. The maximum concentrations could be extremely high, up to 25.5 mg/l, which were observed almost everywhere in the basin. Quite often, such high values were recorded along the tanker and shipping routes connecting the main harbors Odessa, Novorossiysk and Istanbul. The extremes in the coastal shallow waters should be a result of local spills from the ships or discharge from the waste water systems of the large cities. The ballast water discharge emerges one of the most important sources of petroleum pollution [14]. Black Sea rivers can also contribute significantly.

Table 3.1.6. Mean concentration of TPHs (mg/l) and number of measurements (in parantheses) in the different zones of Russian coastal waters in 2002 ? 2006.

Parameter / Zone number 2 3 4 5 6 7 8 9
Surface 0.082

(208)

0.082

(48)

0.053

(49)

0.055

(8)

0.330

(9)

0.145

(12)

0.051

(27)

0.069

(6)

Intermediate 0.034

(98)

0.017

(45)

0.035

(23)

0.107

(3)

0.120

(2)

0.075

(2)

0.097

(3)

-
Near bottom 0.084

(168)

0.102

(41)

0.059

(47)

0.097

(8)

0.217

(9)

0.109

(12)

0.051

(27)

0.047

(6)

?Average 0.073

(474)

0.066

(134)

0.052

(119)

0.081

(19)

0.258

(20)

0.123

(26)

0.054

(57)

0.058

(12)

?Maximum 3.200 1.548 0.235 0.260 0.900 0.550 0.210 0.160
?Date of Maximum? value 27.09.

2003

25.09.

2003

18.10.

2004

16.07.

2005

18.10.

2004

18.10.

2004

13.10.

2004

13.10.

2004

Table 3.1.8. Seasonal variation of the mean concentration of TPHs (mg/l) in Russian coastal waters in 2002 ? 2006.

Months 2 3 4 5 6 7 8 9 10 11
Mean 0.046 0.044 0.060 0.057 0.048 0.086 0.054 0.073 0.113 0.081
Maximum 0.210 0.160 0.080 0.300 0.110 0.640 0.260 3.200 0.900 0.820
Number of samples 22 38 4 52 32 111 178 239 128 64

Despite very high concentrations, about the half of samples can be considered as pollution-free implying very high level of spatial heterogeneity TPHs distribution. As a consequence, the current monitoring station network in the Black Sea appears to be not dense enough in terms of spatial coverage and temporal frequency to monitor oil spills. The field monitoring needs to be supported by satellite and/or aircraft images as routinely in Europe.

Satellite imagery can help identifying spills over very large areas. The Synthetic Aperture Radar (SAR) instrument, which can collect data independently of weather and light conditions, is an excellent tool to monitor and detect oil on water surfaces. This instrument offers the most effective means of monitoring oil pollution. It is currently on board the European Space Agency's ENVISAT and ERS-2 satellites and the Canadian Space Agency?s RADARSAT satellite. In 2000-2004, JRC carried out a systematic mapping of illicit vessel discharges using mosaics of satellite images over all the European Seas (Fig. 3.1.4). These maps and the associated statistics were repeated on an annual basis in order to assess its evolution [6]. This action helped to reveal for the first time the dimension of the oil pollution problem, thus stressing the need for more concerted international actions. For the Black Sea, 1227 oil spills were detected during 2000-2004.

Table 3.1.9. Maximum and mean concentration of Total Petroleum Hydrocarbons (mg/l) in the Black Sea waters in 1992 ? 2006.

Area Year Waters Max Mean
IAEA 1998 Western shelf 0.23 (Constantia) 0.084
IAEA 2000 Eastern open 3.27 (Feodosia) 0.097
Ukraine 1992-1999 coastal 1.20 0.050
Ukraine 2000-2005 coastal 0.18 (Kerch) 0.050
Ukraine 2004 coastal 0.51 (Odessa) 0.12 (Odessa)
Ukraine 2004 coastal 0.85 (Dnieper ? South Bug)
Romania 2001-2005 coastal 2.27 (Mandalia) 0.14-0.28
Turkey 2003 coastal 0.255 (Bosphorus) 0.092
Turkey 2004 coastal 0.077 (Sile) 0.011
Turkey 2005 coastal 25.466 (Danube waters),

1.935 (Danube waters)

0.199 (without 3 extremes)
Georgia 2000 coastal 6.81 (Georgia) 0.13 (140 samples)
Russia 2002-2006 coastal 3.200 (Novaja Matsesta, Sochi) 0.073
Black Sea [10] 1978-1989

Winter

coastal + open, surface 0.89 (central Western shelf) 0.10 (519 samples)
Black Sea [10] 1978-1989

Spring

coastal + open, surface 0.59 (offshore of Crimea) 0.08 (379 samples)
Black Sea [10] 1978-1989

Summer

coastal + open, surface 0.55 (Odessa region) 0.08 (526 samples)
Black Sea [10] 1978-1989

Autumn

coastal + open, surface 1.29 (Sinop region) 0.09 (425 samples)
Black Sea [10] 1978-1989 coastal + open 1.29 (Sinop region) 0.09 (3828 samples)

Fig. 3.1.4. The oil spills in the Black Sea for period 2000-2004. Map of oil spills based on images taken by Synthetic Aperture Radars (SARs) of European satellites ERS-2 and Envisat. The oil spill density has been spatially normalized to the spill widths and the number of images available for the detection http://serac.jrc.it/midiv/maps/.

Satellite detection of oil spills with synthetic aperture radar (SAR) can now provide reasonably reliable information, but it is still a major challenge for coastal environment. Difficulties are compounded when there is no a priori knowledge of the occurrence, location or timing of a spill, when volumes are small, or when the oil is mixed with water as it enters the sea ? just the type of oil pollution that is most common. Thus, systematic multi-sensor routines represent an improvement. The Space Radar Laboratory of the Space Research Institute of RAS (http://www.iki.rssi.ru/asp/lab_554.htm) developed techniques for the synergistic use of satellite data to monitor pollution from pipe-line seeps, waste-water discharges, marine traffic and spillages from routine operations as part of offshore or tanker activities (http://moped.iki.rssi.ru). These techniques need to be implemented for operational monitoring system in coastal waters. First results were obtained during the semi-operational phase of satellite monitoring of the Russian coastal zones of the Black and Azov Seas in 2006-2007 [15, 16, and 17]. The ship routes to the ports of Novorossiysk and Tapes and oil terminal Zhelezny Rog were identified as the most polluted regions. Cumulative charts of oil spills based on the analysis of SAR data are presented (Fig. 3.1.5). Over the period of observations from April to October 2006, around 50 oil spills from ships were registered with the spill sizes of from 0.1 to 13 km2. The integral area of spills detected over the period was around 120 km2. Furthermore, approximately 70 oil spills from ships were detected in the north-eastern part of the Black Sea from April to October 2007, including the catastrophic 11 November 2007 event from the ?Volgoneft-139? tanker accident for in the Kerch Strait which was estimated to disperse to 117.6 km2. The total area of spills recorded during the observation period in 2007 was around 309 km2.

3.1.2. Bottom Sediments

The first attempt to assess the level of TPHs pollution in the Black Sea bottom sediments was done in September-December 1995 during the international cruise aboard RV ?V. Parshin? [8]. The samples were taken at 25 sites at the outlet of Bosporus Strait and along the Ukraine coast including the Danube Delta as well as the vicinity of city Sochi in the southern part of Russian coast (Fig. 3.1.6). In bottom sediments around Crimea peninsula, the content of petroleum hydrocarbons was below 6.6 ?g/g near Yalta (depth 57 m), and 5.8 and 2.1 ?g/g at the shallower stations in the vicinity of Feodosia (18 m) and Kerch (6 m), respectively. The TPHs concentration increased drastically to 310 ?g/g with the mean value of 210 ?g/g at two sites in the northwestern shelf (Odessa area) with the depth of 11 m and 17 m. Similarly, high concentration was recorded at one station in the Danube Delta (220 ?g/g, 3 m depth) whereas it was 49 ?g/g at another shallower site (12 m depth). In the Bosporus vicinity the 10 samples were taken at rather deep places with about 80-130 m depth. The TPHs concentration was low and varied from 12 to 76 ?g/g with the average of 38.7 ?g/g. In the Russian part the high content of hydrocarbons 170 ?g/g was finding only at one station with 8 m depth placed near cost. Four other stations were much deeper (25-40 m) and the hydrocarbons pollution of bottom sediments reduced to 7.6 ? 53 ?g/g with mean 22.9 ?g/g.

The petroleum hydrocarbons pollution of bottom sediment were sampled at shallow coastal stations with the depth less then 12 m as well as Odessa and Dnieper Deeps below 20 m in 1988-1999 [11]. At the slope of Dnieper Deep, the TPHs concentration varied in a range 1600 - 2000 ?g/g dry weight close to the Odessa city, but apart from the ports it was slightly less as 800 ? 1700 ?g/g. The Odessa and Yuzhny ports could be considered as a most important source of petroleum pollution. Beside this, the spectrum size of bottom sediment highly influenced on the TPHs level. The maximum numbers were recorded in the central part of the Odessa Deep in the fine clay sediments where the concentrations reached 3400 ? 5700 ?g/g. At the same time, the minimum was 300 ?g/g only in the sandy sediments close to the coast.

The other set of monitoring data from 169 samples received in the northwestern shelf during 1992-1999 [2]. The maximum reached 825.0 ?g/g while the average value for the whole set was 114.8 ?g/g. The highest pollution was recorded in sediments of the Danube delta region ? the average for 29 samples reached 210 ?g/g, next was the Dniestr Lagoons outlet area with 169 ?g/g for 23 samples. In the Dniepr-Bug Lagoon area the average of 6 samples was 133 ?g/g. The mean concentration in the Odessa area close to the ports of Odessa, Illiechevsk and Yuzhny was 100 ?g/g for 63 samples. The pollution level was, on the other hand, much lower (15.0 ?g/g) in the central part of the shelf away from the main sources of pollution. After 2000, no data were available for petroleum hydrocarbons in bottom sediments along the Ukrainian coast.

Along Romanian coast the petroleum hydrocarbons in sediments were not sampled until 2005. In the period of April-October 2005, the concentration in bottom sediments of shallow parts of the Romanian coast (depths less 20 m) varied in a very large range from 25,6 to 11736,7 ?g/g. The maximum was noted in June close to Constanta at the site of 5 m water depth. The two other very high values of 6729 and 10090 ?g/g were recorded there in April and October, respectively. The concentrations at all other stations were significantly less with an average value 389.7 ?g/g for 68 samples. The spatial distribution was rather uniform (Table 3.1.10). A very high level was recorded near the main harbor Constanta. A slightly increasing level of petroleum hydrocarbons pollution was noted in the Danube Delta and near the village Vama Veche in the south. In general, the Romanian bottom sediments could be considered as highly polluted by petroleum hydrocarbons. The average level for whole coastal line exceeded almost 8 times the concentration of Netherlands standard for bottom sediments, Permission Level 50 ?g/g [7]. The average data for each part of the Romanian coast also was few times higher then 1 PL (Table 3.1.10).

Table 3.1.10. The mean concentration of TPHs (?g/g) and number of measurements within monitoring programme in the different sites of Romanian coast in 2005.

Danube

Delta

Mamaia Constanta

North

Constanta

South

Eforie

Sud

Costinesti Mangalia Vama Veche
Mean 339.2 273.6 221.5 4484.4 231.2 291.9 258.3 499.5
Number of samples 10 13 5 8 8 11 8 8

In June 2006 four samples were taken along the transect off Constanta at depths 14, 36, 45 and 53 m. Total content of petroleum hydrocarbons in the bottom sediments did not exceed 74.4 ?g/g and the average was only 33.7 ?g/g for all four samples with minimum 6.6 ?g/g. Those data are highly different from almost 100 times higher values recorded in 2005. It could be explained by spatial heterogeneity of bottom sediment pollution depending from many factors.

The only petroleum hydrocarbons pollution monitoring of bottom sediments in Turkish coastal area was performed in April and September-October 2005. In April the level of TPHs was low and varied from 1.6 to 233.2 ?g/g in the western part of the Turkish coast. The maximum reached 38.7 ?g/g only, at stations with 12-51 m water depth in the vicinity of Sakarya River. However, near the town Zonguldak, the pollution level drastically increased up to the extremely high number of 11999.1 ?g/g at a site with 13 m water depth, 9025.0 ?g/g at 50 m and 475.5 ?g/g at 100 m water depth. The bottom sediments from Cide to Fatsa in the eastern part were relatively clean with mean value of 165.0 ?g/g for 16 stations placed at the depth range of 9-111 m. The minimum here was 2.3 ?g/g, maximum reached 793.7 ?g/g and was noted for the deepest station near Cide. The mean for 15 stations of the eastern part was 234.7 ?g/g and maximum was 2512.4 ?g/g near Pazar. In general, at 40 sites along the Turkish coast sampled in April 2005 the mean value was 700.3 ?g/g. Almost ten times lower values were recorded in October 2005 with the mean of 77.4 ?g/g for the 63 stations. The maximum was 1016.5 ?g/g near Zonguldak.

