AbstractâThe results of studying tar balls on Baltic Sea beaches (the ... Sambiiskii Peninsula are found to correspond to a mean level of beach pollution.
ISSN 00978078, Water Resources, 2011, Vol. 38, No. 3, pp. 315–323. © Pleiades Publishing, Ltd., 2011. Original Russian Text © I.A. Nemirovskaya, 2011, published in Vodnye Resursy, 2011, Vol. 38, No. 3, pp. 315–324.
WATER QUALITY AND PROTECTION: ENVIRONMENTAL ASPECTS
Tar Balls in Baltic Sea Beaches I. A. Nemirovskaya Shirshov Institute of Oceanology, Russian Academy of Sciences, Nakhimovskii prosp. 36, Moscow, 117997 Russia Received December 21, 2009
Abstract—The results of studying tar balls on Baltic Sea beaches (the summer of 2008) are given with their comparison with other coastal areas. Tar balls in concentrations of 0.01–1.2 g/running m on the beaches of Sambiiskii Peninsula are found to correspond to a mean level of beach pollution. It is shown that, in addition to weathering, even highmolecular homologues in the composition of tar balls are rapidly decaying. There fore, the molecular markers currently in use are not unequivocal indicators to the origin of hydrocarbons. Keywords: tar balls, hydrocarbons, transformation, accumulation, origin. DOI: 10.1134/S0097807811020114
INTRODUCTION Tar balls are among the most widespread forms of oil pollution. They occur in surface waters in both coastal and pelagic areas in different parts of the World Ocean [3, 6, 17, 22, 24, 27]. Tar balls form during the transformation of oil films in the sea and oil transpor tation in tankers. The aggregates are discharged into the sea during the ballasting and cleaning up of tanks. Therefore, their distribution correlates with tanker oil transportation and major currents. The most polluted area is the North Atlantic (between Gibraltar and the Azores), the maximal concentrations of aggregates are mostly concentrated around navigation regions, such as Sargasso and Mediterranean seas. The Indian and Pacific oceans are less polluted, and almost no aggre gates were seen in waters near Antarctica [17]. Tar balls are carried out from dynamically active zones and they accumulate in relatively calm areas and on the coast [1, 6, 27, 28]. Inland seas with intense navigation and developed coastal industry are especially polluted. The input of hydrocarbons (HC) from aggregates into water is insignificant and its annual volume does not exceed 1 mg from 1 g of petroleum residues [10]. No correlation was found to exist between HC con centrations in water and tar balls. This suggests the dif ferent sources and migration paths of these forms of oil pollution [23]. Because of the sorption of phytoplank ton and mineral suspension and the development of colonies of organisms with carbonate or siliceous skel eton, the aggregates sink and eventually settle onto the bed. In coastal zones, liquid aggregates seep in the mass of sediments and, getting rid of volatile compo nents, form a solid mixture of sand and mazut [1]. The aggregates contaminate beaches, thus deterio rating recreation. In some cases, beach pollution is attributed not only to see shipping, but also to conse
quences of oil and gas production on sea shelf [12, 14] or natural seepage from sediment strata [6, 9, 18, 33]. In particular, in Santa Barbara Strait (California, USA), the daily flux of HC in a segment ~1.5 km in length is 10–15 t/day [33]. The large release of HC here is due to the shallow occurrence of oilbearing formations and the favorable tectonic and lithological situation. For example, oil seepage in the Gulf of Mexico is due to salt diapirs (Triassic and Jurassic deposits at depths 6–9 km), where the depth to the dome does not exceed 200 m [22, 33]. Semiliquid oil cakes were found in modern bottom sediments (BS) above diapirs. Their accumulations were observed in the surface BS layer in the Gulf of Mexico and in the vertical section of core columns down to 2 m. Accord ing to most recent estimates, 600000 t of HC annually release from the bed into oceanic water; this accounts for 46% of their total input (1300000 t) [25]. Earlier, the annual amount of HC released in this way was esti mated at 260000 t (11% of the total input of 2350000 t) [17]. Simultaneous discharge of large masses of oil prod ucts takes place during accidental spills in coastal areas, where, according to statistics, most accidents take place [5, 27, 28]. Thus, an accident with the Globe Assimi tanker resulted in that ~5.5 thousand t out of the 16493 t of spilled fuel oil were cast on Lithuanian and, partially, Latvian coasts near Klaipeda. Studies showed that, because of numerous storm discharges, the bed of beach deposits became laminated with mazut seams with a thickness from 0.1–0.2 to 10– 20 cm (mazut seems were recorded in 14 out of 24 sec tions) [5, 6]. The polluted sand bed thickness averaged 0.4–0.6 m, sometimes reaching 0.8–1.0 m; the con centration of sand in the aggregates was 60–70%. Tar balls in the beaches of Sambiiskii Peninsula (the summer of 2008) were studied in the summer of
315
316
NEMIROVSKAYA N
55°20' 108–110 BALTIC SEA
Cu ro nia nS pit
105–107 Morskoe Settl. Efa Dune
55°10'
Rybachii Settl.
