Organic matter in the waters of the Russian sector of the Caspian Sea

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The paper aims to analyse the results of long-term studies of dissolved and suspended organic matter content in the waters of the Northern Caspian and Middle Caspian in the Russian sector of the Caspian Sea. The paper analyses the main sources of input of organic matter, itsseasonal and inter-annual variability, features of its spatial distribution and causes (allochthonous organic matter flow, production and destruction, water temperature, sea level changes, etc.) determining the spatial and temporal dynamics of organic matter content. Thepaper is written on the results of production environmental monitoring conducted atthelicensed areas of LLC LUKOIL-Nizhnevolzhskneft in 2017–2021. The organic matter amount was estimated by organic carbon. The dissolved organic carbon concentration was found to vary from 0.10 to 9.30 mg/dm3 in the surface water layer and from 0.10 to 9.60mg/dm3 in the bottom layer. The maximum enrichment of waters with dissolved organic matter was noted in the northern part of the water area. The concentration of suspended organic carbon in the surface water layer varied within 0.10–23.40 mg/dm3, whereas inthebottom water layer it ranged within 0.05–19.40 mg/dm3. The spatial distribution of suspended organic matter was characterized by seasonal shifts of the area with maximum concentrations northwards. The main factors affecting the organic matter content in water were water temperature, suspended matter concentration in water and hydrogen ion concentration. The level of dissolved and suspended organic matter has not changed in the last 20years of studies. The dependence of dissolved and suspended organic matter concentrations on environment pH indicates the natural origin of the organic matter in the waters of the monitored sea area.

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Introduction

Potential biological productivity of a marine ecosystem is estimated by organic matter (OM) reserves in the water body. Being a product of vital activity of plants and animals, OM determines physical and chemical properties of water and bottom sediments and serves as a source of nutrients 1.

Representative indicators of dissolved organic matter (DOM) and suspended organic matter (SOM) are dissolved organic carbon (DOC) and suspended organic carbon (SOC) concentrations, respectively [1].

In the Caspian Sea, the incoming part of the OM balance is formed by allochthonous and autochthonous organic material, with autochthonous OM playing theleading role2. Phytoplanktonis the main producer of autochthonous OM 2, 3, 4. Allochthonous OM comes mainly with river runoff [2, 3]. Main items of the consumption part of the balance are the OM bottom sedimentation and consumption during mineralisation2.

OM is present in the Caspian waters in dissolved and suspended forms [4]. Carbohydrates and lipids are main biochemical components of DOM [5], while lipids and proteins are those of SOM [3]. OM of allochthonous origin is characterised by a high content of the insoluble fraction2, 3.

According to literature, in the Russian sector of the Caspian Sea, the maximum DOM and SOM content is registered in the north-western part of the Northern Caspian, in the estuaries of the Terek and Sulak Rivers, as well as in the hydrologic front zone. The OM concentration decreases seaward 5 [2, 5].

The OM concentration decreases with depth as a result of aerobic destruction [6]. Biochemical processes intensify in the bottom layer due to periodic turbulence of bottom sediments6. In shallow water areas, OM is distributed uniformly throughout the water columndue to intensive mixing 5.

OM is characterised by seasonal changes: in spring, during phytoplankton blooming, the OM content in the photic water layer increases, and in autumn, it decreases due to the development of destruction and sedimentation [7, 8]. Suspended matter (SM) is the predominant form through which OM transitions from water to sediments 7.

The rate of destruction of organic compounds depends on water temperature, environment pH and aeration conditions3. Increase in water temperature adds to the intensity of mineralisation of organic compounds [9]. Increase in the environment pH indicates more active OM formation under conditions of production intensification, causing a decrease in the partial pressure of carbon dioxide in water, and OM destruction accompanied by an increase in the partial pressure of carbon dioxide leads to a decrease in pH. Oxygen, as the main oxidant in the bottom water layer, isused for mineralisation of organic compounds. The decrease in oxygen concentration in water depends on the amount of oxidised OM4.

