V N Popovichev - Radionuclides and some chemical pollutants in the black sea mussels - страница 1

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МОРСЬКИЙ ЕКОЛОГІЧНИЙ ЖУРНАЛ

УДК 594.124:504.054:577.34 (262.5)

V. N. Egorov, dsc., Head of Dept., G. E. Lazorenko, Dr., senior scientist, N. Yu. Mirzoyeva, junior scientist, N. A. Stokozov, Dr., senior scientist, S. K. Kostova, Dr., senior scientist, L. V. Malakhova, Dr., junior scientist, A. V. Pirkova, Dr., senior scientist, S. I. Arkhipova, principal engineer, N. F. Korkishko, principal engineer,

V. N. Popovichev, junior scientist, O. V. Plotitsyna, principal engineer, L. V. Migal, principal engineer

The A. O. Kovalevsky Institute of Biology of the southern Seas, National Academy of Sciences of Ukraine,

Sevastopol, Ukraine

CONTENT OF 137Cs, 40K, 90Sr, 210Po RADIONUCLIDES AND SOME CHEMICAL POLLUTANTS IN THE BLACK SEA MUSSELS, MYTILUS GALLOPROVINCIALIS LAM.

The concentrations of 137Cs, 40K, 90Sr, 210Ро radionuclides, mercury and polychlorbiphenyls were determined in the Black Sea mussels collected in four different areas of the Crimean coast depending on places of sampling, the shell length of mollusks and the stages of their gonads development. The study was carried out in the framework of CIESM "Mussel Watch" Programme.

Key of words: radionuclides, mercury, polychlorbiphenyls, the Black Sea mussels, the Crimean coast

The coast and shelf of the Crimean Peninsula are the active zones of nature management of Ukraine. Ports of Crimea are the place of basing of military fleets of Ukraine and Russia. Dockyards and terminals for grain, metal, wood, building materials, oil storage tanks and also wharfs for coasting and passenger vessels are located in these ports. As a result, different pollutants including municipal wastes occur at the coast of the Crimea. They form strong anthropogenic impact on the ecosystem of this region. At the same time, the Crimean coast is the recreation area of the international significance. Therefore, it is necessary to test an ecological condition of this region. The Black Sea mussels are one of the main objects of an ecological investigation. These mollusks are dwelling on hard substratum with variable parameters of water exchange. They can characterize the ecological condition most adequately. The aim of this work was to determine contents of radionuclides, mercury and polychlorbiphenyls in the Black Sea mussels collected in four different areas of the Crimean coast.

Materials and methods. The Black Sea mussels Mytilus galloprovincialis Lam. were studied in the framework of the CIESM "Mussel Watch" Programme according to Agreement between the Commission Internationale pour l'Exploration Scientifique de la mer Mediterranee (CIESM) and Institute of Biology of the southern Seas during 1st January - 30rd June, 2005. The random samples of mussels were collected two times during this period in four chosen location of the Crimean coast: the Lake Donuzlav, Strelets-kaya Bay, Laspi Bay and Karadag Bay (Table 1).

The length of mollusks, stage of their gonads and sexual structure were determined in each random sample. 3940 individuals were studied.

70        © V. N. Egorov, G. E. Lazorenko, N. Yu. Mirzoyeva, N. A. Stokozov, S. K. Kostova, L. V. Malakhova, V. Pirkova, S.

I. Arkhipova, N. F. Korkishko, V. N. Popovichev, O. V. Plotitsyna, L. V. Migal, 2006

Table 1. The description of the sampling locations Табл. 1 Характеристика мест взятия проб

Station

Sampling location

Date of

Coordinates

Sampling

number

 

collection

 

depth, m

1

Streletskaya Bay

01.26.05

44o35'670 N; 33o28'200 E

1.2

 

(Sevastopol bays region)

04.22.05

44o35'670 N; 33o28'200 E

1.2

2

Laspi Bay

01.28.05

44o25'130 N; 33o42'570 E

1.2

 

 

05.31.05

44o25'165 N; 33o41'481 E

Up to 2

3

Karadag Bay (the Golden gate)

03.31.05

44o54'877 N; 35o13'870 E

Up to 3

 

Karadag Bay (Kurortnoye village)

03.29.05

44o55'502 N; 35o11'301 E

4

 

Karadag Bay (the Golden gate)

04.27.05

44o54'877 N; 35o13'870 E

Up to 3

 

Karadag Bay (Kurortnoye village)

04.26.05

44o55'502 N; 35o11'301 E

4

4

Lake Donuzlav

02.28.05

45o23'245 N; 33o06'934 E

Up to 2

 

 

05.04.05

45o23'245 N; 33o06'934 E

Up to 2

Artificial radionuclides 137Cs and 40K were measured in ash-laden samples by gamma-spectrometer including the NaI/Tl detector, analyzer/amplifier ORTEC 855 Dual Spec AMP,

Canberra AMP 2026 and Software System MCA

S100. Measuring technique was tested and calib­rated by 137Cs point source (№ 657 1537, Ukraine) [8] and intercalibration samples IAEA-135, IAEA-352. The counting total error was determined by

methods given by EURACHEM [4].