Zelenogradsk T.
1–9
54°50'
sh ski iB ay
Taran Cape
Ku r
55°0'
101–104 Dyuny tour. camp 111–112 Lesnoe Settl.
Sambiiskii Pen.
20°0' 20°10' 20°20' 20°20' 20°40' 20°50' 21°0' E Fig. 1. Map of study area of sampling sites on the beaches of Sambiiskii Peninsula. 1⎯9 etc. are sample ordinal num bers and 111–113 are the numbers of samples.
2008 with the aim to investigate the pollution of the Russian coast of the Baltic Sea (Fig. 1). METHODS OF STUDIES Each sample was averaged by mixing and weighted, after which HC was extracted thrice by methylene chloride in an ultrasonic bath “Sapfir.” The solvent was filtered off, and the amount of sand was deter mined as the difference between the initial weight and the weight of the filter. The filtrate was evaporated in a rotor evaporator, dissolved in 5 ml of tetrachloride, and 0.5 ml of solution was taken for analysis. Individ ual hydrocarbon fractions were determined by column chromatography on silica gel: aliphatic HC (AHC), by hexane and polycyclic aromatic hydrocarbons (PAH), by a mixture of hexane with benzol (3 : 2) [6]. The concentration of AHC was determined by IRmethod (in an equivalent of Simmard mixture: 37.5% of isooc tane, 37.5% of hexadecane, 25% of benzol) at wave length of 2930 cm–1 in IR435 Shimadsu instrument. The sensitivity of the method is 1 μg/ml extract. Alkane concentration was determined by capillary gas chromatography (column length of 30 m, liquid phase ZB5, temperature programming from 100 to 300°C with a rate of 8°/min) on Intersmat GC 1212 chro matograph. The concentration and composition of PAH were determined by highperformance liquid chromatogra phy (HPLC) on MilichromA02 device equipped with a prontosil1205C18 AQ column. A mixture of ace tonitril with water in a gradient regime (from 75 to 100% of acetonitrile) was used as an eluent. The mea surements were carried out at 254 nm; identification
was based on the breakthrough time of individual pol yarenes, obtained from EPA laboratory (Environmen tal Protection Agency, USA). As the result, the follow ing unsubstituted polyarenes were obtained: naphtha lene (N), phenanthrene (PH), anthracene (A), fluoranthene (FL), pyrene (P), triphenyl (TP), chry sene (CR), perylene (PL), benz(a)pyrene (BP), 1,12 benzperylene (BPL). The procedure is described in detail in [6]. RESULTS AND DISCUSSION Sambiiskii Peninsula lies at the end of the Russian segment of Curonian Spit. Sand beaches form a gentle shore slopes with a width of 5–12 m near Taran Cape and up to 30–60 m in other areas. Near Taran Cape, the aggregates occurred both in the form of “oil plac ers”—small weathered lumped in wave splash zone and as individual cakes over the width of the beach (Fig. 2a). The size of the aggregates increased land ward. Oil aggregate accumulations in the Curonian Spit were observed mostly in the zones of maximal surf (Fig. 2b). Waves cast them onto the shore, and black accumulative bands 3–7 m in width could be seen at some distance from water edge. Wave deformation on the subsurface slope consists in manytime boiling, and a translation wave forms at depths of 0–3 m. The result is that all large objects are cast onto the shore. The aggregates on the shore were mixed with sand or rewashed onto the shelf bed by later storms. In abrasion cliff parts of the beaches that experi ence intense destruction and in their abrasion bench parts (moderately destroyed), aggregate contaminated only the surface layer (0–5, rarely 0–10 cm). In these areas, aggregates cast on the shore, were carried by longshore and windinduced currents into accumula tion areas, where they accumulated in the form of seems in the zone of wave activity. The highest con centration was recorded near Efa Dune, where in the 80th area of the beach, near the front of dune (~35 m from water edge), 2.5 kg of aggregates