According to forecasts the volume of oil and oil product transportation through Georgian ports is estimated to be about 50-60 million tonnes per year in 2010-2015. Intense development of marine infrastructure is expected to aggravate current complex ecological state of the marine ecosystem of the sea for which oil pollution is the most dangerous. Within the frame of the international project on the ?Study of the background ecological status of the Eastern part of the Black Sea along the coast of Georgia?, the concentration of petroleum hydrocarbons in the bottom sediments was determined during 2000. Samples of bottom sediments were taken from 75 stations on the Georgian shelf at the depth range from 10 to 1500 m. A gradually decreasing petroleum hydrocarbon concentration was observed along the topographic slope down to the depth of 200 m. The average concentration for the sites with depths less than 50 m was 26.9 ?g/g, from 50 to 100 m - 19.5 ?g/g, and from 100 to 200 m - 11.4 ?g/g. High content of petroleum hydrocarbons was detected in the bottom sediments of the Poti harbour area, 35.3 ?g/g on the average. In the bottom sediments to the north of the Batumi harbour, the concentration of petroleum hydrocarbons also increased up to 17.7 ? 21.7 ?g/g, on the average 10.5 ?g/g. Apparently, flows of sediments contaminated with petroleum products moved from the Batumi area northwards. In the gorge of the Natanebi River petroleum deposits and oil manifestations, petroleum hydrocarbons content was measured at 152.7 ?g/g.

Method used for identification of petroleum hydrocarbons was enabled to identify not only the groups of petroleum products, but the approximate time of oil spills as well [5,6,7]. The TPHs in the bottom sediment was of different origin and differed in terms of light and heavy fractions. Latest spills were mostly found in the regions of Batumi and Poti harbours as well as between estuaries of Khobi and Tsivi Rivers. Their origin was the man-made pollution due to the impact of ports and terminals. In the deep stations starting from the depth of 200 m, concentration of TPHs increased which may likely be due to re-deposition of petroleum products absorbed on the clay particles transported from the coastal water to the deep water area. At the same time, anoxic conditions prevented biogenic degradation of the hydrocarbons.

Table 3.1.11. The concentration of TPHs (?g/g) and other physical and chemical parameters of the bottom sediments of the Georgian part of the Black Sea in June 2006 [9].

Region TPHs (?g/g) EOM (mg/g) Total Organic Carbon, TOC (%) Grain Size Fines, <65.5 ?m (vol%) Total PAHs (ng/g) Total HCHs (pg/g ) Total DDTs (pg/g) Total PCBs (pg/g)
Batumi 6.1 0.031 0.13 42.55 145.1 318 496 864
Kobuleti 202.2 0.43 0.65 54.71 27384.8 1118 16550 4000
Natanebi 76.7 0.45 1.59 79.76 3944.5 1634 5090 6200
Supsa 70.3 0.18 1.66 75.86 4074.6 1336 3679 4320
Poti 15.6 0.042 0.24 9.92 710.3 664 1269 1445

In June 2006, at five sites at 60 m water depth along Georgian coast in vicinity of Batumi, Kobuleti, Poti and estuaries of the Natanebi and Supsa Rivers, the maximum was recorded near Kobuleti and reached the level 202.2 ?g/g [9]. The minimum was 6.1 ?g/g near Batumi and mean value was 74.2 ?g/g. The concentration of extracted organic matter (EOM) in the bottom sediments varied between 0.03 and 0.45 mg/g and, in general, the high concentration of TPHs is correlated with the high EOM content. The same correlation was also evident with the grain size of bottom sediments. The coarse ground had less concentration of petroleum hydrocarbons (Table 3.1.11). Majority of fine sediment near estuary Natabeni and Supsa was not heavily polluted by hydrocarbons and could not be regarded as ?hot spots?.

Prior to 2000, high content of hydrocarbons (170 ?g/g) was found only at one coastal station at 8 m depth in Russian coastal waters. At other deeper stations (25-40 m) the hydrocarbons pollution was in the range of 7.6 ? 53 ?g/g with mean 22.9 ?g/g [8]. In December 2000, the southern part of the Russian coast from the town Gelendzhik to the village Adler (8 stations placed at 26-41 m water depth) was characterized by the minimum concentration level of 10.7 ?g/g (measured at the traverse of estuary Chyhykt River close to Lasarevskoe). The maximum reached 117.0 ?g/g at the traverse of the Sochi harbour. The average was 32.8 ?g/g.

In June-July 2002, monitoring of the TPH pollution level of sediments showed drastic differences to south of Taman. The aliphatics fraction reached the level of 45-84 ?g/g and aromatics 35-62 ?g/g in deep parts, while they had only 5-9 ?g/g and 2 ?g/g, respectively, in shallow stations. The 10-20 fold differences could be the result of size spectrum of bottom sediment particles, which is much smaller in the deep zone with active sedimentation.

In August 2004, the concentration of total petroleum hydrocarbons in the bottom sediments in the southern part of the Russian coast, between the rivers Hosta and Shapsukho near Tuapse, varied in a very wide range from 11.9 to 2840.0 ?g/g with the average of 394.4 ?g/g. Two most extreme values were registered in the shallow estuaries of the rivers Tuapse (2840.0 ?g/g) and Sochi (1400.0 ?g/g) at 6-7 m water depth. Without these extremes, the average value still remained very high (221.8 ?g/g, more then 4 PL [7]) and demonstrated a rather wide spreads of petroleum pollution along southern and central part of Russian coast. In estuaries of the Hosta and Sochi Rivers of the southern zone 2, the mean was 227.0 ?g/g. The mean concentration near villages Loo, Lazarevskoe and the Shahe River at the depth about 40-60 m, on the other hand, was much lower with a value 28.5 ?g/g. Slightly to north, the pollution of bottom sediments by TPHs was below 1 MAC at all points at the distance 2 nm from the coast and depth 40-60 m up to the Shapsukho River.

In general, the TPHs pollution level in coastal bottom sediments can be divided into two groups: the offshore stations at more than 2 nm away from the coast located at depths 40-60 m and inshore shallow stations. The average level for the offshore sites was 31.3 ?g/g and the variation was only from 11.9 to 74.1 ?g/g. The inshore group contained the shallow estuaries of the Sochi River with the mean 481.0 ?g/g, and estuary of the Tuapse River with the mean 787.0 ?g/g. The difference in petroleum hydrocarbons concentration up to 10-20 times in inshore and offshore regions is evident and should be related to large volumes of municipal and manufacturing waste from two large cities and the discharges from two rivers.

The investigations of bottom sediments pollution by petroleum hydrocarbons in the northern part of Russian coast were carried out in October 2004. Inside the Gelendzhik Bight the concentration of TPHs in the bottom sediments was 61.2 ?g/g. Significantly higher values between 122.0 ?g/g were measured near the pear in Sheskharis and 1900.0 ?g/g in the western part of Novorossiysk harbor. The mean value was 911.0 ?g/g. An opposite situation was observed in the Anapa Bight slightly to north. Two samples from the 5 m water depth showed only 5.0 and 88.0 ?g/g TPHs concentrations therefore much lower than the southern parts. Similar moderate values (59.5 ?g/g) were received in bottom sediments of the port Kavkaz in the Kerch Strait at the point of 6 m depth.

In July 2005, several samples were collected in the southern part of the Russian coast from the River Sochi up to the village Dzankhot in the north near Gelendzhik. All samples were taken at the depth 30-50 m slightly away from the shore. The concentration was rather moderate and varied in the narrow range from 35.3 to 88.0 ?g/g with the average value of 54.0 ?g/g. The only station in the shallow estuary of the River Mzumta (9 m depth) showed the maximum recorded level.

Summary: During the last 10 years, the mean concentration of petroleum hydrocarbons in the bottom sediments of coastal parts of the Black Sea varied from very low level up to high value of about 0.8 mg/g (Table 3.1.12). Usually in the most sites of the coast the average concentration was about 1 PL (50 ?g/g, [7]) but several maxima exceeded this threshold 13-16 times. Those extremely polluted sites are placed in Romania, Turkish and Russian waters, close to the main sources of TPHs, namely large ports, oil refinery or oil terminals for transportation. The maximum values around 12 mg/g were recorded at Romanian and Turkish coasts at the very shallow depths and most likely represented fresh oil spills in 2005. Due to high patchiness of oil distribution in the sea such occasional extreme values are expected.

Table 3.1.12. Maximum and mean concentration of TPHs (?g/g) in the bottom sediments of the Black Sea in 1995 ? 2006.

Project Year Region Max. value Max. Depth? (m) Mean (Depth <20 m) Mean (Depth >20 m) Mean
Screening 1995 Crimea 310.0 11 116.2 4.7 71.6
Screening 1995 Russian 170.0 8 170.0 22.9 52.3
Screening 1995 Bosporus 76.0 107 - 38.7 38.7
Research 1988-1999 Ukraine 5700.0 - - - -
Monitoring 1992-1999 Ukraine 825.0 - - - 114.8
Monitoring 2005 Romania 11736.7 5 775.4 - 775.4
BSERP 2006 Romania 74.4 36 6.6 42.8 33.7
Monitoring 04.2005 Turkey 11999.1 13 2078.1 457.2 700.3
Monitoring 10.2005 Turkey 1016.5 51 84.0 76.4 77.4
Research 2000 Georgia 152.7 88 19.0 19.0 19.0
BSERP 2006 Georgia 202.2 60 - 74.2 74.2
Research 2000 Russia 117.0 41 - 32.8 32.8
Research 2002 Russia 144.0 70 - 60.5 60.5
Research 2003 Russia 152.0 50 25.5 96.3 36.7
Monitoring 08.2004 Russia 2840.0 7 646.0 31.3 394.4
Monitoring 10.2004 Russia 1900.0 15 671.0 122.0 625.2
Monitoring 2005 Russia 88.0 9 88.0 49.1 54.0

TPHs concentrations in the bottom sediments decreased with increasing depth; i.e. towards offshore (Table 3.1.12). The average level of concentrations was usually highest at depths shallower than 20 m. Some uncertainties came from the sampling strategy; i.e. due to different number of sampling in each site. Irregular and often patchy sampling in many parts of the sea greatly limited a better evaluation of the TPHs pollution. In many cases, the pollution assessment was made on the basis of only few samples of bottom sediments taken during the last 10 years or even none at all. The further monitoring program is much desired for more reliable description of bottom sediments pollution by petroleum hydrocarbons especially in vicinity of main oil sources.

3.2. The State Of Chlorinated Pesticides

Alexander Korshenko

State Oceanographic Institute, Moscow, RUSSIA

Sergei Melnikov

Regional Centre ?Monitoring of Arctic?, Sankt-Petersburg, RUSSIA

3.2.1. Water

The pesticides investigation in the Black Sea waters significantly differs from the petroleum hydrocarbons studies. Due to low concentration of chlorinated hydrocarbons in the marine water this parameter was not included into the measurements list neither during the international IAEA Cruise of the RV "Professor Vodyanitskyi" in 11-20 September 1998, nor in the second IAEA cruise of the RV "Professor Vodyanitskyi" during 22 September ? 11 October 2000 [1]. The main source of the information on the pattern of pesticides distribution was provided by the national scientific and monitoring programs.

177 water samples were collected for chlorinated hydrocarbon measurements in the surface layer of shallow waters of the North-Western part of the Black from 1988 to 1999 [2]. In general, the level of pesticides was low. The average concentration of lindane (γ-HCH) was 0.48 ng/l (Table 3.2.1). The data varied within the range from analytical zero to 4.0 ng/l. The DDT and its metabolites DDE and DDD had a slightly higher level ? average 1.08 ng/l with the range 0.0 ? 14.4 ng/l; 0.55 ng/l (0.0 ? 5.4 ng/l); 0.38 ng/l (0.0 ? 6.3 ng/l), respectively. Important point is to note the predominance of DDT in comparison with its metabolites. It suggests a more recent and ongoing water pollution in the studied area. The method of liquid-gas chromatography applied at the end of this monitoring period allowed to identify very low concentrations of some other chlorinated pesticides like hexa-chlorbenzene, aldrin and heptachlor. Their average and maximum concentration in 1999 was 0.26 and 4.18 ng/l for hexa-chlorbenzene, 0.22 and 3.12 ng/l for aldrin, 0.01 and 0.22 ng/l for heptachlor, respectively.