Artificial radionuclide 90Sr was extracted from investigated mussels and water in accordance with radiochemical procedures [6, 11]. Stable Sr was a yield tracer. Its measuring was carried out on the Flame photometer. The concentrations of 90Sr in samples were calculated by using its daughter radionuclide 90Y measurement. The Cherenkov's method and the liquid scintillation counter (LSC) of "the low background level" LKB Quantilus 1220 were applied for this purpose. The minimum detective activity (MDA) for mussels was equal 0.04 Bq-kg-1. The total uncertainty was calculated by standard method [15].

For the extraction of natural occurring radionuclide 210Po from soft tissues of mussels and water the radiochemical procedures of RISOE National Laboratory was used [3]. 208Po was added as a yield tracer. Polonium was spontaneously plated on silver disks. Alpha counting of 208Po and 210Po was done using

Морський екологічний журнал, № 3, Т. V. 2006

ОСТЁТЁ РС EG&G ORTEC alpha-spectrometer with MDA equal to 0.01 Bq-kg-1. The mean values of 210Po concentrations in mussels are presented in Bq-kg-1 wet weight (WW). The range of standard deviation for all mean concentrations was 10-15 %.

Uniformed methods of the monitoring of environment background contamination [13] and the technique of nonflaming atomic absorptive spectrophotometry [7] were used for the determination of mercury in mussels soft tissues. The measurement of Hg in samples was made by the analyzer "Julia-2" with sensitivity 1-10-3 ^g. Relative error of Hg determination in soft tissues of mussels was equal 13.4 %.

The organochlorine compounds in the Black Sea mussels were tested by procedures [13, 14]. PCBs (expressed by reference to Aroclor 1254) were measured by gas chromatograph Varian 3800 or Varian 3700 with 63Ni electron capture detector ECD. Determination errors calculated by standard methods [15] were about 15 %.

Results and discussion. The Black Sea mussels have six stages of the gametogenesis and two (sometimes three) spawnings for the year [12]. Mussels collected along the Crimean coast were in different condition (Fig.1).

The random samples from the Streletskaya Bay (26 January 2005 and 4 April 2005) contained 50 and 57 individuals accordingly. The range of mussel shell lengths was 30 - 60 mm, with medium 40 mm.

Fig. 1. Frequency of occurrence of the Black Sea mussels with different shell lengths, the same stage of gametogenesis and sexual structure of the random accesses: 1 - first collection; 2 - second collection

Рис. 1. Частота встречаемости мидий разной длины створок, стадий гаметогенеза и половой структуры в произвольных выборках: - 1 - первый отбор; 2 - второй отбор

Content of 137Cs, 40K, 90Sr, 210Po radionuclides . „

In winter the investigated mollusks gonads were at the 2 - 5 stages of gametogenesis with maximum at the 3rd stage. The stages 2 - 6 were registered in spring. The spawning was marked in the individuals with the shell lengths of 30 - 60 mm. The domination of males was observed. Six hermaphrodites were found in winter sample.

The random samples from Laspi Bay were collected 28 January 2005 (n = 58 animals) and 31 May 2005 (n = 80 animals). Most of mussels (46 %) of the first sample were at the third stage of gametogenesis with domination of males. Most of mussels (52 %) of the second sample were at the 2nd stage of active gametogenesis with domination of males too.

The size spectrum of mussels collected in area of the Golden gate (Karadag Bay, 29 March 2005) ranged from 30 to 80 mm with most of mussels at the 3rd and the 4th stages of gametogenesis. The shell lengths of mussels collected in April varied from 40 to 80 mm with excess of males over females. In this period 40 % of mussels were at the 5th stage (spawning stage). Two hermaphrodites have been found.

The shell lengths of mussels collected in

100 и        ,-.

137Cs concentrations in the same samples varied from 0.66 up to 1.50 Bq-kg"1 WW with total relative error 21 -33% (Fig. 2) which are in agreement with A. S. Bologa data [2]. Obtained results have not shown significant and reliable geographical differences.