were collected during one day (31.2 g/running m). On the beach, they were transported by water flows. The collected aggregates were of different types. Some were liquid formations (2–3 cm in diameter), while others were solid, consisting of a mixture of oil products with sand. The presence of large amounts of sand in the aggregates (from 13 to 93%), allows them to be regarded as carriers of sediment—a form of transport of sedimentary material [2]. The amount of HC in tar balls varied within a wide range: for AHC, from 1.83 to 36.73 mg/g (Table 1). This is due to the fact that oil transformation is accom panied by the largest changes in the amount and com position of HC [6, 25]. This mostly takes place through the loss of light fractions and dissolution. The most readily degradable are nalkanes, followed by isoalkanes and, next, aromatic compounds. Typical features of all examined samples are the absence of a WATER RESOURCES
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Relative concentration
TAR BALLS IN BALTIC SEA BEACHES
317 (а)
17 18 Pr Pf 28
Relative concentration
20
(а)
40
60 min
25
(b)
18
32
17 Pf Pr 20
40
60 min
Fig. 3. Typical chromatogram of alkanes from tar balls. (a, b) Samples 1 and 109, respectively.
(b) Fig. 2. Tar balls on beaches (a) near Taran Cape (sample 1) and (b) near Morskoe Settl. on Curonian Spit (sample 106).
“hump” in alkane chromatograms (a mixture of naph thenearomatic compounds nonseparated by chroma tography) and the predominance of highmolecular homologues (Fig. 3). However, the configuration of alkane chromatograms and the distribution of molec ular markers suggest different composition of HC (Table 1, Fig. 4). Alkanes in oils are assumed to have a smooth distribution of homologues [6, 34] and a simi lar ratio of odd to even compounds in the highmolec ular domain (CPI = 1). Maximums in lowmolecular domain are typical of autochthonous alkanes, and those in highmolecular domain, of allochthonous alkanes. In most samples of aggregates, alkanes have no peaks in their composition. The percentage of homo logues (C18–C31) varied insignificantly. In the high molecular domain, the values of CPI were close to 1. The predominance of alkanes C26–C29 may be the result of a high degree of weathering of HC (Figs. 4a, 4b). However, in addition to the typical oil composi tion, odd alkanes prevailed in highmolecular domain in samples of aggregates 8, 109, 112, as is typical of allochthonous compounds. The values of CPI for samples of aggregates 1 and 109 were even P(20) > PH(18) > FL(17) > AN(8) >BP(7%). The oil genesis of PAH is reflected in the higher concentration of N and alky lated homologues [6, 12, 35] or N/PH ratio, which when >1 marks nonweathered oil products [31]. In the HPLC method, we determine mostly nonsubstituted polyarenes. N/PH ratio in the examined aggregates varied from 0.00 to 6.67 (Table 2). However, it was >1 in most samples and averaged 1.8. N is the most vola tile among the identified PAH and readily decomposes in water. Therefore, its concentration in natural objects, especially in summer, is near the analysis sen sitivity limit [8]. It is the likely cause of their low con centrations in samples 1 and 112. At the same time, the share of N in PAH reaches 67% in samples 7 and 105 (liquid lumps). P, FL, and PH are also dominating compounds in the composition of PAH. The high concentrations of FL and P (Fig. 5) are supposed to be due to the input with aerosols of combustion products of different types of fuels [6, 16, 35]. FL, as the most stable among the identified PAH, dominates in many water bodies, even in areas remote from pollution sources. The share of P is commonly greater than that of FL in soils near the combustion sites [6]. However, high concentra tions of these polyarenes are also typical of the exam ined tar balls, and FL/P < 0.5 in most samples, i.e., the WATER RESOURCES