57 samples analysis were taken for pesticide analysis in Romanian coastal waters during April, July and October 2005 within the framework of national monitoring program [3]. The stations were placed along Romanian coastline at shallow sites at depths less than 20 m. The pesticides concentration of the DDT group exceeded the detection limit of the method used (DL = 0.001 ng/l) only in 18 water samples. The maximum 14.75 ng/l total concentration of DDT group was recorded in April near Mangalia close to beach at 5 m depth isobath. Individual concentration of DDT there was 6.95, DDD 5.91 and DDE 1.89 ng/l. The DDT level exceeded the detection limit, DL, only in this one sample, and the DDT was not registered in other cases. Except this outstanding sample, DDD was recorded 5 times with an average 0.32 ng/l and the maximum 1.01 ng/l. DDE exceeded the DL 17 times. Its average was 0.12 ng/l and the maximum 0.47 ng/l.

Among pesticides of the HCH group, the lindane (γ-HCH) was found rather often in all places along the Romanian coast and in the Danube Delta. Its concentration exceeded the DL (0.001 ng/l) in 34 samples. The average of all samples was 0.064 ng/l and the maximum reached 0.3 ng/l in July near Costanesti. The average for samples where concentration of γ-HCH was higher than its DL was 0.108 ng/l.

No data were available to make an assessment of water pesticides pollution along the Bulgarian, Turkish and Georgian coasts. These pollutants were not included into routine national monitoring programs.

Water samples were collected along the Russian coastal waters from 23 May 2002 to 23 November 2006. Investigations were performed within the frame of national monitoring program. In May, October and November 2002, 48 water samples obtained in the southern region close to the city Sochi showed no pesticides concentration above the DL which seems to be rather unrealistic and suggest either false sampling or measurement. These monitoring data were thus excluded from the analysis. The same also applies for the February 2003 data set.

The September-October 2003 samplings were performed as a part of the ?Aero visual monitoring program? and covered the southern and central parts of the Russian coast between the Cape Inal close to Dzubga [3]. The average of total DDT concentration was 0.84 ng/l and varied within range of 0.17-3.26 ng/l (Table 3.2.1). Maximum concentrations of total DDTs, as well as 2.30 ng/l for DDT and 0.96 ng/l for DDE were recorded in the near bottom layer at a shallow station (8 m depth) close to the village Novaja Matsesta in the Sochi region. The next highest total DDTs values of 2.20 ng/l and DDT of 1.36 ng/l were also recorded in the upper layer at the same station.

The spatial distribution of total DDTs group pesticides was rather uniform. The average for different zones of coastal waters was almost the same: for zone 2 ? 0.81 ng/l, for zone 3 ? 0.89 ng/l, zone 4 ? 0.83 ng/l. The vertical variations were also small; the average for samples taken above 20 m depth horizon was 0.89 ng/l and slightly higher than 0.74 ng/l below 20 m. See Fig. 3.1.3 for the locations of these zones.

Among different DDTs forms and metabolites, the dominant role belonged to 4,4-DDT with the average for the whole set of data 0.42 ng/l and maximum 2.00 ng/l. The average and maximum of 2,4-DDT were 0.06/0.30 ng/l; metabolites 2,4-DDE ? 0.04/0.27 ng/l; 4,4-DDE ? 0.30/0.84 ng/l; 2,4-DDD ? 0.00/0.18 ng/l; 4,4-DDD ? 0.01/0.36 ng/l. This structure of group concentration suggests rather ?fresh? DDT pollution of marine coastal waters in the region.

Table 3.2.1. Maximum and average concentration of pesticides (ng/l), and number of observations (in parantheses) in marine waters of the Black Sea in 1992 ? 2005.

Project Year Region γ-HCH Α-HCH β-HCH HCH total DDT DDE DDD DDT total HCB* Other
Monitoring

[2]

1992-1999

Ukraine

4.0/0.48

(177)

-

-

-

14.4/1.081

(77)

5.4/0.55

(177)

6.3/0.38

(177)

-

4.18/0.26

(?**)

3.34/0.23

(?**)

Monitoring

[3]

2005

Romania

0.3/0.064

(57)

-

-

-

6.95/0.12

(57)

1.89/0.07

(57)

5.91/0.13

(57)

14.75/0.32

(57)

-

-

IAEA Cruise [1]

09.1998

Western Black Sea

-

-

-

-

-

-

-

-

-

-

IAEA Cruise [1]

09.2000

Eastern Black Sea

-

-

-

-

-

-

-

-

-

-

Monitoring

[3]

2005

Bulgaria

-

-

-

-

-

-

-

-

-

-

AeroVisual Monitoring

2003

Russia

2.33/0.23

(40)

2.32/0.39

(40)

3.88/2.70

(40)

6.50/3.31

(40)

2.30/0.48

(40)

0.96/0.34

(40)

0.36/0.02

(40)

3.26/0.84

(40)

0.32/0.06

(40)

0.86/0.26

(40)

AeroVisual Monitoring

07-08.

2004

Russia

3.60/0.14

(80)

0.59/0.11

(80)

4.99/3.14

(80)

7.21/3.38

(80)

1.28/0.17

(80)

0.39/0.04

(80)

0/0

(80)

1.66/0.21

(80)

0.28/0.06

(80)

0.18/0.01

(80)

AeroVisual Monitoring

10.2004

Russia

0.19/0.13

(100)

0.20/0.12

(100)

3.42/2.74

(84)

3.76/2.85

(100)

0/0

(84)

0.34/0.05

(84)

0/0

(84)

0.34/0.05

(84)

0.11/0.09

(84)

0/0

(84)

AeroVisual Monitoring

07.2005

Russia

0.35/0.16

(59)

0.68/0.43

(59)

6.81/3.98

(59)

7.80/4.55

(59)

0.64/0.15

(59)

0.23/0.02

(59)

0.77/0.08

(59)

1.29/0.20

(59)

0.14/0.07

(59)

0.18/0.09

(59)PCB

Notes: The bold number exceed the 1 MAC = 10 ng/l.
HCB* - hexachlorobenzene,
** - the only samples treated in 1999.
0.18/0.09/59PCB - pentachlorobenzene, maximum, average and number of samples.

The total HCH concentration was much higher than DDT and varied from 2.12 to 6.50 ng/l; the average for 40 samples was 3.31 ng/l. The highest concentrations of 6.50 and 5.78 ng/l were recorded in shallow places with 6-8 m depth close to villages Novaja Matsesta and Nizne-Nikolaevka situated between Hosta and Sochi where DDT pollution was also highest. Similar to DDT the spatial distribution of these pesticides was rather uniform. The average was 3.49 ng/l in the second zone; 2.98 ng/l in the third zone; 3.47 ng/l in the fourth. The average was 3.36 ng/l for shallow stations less than 25 m, and 2.95 ng/l for deeper stations.

Among different forms of HCH, the dominant one with the average level of 2.70 ng/l and maximum 3.88 ng/l was the β-HCH (Table 3.2.1). The lindane and α-HCH had the mean concentrations of 0.23/2.33 ng/l and 0.39/2.32 ng/l, respectively.

Hexachlorobenzene content exceeded the DL = 0.01 ng/l in 19 samples. The average for all studied area was 0.06 ng/l and the maximum reached 0.32 ng/l. Heptachlor had a maximum (0.86 ng/l) in vicinity of Sochi and the average value for all stations was 0.06 ng/l. Aldrin concentration (maximum 0.48 ng/l) was also marked near Sochi. Cischlordane concentration exceeded the DL only in 7 samples, maximum was 0.11 ng/l, cisnonachlor spreaded much wider over the whole area and was registered in 24 samples; the average was 0.14 ng/l and maximum reached 0.40 ng/l at a coastal station close to the village Chemitokvadzhe near Lazarevskoe. The concentration of octachlorstyrene, heptachlorepoxide, transchlordane, transnonachlor, photomirex and mirex did not exceed the DL in all samples.

In the second round of ?Aero visual monitoring programme? during July-August 2004, 80 water samples were taken within the central and southern parts of the Russian coast. The total DDT concentration exceeded DL=0.05 ng/l in 39 samples and reached the maximum 1.66 ng/l at a station located 2 nautical miles away from the coast off the River Shapsukho mouth close to the town Tuapse. The average for the whole set of samples was 0.21 ng/l. The DDT content was much higher in the central part of coast in the fourth zone (average was 0.34 ng/l), 5 times lower (0.07 ng/l) in the third zone, and slightly higher in the second zone (0.16 ng/l).

Among the forms of DDT group, 4,4-DDT exceeded the DL in 36 samples and reached 0.94 ng/l and the average was 0.14 ng/l. The spatial distribution of 4,4-DDT showed a maximum (average 0.219 ng/l) in the central part of Russian coast (zone 4). It reduced southward to 0.06 ng/l in the zone 3 and was twice higher in the Sochi area (0.11 ng/l). The 2,4-DDT reached maximum 0.54 ng/l but average was as low as 0.03 ng/l. The average content of another form 4,4-DDE, although measured up to 0.39 ng/l, was 0.04 ng/l only. The 2,4-DDE was practically absent and its maximum was only 0.07 ng/l. The concentration of both DDD forms did not exceed DL in all samples.

Similar to previous year, the HCHs concentration was an order of magnitude higher than the DDT group. The maximum of total HCHs reached 7.21 ng/l and average was 3.38 ng/l. The maximum was recorded in the subsurface layer off Tuapse at a distance 7 nm from the coast. In general the HCH was distributed evenly over the investigated area of coastal waters. The averages for three different zones were very close: 3.65 ng/l for the zone 2, 3.05 ng/l for the zone 3, and 3.41 ng/l for the zone 4. Also there was no appreciable difference between the shallow and deep stations; the average was 3.52 ng/l at stations shallower than 20 m, and 3.26 ng/l for deep ones.

The maximum of β-HCH concentrations reached 4.99 ng/l and average was 3.14 ng/l. Much lower concentrations were recorded for α-HCH (0.59/0.10 ng/l) and lindane (3.60/0.14 ng/l). Among other pesticides, hexachlorobenzene was recorded rather often in all places along the Russian coast with the maximum and average concentrations of 0.28, 0.06 ng/l, respectively. Pentachlorobenzene seldom traced in the water column at a maximum concentration 0.18 ng/l. The concentrations of heptachlor, aldrin, octachlorstyrene, heptachlorepoxide, transchlordane, cischlordane, cisnonachlor, transnonachlor, photomirex and mirex did not exceed the DL in all samples.

During 9-19 October 2004, the entire Russian shelf was studied from Sochi in the south and to the Kerch Strait in the north. Among 84 samples of marine waters collected, the concentration of DDE exceeded the DL (0.05 ng/l) only in 25 cases. The average level was 0.05 ng/l. The maximum of DDE (0.34 ng/l) was measured inside the Novorossiysk port. Other forms of this group never exceeded the DL (Table 3.2.1). The HCH was again significantly higher and rather uniform. No special place or patches with high concentration was found. The average for the 100 samples was 2.85 ng/l and they varied within a narrow range from 0.90 to 3.76 ng/l and no single sample was free of these pesticides. The maximum was recorded at station placed at 2.5 miles away from the coast near the village Olginka in the zone 4. The averages for different zones varied between 2.44 and 3.17 ng/l. The mean level of α-HCH for 40 samples was 0.12 ng/l and the maximum was 0.20 ng/l. The corresponding values were 2.74 and 3.42 ng/l for β-HCH and 0.13 and 0.19 ng/l for γ-HCH. The concentrations of other pesticides did not exceed the DL in all samples with the exception of relatively high hexachlorobenzene (0.07 and 0.11 ng/l) measured in two samples from Novorossiysk Bight.

During the 4-18 July 2005 ?Aero visual monitoring? measurement program, the DDT pesticides were found in low quantities (Table 3.2.1). However, in contrary to the previous investigations, the DDT and DDD were also recorded in the samples. The average and maximum levels of total DDT for the entire Russian coastal stations were 0.20 ng/l and 1.29 ng/l, respectively that exceed the 0.1 MAC level. The pattern of geographical distribution showed decreasing of DDT content in the waters from south to north (Table 3.2.2). The highest concentration was found in near-bottom layer of 50 m deep station in the vicinity of Katkova Szel close to Lazarevskoe (zone 3). DDTs showed a vertically uniform distribution with the equal mean concentration of 0.25 ng/l in the subsurface and near-bottom layers.

Table 3.2.2. The average concentration of chlorinated pesticides (ng/l) in the different zones of Russian costal waters in July 2005.

Average 2 3 4 5 6 7 8 9
DDT total

0.24

0.43

0.73

0.21

0.18

0.40

0.00

0.04

0.07

HCH total

4.55

4.61

4.79

4.95

5.15

4.91

3.79

4.45

3.08

The concentration of pesticides from HCH group was almost 5 times higher than DDT mainly due to a high contribution of β-HCH (Table 3.2.1). The dominance of this form of HCH could be the sign of old pollution and contrasted with low lindane concentrations with the average 0.16 ng/l and the maximum 0.35 ng/l observed near Cape Codosh close to Tuapse. The concentration of β-HCH reached the maximum level 6.81 ng/l in near bottom waters at 60 m depth close to the Cape Uch-Dere and Dagomys River estuary. Their content in the near-bottom layer was slightly higher than in the surface; 4.26 ng/l and 3.73 ng/l, respectively. The HCH distribution did not exhibit a visible geographical trend. All coastal zones were almost equally polluted by HCH (Table 3.2.2).