An important role in OM mineralisation belongs to bacteria capable of decomposing dead OM (including oil products) and transforming its destruction products into forms suitable for assimilation by aquatic vegetation8 [10].

Study of the peculiarities of OM content and distribution in water bodies subject to organic pollution is especially relevant.

In the Russian sector of the Caspian Sea, deterioration of the quality of the marine environment has been observed in the modern period, which is primarily caused by the inflow of pollutants, including organic compounds (petroleum hydrocarbons, phenols, organochlorine pesticides, synthetic surfactants) from the Volga, Terek, and Sulak rivers9 [11–15]. In addition, eutrophication has been intensively occurring in the Northern Caspian and Middle Caspian, leading to an increase inthe DOM and SOM amount [4, 16].

Sea level fluctuations result in quantitative changes in OM. Recent studies of OM distribution in the Caspian Sea waters in 2010–2015 showed that during that period of sea level decline, the DOC concentration had been almost unchanged [10]. However, the Caspian Sea level has decreased by more than 70cm since 2016, and its further decline is predicted [17].

Under these conditions (continuing pollution, eutrophication, sea level decrease), it is necessary to estimate the OM content in the Caspian Sea waters in the modern period.

The work aims to determine the main sources of organic matter in the water area of the Russian sector of the Caspian Sea and the factors determining the spatial and temporal dynamics of the content of organic matter, its suspended and dissolved forms.

Materials and methods

The paper is written on the results of production environmental monitoring conducted at the licensed areas of LLC LUKOIL-Nizhnevolzhskneft in 2017–2021. Monitoring was carried out twice a year (spring–summer and autumn periods). Samples were taken consecutively at 58 stations (Fig. 1) in the surface and bottom layers.

 

Fig. 1. Sampling scheme

 

First day analyses (water temperature, pH) were carried out by standard methods. Water samples (347 items) were processed in accredited laboratories. Nationally recognised test methods, certified measurement procedures, calibrated and verified measuring instruments were used in the chemical analyses. The amount of organic matter was estimated by organic carbon in accordance with GOST 31958-2012. Statistical analysis was carried out according to paper 10.

Results and discussion

The hydrochemical regime was characterised by an increase in water temperature from spring to summer with preservation of sufficiently high temperature values in autumn (Table 1). Seasonal increase in hydrogen index values indicates production activation in summer and autumn period. The decrease inthe amount of suspended sediment insummer and autumn is explained by the seasonal decrease in the volume of solid runoff with the Volga waters.

 

Table 1. Average values of hydrochemical indicators

Season

Water temperature,
°C

Water pH

Suspended matter, mg/dm3

Surface

Bottom

Surface

Bottom

Surface

Bottom

Spring

15.5

11.1

8.36

8.37

6.44

5.76

Summer

25.6

19.6

8.40

8.38

6.21

4.91

Autumn

19.5

17.0

8.46

8.43

2.88

2.51

 

The DOC concentration varied from 0.10 to 9.30 mg/dm3 in the surface layer and from 0.10 to 9.60 mg/dm3 inthe bottom layer (Table 2). On average, during the entire study period, the DOC content was higher near the surface due to the OM primary production in the photic layer and OM decomposition in the water column. However, due to the shallowness of the study area, vertical differences were minimal. The correlation between the values of DOC concentration in the surface and bottom layers was revealed. In spring, under high flood conditions and, consequently, high hydrodynamic activity, the correlation coefficient (r) was lower (r=0.48; n=134; α=0.05) thanin summer (r=0.74; n=72; α=0.05) and autumn (r=0.79; n=142; α=0.05).

 

Table 2. Concentration of organic carbon in the water of the Northern Caspian, mg/dm3

Season

Layer

Dissolved organic carbon

Suspended organic carbon

Range

Average

Range

Average

Spring

Surface

0.10–9.30

3.12

0.20–23.40

3.06

Bottom

0.10–9.60

2.81

0.10–19.40

2.49

Summer

Surface

1.50–4.11

2.35

0.10–13.30

1.64

Bottom

1.18–3.50

2.19

0.10–9.20

1.36

Autumn

Surface

0.75–6.00

2.43

0.10–6.86

1.17

Bottom

0.45–5.00

2.21

0.05–4.80

0.96

 

Despite the increase in the hydrogen ion concentration (pH) indicating the activation of OM primary production (Table 1), a decrease in the DOC content was observed from spring to autumn, both in the surface and bottom layers, which is explained by the increased insolation inhibiting photosynthesis in the summer and autumn period 11).