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TAR BALLS IN BALTIC SEA BEACHES
effect of pyrogenic processes on PAH composition can be supposed. It is likely that, as was the case with alkanes, these markers cannot by unambiguously used to interpret the genesis of polyarenes. PH occurs in all objects, either natural or subject to anthropogenic impact, and in oils; therefore, its high concentrations are not surprising [35]. BP is a minor component (on the average, 8%) in the composition of PAH in tar balls. The concentra tion of BP, which has the highest carcinogenic activity among unsubstituted PAH, is used to assess the extent of environmental pollution by carcinogenic polyare nes [6]. That is why, considerable attention in the stud ies of PAH is paid to BP. However, the share of BP in marine objects is commonly not large and does not exceed 15% of the total amount of PAH. It is worth mentioning that biotic and abiotic natural processes facilitate the formation of modern biogenic back ground level of BP and PAH as a whole [4]. The pres ence of polyarenes can be seen even in Antarctic ice, as well as in permafrost layers of 10000 year age [13]. Detailed studies of the composition of PAH of tar balls on the beaches of Prince William Strait (Alaska) after Exxon Valdez oil spill also showed that N con centrations first dropped because of dissolution and weathering [29, 30]. Later, the concentrations of both light and heavy fractions also dropped. Next, in the process of photooxidation and biodegradation, the amount of alkylated homologues of H decreased. Their concentrations became comparable with the concentration of PH, though the amount of the latter in the spilled oil was three times greater. Next, a decrease was recorded in the concentrations of alky lated homologues of FL and PH, containing 3 ben zene rings, and 8 years later, those with 4 benzene rings (chrysenes and naphthbenzthiones). It was found that under Arctic conditions, even 8 years after the spill, and despite the loss of lowmolecular polyarenes (heavily weathered PAH dominated), the composition of lumps remained “petrogenic,” since alkylated homologues P and CR of relatively unsubstituted pol yarenes [24]. Thus, tar balls can be considered as a permanent pollution form of Baltic beaches. Previously, tar balls occur in the beaches of the Lithuanian coast in con centrations from 0.03 to 3.18 g/running m with higher concentration near Klaipeda [6]. According to the current classification, the beaches of Sambiiskii Pen insula can be referred to water areas with low or medium pollution (Table 3) [27]. The nonuniform dis tribution of tar balls on the beaches is most likely an indication to the limited paths of their migration. For comparison, after a considerable wave event on a sand beach in Bolt Sirt Bay (Lebanese coast of the Mediter ranean Sea), 235 m in length, their concentration was 12300 kg per 1 km of the beach; after another, weaker wave event with the same direction, the concentration was 3700 kg per 1 km [2]. On sand beaches of Bolt Sirt Bay, where small (up to 1 m) precipices were forming, WATER RESOURCES
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% 12 10 8 6 4 2 0 % 14 12 10 8 6 4 2 0 % 18 16 14 12 10 8 6 4 2 0
319 (а) 102 106 109
14 16 18 20 22 24 26 28 30 32 34 (b) 110 4 1
15 17 19 21 23 25 27 29 31 33 35 (c) 9l 11l 6 3
15 1617181920 21222324252627282930 31 Number of carbon atoms
Fig. 4. Alkane distribution in tar balls with (a) weathered oil and (b) biotransformed composition and (c) from BS. Here and in Fig. 5: 1, 3, 4, 6, 9l, 11l, 13, 102, 106, 109, 110, and 112, are sample numbers. BS samples 9l and 11l were taken on a testing ground near oil platform B6, samples 3 and 6 were taken near Sambiiskii Peninsula.