The concentrations of chlororganic pesticides heptachlor, aldrin, octachlorstyrene, heptachlorepoxide, transchlordane, cischlordane, cisnonachlor, transnonachlor, photomirex, 1,2,3,4 TCB, 1,2,3,5 TCB, 1,2,4,5 TCB and mirex were lower then their detection limit 0.05 ng/l in all samples. Hexachlorobenzene occured in 11 samples in the range from DL to 0.14 ng/l (Table 3.2.1). Maximum content was measured in the near bottom layer at depth 47 m off the village Ashe in the zone 3. Pentachlorobenzene occurred only in five samples with the maximum 0.18 ng/l in bottom waters at 50 m depth in the vicinity of Cape Codosh in the zone 4.

Summary: The measurements of pesticide concentration in water were performed rather seldom due to their very low concentrations (Table 3.2.1) and in the frame of international monitoring programme on the Black Sea (BSIMAP) their measurements in water were optional as well as in most of the international monitoring programs. Despite the fact that most of the samples practically free from pesticides due to their concentrations below the Detection Limit (0.05 ng/l), some very condense patches were however detected. Their patchiness may be related to unusual physical conditions like stormy weather or large freshwater discharge into the sea after floods. The densest patch was recorded in Romanian coastal waters (along 5 m isobath) near town Mangalia in April 2005. In this sample the BOD5 also low probably due to the stabilization effect of high pesticides concentration on microbiological community. This patch was a local feature since no pesticides were found in the neighboring stations along 20 m isobath.

The results of Russian monitoring programs suggested very low DDT concentrations in marine waters. Their maxima reached 0.1-0.3 MAC. The DDT pollution in southern part of the Russian coastal waters was much higher than the northern part. The HCH content was about 10 times higher mainly because of the accumulation of ?old? β-HCH. Nearly uniform pesticide concentrations in surface and near bottom layers support the idea of their spreading from coastal point sources.

In summary, very low level pesticide pollution was observed in coastal waters in general except some occasional patches with very high pesticides concentrations in different layers. The pollution by pesticides could be considered as an ?old? pollution due to low contributions of DDT and lindane in comparison with its metabolites.

3.2.2. Bottom Sediments and Biota

During the first international cruise in September 1995, 10 samples were taken along the Ukraine coastline from the town Kerch on the eastern side of the Crimea peninsula to the Danube delta on the west (Table 3.2.3). The depths of sampling were in the range from 3 m to 78 m. The bottom sediments around Crimea (sampling sites were Karkinitsky Gulf, Balaklava, Yalta, Feodosiya, Kerch) practically free from the HCH pesticides. Their amount varied from 0.016 to 0.189 ng/g. The strong contrast was observed in sediments from the northern-western shelf. The total concentration of HCH had a minimum 1.25 ng/g, average 1.69 ng/g and maximum 2.25 ng/gin Illichevsk port, Odessa bay and Danube Delta region. Among metabolites, α-HCH and β-HCH were slightly more important than lindane. Hexachlorobenzene (HCB) had a similar spatial distribution with the average 0.221 ng/g, and the maximum 1.300 ng/gwas measured in the Danube Delta.

The DDT had extremely high concentration in the NW Shelf sediments contrary to its absence around Crimea. The maximum of total DDTs concentration reported for Odessa Bay exceeded highest level of the Crimean concentrations more then 110 times (Tabl. 3.2.3).

For the NW Shelf of the Black Sea, the historical data from the period 1992-1999 showed rather low concentrations of g-HCH in the bottom sediments. The average of the data from 182 samples was 0.38 ng/g varying in the range between analytical zero and 4.5 ng/g [2]. This data set showed lindane concentration in zooplankton at an average value of 12.74 ng/g comprising a wide range between zero and 78.92 ng/g. Similar estimation for benthic animals was one order of magnitude lower: with the average of 1.54 ng/g for the range from below the detection limit to 16.2 ng/g (Table 3.2.3). The average concentration of lindane varied within the narrow range of 0.26-0.79 ng/g during 1992-1999 (Table 3.2.3).

The average and maximum concentrations were 2.38, 54.2 ng/g for DDT, 2.65, 54.3 for DDE and 3.08, 48.8 for DDD. They were not significant except in the Danube area where their total average concentration was 20.4 ng/g exceedin the permission level, PL, almost 10 times (Table 3.2.3). Very high level of DDT group was registered in zooplankton organisms, one order of magnitude higher than in sediments. Approximately equal concentrations of DDT and its metabolites appear to indicate a mixture of new and old pollution. In all sub-regions of the NWS the total concentration of DDT averaged over the period 1992-1999 exceeded the PL for bottom sediments.

Table 3.2.3. The average concentration of pesticides in the bottom sediments in the North-Western Shelf of Ukrainian waters, ng/g.

1992-99[2] Odessa

region

Dnieper-

Bug

Dniester Danube Open part of NWS Zoo-plankton Zoo-benthos Suspend-

ed matter

g-HCH

0.36

0.47

0.33

0.79

0.26

12.74

1.54

0.23

DDT

1.22

1.24

2.81

6.38

2.14

17.11

DDE

2.35

1.89

3.19

5.30

1.27

19.1

DDD

1.92

1.16

4.14

8.76

0.56

5.08

DDTtotal*

5.49

4.29

10.14

20.44

3.97

7.01

345.0

DDTtotal

2000[1]

2.50

19.57

DDTtotal

2005[3]

18.86

16.52

6.1

6.5

Sevastopol

0.53

Kerch

0

- total concentration of DDT and its metabolites (sum of DDT, DDE, DDD).

The bold values show higher than the permission level (PL) according Neue Niederlandische Liste. Altlasten Spektrum 3/95: total of DDT group is 2.5 ng/g, for g-HCH is 0.05 ng/g.

Rather moderate level of the total DDT concentration (2.50 ng/g) measured at two samples of bottom sediments in June 2000 near the Tendra split of the Ukrainian Coast compared well with the previous data (Table 3.2.3). The same also occurred in the Danube region reflecting its traditional high level of DDT pesticides pollution. In the bottom sediments of the Odessa harbor the pesticides measurements in May and October 2004 showed that the g-HCH content varied from 0.12 to 0.17 ng/g of dry bottom sediments, DDT from 2.91 to 3.24 ng/g, DDE from 0.16 to 0.31 ng/g, and DDD from 0.21 to 0.39 ng/g. The important feature was the predominance of the ?fresh? pollution, and lower level of metabolites than DDT itself.

In the vicinity of Odessa harbor at the depth 24 m, the sediment core was sampled in 6 October 2003 and then split into 10 samples for the analysis of organic contaminants [18]. The most polluted part by pesticides of HCH group was the upper 9 cm. In this thin layer the average concentration of total HCH was 3,59 ng/g (maximum 5,04 ng/g) whereas it was only 0,42 ng/g (max 0,59 ng/g) within the rest of the core. The average value in the whole column of core was 1,69 ng/g. In general the HCH pollution of bottom sediments here was not too high and agreed with the previous data.

An opposite situation was however noted for the DDT group. These pesticides showed extremely high concentration all around the Black sea. The main feature was a ?fresh? character of pollution due to dominance of DDT. In the upper 9 cm its concentration reached the extremely high level of 58000 ng/g. Further below in the sediment core DDT concentration decreased almost 2000 times. The total content of the DDT group attained here 63950 ng/g or 25580 PL according the Neue Niederlandische Liste [7].

During the observation at five stations in 4-19 January 2005, an extremely high concentration of DDT and its metabolites were found in the Odessa harbor (72.83 ng/g). Without this extreme value, the average DDT content was only 3.37 ng/g. At nearby stations (Dnieper and Bug Liman), the DDT concentration was also high, 16.52 ng/g, but about three times lower in the Dniester region to the south. In general, one can note that the concentration of DDT group was relatively low in the Danube region during 2005. In the Sevastopol harbor, the total concentration of DDT was also low.

First extended investigation of bottom sediments pollution by wide spectrum of pesticides in the coastal waters of Romania was done in 1993 by sampling at 15 stations from the Danube Delta to the southern border of Romania [8]. The total concentration of HCH group for 4 stations in the Danube Delta was very high and reached the level of 40.0 ng/g with an average value of 13.15 ng/g. The maximum concentration of 3.02 ng/g was recorded near the port Constanta while the average for the marine stations was 1.48 ng/g only. The lindane (γ-HCH) was widely presented in the bottom sediments, especially in the Danube area. Its averages for Danube and the rest of Romanian coast were 8.63 and 0.65 ng/g, respectively. For α-HCH those numbers were 3.70 and 0.36 ng/g; for β-HCH ? 0.82 and 0.46 ng/g. Pesticides of DDT group were widely presented in the bottom sediments off Romanian coast in 1993 as well. The total content was very high and reached the level 71.63 ng/g and the average for all fifteen stations was 12.73 ng/g. DDD was the second most abundant after DDT. The most polluted region by DDD was the sediments in the Danube delta (the average 16.5 ng/g, and the maximum 43.1 ng/g) followed by the Constanta port (31.5 ng/g). The average DDT concentration in the Danube delta was 7.08 ng/g and maximum ? 20.00 ng/g. The concentration of hexachlorobenzene (HCB) varied from analytical zero to 23.00 ng/g. The most polluted region by HCB was, once again, two stations in the Danube delta and two stations near Constanta. Heptachlor, aldrin, dieldrin and endrin occurred mainly in the port Constanta with rather low concentrations in the range 0.17-0.25 ng/g.

Three sediment cores were sampled in the Danube delta and near the Constanta port in autumn 2003 [18]. The average concentration of HCH for the whole column of bottom sediments was 1.55 ng/g. Among single metabolites, lindane was less abundant. Among the sampling sites, the Danube delta was generally found much more polluted by HCH due to its high lipid content. In the Romanian shelf sediments DDTs concentration was very high with the average total content of 25.67 ng/g and maximum 83.80 ng/g. In particular, the DDT pollution in the Danube delta exceeded 10-folds the Constanta area with the respective average values of 29.48 ng/g and 2.94 ng/g. Among different forms of DDT group the DDD dominated wherever DDT had 20.3% from the total.

In April, June, July and October 2005 the average level of total concentration of pesticides from DDT group in 34 monitoring samples of bottom sediments was 0.047 ng/g. In most samples the concentration was rather low and only much higher at five stations. Its maximum was recorded in July at 5 m depth near Constanta Sud where total DDT reached 1.26 ng/g and consisted of 0.79 ng/g DDT, 0.43 ng/g DDD and 0.045 ng/g DDE. The lower values for metabolites could be a sign of ?fresh? pollution. The maximum of lindane concentration (0.98 ng/g) was recorded in April 2005 at shallow place in the vicinity of Sf. Gheorghe in the Danube Delta. The second highest concentration 0.82 ng/g was also recorded during the same period in the Danube Delta near Buhaz and varied between 0.002 and 0.37 ng/g in other stations. The average for the whole data set was 0.13 ng/g.

In June, 7, 2006 during the international cruise ?Monitoring Survey for the Black Sea ? 2006?, bottom sediments were sampled along a transect at 1, 10, 20 and 30 nm from the city Constanta. The depth at these points was 14, 36, 45 and 53 m. The total concentration of pesticides of DDT group was rather high and varied between 1.29 and 9.87 ng/g. The highest concentrations (8.71 ? 9.87 ng/g) were recorded in the central stations while it was much lower (1.29 ? 1.36 ng/g) near both ends. It could be due to the size spectrum of bottom sediments particles. In the central stations, the percentage of small-size fractions less then 65 ?m was as high as 42-43.4 % while its contribution was only 32 % at other stations. The positive correlation between organic pollutants concentration and increasing the percentage of small particles is well-known.

The Total Organic Carbon (TOC) and Extracted Organic Matter (EOM) contents were also found to be higher at central stations (1.25-1.44 %; 0.110-0.270) with respect to others (0.16-0.61 %; 0.047-0.064 mg/g). Among different forms, the metabolites of DDT took the main role. The average of DDD concentration was 2.82 ng/g, DDE 1.43 ng/g and DDT only 0.46 ng/g. It could be considered as an ?old? pollution by the DDT group. The total HCH concentration in the area near Constanta varied from 0.36 to 2.37 ng/g. As for other pesticides the maximum was recorded in the centre of transect. The mean lindane concentration was only 0.12 ng/g, but β-HCH reached 1.70 ng/g (average 0.77 ng/g) and α-HCH 0.38 ng/g(average 0.17 ng/g). Among other pesticides, the hexachlorobenzene (HCB) occurred in relatively high concentrations up to 0.42 ng/g and the average for four samples was 0.18 ng/g. The others, including cis Chlordane, trans Chlordane, trans-Nonachlor, Heptachlor, Aldrin, Dieldrin, Endrin, Heptachlor epoxide, Methoxychlor, a-Endosulfan, b-Endosulfan and Endosulfan sulfate, all together, did not exceed 0.20-0.22 ng/g. The total concentration of all pesticides in June 2006 was 3.59; 22.77; 22.32 and 3.67 ng/g at four stations at Constanta transect.

