Mathematical modeling of oil hydrocarbon transformations in different parts of the White Sea

The available observational data on variations of oil hydrocarbon concentrations in White Sea tributaries and in individual parts of the sea are analyzed, and the contributions of different external sources to marine environment pollution are evaluated. The results of calculations are used to determine the possible total input of hydrocarbons from additional potential sources—internal natural (production by microorganisms) and external anthropogenic (navigation and sea shipping), which are most active in the summer and autumn. The hydroecological CNPSi-model is used to reproduce the processes of pollution of nine areas in the White Sea by oil hydrocarbons and their subsequent biodegradation in the marine environment. The annual dynamics of hydrocarbon concentrations was calculated using the long-term annual observations of monthly variations of the temperature, light intensity, and transparency of water, data on the morphometry of sea areas (the squares, mean depths, and water volumes) and water exchange between the chosen areas, calculated by a hydrodynamic model. For large bays (Dvina, Kandalaksha), the calculated concentrations of oil hydrocarbons are shown to be in agreement with the available estimates (the mean and maximal concentrations). The annual variations of oil hydrocarbon concentrations; the biomasses, oxidation activity and bioproduction characteristics of oil hydrocarbon-oxidizing bacteria are characterized. The calculated internal fluxes of oil hydrocarbons (the inputs from different sources, horizontal transport, and biotransformation) were used to calculate their annual balances for individual areas and the sea as a whole, showing the balanced character of their fluxes with the total balance discrepancies for individual areas varying within 0.3–4.1%.     

Petroleum hydrocarbons in the waters of major tributaries of the White Sea and its water areas: A review of available information

The White Sea is a natural analogue of arctic seas. The pollution of the sea by petroleum hydrocarbons is not high now. However, the load on sea ecosystem can increase in the nearest future because of the anticipated industrial development in its watershed, including an increase in oil, coal, and diamond production. The specific features of the nature of arctic marine systems (hydrological, ice, hydrobiological, hydrochemical, and radiation regimes), and the poor knowledge of the conditions of dispersion, transformation, and utilization of petroleum hydrocarbons in such seas make their ecological studies especially important. Petroleum hydrocarbon concentrations in the waters of tributaries and water areas of the White Sea (for 1980–2006 and 1989–2006, respectively) were evaluated using literary and authors’ data. Analysis of the collected materials shows that the majority of petroleum hydrocarbons enter the sea’s water areas with river runoff. Petroleum hydrocarbon concentrations were evaluated in major tributaries of the sea, including the rivers of Northern Dvina, Onega, Mezen, Niva, Kem, and Keret, delivering petroleum hydrocarbons into the bays of Dvina, Onega, Mezen, and Kandalaksha, water area near the Solovetskie Islands, and Chupa Bay, respectively (Bay — Gulf). Model calculations should yield within-year variations in petroleum hydrocarbon concentrations in different part of the sea (under a correctly specified load) and the conditions of their biotransformation and horizontal transport through the boundaries between areas within the sea.     

Hydrocarbons in the White Sea: Their inflow and transformation in the marine environment in different regions

Literary data have been used to assess the inflow of petroleum hydrocarbons (with river runoff, precipitation, wastewaters, sea transport, and at ice thawing) into different regions of the White Sea. The hydroecological CNPSi-model was used as an instrument to reproduce the annual dynamics of hydrocarbon concentrations at their parallel inflow and subsequent transformation in the waters of the nine White Sea regions (the bays of Kandalaksha, Onega, Dvina, and Mezen; the Solovetskie Islands; the deep-water part: Bassein, Gorlo, Voronka, and Chupa Bay). The calculations were based on normal annual values of monthly variations of water temperature, light intensity, and transparency, the morphometric parameters of the regions (water areas, mean depths, and water volumes) and water exchange between the regions and with the Barents Sea (calculated by a hydrodynamic model). The calculated concentrations of hydrocarbons, the biomasses and activity characteristics of hydrocarbon-oxidizing bacteria have been analyzed (their values were estimated for the 2-m surface water layer). The results of calculations were used to evaluate hydrocarbon balances for regions and the sea as a whole. The calculations demonstrate the balanced character of hydrocarbon fluxes, the balance discrepancy for the regions being <0.1–16.1%.     