horizons of oil formations with a thickness of up to 5– 6 cm, could be seen running all along the steep shore. In this case, oil pollution is a component of the sedi mentary strata, or one of its layers. Such layers hamper the chemical exchange during the formation of the sedimentary strata and form a kind of aquicludes. Aggregates accumulate on the bed and in fractures of sandstone, forming elongated bands. The displacement of aggregates on the bed takes place under the effect of bottom orbital wave speeds, and their motion on a beach is governed by water splashes. Considerable amounts of oil products with the accumulation of tar balls in the amount of 3.5 kg/m of shoreline were also recorded in the eastern Mediterranean Sea on Israeli coast [19]. In the coastal zone of the northwestern Mediterranean Sea, the majority of aggregates concentrate between Turkey
320
NEMIROVSKAYA
Table 2. PAH concentration and composition in tar balls PAH, total
N
PH
Sample 1
AN
FL
P
BP
µg/g 107
1
31
–
22
44
3
Markers N/PH
FL/P
PH/AN
BP, % PAH
0.03
0.50
–
2.6
2
111
4
19
11
12
25
10
0.21
0.47
1.7
9.0
3
117
58
20
11
7
15
1
2.90
0.26
–
0.9
4
546
1
33
33
66
253
11
0.03
0.26
1.0
2.0
5
106
24
17
11
8
17
28
1.41
0.47
1.5
26.3
6
173
74
19
11
8
17
2
3.89
0.47
1.7
1.2
7
541
362
59
33
13
28
47
6.14
0.46
1.8
8.7
8
516
24
46
41
80
189
14
0.52
0.42
1.1
2.7
9
61
12
17
9
8
10
2
0.71
0.80
1.9
3.3
103
56
36
11
6
0
3.27
0.40
1.8
0.7
104
1066
106
598
0
66
0.2
69
197
0.18
0.96
–
18.5
105
940
620
93
52
39
88
42
6.67
0.44
1.8
4.5
109
485
0
15
73
166
88
0
0.00
1.89
0.2
0.0
110
1630
168
166
145
571
324
91
1.01
1.76
1.1
5.6
112
334
2
24
13
73
164
20
0.08
0.45
1.8
6.0
and Cyprus. The total annual input of oil products into the Mediterranean Sea is estimated at 880 thousand t, of which 180 thousand t are resin balls on beaches, and 9 thousand t is floating in the sea [17]. The character of sea currents and atmospheric circulation causes the mixing and motion of oil products all over the sea area, resulting in the pollution of its shelf and shore. The burial depth of oil residues was found [20, 28, 29] to be determined by the sea wave energy, shore geometry, and the type of sediment. Their maximal burial depth is achieved in the coastal areas with high wave energy and sand substrate. Oil cannot approach coastal zones with steep shore because of wave reflec tion, hence these zones are practically clear [3]. The mechanical fragmentation of aggregates does not play significant role in their destruction. This refers to both to highly viscous tar aggregates and lumps of chocolate mousse, which withstand dynamic loads produced by sea waves [2]. In particular, after the accident with the Exxon Valdez (37 thous. t), the level of coast pollution by mazut was 19 m3/km, and that after the Erica oil spill (20 thous. t), it was 53 m3/km shoreline [28]. Table 3. Classification of coast by tar ball pollution [27] Concentration, g/running m
Pollution level
0–1 1–10 10–100 >100
Insignificant Low Medium High, cannot be used for recreation
0.5
Tar balls buried in the sediment mass preserve their toxicity longer than the aggregates that form under subaerial conditions [1]. Apparently, because of this, when oilpolluted sediments expose near the water edge, the abundance of sandhoppers declines. More over, seams consisting of a mixture of mazut and sand, when loosened, even within a year, lead to the forma tion of a slick on water surface. Considering the rapid transformation of HC in tar balls, it is difficult to find out their origin. The compo sition of HC is the same as in its source only at the moment of their first appearance. Thus, based on the composition of HC in resin aggregates collected on the coast of