No routine monitoring data were available on pesticides concentration in the bottom sediments along Bulgarian coast line. These substances were not included into the national monitoring program. During international cruise ?Assessment of Marine Pollution in the Black Sea Based on the Analysis of Sediment Cores? 24-27 September 2003, three sediment cores were sampled in the vicinity of Bourgas, Varna and Cape Kaliakra at 15 m depth [18]. At all stations the upper 10 cm layer of bottom sediments was found to be most polluted by all types of pesticides, but the pollution level significantly decreased at deeper levels. The average total HCH concentration was measured in the upper layer as 1.27 ng/g and the highest value of 2.12 ng/g was spotted near Bourgas. The pollution level in the vicinity of Varna was comparable to Bourgas, but the Cape Kaliakra site attained significantly lower level of HCH content with an average value of 0.21 ng/g. The different forms of HCH contributed to the pollution at an almost similar rate, but the DDT took 37% of total DDTs. The average DDTs concentration in the Varna core was 8.32 ng/g, in the Bourgas area 1.98 ng/g, and reduced to 0.35 ng/g in the Cape Kaliakra site. Among other pesticides cis-chlordane, trans-nonachlor, heptachlor, aldrin and dieldrin had average concentration 0.01 ng/g, and trans-chlordane was twice higher. Almost all concentration of endrin, α-endosulfan, β-endosulfan and endosulfan sulfate was lower then detection limit (0.001 ng/g).

During international cruise in September 1995 in the Bosporus outlet area, 10 samples were taken at depth range 80-131 m [8]. Among DDT group all metabolites were presented almost in equal proportion. The total values reached 7.21 ng/g and the average was 3.54 ng/g. The concentration of pesticides from HCH group were about ten times lower in the studied area. The average level of total content for the group was 0.30 ng/g. Similar to the total DDT, its different forms were in relatively equal concentrations. No hexachlorobenzene pollution was recorded in bottom sediments. From other pesticides only aldrin (maximum concentration 0.18 ng/g) and dieldrin (maximum concentration 0.077 ng/g) were recorded in all samples. Endrin was found in a few samples but reached the maximum concentration 0.25 ng/g in one sample. Heptachlor occurred in two places with negligible amount.

In 15-19 June 2006 during the international cruise ?Monitoring Survey for the Black Sea ? 2006? in vicinity of Georgian towns and rivers Batumi, Kobuleti, Natanebi, Supsa and Poti the bottom sediments were sampled at depth 60 m [9]. The total HCH average concentration for the all sampled sites was 1.01 ng/g. The ratio between metabolites was 1:2.6:7.4 for γ-HCH, α-HCH and β-HCH, respectively. The maximum and minimum HCHs were recorded near Natanebi and Batumi. Similar to other regions, DDTs concentration along Georgian coast was much higher in comparison with HCH. Maximum DDT total concentration reached 16.55 ng/g (6.6 times of the PL) close to Kobuleti. The ratio of metabolites was approximately 1:3:15 for DDT, DDE and DDD. Other chlorinated hydrocarbons were found at lower quantities: HCB (maximum 0.42 ng/g), cis-chlordane (0.04 ng/g), trans-chlordane (0.09 ng/g), trans-nonachlor (0.003 ng/g), heptachlor (0.02 ng/g), aldrin (0.002 ng/g), dieldrin (0.06 ng/g), endrin (0.04 ng/g), heptachlor epoxide (0.02 ng/g), methoxychlor (0.02 ng/g), α-endosulfan (0.02 ng/g), β-endosulfan (0.05 ng/g), endosulfan sulfate (0.05 ng/g).

Along the Russian coast, five samples of bottom sediments were taken from the depth 8 m inside of port Sochi, and 25-40 m from other sites in the area between cities Sochi and Adler close to Georgian border during the December 1995 cruise. The maximum of total content of HCH group was 0.81 ng/g. Among their metabolites the β-HCH dominated. The concentration of γ-HCH exceeded the permission level (PL) for bottom sediments almost two times [7]. The DDTs were much more abundant in the bottom sediments. Their total concentration reached 12.36 ng/g (4.9 PL). In contrary with HCH, in the metabolites structure the DDT played main role and it can be considered as a ?fresh? pollution.

Table 3.2.4. The concentration (ng/g) of organic pollutants in biota and bottom sediments along the Russian coast in August-September 2003.

2003 Kerch Strait Anapa Novoros

siysk

Gelend

zhik+Blue

Arkhipo-Osipovka Tuapse Lazarev

skaya

Sochi Adler
HCHtotal

0.14

0.05

0

0.37

1.29

0.75

0.81

0.98

0.94

HCHbiota**

3.11

2.10

DDT total

0.86

0.33

1.370

8.73*

5.29*

2.04

4.83*

8.40*

5.82*

DDTbiota

0.75

3.74

Other Pesticides

0.20

0

0

0.10

0.38

0.11

0.31

0.24

0.18

  • The bold value exceeds the permission level (PL) according Neue Niederlandische Liste. Altlasten Spektrum 3/95: Total of DDT group is 2.5 ng/g, for g-HCH is 0.05 ng/g[7].
  • ** biota ? Bivalvia.

Along the Russian coastline, bottom sediment pollution by organic substances was investigated in the shallow waters in June-July 2003. In the Kerch Strait near the island Tuzla, the concentration of HCH in the bottom sediments was under the detection limit (0.05 ng/g of dry material). Slightly to the south at the anchor place near the Cape Panagia, the concentration of α-HCH (0.05 ng/g) and β-HCH (0.09 ng/g) exceeded the detection limit (Table 3.2.4). At the same time all forms of HCH were 10-20 times higher in the body of bottom invertebrates; α-HCH 0.56 ng/g, β-HCH 1.99 ng/g, γ-HCH 0.56 ng/g (maximum). Not all forms of the DDT group existed in bottom sediments at significant values, but 4,4 DDE (0.60 ng/g) and 4,4 DDD (0.45 ng/g) reached rather high concentrations. This type of pesticides was however found only in a minor level in the body of mollusks in this area.

Other types of chlorinated hydrocarbons, namely heptachlor, aldrin, octachlorstyrene, heptachlorepoxide, trans-chlordane, cis-chlordane, trans-nonachlor, cis-nonachlor, photo-mirex and mirex were not recorded in sediments at this time, even if their heavy agricultural use around the Azov Sea. The only hexachlorobenzene was observed in bottom sediments near the island Tuzla with concentration 0.20 ng/g and few times more in the tissue of the benthic animals ? 0.79 ng/g.

Slightly to the south along the coastal line (in shallow waters) at the traverse of the Bugaz Lagoon, β-HCH (0.05 ng/g), 4,4 DDE (0.16 ng/g) and 4,4 DDD (0.09 ng/g) were detected. Near the town Anapa only 4,4 DDE (0.22 ng/g) was found in sediments. In the vicinity of harbor Kabardinka, near Novorossiysk, almost all forms of the group DDT were presented in rather significant quantity ? 2,4 DDE (0.06), 4,4 DDE (0.48), 2,4 DDD (0.24), 4,4 DDD (0.53), 2,4 DDT (0.06 ng/g). Other pesticides were below the detection limit. From two places close to the Gelendzhik Bay and Blue Bay only the latter had a visible content in sediments (α-HCH 0.08 ng/g, β-HCH 0.67 ng/g) and a high level of this group was recorded in the tissues of bottom invertebrates near Gelendzhik Bay: α-HCH 0.57 ng/g, β-HCH 1.44 ng/g, γ-HCH 0.09 ng/g. Again, sediments in the Blue Bay consisted of very high concentrations of DDT group: 2,4 DDE 0.21 ng/g, 4,4 DDE 5.21 ng/g, 2,4 DDD 1.21 ng/g, 4,4 DDD 5.04 ng/g, 2,4 DDT 0.34 ng/g, 4,4 DDT 1.99 ng/g. Maximum total DDT level of 14.00 ng/g was recorded for the whole Russian coast. In the Gelendzhik Bay these pesticides were found approximately at equal levels in bottom sediments and in biota but they were about five times lower than in the Blue Bay. Among other pesticides, only hexachlorobenzene was in relatively significant concentrations in bottom sediments (0.09 ng/g) and biota (0.20 ng/g). A slightly to south along coast in vicinity of the village Arkhipo-Osipovka the content of pesticides in bottom sediments was rather high not only for the groups HCH (α-HCH 0.05 ng/g, β-HCH 1.24 ng/g) and DDT (2,4 DDE 0.09 ng/g, 4,4 DDE 1.60 ng/g, 2,4 DDD 0.58 ng/g, 4,4 DDD 2.64 ng/g, 4,4 DDT 0.39 ng/g), but for also for phenylpolychloride (0.12 ng/g), hexachlorobenzene (0.15 ng/g) and cis-nonachlor (0.11 ng/g).

In shallow waters near the town Tuapse, the concentration of pesticides from the HCH group was not too high, α-HCH 0.08 ng/g, β-HCH 0.67 ng/g. Almost all forms of DDT were marked in bottom sediments with the maximum level 1.85 ng/g for 4,4 DDD. Also minor quantity of phenylpolychloride (0.07 ng/g) and hexachlorobenzene (0.16 ng/g) were found in a single sample. Concentrations of α-HCH (max. 0.14 ng/g) and β-HCH (max. 1.15 ng/g) were not high in the bottom sediments near ?Lazarevskaya?. The DDT group was much higher in 4 samples; the maximum reached 0.08 ng/g for 2,4 DDE, 1.70 ng/g for 4,4 DDE, 1.09 ng/g for 2,4 DDD, 4.40 ng/g for 4,4 DDD, 0.10 ng/g for 2,4 DDT and 0.68 ng/g for 4,4 DDT. The average level exceeded twice the permission level for the bottom sediments. Like in the other parts of the Russian coast, the phenylpolychloride (0.07-0.10 ng/g) and hexachlorobenzene (0.09-0.46 ng/g) were also detected in the samples. For the area around the town Sochi, the concentration of HCH in 5 samples was not high and the variation of the data was very small suggesting a rather uniform spatial distribution in this part of the basin: α-HCH varied from 0.10 to 0.14 ng/g; β-HCH varied from 0.30 to 1.16 ng/g in bottom sediments. Among DDT group, some parts of the area showed abnormally high peaks. For instance, the maximum of 4,4 DDE (3.960 ng/g) and 4,4 DDT (5.100 ng/g) were recorded in the sediments inside of the Sochi harbor. At the same time maximum 4,4 DDD concentration (6.49 ng/g) was recorded in another sample. In general, the DDT was very high in this area and comparable with the Gelendzhik and Blue Bay areas. Among other pesticides the phenylpolychloride (0.07 ng/g) and hexachlorobenzene (0.07-0.71 ng/g) were found at quantities above the detection limit. The part of the area bordering Georgia often considered as highly polluted due to high discharge from the river Mzumta. Nevertheless, the concentration of pesticides was not too high. The content of α-HCH (0.18-0.24 ng/g) and β-HCH (0.58-0.85 ng/g) was similar to other parts of this area. The same also applies for the DDT metabolites with the exception of 4,4 DDD showing a maximum 5.81 ng/g, and consequently total DDT content reached 10.28 ng/g. The hexachlorobenzene was presented in all 4 samples (0.05-0.16 ng/g, average level 0.09 ng/g); phenylpolychloride - only in two (0.17-0.19 ng/g).

The pesticides content in bottom sediments along Russian coast had several main features during August-September 2003. The concentration of g-HCH (lindane) never reached the detection limit in sediments, but this pesticide were found at large quantities in bodies of bottom invertebrates. The other isomers of HCH were widely distributed but never occurred at high quantities; maximum was less 2.00 ng/g. The DDT pesticides occurred more often at high concentration especially in the south. The maximum reached 14.00 ng/g and was beyond the permission level about 3.6 times. The average values for DDT and its metabolites (DDT 1.10 ng/g, DDE 3.07 ng/g and DDD 1.29 ng/g) clearly showed the dominance of metabolites over DDT that suggested an old pollution. Among others pesticides, only hexachlorobenzene and phenylpolychloride were generally observed in minor quantities, and cis-nonachlor and cis-chlordane were detected in bottom sediments only once.

In August and October 2004 the study of bottom sediment pollution was performed along the entire Russian coasts. In comparison with the similar investigations in 2004, a significant increase in the level of pesticides pollution was recorded in bottom sediments of the Novorossiysk, Tuapse and Sochi harbors. The maximum concentration of g-HCH and total DDT reached 0,50 ng/g (9,8 PL) and 155 ng/g (61,9 PL), respectively.