Морський екологічний журнал, № 3, Т. V. 2006

the area near Kurortnoye village (Karadag Bay) ranged from 30 to 60 mm (the sample from 29 March 2005) with domination of females and from 40 to 60 mm (26 April 2005) with the domination of males. Most of mussels of the first sampling were at the 4th stage of gametogenesis. To the end of April most of animals were at the 2 and 3rd stages (before spawning) and 6th stage (after spawning).

The range of size spectrum of mussels collected in the Lake Donuzlav was 20 - 50 mm with medium 40 mm. Most of mussels were at the 1st"4th stages of gametogenesis with domination of females in March. Four individuals (5.7 %) of juvenile stage were found. The investigated mussels were at the 2 - 4th and 5 - 6th stages with equal quantity of males and females in May.

The range of 40K concentrations in mussels collected along the Crimean coast in 2005 was 66 - 95 Bq-kg"1 WW with total relative error

8 -10 % (Fig. 2).

Fig. 2 Concentrations of 137Cs and 40K in the Black Sea mussels

Рис. 2 Концентрации 137Cs и 40K в черноморских мидиях

137Cs concentration in the Black Sea water was equal 15 Bq-m-3. So, 137Cs concentration factors (CF) calculated for the Black Sea mussels ranged from 50 to 100.

90Sr concentrations were measured only in shells of mussels because in the soft tissues they

73

Q

'tg

ffl

10

0,1

□ Cs-137

□ K-40

Streletskaya   Karadag Bay Lake Bay Donuzlav

1

were lower than minimum detection activity. 90Sr concentrations in the Black Sea mussel shells did not depend on season of sampling, sex structure and gonad stages of these mollusks. The average values of concentrations and CF for this radionuclide in the Black Sea mussels depended on shell lengths (Fig. 3, 4).

& m

о

20 40 60

Shell size, mm

и

о о

св Й

~й Й

о й о О 400

300

200

100

0

204060

Shell length, mm

Fig. 3. The dependency of 90Sr average concentration in   Fig. 4. The dependency of average value of 90Sr OF in

the mussels on their shell length

Рис. 3. Зависимость средних концентраций 90Sr в мидиях от длины их раковин

Concentrations of 90Sr were very close (2.4 - 2.5 Bq-kg-1 WW) for mollusks collected in Laspi Bay, Streletskaya Bay and the Lake Donuzlav. Its highest value was found in samples

from the Golden gate (2.9 Bq-kg-1 WW). The mussels on their shell length

Рис. 4. Зависимость средних величин КН 90Sr в мидиях от длины их раковин

lowest one was determined in mollusks from

Kurortnoye village (1.8 Bq-kg-1 WW).

210Po concentrations in soft tissues of mussels depended on their sex and stage of gametogenesis (Fig. 5).

m

О

60

40

20

□ Male

□ Female

1 2 3 4 5 6

Gonad stage

Fig. 5. The dependency of 210Po concentration average values in the Black Sea mussels on their sex attributes and gametogenesis stages. Рис. 5. Зависимость средних величин концентраций 210Po в черноморских мидиях от их половой принадлежности и стадий гаметогенеза

Морський екологічний журнал, № 3, Т. V. 2006

4

3

2

0

0

0

0

The range of average values of 210Po concentrations was 21.2 - 41.3 Bq-kg-1 WW with highest values in the 4th stage of gametogenesis. As one can see the level of 210Po concentrations in the Black Sea mussels changed significantly during one cycle of gametogenesis. It may be connected with changes of the weight of mussel soft tissues in this period. The losses of soft tissue weight together with sex products can reach 11 -29 % from initial energy equivalent of body during spawning [5].

210Po concentration in soft tissue of animal depended on its individual weight. Their highest values were found in mussels with small sizes and weights of individuals from the Golden gate, Kurortnoye village and the Lake Donuzlav.

210Po concentrations in water of investigated   regions   varied   from   0.78 to 0.89 Bq-m-3. The ability of the Black Sea mussels to accumulate natural radionuclide 210Po from water was estimated by its CF. They ranged from 1.7 x104 to 4.7x104.

Thus, average value of CF for 210Po in investigated mussels inhabiting the Crimean coast (3.2 x104) is in excellent agreement with the World Ocean average value given in [1] for this radionuclide for shellfish (3x104).

Hence, the accumulative ability of the Black Sea mussels in relation to the natural radionuclide 210Po is comparable with that of similar species from others marine and oceanic areas.