Malaysia Peninsula, the conclusion was made that the pollution of the western coast is mostly due to tanker washing, because the pollution compo sition was similar to that of crude oil [26]. The sources of tar balls on the eastern coast are supposed to be oil platforms in the South China Sea, since the composi tion of the aggregates is similar to that of Sumatra oil. The comparison of HC composition with that of various oil products on the beaches of Sambiiskii Pen insula, made it possible to identify two types of tar balls. The first includes petroleum residues after vari ous transformations, which can be caused by oil prod uct degradation in the coastal zone (possibly, mazut). The distribution of homologues in these samples (8, 4, 110, 112) is bimodal (Fig. 4). Weathered oil products with a peak at nC19–C21 dominated in lowmolecular domain, and odd homologues nC27–C31, which is typical of terrigenous HC, dominated in highmolec ular domain. The second type includes samples with WATER RESOURCES
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TAR BALLS IN BALTIC SEA BEACHES ng/g 80
321
(а) 112 5 110 4
70 60 50 40 30 20
Chrysene
Pyrene
Fluoranthene
Anthracene
Benz(A)pyrene
ng/g 120
Phenanthrene
0
Naphthalene
10
(b) 9l 13 3
100
80
60
40
Benz(A)pyrene
Perylene
Chrysene
Pyrene
Fluoranthene
Anthracene
Phenanthrene
0
Naphthalene
20
Fig. 5. PAH composition in (a) tar balls and (b) BS.
dominating oil (monotonic) distribution of alkanes. It is likely that these oil residues have formed during oil leaks from ships or because of natural oil seepage from seabed as the result of its natural distillation in the water–sediment barrier zone. Later, these oil residues WATER RESOURCES
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experienced further weathering. Therefore, the chro matograms of alkanes and PAH, isolated from tar balls, do not match the chromatograms of HC from BS near the Kravtsovskoe Deposit (Figs. 3–5). The peak in the chromatograms of aggregates corresponds
322
NEMIROVSKAYA
to homologues nC26–C29, while that of AHC from BS, to nC27, C29. Oil residues with similar HC composition were recorded earlier in aleuritic BS near Klaipeda and on beaches in other Baltic regions [9]. The mechanism of so deep transformations of HC is still unclear, because their composition principally does not match that of the oils produced in the area. It appears likely that there exist some natural distillation (fractionation) of oil, at which lowmolecular components are released into bottom water, and highmolecular alkanes are selectively accumulated in BS horizons where Eh abruptly changes, as is the case in the sedimentary strata near fluids. Clearly, the composition of seeping HC depends on the depth of the oilbearing beds and the tectonic and lithological situation in the area. Summing up the data given above, we can conclude that tar balls can be regarded as the final migration form of oil products in the process of their transforma tion in the sea. After oil spills in coastal areas, oil prod ucts reach the shore. Shoreline restoration after Globe Assimi accident ended in the removal of sand–mazut mixture from beaches. The accident on the coast was eliminated; however, its consequences became evident as early as the next year: more than 900 thousand t of sand was washed out from a 25km shore segment with beaches, dunes, and shore cliffs during a heavy storm. At the same time, only 250 thousand t of sand was washed out from an abrasion segment of Curonian Spit 38 km in length, i.e., a beach with undisturbed profile was eroded 6 times slower. The deficiency of sand material causes a catastrophic destruction of the shore. An oil spill took place in Kerch