Modeling of the marine environmental pollution by petroleum hydrocarbons and their biotransformation in Tatar Strait waters

A hydroecological model is used for simultaneous studying water pollution processes by petroleum hydrocarbons and their decay under the oceanographic conditions of Tatar Strait. The model calculations were based on long-term averaged observational data on interannual variations of water temperature, light intensity, and transparency. Some oceanographic characteristics of the strait were reconstructed with the help of GIS “Sakhalin Shelf.” The strait’s water area was divided into three regions, and water exchange between them and the neighboring regions of the Sea of Japan was estimated by a hydrodynamic model. The results of the study made it possible to assess interannual variations in the concentrations and inner fluxes of petroleum hydrocarbons, oil-oxidizing bacteria biomasses, and the characteristics of their oxidation activity.     

Long-Term variations in water levels in the Volga mouth area and their dependence on the Caspian Sea level variations

Long-term water level variations in the Volga mouth area and the effect exerted on them by the river’s flow and the Caspian Sea’s level variations are considered. Quantitative relationships were identified between the mean annual water levels at different gages in the mouth and the sea level. A backwater component was isolated in the long-term variations in water level in the Volga mouth area. Relationships between the daily water levels in the mouth and the Caspian Sea’s level at fixed water flow in the delta apex are presented. The magnitude and the propagation distance of backwater from the sea into the delta are specified. The responses of the mouth areas of rivers emptying into the Caspian Sea to sea level variations in the past century are compared.     

Petroleum hydrocarbon runoff in rivers flowing from oil-and-gas-producing regions in Northwestern Siberia

A method is proposed for evaluating the overland and river runoff of petroleum hydrocarbons originating from disperse pollution sources. The method is used to calculate their export from oil-and-gas-producing areas in Northwestern Siberia through the Pur River, a major artery in the Arctic region. The potential petroleum hydrocarbon input into the river is evaluated for different extent of petroleum pollution in the drainage basins of its tributaries.     

Nutrient Input into the Caspian Sea with River Runoff

Long-term observational data are used to compare and analyze time and space variations in the concentrations of nutrients in the water of major rivers flowing into the Caspian Sea and assess the nutrients runoff into the sea. Annual variations in the normal monthly values of river runoff and nutrient compound concentrations and input into the sea are considered (18 compounds and considered for the Volga, Ural, Terek, Sulak, and Samur, and 7 compounds are considered for the Kura). The Volga contribution to nutrient input into the sea is found to vary from 77 to 94% with the average of 86%.     

Nonlinear dynamics of level variations in the Caspian Sea

Caspian Sea level variations, which have several equilibrium states, are studied by the methods of the theory of nonlinear dynamic systems. Normal monthly values of sea level according to data collected at Makhachkala gauge from 1900 to 2000 are considered. The diagnostic characteristics of dynamic chaos are used to show that sea level variations have some properties of series with chaotic behavior. A model of level variations in the Caspian Sea, comprising a system of water balance equations for the sea basin, the dynamics of river runoff, and water balance of the sea itself, is proposed. Equation of a nonlinear oscillator is derived and shown to have solutions with chaotic regimes at some combinations of parameters.     

Hydrocarbons in the Suspension and Sediments of the Baltic Sea

The article gives the results of studying the concentration and composition of aliphatic and polycyclic aromatic hydrocarbons in suspension in surface waters at sections from the English Channel and Skagerak Strait to various regions of the Baltic Sea (2010–2015) and in water and bottom sediments of the southeastern part of the sea in the water area of the Kravtsovskoe field (2008–2015). In recent years, the surface waters of open areas of the Baltic Sea showed a decrease in hydrocarbon concentrations down to background levels (12–33 μg/L). The maximal concentration of hydrocarbons (in excess of the MAC) was recorded in different seasons in navigation areas, including the English Channel and Pregola R. mouth. In the zone of the Kravtsovskoe field, the concentration and composition of hydrocarbons in water depends on their inflow from the bank, and the same characteristics in bottom sediments, on the rate of their leakage from sediment stratum. A decline in these processes have led to a decrease in hydrocarbon concentrations in the sediments of a local area near D-6 platform to background levels (5–7 μg/g) and to the predominance of terrigenous, rather than petroleum, alkanes in hydrocarbon compositions.     

Suspended and Dissolved Forms of Nutrients: Their Relationships and Interaction in the Major Tributaries of the Caspian Sea

Normal annual data are used to evaluate the within-year variations in the concentrations of biogenic substances (organic and mineral components of N and P, dissolved organic carbon, inorganic Si) in the major tributaries of the Caspian Sea. Variations in the concentrations of biogenic substances are analyzed, the relationships between their mass concentrations in individual months are evaluated, and correlation between the organic and mineral components of N and P and their aggregated fractions are established. The obtained high-significance correlation between the concentrations of N and P components suggests that the rates of biochemical processes of biogenic substance transformation taking place in the water of tributaries are commensurable.     