Mercury concentrations in soft tissues of mussels from different regions of the Crimean coast varied significantly (Fig. 6).

2 3 4 5 6

Gonad stages

Fig. 6 Hg concentration (ng-g-1 WW) in soft tissues of the Black Sea mussels collected along the Crimea coast Рис. 6 Концентрации Hg (нг-г-1 сырой массы) в мягких тканях черноморских мидий, собранных вдоль побережья Крыма

They did not depend on sex belonging of mussels and their shell sizes. Maximum values of Hg concentrations were registered in animals from Streletskaya Bay (17 - 83 ng-g-1 WW). The lowest of them (3 - 7 ng-g-1 WW) was found in samples collected in region of the Colden gate (Karadag Bay). They ranged from 3.1 to 13 ng-g-1 WW in mussels from other locations. As one can see, Hg concentrations   were   lower   than maximum permissible limit for this element (200 ng-g-1 WW) [10] in investigated mussels.

The dependency of Hg concentrations in the Black Sea mussels on season of study was observed in samples from Streletskaya Bay only.

In the time of investigation the PCBs mean concentrations in the Black Sea mussels varied from 7 to 115 ng-g-1 WW (Fig. 7).

Fig. 7 Average concentrations of PCBs (ng-g-1 WW) in the Black Sea mussels

Рис. 7 Средние концентрации ПХБ (нг-г-1 сырой массы) в черноморских мидиях

PCBs highest concentration (115 ng-g-1 WW) was found in soft tissues of mussels collected in Streletskaya Bay characterized as polluted area. The minimum of the PCBs concentration (7 ng.g-1 WW) was determined in mussels from Karadag Bay. The comparison of PCBs data for animals collected in Karadag Bay in 2005 and 1981 - 1991 (176 ng-g-1 WW with range 34 - 566 ng-g-1 WW [16]) has shown that

PCBs concentrations in investigated region have decreased.

PCBs data demonstrate that there are some sources with still high concentration of these pollutants in Streletskaya Bay, Laspi Bay and the Lake Donuzlav (Fig. 7).

At the same time overall picture of dependency of investigated mussels ability to accumulate PCBs was observed: the highest

values of PCBs concentrations were determined at the 4th -5th stages of gametogenesis.

Conclusion. The analysis of biological characteristics of the Black Sea mussels has shown that the samples collected in locations chosen along the Crimean coast were in different condition. The ranges of 137Cs and 40K concentrations in the soft tissues of mussels were

0. 66 - 1.5 Bq-kg-1 WW and 66 - 95 Bq-kg-1 WW respectively without significant and reliable geographical differences. At present time 90Sr concentrations in the Black Sea mussels are up to levels before the Chernobyl NPP accident [9]. Their values depend on the length of the mussel shells. The ability of the Black Sea mussels to accumulate natural radionuclide 210Po is comparable with that of similar species from

1. Aarkrog A., Baxter M. S., BettencourtA. O. et al. A comparison of doses from 137Cs and 210Po in marine food: A Major International Study // J. Environ. Radioactivity - 1997. - 34. - P.69 - 90.

2. Bologa A. S. Monitoring of 137Cs in mussels (Mytilus galloprovincialis L.) from the Romanian sector of the Black Sea / Mediterranean Mussel Watch. CIESM Workshop, Marseille, France, 18­20 April 2002. - 2002. - P.13 - 16.

3. Chen Q., Dalhgaard H., Nielsen S.P et al. Determination of 210Po and 210Pb in Mussel, Fish, Sediment, Petroleum / Department of Nuclear Safety Research and Facilities, Risoe National Laboratory, Denmark. November 1998. - 1998. -10 p.

4. EURACHEM. Quantifying uncertainty in Analytical Measurements / First Edit.: ISBN 0948926-08-2, 1995. - 120 p.

5. Finenko G. А., Romanova Z. А., Abolmasova G.I. Ecological energy of the Black Sea mussels / eds. Shulman G. E., Finenko G.A. Bioenergy of hydrobionts. - Kiev: Naukova dumka, 1990. - P. 32 - 72 (in Russian).

6. Harvey B. K., Ibbett R. D., Lovett M. B. et al. Analytical procedures for the determination of strontium radionuclides in environmental materials / Aquatic Env. Prot.: Analytical Methods, Lowestoft, 1989. - 33 p.