During the study period, the area of maximum DOC concentration was thenorthern part of the water area (Fig. 2).

 

Fig. 2. Spatial distribution of dissolved organic carbon (mg/dm3) in the surface water layer in spring 2020 (a) and autumn 2021 (b). The line denotes the border between theNorthern and Middle Caspian

 

The SOC concentration varied in the range of 0.10–23.40 mg/dm3 in the surface water layer and in the range of 0.05–19.40 mg/dm3 in the bottom water layer (Table 2). The SOC vertical distribution and seasonal dynamics repeated changes inthe SM concentration (Table 1). The maximum SOC values recorded in the spring period are explained by the input of allochthonous organic matter with the Volga River runoff during the high flood period. However, from spring to autumn, the correlation between SOC content in the surface and bottom water layers became weaker. Thus, correlation coefficient was 0.66 (n=134; α=0.05) in spring; 0.61 (n=72; α=0.05) in summer; 0.48 (n=142; α=0.05) in autumn. The decrease in the correlation ratio between these parameters is due to the fact that inspring SOC was a part of allochthonous (hard-to-mineralise) OM supplied with the Volga waters during high floods, and almost did not decompose in the water column, while in autumn it was a part of autochthonous (easily acidifiable) OM mineralised in the whole water column.

The SOC spatial distribution corresponded to the DOC distribution in autumn (Fig. 3). In the spring period, the area of the highest values was located on the traverse of the Agrakhan Peninsula, which can be caused by the Volga water export to this area against the background of increased water flow.

 

Fig. 3. Spatial distribution of suspended organic carbon (mg/dm3) in the surface water layer in spring 2020 (a) and autumn 2021 (b). For the line notation see Fig. 2

 

No statistically significant correlation between the content of DOC and SOC was found throughout the study period. The level of content as well as the characteristic features of the spatial distribution of DOC and SOC have not changed over the last 20 years of studies [18].

In the spring period, the DOC concentration was inversely related to water temperature. Correlation coefficient was –0.46 (Fig. 4) for the surface layer and –0.35 for the bottom one (n=137; α=0.05). The SOC content was in direct correlation with the SM amount: r=0.77 (surface) (Fig. 5) and r=0.71 (bottom) with n=137; α=0.05. This indicates that SOC occurs as part of allochthonous, hard-to-mineralise OM in the spring period.

 

Fig. 4. Dependence of dissolved organic carbon С (mg/dm3) on water temperature (°C) in the surface water layer during spring

 

Fig. 5. Dependence of suspended organic carbon concentration (mg/dm3) on suspended matter concentration (mg/dm3) in the surface water layer during spring

 

Correlation dependence of DOC and SOC concentration on water pH was revealed in summer. The SOC dependence of pH (r = 0.67 and 0.62 for the surface (Fig. 6) and bottom layer, respectively) was stronger than the DOC dependence of pH (r = 0.48 and 0.57 for the surface and bottom layer, respectively). For all theabove mentioned dependencies, n=74; α=0.05.

 

Fig. 6. Dependence of suspended organic carbon concentration (mg/dm3) on рН in the surface water layer during summer

 

No statistically significant correlations were found in the data array for the autumn period.

The seasonal dynamics of SM, DOC and SOC differed at different stages of the marginal filter.

According to literature, the maximum amount of SM is registered in the “mud area” (water area with salinity not exceeding 4‰) [19]. However, our studies revealed that this pattern was observed only in summer and autumn (Table 3). Inspring, during high floods, the main part of SM is carried further seaward. Theincrease in the SM and SOC content was observed in summer, in the DOC content – in spring.