Strait in November 2007. About 2 thousand t of mazut was discharged into the sea. Only 103 m3 of mazut–water mixture was col lected, while the major portion of mazut reached the shore and sunk onto the bed. As in the case with Globe Assimi accident, the only way to respond was the removal of polluted sand from the beaches. Even after 25 years, the only way to control beach pollution remains the mechanical removal of pollution. There fore, it is necessary to search for methods to prevent aggregates from reaching the coast and to transform them into their migration forms least hazardous to water bodies and aquatic organisms. CONCLUSIONS Tar balls are a permanent form of Baltic beach pol lution. The concentration of aggregates on the beaches of Sambiiskii Peninsula (0.01–31.2 g/running m) cor responds, according to the existing classification, to a medium pollution [27]. Their maximal amounts were recorded in the accumulation area in the splash zone near Efa Cape. Because of the diversity of sources that form the integral composition of HC and their fast transforma tion, the molecular markers now in use cannot serve
unambiguous indicators to their origin. Two types of tar balls were identified based on HC composition. The first type includes the aggregates that have formed during oil spills and degradation in coastal zone, while the second type includes those forming during oil seepage from the bed. Beach pollution depends not only on the amount of the oil product spilled, its composition, the meteo rological situation in the area, but also on the type of sedimentary rock on the coast. Beach remediation by exclusively mechanical methods, disturbs the natural dynamic state of the coastal zone, and its restoration is a manyyear pro cess. Therefore, the stability of tar balls should be taken into account when developing means used to eliminate the consequences of oil spills. ACKNOWLEDGMENTS The author is grateful to E.V. Bulycheva, A.D. Gavrilova, and G.I. Sychkova (Institute of Oceanology, RAS) for their help in sampling and analyses. This study was supported by the company OOO LukoilKMN; Russian Foundation for Basic Research, project nos. 080500094a, 090513510 ofi_ts; Program no. 20 of basic research of RAS Pre sidium. REFERENCES 1. Aibulatov, N.A. and Artyukhin, Yu.V., Geoekologiya Shel’fa i Beregov Mirovogo Okeana (Geoecology of Shelf and Shores of the World Ocean), St. Petersburg.: Gidrometeoizdat, 1993. 2. Aibulatov, N.A., Nemirovskaya, I.A., and Nesterova, M.P., Characteristic of Pollution of the NorthAfrican Shelf of the Mediterranean Sea, Okeanologiya, 1981, vol. 21, no. 5, pp. 831⎯835. 3. Biologicheskoe vozdeistvie na zagryazneniya okruzhay ushchei sredy neft’yu: berega, obrazovannye osadoch nymi porodami (Biological Impact on Oil Environmen tal Pollution: Shores Composed of Sedimentary Rocks), London: IRIESA, 2000. 4. Gerlach, S.A., Marine Pollution: Diagnosis and Therapy, Berlin: Springer, 1981. 5. Katastrofa tankera “Globe Assimi” v portu Klaipeda i ee ekologicheskie posledstviya (Globe Assimi Tanker Acci dent in Klaipeda Port and Its Environmental Conse quences), Moscow: Gidrometeoizdat, 1990. 6. Nemirovskaya, I.A., Uglevodorody v okeane (snegled vodavzves'donnye osadki) (Hydrocarbons in the Ocean (SnowIceWaterSuspensionBottom Sedi ments)), Moscow: Nauch. mir, 2004. 7. Nemirovskaya, I.A., Hydrocarbon Distributions in Northern Dvina Delta during Spring Flood, Geokhimiya, 2011, no. 2, pp. 1⎯14 [Geochem. Int. (Engl. Transl.), no. 2]. 8. Nemirovskaya, I.A. and Brekhovskikh, V.F., Origin of Hydrocarbons in the Particulate Matter and Bottom WATER RESOURCES
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WATER RESOURCES
Vol. 38
No. 3
2011