7. Igoshin А. М., Bogusevich L. N. Flameless atom-adsorption method of determination of mercury in others marine and oceanic areas. The values of 210Po concentrations in the Black Sea mussels depend on their sex belonging and stages of gametogenesis. Maximum values of Hg concentrations were found in samples from Streletskaya Bay. They were higher in spring. Hg concentrations in soft tissues of investigated mussels were lower than maximum permissible limit for this element. The correlation between sex belonging of these mollusks and their accumulation of mercury has not been registered. PCBs data demonstrated that there are some sources with still high concentrations of these pollutants in Streletskaya Bay, Laspi Bay and the Lake Donuzlav. The ability of the Black Sea mussels to accumulate PCBs depended on the stages of gametogenesis.

water // Hydrochemical materials. - 1969. - 47. -P. 150 - 156 (in Russian).

8. Marey A. N., Zikova A. S. The methodical recommendations for monitoring of radioactive substances in the environmental. - Moscow: Hydrometeoizdat, 1980. - 336 p. (in Russian).

9. Marine radioecology / ed. G. Polikarpov. - Kiev: Naukova dumka, 1970. - 275 p. (in Russian).

10. Maximum permissible concentrations of heavy metals and arsenic in food materials: SanPiN 42­123-4089-86 /All-union health, sanitary-antiepidemic regulations and standards. - Moscow, 1986. - 11 p. (in Russian).

11. Measurement of Radionuclides in Food and Environment / Guidebook. Technical Report Series 295, IAEA, Vienna, 1989. - 274 p.

12. Pirkova A.V. The reproduction of mussel Mytilus galloprovincialis Lam. and elements of its cultivation: Abst. PhD thesis. - Sevastopol, 1994. -25 p. (in Russian).

13. Uniform methods of background monitoring of environment. - Moscow: Hydrometeoizdat, 1986. -P.82 - 95 (in Russian).

14. UNEP/IOC/IAEA. Determination of DDTs and

PCBs in selected marine organisms by capillary column gas chromatography, reference methods for marine pollution studies. No. 40. - Nairobi: United Nations Environment Programme, 1989. -18 p.

15. Urbakh V. Yu. Biometrics methods. - Moscow: Nauka, 1984. - 362 p. (in Russian).

16. Zherko N. V., Malakhova L. V., Bochko O. Yu. The comparative assessment levels of pollution by organochloric substances of mussels and bottom sediments from Karadag and Sevastopol bays areas // Ecology of the Sea. - 2002. - 61. - P. 81 - 84 (in Russian).

Поступила 28 марта 2006 г.

Вміст радіонуклідів 137Cs, 40K, 90Sr, 210Po та ряду хімічних забруднювачів в чорноморських мідіях Mytilus galloprobvincialis Lam. В. М. Єгоров, Г. Є. Лазоренко, Н. Ю. Мірзоєва, М. О. Стокозов, С. К. Костова, Л. В. Малахова, Г. В. Піркова, С. І. Архіпова, Н. Ф. Коркішко, В. М. Поповічев, О. В. Плотіцина, Л. В. Мігаль. Концентрації радіонуклідів 90Sr, 137Cs, 210Ро, поліхлорбіфенілів та ртуті, визначенних у мідіях Чорного моря, зібранних у чотирьох різних бухтах узбережжя Криму, залежали від місця відбору проб, довжини раковин молюсків та стадій розвитку їх гонад. Дослідження виконано в рамках програми CIESM "Mussel Watch".

Ключові слова: радіонукліди, поліхлорбіфеніли, ртуть, чорноморські мідії, узбережжя Криму

Содержание радионуклидов 137Cs, 40K, 90Sr, 210Po и ряда химических загрязнителей в черноморских мидиях Mytilus galloprobvincialis Lam. В. Н. Егоров, Г. Е. Лазоренко, Н. Ю. Мирзоева, Н. А. Стокозов, С. К. Костова, Л. В. Малахова, А. В. Пиркова, С. И. Архипова, Н. Ф. Коркишко, В. Н. Поповичев, О. В.

90        137 210

Плотицина, Л. В. Мигаль. Концентрации радионуклидов 90Sr, 137Cs, 210Ро, полихлорбифенилов и ртути, определенные в мидиях Черного моря, собранных в четырех разных бухтах побережья Крыма, зависели от мест отбора проб, длины раковин моллюсков и стадий развития их гонад. Исследование выполнено в рамках программы CIESM "Mussel Watch".

Ключевые слова: радионуклиды, полихлорбифенилы, ртуть, черноморские мидии, побережье Крыма

Морський екологічний журнал, № 3, Т. V. 2006

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V N Popovichev - Radionuclides and some chemical pollutants in the black sea mussels