Hydrocarbons in the modern sediments of the Caspian Sea

The presented results have been obtained in a study of the concentrations and composition of aliphatic and polycyclic hydrocarbons in bottom sediments of Volga delta branches and in its shallow zone (2009–2010), as well as the Caspian Sea proper (2010–2013). Oil hydrocarbon pollution has been found to manifest itself mostly in Volga delta branches, which, despite the low concentrations (up to 54.5 μg/g), showed higher hydrocarbons share in C_org (up to 33.8%), while the composition of alkanes suggested their oil genesis. The geochemical barrier the Volga–the Caspian Sea prevents anthropogenic hydrocarbons from entering the open parts of the Caspian. Bottom sediments in the shallow zone of the Northern Caspian, represented by coarse-grained material, are now polluted by oil hydrocarbons to a lesser extent compared with other areas. The highest concentrations of aliphatic hydrocarbons (up to 178 μg/g) were recorded in the deepsea bottom sediments of Derbent Depression and in depressions of the Middle and Southern Caspian. These areas show a higher concentration of C_org (up to 9.884%) and a low concentration of hydrocarbons in C_org (up to 0.16%), while odd high-molecular homologues (n-C₂₅–C₃₁) dominate in the composition of alkanes.     

Mathematical Modeling of Organogenic Material Biotransformation Processes for Studying the Conditions of Water Eutrophication in the Caspian Sea Surface Layer

A mathematical model based on average long-term data on water temperature, illumination, transparency, and nutrient content is used to calculate annual variations in the concentrations of organic and inorganic fractions of nutrients (C, N, Si, and P) in ten water areas in the Caspian Sea. The eutrophication of sea environment is examined with special emphasis on the increase in the biomass of aquatic animals (in particular, phyto- and zooplankton), the rate and duration of periods of plankton blooming, and changes in the conditions of nutrient limiting of primary production processes in different parts of the sea. Relationships between the inorganic components of N and P in river runoff and sea water areas are established. The obtained N_min/DIP ratios show P primary production to be limited in the zone of influence of the Volga runoff, P and N primary production to be limited in other northern parts of the sea, and N primary production to be mainly limited in the middle and southern parts of the sea.     

Biotransformation of oil hydrocarbons in Karkinitskii Bay of the Black Sea: Assessment based on mathematical modeling

The transformation conditions of oil hydrocarbons in water are considered for the case of Karkinitskii Bay, the Black Sea, where gas deposits have been developed actively in recent years and oil product pollution of marine environment has been recorded repeatedly. Data on measured oil hydrocarbon concentrations, their input into the northwestern part of the Black Sea, and experimental estimates of oil decomposition in the marine environment are presented. The biotransformation conditions of oil hydrocarbons are simulated by reproducing the biochemical activity of microflora and effecting substrate consumption processes, metabolic product excretions, and biomass decay. These processes maintain the biogenic substance turnover in water environment. The calculations are based on the morphometric characteristics of Karkinitskii Bay, and mean long-term data on the monthly dynamics of marine environmental characteristics (temperature, light intensity, transparency, atmospheric precipitation, and the characteristics of water regime and Danube runoff). A check calculation was performed to reproduce the concentration dynamics of biogenic substances and oil products with allowance made for the effect of river runoff and background pollution of the marine environment. The numerical scenarios take into account the marine environmental pollution conditions (an immediate discharge of 1000, 500, or 200 t of oil products per week) in winter, spring, summer, and autumn. The obtained model estimates of the rates of oil product decomposition and oxygen consumption are shown to agree well with experimental data. The time required for the concentration of oil products to reach the MAC after pollution of the marine environment is estimated.     

Biohydrochemistry of marine environment and transformations of biogenic substances and oil hydrocarbons on the southeastern Sakhalin shelf

Mathematical simulation is used to study the biotransformation conditions of compounds of organogenic elements (C, N, P, Si) and oil hydrocarbons in the water of southeastern Sakhalin shelf. The input data for calculations were evaluated with the use of Sakhalin Shelf GIS or taken from the reference literature and materials of expedition studies. The values of water discharges through the boundaries of the zones chosen within the shelf water area and through the interface with the Sea of Okhotsk were derived from the characteristics of currents estimated by means of Bergen University oceanic model based on normal long-term monthly thermohaline parameters obtained from the Sakhalin Shelf GIS. The intraannual variations of the concentrations of organic and mineral compounds of C, N, P, and Si, as well as oil hydrocarbons because of biotransformation of substances by organisms of the community (bacteria, phytoand zooplankton) were evaluated in calculations with CNPSi-model. The results of calculations, revealing the features of the dynamics of substances, the biomass of organisms, and their activity in matter biotransformations were analyzed.     