 

Table 3. Average concentration of suspended and organic substances in the water of theNorthern Caspian, mg/dm3

Season

Suspended
matter

Dissolved
organic carbon

Suspended
organic carbon

Surface

Bottom

Surface

Bottom

Surface

Bottom

Salinity < 4‰

Spring

1.55

1.60

7.75

5.75

1.25

1.05

Summer

11.15

3.55

2.38

2.32

7.80

6.68

Autumn

7.33

1.42

2.11

2.00

2.42

0.10

Salinity 4–7‰

Spring

6.40

5.52

3.53

2.93

3.36

2.51

Summer

9.22

9.12

2.82

2.56

4.12

4.07

Autumn

3.83

4.06

3.08

2.54

1.59

1.23

Salinity > 7‰

Spring

6.53

5.86

2.99

2.75

3.06

2.51

Summer

5.82

4.62

2.32

2.16

1.25

1.01

Autumn

2.71

2.36

2.37

2.17

1.10

0.94

 

In the “elementorganic area” (water area with salinity of 4–7‰), transition of organic substances into bottom sediments takes place as a result of flocculation and sorption activation [19]. Decrease in DOC concentration in water in the “elementorganic plug” in comparison with the “mud area” is observed only in spring. Insummer and autumn, SOC decreases in the “elementorganic plug” (in autumn only in the surface layer).

In the “biological part” of the marginal filter (with salinity over 7‰), the OM bioassimilation takes place due to intensification of living organisms activity. TheDOC and SOC concentration decreases compared to the OM content in the “elementorganic area”. The DOC concentration decreased insignificantly, the SOC concentration decreased 3.3 times in the surface water layer and 4 times in the bottom water layer in summer. The SOC sharp decrease near the surface is a consequence of destruction, which is more intensive in the surface water layer under conditions of high oxygen saturation of water. Sharp decrease in the SOC amount in the bottom horizon is probably caused by the development of such filter-feeding molluscs as Cerastoderma glaucum (Bruguière, 1789) inhabiting at salinities of atleast 5‰; Monodacna colorata (Eichwald, 1829), optimum salinity for which is 6–10‰; Didacna protracta (Eichwald, 1829) preferring salinities above 8‰, etc., in the biological part of the marginal filter [20, 21].

Conclusion

The DOC and SOC concentration in the surface water layer of the Russian sector of the Caspian Sea is higher than in the bottom one due to the primary production of OM in the photic layer and decomposition of OM in the water column. Seasonal dynamics is characterised by a decrease in DOC and SOC from spring to autumn, which is explained by natural hydrochemical reasons (increased insolation inhibiting photosynthesis in the summer and autumn period, beginning of the destruction development in autumn and decrease in allochthonous OM input with theVolga River runoff).

The main factors affecting the OM content in water are water temperature (negative trend) and the amount of suspended sediment and water pH (positive trend).

The level of DOM and SOM has not changed in the last 20 years of studies. The dependence of DOM and SOM concentrations on environment pH assumes thenatural origin of the organic matter in the waters of the monitored sea area.

 

1 Maystrenko, Yu.G., 1965. [Organic Matter of Water and Bottom Sediment of Ukrainian Rivers and Water Bodies (the Dnieper and Danube Basins)]. Kiev: Naukova Dumka, 239 p. (in Russian).

2 Datsko, V.G., 1957. [Content of Organic Matter in the Caspian Sea Waters and its Approximate Balance]. Gidrokhimicheskie Materialy, XXVII, pp. 10–20 (in Russian).

3 Romankevich, E.A., 1977. [Geochemistry of Organic Matter in the Ocean]. Moscow: Nauka, 256 p. (in Russian).

4 Bordovskiy, O.K. and Ivanenkov, V.N., eds., 1979. [Ocean Chemistry. Vol. 1. Chemistry of Ocean Waters]. Moscow: Nauka, 521 p. (in Russian).

5 Pakhomova, A.S. and Zatuchnaya, B.M., 1966. [Hydrochemistry of the Caspian Sea]. Leningrad: Gidrometeoizdat, 342 p. (in Russian).