Summary: Among the chlorinated pesticides, the HCHs and DDTs were most important pollutant in bottom sediments of the Black Sea during the last several decades. They both belong to the group of very dangerous chemical substances and their consumption was prohibited long time ago in the Black Sea basin. Nevertheless, their huge amount stored in the agricultural fields or old dilapidated storage places in the past are still the source of pollution today. In the absence of the quality standards for sediment pollution in the Black Sea riparian countries, the Netherlands Permission Levels (PL) for pollutants in the sediments [7] are used as the guidelines of the pollution levels in the Black Sea sediments. The permission level is 0.05 ng/g for lindane and 2.5 ng/g for DDTs total. Based on the Russian standards for the level of Extremely High Pollution (EHP) that is "5 times higher than the level of Maximum Allowed Concentration?, the EHP levels are considered to be 0.25 ng/g for γ-HCH and 12.5 ng/g for DDTs total.

HCH pollution. Maximum lindane concentration exceeded the EHP level practically in all measurements performed during the last 13 years (Fig. 3.2.1). Each country had specific hot spots with very high lindane concentration in sediments due to fresh lindane discharges into the sea. The highest values of 4.5 ng/gin Ukrainian shelf in 1992 and 29.0 ng/g in Romanian coastal area in 1993 were never repeated again despite that highly polluted lindane patches exceeding the EHP level were recorded in Romania (the Danube Delta and port Constanta in 2003, the Danube Delta in 2005), Bulgaria (Varna and Bourgas Bays in 2003), Turkey (Bosporus Outlet in 1995), Russia (Kerch Strait in 2003, Novorossiysk harbor and estuary river Sochi in 2004), and Ukraine (the Danube Delta and Odessa Bay in1995, Odessa Bay in 2003). Maximum concentrations of HCH metabolites were usually comparable with lindane (Table 3.2.5).

Fig. 3.2.1. The maximum concentration of γ-HCH (ng/g) in the different regions of the Black Sea (the maximums 4.5 ng/gin Ukrainian waters 1992 and 29.0 ng/gin Romanian water 1993 are not presented in the figure). The duplication of some years means different seasons of expeditions.

The average γ-HCH concentration was about two-fold lower than its extremes, nevertheless many average data exceed the PL (Fig. 3.2.2 and Table 3.2.6). Based on a rather sparse data set, it is difficult to assess the long-term trend of γ-HCH concentration in sediments of the basin. Taking into account the historical data, it is appropriate to set EHP = 0.25 ng/g as a measure of extremely high local pollution of γ-HCH.


Table 3.2.5. Maximum and mean concentration of pesticides (ng/g), and number of measurements (in parentheses) in the bottom sediments of the Black Sea in 1993 ? 2006.

Project Year Region γ-HCH α-HCH β-HCH HCH

total

DDT DDE DDD DDT

total

HCB* Depth range
Monitoring

[2]

1992-1999

Ukraine

4.5/0.38 (182)

-

-

-

54.2/2.38

(182)

54.3/2.65

(182)

48.8/3.08

(182)

-

-

-

Screening

[8]

1995

Ukraine,

NW Shelf

0.55/0.33

(4)

1.10/0.74

(4)

0.90/0.63

(4)

2.25/1.69

(4)

20.00/11.74

(4)

4.47/2.56

(4)

40.50/23.68

(4)

65.0/38.0

(4)

1.30/0.54

(4)

3-17 m

Screening

[8]

1995

Ukraine,

Crimea

0.027/0.016 (6)

0.048/0.015 (6)

0.14/0.038

(6)

0.19/0.07

(6)

0.002/0.01

(6)

0.28/0.13

(6)

0.38/0.18

(6)

0.59/0.31 (6)

0.024/0.01

(6)

6-78 m

Monitoring

2000

Ukraine

-

-

-

-

-

-

-

19.6/11.0

(2)

-

18-23 m

Screening [18]

2003

Ukraine

(0-9 cm)

0.82/0.55

(4)

0.56/0.43

(4)

3.90/2.60

(4)

5.04/3.59

(4)

58000/16224

(4)

2840/815

(4)

3110/1155

(4)

63950/

18194

(4)

0.42/0.34

(4)

24.0

Screening [18]

2003

Ukraine

(9-36 cm)

0.48/0.31

(6)

0.09/0.06

(6)

0.08/0.05

(6)

0.59/0.42

(6)

29.60/8.58

(6)

5.20/1.55

(6)

6.90/2.77

(6)

41.7/12.9

(6)

0.33/0.20

(6)

24.0

Monitoring

2004

Ukraine, Odessa

0.17/-

(-)

-

-

-

3.24/-

(-)

0.31/-

(-)

0.39/-

(-)

-

-

-

Monitoring

2005

Ukraine

-

-

-

-

-

-

-

72.8/12.4

(10)

-

2-23 m

Screening

[8]

1993

Romania

29.00/2.78

(15)

8.60/1.25

(15)

2.40/0.56

(15)

40.00/4.59

(15)

20.00/2.43

(15)

8.53/2.28

(15)

43.1/8.02

(15)

71.6/12.7

(15)

23.00/2.28

(15)

-

Screening [18]

2003

Romania

0.94/0.37

(27)

2.10/0.50

(27)

2.00/0.71

(27)

5.04/1.55

(27)

41.20/5.20

(27)

7.00/2.61

(27)

57.00/17.86

(27)

83.80/25.67

(27)

22.00/1.87

(27)

14-18 m

Monitoring

2005

Romania

0.98/0.13

(34)

-

-

-

0.79/0.03

(34)

0.05/0.004

(34)

0.43/0.014

(34)

1.26/0.047

(34)

-

0-20 m

Screening [9]

2006

Romania

0.24/0.12

(4)

0.38/0.17

(4)

1.70/0.77

(4)

2.37/1.08

(4)

0.89/0.46

(4)

2.78/1.42

(4)

5.10/2.82

(4)

9.87/5.31

(4)

0.42/0.18

(4)

14-53 m

Screening [18]

2003

Bulgaria

0.81/0.23

(28)

0.42/0.18

(28)

0.90/0.32

(28)

2.12/0.74

(28)

5.23/1.08

(28)

3.9/1.24

(28)

7.0/1.87

(28)

14.0/4.18

(28)

10.00/0.94

(28)

15.0-15.8 m

Screening

[8]

1995

Turkey

0.79/0.14

(10)

0.21/0.09

(10)

0.22/0.07

(10)

1.10/0.30

(10)

1.54/1.15

(4)

2.85/1.49

(7)

4.32/2.03

(10)

7.21/3.54

(10)

0.25/0.09

(10)

80-131 m

Screening [9]

2006

Georgia

0.13/0.09

(5)

0.41/0.23

(5)

1.10/0.67

(5)

1.63/1.01

(5)

0.89/0.41

(5)

2.78/1.10

(5)

13.3/3.35

(5)

16.55/5.4

(5)

0.42/0.17

(5)

60 m

Screening

[8]

1995

Russia, Sochi

0.09/0.05

(5)

0.19/0.15

(5)

0.56/0.36

(5)

0.81/0.57

(5)

8.69/3.43

(5)

2.74/1.60

(5)

5.56/2.86

(5)

12.36/7.8

(9)

(5)

0.26/0.08

(5)

8-40 m

Aero-Visual Monitoring

2003

Russia**

0.56/0.03

(25)

0.57/0.13/25

1.99/0.68

(25)

3.11/0.83

(25)

5.73/0.71

(25)

5.42/1.25

(25)

7.88/2.82

(25)

14.0/4.78

(25)

1.26/0.20

(25)

6-100 m

Aero-Visual Monitoring

2004

August

Russia

0.41/0.04

(22)

1.07/0.20

(22)

1.57/0.64

(22)

3.06/0.88

(22)

25.87/4.84

(22)

10.97/2.98

(22)

72.79/9.53

(22)

89.0/17.34

(22)

1.30/0.43

(22)

6-68 m

Aero-Visual Monitoring

2004

October

Russia

0.49/0.07

(12)

0.44/0.15

(12)

0.89/0.40

(12)

1.63/0.63

(12)

28.43/11.89

(12)

40.24/9.38

(12)

120.13/28.9

(12)

154.7/50.17

(12)

0.89/0.30

(12)

5-25 m

Aero-Visual Monitoring

2005

July

Russia

0.11/0.04

(8)

0.32/0.15

(8)

0.69/0.41

(8)

0.86/0.59

(8)

2.07/0.82

(8)

7.20/3.24

(8)

8.82/3.96

(8)

18.09/8.01

(8)

0.50/0.25

(8)

9-52 m

HCB* - hexachlorobenzene

Russia** - averaged for all Russian coastal waters in 2003.

Table. 3.2.6. The repetitions of high γ-HCH concentration in the bottom sediments exceeds the PL 0.05 ng/g in the different sets of samples (in per cent).

Project Year Region Max γ-HCH (ng/g) Average γ-HCH (ng/g) γ-HCH > PL 0.05 ng/g(%)
Screening

1995

Ukraine, NW Shelf

0.55

0.33

100

Screening

1995

Ukraine, Crimea

0.027

0.016

0

Screening

2003

Ukraine (0-9 cm)

0.82

0.55

100

Screening

2003

Ukraine (9-36 cm)

0.48

0.31

100

Screening

1993

Romania

29.0

2.78

100

Screening

2003

Romania

0.94

0.37

100

Monitoring

2005

Romania

0.98

0.13

41.1

Screening

2006

Romania

0.24

0.12

75

Screening

2003

Bulgaria

0.81

0.23

100

Screening

1995

Turkey

0.79

0.14

50

Screening

2006

Georgia

0.13

0.09

80

Screening

1995

Russia, Sochi

0.09

0.05

50

Monitoring

2003

Russia

0.56

0.03

4

Monitoring

2004

Russia, Southern

0.41

0.04

22.7

Monitoring

2004

Russia, Northern

0.49

0.07

50

Monitoring

2005

Russia

0.11

0.04

50

DDT pollution. Similar to the HCH group, maximum concentration of the DDTs group in sediments exceeded the EHP level of 12.5 ng/g practically at all regions of the Black Sea (Fig. 3.2.3). Enormously high pollution (63950 ng/g) in the Odessa area in 2003 can only be explained as an accidental event. Nevertheless, other sites in coastal zones around the Black Sea were also highly polluted by DDTs. Those ?hot spots? are - Danube Delta, Odessa Bay and Illichevsk port (1995), Danube River mouth (2000), Odessa Bay (2003), Odessa and Uzhnui ports, Dniepr and South Bug Mouth (2005) in Ukraine; the Danube Delta, port Constanta and Sinoe (1993), Sf.Gheorghe and Sulina (2003) in Romania; ? Varna (2003) in Bulgaria; Kobuleti (2006) in Georgia; Sochi port and Adler Canyon (1995), Sochi harbour, Sochi river estuary, Tuapse river estuary, Loo village, Blue Bight (Gelendzhik), Novorossiysk harbor (2003) in Russia (Fig. 3.2.4).

Fig. 3.2.2. The repetition factor of exceeding of PL by average concentration of γ-HCH (ng/g) in the bottom sediments of different regions of the Black Sea. The outstanding 2.78 ng/gin Romania 1993 is not presented in the figure. The duplication of some years means different seasons of expeditions. The Permission Level is 0.05 ng/g.

Fig. 3.2.3. The maximum concentration of pesticides DDTs group (ng/g) in the bottom sediments of different regions of the Black Sea (the maximum 63950 ng/gin Ukrainian waters 2003 is not presented in the figure). The duplication of some years means different seasons of expeditions. Total number of analyzed bottom sediments samples is 217.

Table. 3.2.7. The repetitions of high DDTs concentration in the bottom sediments exceeds the PL 2.5 ng/g in the different sets of samples (in per cent).

Project Year Region Max DDTs (ng/g) Average DDTs (ng/g) DDTs > PL 2.5 ng/g(%)
Screening

1995

Ukraine, NW Shelf

64.97

37.97

100

Screening

1995

Ukraine, Crimea

0.59

0.31

0

Monitoring

2000

Ukraine

19.57

11.03

100

Screening

2003

Ukraine (0-9 cm)

63950

18194

100

Screening

2003

Ukraine (9-36 cm)

41.7

12.9

83.3

Monitoring

2005

Ukraine

72.83

12.40

40

Screening

1993

Romania

71.63

12.73

100

Screening

2003

Romania

83.8

25.67

77.8

Monitoring

2005

Romania

1.26

0.05

0

Screening

2006

Romania

9.87

5.31

50

Screening

2003

Bulgaria

14.03

4.18

46.4

Screening

1995

Turkey

7.21

3.54

70

Screening

2006

Georgia

16.55

5.37

60

Screening

1995

Russia, Sochi

12.36

7.89

100

Monitoring

2003

Russia

14.03

4.18

64.0

Monitoring

2004

Russia, Southern

89.0

17.34

81.8

Monitoring

2004

Russia, Northern

154.71

50.17

83.8

Monitoring

2005

Russia

18.09

8.01

87.5

High level of pollution by pesticides from DDTs group in bottom sediments are also clearly evident in the data set consisting of 222 samples since 1995. Almost all samples collected in the coastal zone around the Black Sea showed total concentration of pesticides of DDT group higher than 50% of the Permission Level. The relatively low concentrations in sediments around the Crimea peninsula should be related to their low level discharges from local rivers into the sea, even though the usage of pesticides in grape and wine manufacturing is common in the region. Along the Russian coast with highly developed wine industry (e.g. Gelendzhik region), the pollution by DDTs pesticides in general much higher. When the entire data set was taken into account, 61.3% of samples contained the DDTs concentration comparable with its PL level of 2.5 ng/g (Table 3.2.7).

As a conclusion, practically the entire coastal waters around the sea contained a very high level of DDTs pollution in bottom sediments without any clear indication of reduction in such highly dangerous anthropogenic pollution.

Other pesticides were close to their detection limits for all costal zones of the Black Sea, except rather high concentrations of hexachlorobenzene in sediments along the Romanian and Bulgarian coasts (Table 3.2.7). It could be clear the absence of worries concerning different marked in the bottom sediments usually. The content of these modern chlorinated pesticides in the Black Sea therefore contradicted with high concentration of lindane and DDT.


3.3. The State Of Trace Metals

Alexander Korshenko

State Oceanographic Institute, Moscow, RUSSIA

Yury Denga

Ukrainian Scientific Centre of the Ecology of Sea, Odessa, UKRAINE

B.Gvakharia and Nino Machitadze

?Gamma?, Tbilisi, GEORGIA

Andra Oros

National Institute for Marine Research and Development, Constanta, ROMANIA

3.3.1. Ukrainian sector of the Black Sea - Northwestern region

Water: The most recent trace metals measurements in Ukrainian coastal waters were performed within the framework of the marine ecological monitoring programme in December 2004-January 2005. These measurements clearly indicated a low level trace metal pollution in coastal waters. The trace metal contents at all measurement sites were typically one or two order of magnitude below the Maximum Allowed Concentration (MAC) accepted for Ukrainian waters (Table 3.3.1).

According to the earlier measurements conducted during 1995-2000, trace metal concentrations in different marine waters of the northwestern Black Sea were also found to be rather low. These concentrations represented the sum of the dissolved and suspended forms due to the conservation of samples aboard by nitric acid. A summary of the trace metal levels are provided below.

Cadmium: The contamination of marine waters by cadmium could be evaluated as insignificant since its concentration was persistently 30-50 times lower than the MAC value in all investigated regions, except the dredged materials dumping site close to Odessa where maximum cadmium concentration near the bottom reached 0,56 ?g/l in 1999 (Fig. 3.3.1).

Mercury: Like cadmium, mercury concentration did not exceed 0.1 MAC (Fig. 3.3.2) except the damping sites where it was roughly 0.2 MAC.

Lead: Maximum lead concentration of 17.0 ?g/l exceeded 1 MAC level by 1.7 times only at the Waste Waters Treatment Plant (WWTP) site of the town Illiechevsk in 2000 (Fig. 3.3.3). In other regions of the Black Sea, concentration in marine waters varied mainly in the range 0.5-2.0 ?g/l with slightly higher values in the Danube discharge region (3.1 ?g/l) and Dnieper- South Bug lagoon (5.2 ?g/l).

Table 3.3.1. The trace metals concentration (?g/l) in Ukrainian waters of the Black Sea in December 2004 - January 2005 (25th cruise of R/V ?Vladimir Parshin?).

No of station Areas Hg Cd Co Cu Pb Zn As Fe

MAC (?g/l)

0,1

10

5

5

10

50

10

50

1

External raid of Odessa port

0,012

0,06

<0,5

3,0

5,8

11,3

1,8

<50

3

Waste waters discharge ?North? in Odessa

0,012

0,09

<0,5

1,0

9,3

7,1

1,6

<50

4

Mouth of port Yuzhny in Odessa Bay

<0,010 <0,05 <0,5 1,8 1,7 2,0 2,0 <50
6

Mouth of Dnieper -Bug lagoon

<0,010 <0,05 <0,5 2,0 1,9 5,8 1,2 <50
8

Odessa shallows

<0,010 <0,05 <0,5 0,6 2,5 3,5 1,5 <50
10

Odessa shallows

<0,010 <0,05 <0,5 0,9 <1,0 2,1 1,6 <50
11

Place of damping

<0,010 <0,05 <0,5 0,4 <1,0 1,4 2,0 <50
12

Waste waters discharge ?Sourth? in Odessa

0,011 0,08 <0,5 2,0 <1,0 2,8 1,4 <50
13

Mouth of port Illiechevsk in Odessa Bay

<0,010 0,08 <0,5 0,7 <1,0 0,5 1,9 <50
14

Place of damping

<0,010 0,15 <0,5 2,1 1,7 3,8 2,2 <50
15

Mouth of Dniestr lagoon

<0,010 <0,05 <0,5 0,7 <1,0 7,4 1,2 <50
24

Centre of Northern-Western shelf

<0,010 0,07 <0,5 2,3 <1,0 2,1 <1,0 <50
30

Mouth of Danube (north)

<0,010 <0,05 <0,5 1,7 1,2 4,9 1,4 <50
56

Cup Tarkhankut in Crimea

<0,010 0,06 <0,5 0,7 <1,0 5,4 2,0 <50
60

Yalta

<0,010 <0,05 <0,5 0,3 <1,0 1,7 <1,0 <50
73

Kerch Strait (centre)

<0,010 <0,05 <0,5 0,7 <1,0 2,5 1,2 <50
75

Kerch Strait (exit)

<0,010 <0,05 <0,5 1,3 <1,0 4,1 1,4 <50

Zinc: Concentration of zinc higher then 1 MAC was observed in the dumping area (145 ?g/l) and the Illiechevsk WWTP site, where the maximum concentration (823 ?g/l, more than16 MAC) was measured in 2000 (Fig. 3.3.4). In comparison with other areas, zinc concentration attained slightly higher values of 20 ?g/l and 30 ?g/l in the Danube and Dniepr estuaries, respectively.

Copper: In four of the total 11 measurement sites, copper concentration in marine water was higher then 1 MAC. These sites are as follows: near Odessa WWTP ?South? (1.4 MAC), damping site (1.6 MAC), Dnieper and Bug estuarine zone (5.0 MAC) and the Illiechevsk WWTP (30 MAC) (Fig. 3.3.5).

Arsenic: Concentration of this metal in marine waters was insignificant and did not exceed 1 MAC. In comparison with other places, the arsenic content was slightly higher in the Danube estuarine waters and in Karkinitsky Gulf (Fig. 3.3.6).

Chromium. Chromium concentration was below 1 MAC level at all measurement sites with the highest concentration of 2.8 ?g/l in the Danube discharge area and 1.0 ?g/l in the Odessa damping site and the WWTP ?South? site (Fig. 3.3.7).

In summary, higher metal concentrations were observed mostly in coastal areas with clear anthropogenic influence from the main land-base sources. They were, however, lower than the MAC levels. In the open areas of the Black Sea, they were close to their natural background values.

Bottom Sediments: The current data on metals concentration in the bottom sediments in the Ukrainian coastal zone of the northwestern Black Sea were obtained during the R/V ?Vladimir Parshin? cruise in December 2004-January 2005. In contradiction with marine waters, bottom sediments often showed a rather high level metal pollution with maximum concentrations measured in the Danube discharge region (Table 3.3.2). Even though mercury content, known to be the most toxic metal, never exceeded the Permission Level (PL), it increased significantly close to the Odessa port, the vicinity of Danube estuarine zone, and the Crimean cities Sevastopol and Alushta. Cadmium concentration varied in the range from 0.1 PL to 0.7 PL measured in the Danube discharge region. A similar distribution was also noted for cobalt where data from different sites varied between 3.1 and 12.1 ?g/g (0.2-0.6 PL).

On the contrary, copper concentration in bottom sediments, in general, was high and exceeded the PL in 8 cases; close to the Odessa port (82 μg/g), the dumping site, the Danube discharge area, and the vicinity of Crimean towns Sevastopol, Balaklava, Yalta and Alushta. The average for the Ukrainian shelf was 26.36 μg/g. Lead concentration varied in the range of 5.2-46.2 μg/g, and the average was 20.92 μg/g. This level was significantly less than the threshold. Zinc concentration exceeded the PL more than twice in the dumping place and only slightly in the Danube estuarine region. The North-Western shelf was not found to be polluted by arsenic. Its content was high only near Crimea and in the Kerch Strait. Pollution of bottom sediments by chromium exceeded the PL at several sites. Maximum level of metal pollution was noted for nickel. Its content varied from 7.0 up to71.7 μg/g with an average value of 31.06 μg/g. Its concentration therefore was higher than its PL in 16 cases from 39 samples (41%).

Table 3.2. The trace metals concentration (?g/g) in the bottom sediments of Ukrainian part of the Black Sea in December 2004 - January 2005 (25 cruise of R/V ?Vladimir Parshin?).

N of station Areas Hg Cd Co Cu Pb Zn As Cr Ni Al*

PL (?g/g) [7]

0.3

0.8

20

35

85

140

29

100

35

n.a

1

External raid of Odessa port

0.150

0.49

7.3

81.9

26.2

117

9.00

164

27.0

28900

3

Waste waters discharge ?North? in Odessa

0.037

0.20

3.1

6.30

5.20

38.0

6.20

12.4

7.0

5640

4

Mouth of port Yuzhny in Odessa Bay

0.034 0.41 8.1 34.8 25.4 97.6 11.4 63.8

43.6

30300
6

Mouth of Dnieper - Bug lagoon

0.034 0.35 4.7 19.8 12.1 61.7 5.70 40.0

9.2

21600
8

Odessa shallows

0.038 0.42 6.5 31.2 30.3 78.1 1.5 67.4

35.4

27300
10

Odessa shallows

0.50 5.3 27.9 18.9 59.9 6.50 71.6

15.7

30600
11

Place of damping

0.020 0.25 8.2 19.7 16.5 64.1 7.30 72.6

17.7

38900
12

Waste waters discharge ?Sourth? in Odessa

0.098 0.38 7.2 31.8 24.8 97.3 6.00 89.5

28.0

27600
13

Mouth of port Illiechevsk in Odessa Bay

0.056 0.34 6.4 28.8 22.3 88.8 14.4 135

37.8

28200
14

Place of damping

0.063 0.39 7.5 39.7 29.7 302 10.2 71.8

29.5

33500
15

Mouth of Dniestr lagoon

0.021 0.12 3.1 4.60 8.00 29.7 2.80 32.0

10.6

12600
24

Centre of Northern-Western shelf

0.020 0.10 3.0 8.87 9.87 22.0 3.4 13.4

20.1

6540
29

Mouth of Sasyuk lake

0.094 0.28 6.7 30.8 29.1 92.7 15.7 69.2

36.9

30600
30

Mouth of Danube (north)

0.067 0.17 4.7 9.60 10.8 34.8 2.60 26.6

16.0

18800
34

Mouth of Danube (north)

0.250 0.52 9.6 54.2 37.3 144 10.4 108

60.6

45600
35

Mouth of Danube (south)

0.283 0.58 10.6 71.6 46.2 177 16.1 120

71.7

53000
39

Mouth of Danube (east)

0.048 0.15 6.1 16.2 18.1 51.6 9.00 46.7

21.0

23900
40

Mouth of Danube (east)

0.025 0.09 3.1 8.48 9.10 24.5 6.40 22.0

14.2

16600
41

Mouth of Danube (east)

0.042 0.10 3.9 11.1 11.7 30.8 6.20 24.6

14.8

15400
42

Mouth of Danube (east)

0.041 0.16 3.2 12.2 11.3 26.6 5.30 18.1

11.7

12200
43

Mouth of Danube (east)

0.058 0.14 5.4 15.1 13.0 46.8 7.80 38.2

23.4

19700
44

Mouth of Danube (east)

0.049 0.21 7.4 24.6 18.8 67.8 12.2 68.8

34.6

29800
45

Mouth of Danube (east)

0.064 0.20 5.5 18.3 18.1 56.4 12.2 41.8

19.7

23300
46

Mouth of Danube (east)

0.142 0.37 9.2 35.4 44.2 115 20.4 88.2

47.7

30000
47

Mouth of Danube (east)

0.042 0.18 5.4 20.4 13.2 58.6 13.1 45.9

33.5

18500
49

Mouth of Danube (east)