6 Fedosov, M.V., 1957. [Chemical Basis of Southern Seas Fodder and their Water Regime]. Informatsionny Sbornik VNIRO, (1), pp. 14–19 (in Russian).

7 Romankevich, E.A., Artemiev, V.E., Belyaeva, A.N. and Lyutsarev, S.V., 1982. [Biogeochemistry of Dissolved and Suspended Organic Matter in the Ocean]. In: A.V. Sidorenko and A.A. Geodekian, eds., 1982. [Organic Geochemistry of Waters and Exploration Geochemistry: Proceedings of
the 8th International Organic Chemistry Congress]. Moscow: Nauka, pp. 7–17 (in Russian).

8 Bordovsky, O.K., 1964. [Accumulation and Transformation of Organic Matter in Marine Sediments (Study on the Origin of Oil)]. Moscow: Nedra, 128 p. (in Russian).

9 Gurpanbur, Sh.B., 2010. [Ecological Problems of the Caspian Sea]. Molodoy Ucheny, I(5), pp. 128–131 (in Russian).

10 Smagunova, A.N. and Karpukova, O.M., 2012. [Methods of Mathematical Statistics in Analytic Chemistry]. Rostov-on-Don, Feniks, 346 p. (in Russian).

11 Boulion, V.V., 1983. [Primary Prodution of Plankton of Inland Water Bodies]. Leningrad: Nauka, 150 p. (in Russian).

×

Sobre autores

Larisa Degtyareva

FSBI Caspian Marine Scientific Research Center

Email: kaspmniz@mail.ru
ORCID ID: 0000-0003-1337-2797
Código SPIN: 5772-1402

Leading Research Associate, PhD (Biol.)

Rússia, Astrakhan

Olga Bakun

LLC LUKOIL-Nizhnevolzhskneft

Email: ozornikova@mail.ru
ORCID ID: 0000-0002-8149-9389
Código SPIN: 4783-4231

Leading Engineer for Environmental Protection, PhD(Biol.)

Rússia, Astrakhan

Maxim Ocheretniy

FSBI Caspian Marine Scientific Research Center

Autor responsável pela correspondência
Email: kaspmniz@mail.ru
ORCID ID: 0009-0008-0667-9292
Código SPIN: 1998-8801

Research Associate

Rússia, Astrakhan

Bibliografia

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  11. Abdusamadov, A.S., Abdurakhmanov, G.M., Dohtukaeva, A.M. and Dudurhanova, L.A., 2011. Contamination of the Shallow Coastal Zone and Desalinated Shelf West of theCaspian Sea and its Impact on Biota and Reproduction of Fish. The South of Russia: Ecology, Development. (2), pp. 37–62 (in Russian).
  12. Karygina, N.V., 2019. [On the Content, Distribution and Genesis of Hydrocarbons inthe Waters of the Northern Caspian Sea]. In: D. V. Kashin, ed., 2019. [Problems of Preservation of the Caspian Ecosystem During Oil And Gas Fields Development: Proceedings of the 7th Scientific and Practical Conference with International Participation. Astrakhan, 18 October 2019]. Astrakhan, KaspNIRKH, pp. 83–88 (in Russian).
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2. Fig. 1. Sampling scheme

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3. Fig. 2. Spatial distribution of dissolved organic carbon (mg/dm3) in the surface water layer in spring 2020 (a) and autumn 2021 (b). The line denotes the border between theNorthern and Middle Caspian

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4. Fig. 3. Spatial distribution of suspended organic carbon (mg/dm3) in the surface water layer in spring 2020 (a) and autumn 2021 (b). For the line notation see Fig. 2

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5. Fig. 4. Dependence of dissolved organic carbon СРОУ (mg/dm3) on water temperature (°C) in the surface water layer during spring

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6. Fig. 5. Dependence of suspended organic carbon concentration СВОУ (mg/dm3) on suspended matter concentration СВВ (mg/dm3) in the surface water layer during spring

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7. Fig. 6. Dependence of suspended organic carbon concentration СВОУ (mg/dm3) on рН in the surface water layer during summer

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