0.038 0.16 5.3 16.9 6.10 35.5 10.1 20.2

22.2

9460
54

Karkinitskiy Gulf

0.020 0.16 3.3 12.3 17.5 44.2 6.40 52.3

44.5

26800
56

Cup Tarkhankut in Crimea

0.030 0.16 5.8 30.2 28.1 76.9 5.30 53.1

30.1

31400
57

Mouth of port Sevastopol

0.136 0.24 8.1 39.7 24.1 97.0 25.2 77.5

42.1

53400
58

Mouth of port Balaklava

0.085 0.20 7.8 38.6 32.0 101 24.0 81.5

41.1

50800
60

Yalta

0.072 0.17 9.2 37.6 27.4 110 13.9 86.0

55.3

35000
61

Alushta

0.205 0.14 10.5 35.6 32.0 120 31.5 106

46.2

62200
62

Feodosia

0.075 0.20 9.1 34.7 24.0 108 14.8 94.1

45.4

50200
69

Kerch Strait (centre)

0.019 0.13 6.5 8.60 14.6 61.6 6.40 81.0

14.5

25600
70

Kerch Strait (centre)

0.020 0.08 6.0 4.70 11.4 42.1 10.5 81.6

17.0

25600
71

Kerch Strait (centre)

0.028 0.09 6.0 6.80 10.2 53.5 45.2 49.3

15.2

17900
73

Kerch Strait (centre)

0.086 0.22 11.9 31.9 25.2 113 15.6 97.2 51.5

53200
74

Kerch Strait (centre)

0.060 0.27 12.1 33.7 26.2 120 22.2 108

48.7

64400
75

Kerch Strait (exit)

0.059 0.32 10.8 33.5 27.0 118 10.6 106

50.3

51200

* - Aluminum used only as indicator of fine fraction of bottom sediments

n.a ? not available

Trace metal concentrations in bottom sediments of the Phyllophora field occupying the central part of the northwestern shelf was monitored during July-August 2007 (26th cruise of R/V ?Vladimir Parshin?). This data set indicated low level of mercury, cadmium, lead, arsenic and chromium pollution (Table 3.3.3). Nickel concentration exceeded the PL in 75% of the samples and reached the maximum 92.1 ?g/g. Copper concentration was also above PL in 50% of the samples but the level of pollution wasn?t too high. Cobalt and arsenic in bottom sediments were detected in moderate levels, mostly below the PL.

In general for the Ukrainian coastal zone not too much cases of high pollution of bottom sediments were noted during last 10 years. The copper and chromium pollutions were wide spread over the NWS (Fig. 3.3.8a,b). High chromium concentration was also found along the Crimea coast. Over the last decade the tendency of decreasing of maximum mercury and cadmium concentration in the Danube region were noted. No appreciable level of lead pollution was registered in bottom sediments.

3.3.2. Russian sector of the Black Sea - Northeastern region

Bottom Sediments: Metal concentration measurements in bottom sediments performed in June-July 2002 to the south of Taman showed large variations irrespective of sampling depths at 20m, 40m, 70m, and 100m (Table 3.3.4). Minimum concentrations of aluminum, vanadium, chromium, manganese, nickel, copper and arsenic were measured at 40 m depth. The opposite case occurred at 70 m depth where these elements attained maximum values, except manganese. Lead concentration increased to nearly 7.6 μg/g along the shore at 20m depth. The cadmium was below the detection limit at all sites.

Table 3.3.3 The trace metal concentration (?g/g) in the bottom sediments of Phyllophora field and NW Shelf of the Black Sea in July-August 2007 (26 cruise of R/V ?Vladimir Parshin?).

Hg Cd Co Cu Pb Zn As Cr Ni
PL (?g/g) [7]
Number of stations Depth m 0.3 0.8 20 35 85 140 29 100 35
2 32 <0.001 0.02 0.92 1.60 3.60 5.3 0.98 4.30 7.5
39 0.043 0.30 8.13 34.8 28.9 73.7 6.90 41.4 46.2
45 0.039 0.33 12.2 44.0 37.0 96.2 8.00 55.1 55.9
75 0.020 0.17 4.90 12.7 10.2 35.3 4.00 13.1 24.2
84 44 0.023 0.29 7.92 27.5 19.4 57.2 5.90 25.2 41.6
142 39 0.033 0.31 11.2 27.4 19.9 80.3 8.80 32.3 49.0
157 39 0.032 0.27 10.4 22.6 26.2 66.2 5.30 29.2 35.4
177 0.088 0.31 11.0 37.3 37.4 166 8.00 53.3 67.7
221 50 0.080 0.29 22.8 46.9 32.1 99.2 22.1 46.7 92.1
234 66 0.028 0.22 15.6 38.7 38.2 104 17.6 52.4 62.3
246 32 0.127 0.46 17.4 38.0 18.6 95.7 9.70 52.8 71.2
262 1000 0.095 0.50 14.6 38.2 20.7 70.7 9.80 58.2 54.4

Table 3.3.4 Metal concentration (μg/g) in bottom sediments measured during June-July 2002 to the south of Taman.

Depth, m Al V Cr Mn Ni Cu Zn As Cd Pb
20

2184

128,4

47

661

28,6

53

31,06

7,25

0

7,6

40

876

54

27

163,5

5,5

38

30,08

2,02

0

4,3

70

3206

293

64

377,5

44

92

56,28

4,47

0

0,6

100

1488

115,2

42

255

32,2

79

25,61

5,35

0

5,0

3.3.3. Georgian sector of the Black Sea - Southeastern region

Bottom Sediments: Concentrations of Fe, Mn, Cu, Zn, Cr, V, Ni, Pb, Mo were measured in 186 samples of bottom sediments during 1993-1995 at shallow areas (3-15 m depth range) of the Georgian shelf.? Additional trace metal measurements (Fe, Al, Cu, Zn, Cr, As, Ba and Pb) were performed in 2000 [19, 23, 24, 25]. 170 samples from 75 stations of the sea were collected throughout the entire Georgian shelf covering the depth range from 10 to 1500 m. A summary of these measurements is provided in Table 3.3.5.

Table 3.3.5. The metals concentration (μg/g) in the bottom sediments of Georgian shelf in 1993-1995 and 2000.

Cr Mn Cu Zn As Pb

1993-1995

min/max

10/1300

700/9300

40/900

60/300

-

7,0-48

Average

215

1937

50

136

-

17,7

2000

min/max

40/700

-

20/325

60/260

5,0/95

7-50

Average

81

-

81

102

15

20

Copper and Zink: High concentrations of Cu (325 μg/g) and Zn (260 μg/g) were found in bottom sediments collected from shallower depths near the estuary of Chorokhi River in response to the wastes discharged from mining enterprises in Murgul and Artvin regions of Turkey, in the immediate proximity of the boundary with Georgia and from Meria (Adjaria) within the Georgian sector. They however decreased to the north. In sediments of the underwater slope of Kolheti lowland, Cu and Zn were distributed evenly at their background levels ranging from 20 to 45 (the average: 30 μg/g) for Cu and from 62 to 170 (the average: 110 μg/g) for Zn.

Arsenic: The distribution of arsenic in the shallow bottom sediments within Adjara section of underwater slope was analogous with distribution of Cu and Zn. Arsenic was introduced as a part of the sulphide minerals discharged into the sea together with other chalcophilic elements from the mining regions of Georgia and Turkey.

Chromium: This metal was distributed unevenly in bottom sediments. It mainly accumulated in sediments of the Chakvistskali-Supsa inter-mouth region with maximum concentrations 700 μg/g in the estuarine regions of the Chakvistskali and Natanebi Rivers. The main carriers of chromium are dark minerals (magnetite, biotite, pyroxene), the rock-forming minerals of the volcanic ores of basic composition (basalts, andesites, porphyrites, tuffs, tuff breccias, etc.) by the small rivers of the region (Korolistskali, Chakvistskali, Choloki, Natanebi, Supsa) [20]. In contrast to the copper and zinc, accumulation of chromium is natural, since it is not connected with any anthropogenic action. The difference between 1995 and 2000 was mainly related to the difference in sampling depths.

Lead: Lead was distributed evenly throughout the Georgian shelf. The maximum concentration did not exceed 50 μg/g, minimum was 7 μg/g, and the average for all Georgian shelf was 18 μg/g that corresponded to the local background level. Situation has not changed since mid-1990s.

Barium: High content of barium in bottom sediments was mainly confined into coastal zone of the Georgian shelf. The maximum concentration (in the limits of 0.1-0.2%) was found in the region between the Chorokhi River mouth to Batumi. Its distribution was related to the products of weathering of the barites- polymetallic layers of the South Caucasus, transported to the sea by the Chorokhi River. Accumulation of barium was also observed in the estuary sediments of Kintrishi River (0.05-0.1%). In coastal regions of the West Georgia, metamorphic geological formations containing clay minerals (in particular zeolites), rich in barium, were found. Possibly, that terrigenous material was enriched by above mentioned minerals, which explains comparatively high content of barium along the coast.

Aluminium: Being one of the basic rock-forming elements, aluminium constituted 2% to 7.5% of sediments of the Georgian shelf which are found at higher proportions in the area of Kolkheti lowland. On the average, in the northern part of the Georgian shelf, aluminium content was 3-4% higher than in south because of gradually increase of clay fractions in sediments in the northwards direction.

Iron: Coastal region of the shelf located in the inter-mouths of Korolistskali, Chakvistskali, Kintrishi, Natanebi and Supsa Rivers was characterized by high content of iron (>11%). These rivers drain the western extremity of Adjara-Trialeti folded system and carry the products of red sol crust weathering into the sea. High content of iron is related with the dark minerals (magnetite, black mica, etc.) [21, 22]. In this region, high content of iron coincided with high content of chromium, which pointed to their common source. Within the limits of Kolkheti lowland, iron content varied from 3% to 5% in sediments of the underwater slope.

Manganese: In sediments from Chorokhi River estuary to the town Kolkheti, Mn distribution was practically homogeneous and equal to the natural background level from 0.07 to 0.27% with 0.13% on the average. This level corresponds to Mn concentration in the red-colored soil of coastal zone of Adjaria and Gurii. In the area between Natanebi and Supsa Rivers, thickness of this type of soil is maximal and the discharge into the sea is therefore most intensive. To the north of the Supsa estuary, Mn content in sediments increased stepwise up to 0.93%, on the average 0.25%. It came into the sea in a large volume with suspended solids and particles of the Rioni River waters. In 1950-to-80s, Mn content in river particles was as high as 5.0-5.9%, and reached 5.0-14.8% level in sediments close to the northern branch of Rioni. That was however decreased to 0.3% in 1995. The decreasing Mn content in the Rioni discharge depends upon reduction of activity at the Chiature mining factory.

3.3.4. Romanian sector of the Black Sea - Western region

The investigations carried out in 2000?2005 on trace metals levels in water and sediments along the Romanian coastal zone evinced the following mean values and ranges:

Seawater (total concentrations): copper 14.09 ?g/l (1.46 ? 27.31 ?g/l); cadmium 2.15 ?g/l?? (0.27 ? 4.60 ?g/l); lead 11.58 ?g/l (1.03 ? 30.04 ?g/l); nickel 4.23 ?g/l (0.65 ? 8.74 ?g/l); chromium 5.28 ?g/l (1.50 ? 12.23 ?g/l); manganese 17.01 ?g/l (2.72 ? 36.58 ?g/l); zinc 9.06 ?g/l (0.40 ? 26.98 ?g/l).

Sediments: copper 61.83 ?g/g dw (18.71 ? 134.35 ?g/g dw); cadmium 1.81 ?g/g dw (0.37 ? 3.35 ?g/g dw); lead 55.52 ?g/g dw (15.71 ? 107.35 ?g/g); nickel 32.24 ?g/g dw (4.30 ? 89.05 ?g/g dw); chromium 12.01 ?g/g de (3.01 ? 23.34 ?g/g dw); manganese 185.13 ?g/g dw (78.90 ? 399.67 ?g/g dw); zinc 117.90 ?g/g dw (26.98 ? 181.63 ?g/g dw).

Trace metals distribution in seawater and sediments along the Romanian littoral during 2000?2005 presented a wide range of concentrations, under the influence of natural and anthropogenic factors. Strong impact of human activities was reflected, for instance, in the increased values of some metals in harbour sediments (Constanta Port). In comparison with the central sector of the littoral (Mamaia Bay) and the southern extremity, that were characterized by moderate? values, in front of the Danube mouths higher concentrations of metals were measured, both in water and sediments. (Fig. 1B;? Fig. 2).

Acknowlegments. The authors are grateful to the Secretariat of Black Sea Convention for providing the data collected for riparian countries used for this assessment. Special thanks to the personnel who were involved with sampling at sea and their analysis, particularly those working in ?Typhoon? in Obninsk, O. Mjakoshin and Y. Yurenko in Sochi Hydrometeorological Centre, and Vakhtang Gvakharia (Georgia).

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