A Procedure for Calculating Extreme Characteristics of the Northern Caspian Sea Level

A procedure is proposed for calculating extreme characteristics of the level of a sea with allowance for positive and negative setups. Analysis is made of past storm events in the Northern Caspian Sea that have caused strong setups. Sixty-three storm weather patterns are chosen from a period of 45 years. Time ring synoptic maps are used to digitize the atmospheric pressure fields and calculate the field of its gradient and the wind near water surface. Based on these data, the sea level values and currents are calculated through two- and three-dimensional hydrodynamic models. A probabilistic model along with computer-aided data treatment procedures are used to calculate the fields of extreme characteristics of the sea level at the Lagan gage with the occurrence of once per N years at the average Caspian Sea level of 27 m below SL.     

Transformations of Organogenic Substances in the White Sea Ecosystem: Assessment Based on the Results of Mathematical Modeling

Methods of systems analysis and mathematical modeling are used to generalize hydrological, hydrochemical, and hydrobiological observational data with the aim to study the biohydrochemical conditions of organic and biogenic substance transformations in eight water areas in the White Sea. A hydroecological model describing transformations of N, P, and Si compounds and dissolved organic C, as well as the regime of O₂ was used as a means of the study. Water exchange between water areas was evaluated using a hydrodynamic model. Averaged data on annual variations in water temperature, illumination, and transparency, as well as run-off characteristics (water flow in river mouths and organic and biogenic matter concentrations in the river water entering the sea) were used to calculate the dynamics of organic and mineral compounds of nutrients in different areas of the sea. The principal attention is paid to the verification of the model against field observational data, assessment of the biomass development conditions of aquatic animals, analysis of model results regarding the turnover time of organic and mineral components, and the evaluation of balances of organic dissolved and particulate N and P forms.__________Translated from Vodnye Resursy, Vol. 32, No. 4, 2005, pp. 435–451.Original Russian Text Copyright © 2005 by Leonov, Filatov, Chicherina.     

Aliphatic and aromatic hydrocarbons in coastal Caspian Sea sediments

This investigation represents the first extensive study of the spatial distribution and sources of aliphatic (n-alkanes and unresolved complex mixture of fossil hydrocarbons) and polycyclic aromatic hydrocarbons (PAHs) in coastal sediments from the Caspian Sea. PAH concentrations, n-alkanes and biomarker profiles all suggested that there was limited petrogenic contamination in the shallow North Caspian Sea sediments, which are coarse with a low total organic carbon content. In contrast, moderate to high petrogenic contamination was found in the South Caspian Sea, in particular in the offshore oil fields near Baku, Azerbaijan. Contaminant patterns indicated that the PAHs were mainly from fossil sources, with higher contributions of pyrolytic only near industrialized and urban areas. A high contribution of perylene, a geochemically derived PAH, to the total PAHs was found in the west and south at sites influenced by the Kura, Safid Rud, Terek, Sulak and Samur Rivers.     

The frequency response of the Seto Inland Sea to several time-varying inputs

The frequency response characteristics of the Seto Inland Sea to three types of input of heat or materials are investigated. The types are uniform input to the entire inland sea, input from the rivers and input from the open ocean. The frequency response functions are obtained by a Fourier transform of the remnant functions, which are a kind of impulse response function and obtained by the hydraulic model experiments. The characteristics of the frequency response functions obtained are fairly different from one another, especially that for the input from the open ocean is different from the other two. Variations of the average water temperature and average salinity of the inland sea are discussed by using these results, and contributions of the main factors to their annual variations are revealed.     

Cytochrome P4501A expression,chemical contaminants and histopathology in roach,goby and sturgeon and chemical contaminants in sediments from the Caspian Sea,Lake Balkhash and the Ily River Delta,Kazakhstan

Roach, goby and sturgeon were examined for cytochrome P4501A (CYP1A) expression and histopathology, in relation to contaminant burdens in fish and sediment. Gradients of induction of CYP1A were observed. Roach from the Ural and Ily River Deltas and roach and goby from the two stations nearest the Caspian Sea oil fields displayed higher levels of CYP1A expression in several organs than was observed in fish from further offshore. Great sturgeon and Russian sturgeon showed higher levels of CYP1A expression than was seen in starred sturgeon and gobies in the Ural delta. No fish showed evidence of contaminant-related histopathologies in the organs examined, despite the elevated CYP1A levels. Low levels of polychlorinated biphenyls and elevated levels of inshore and riverine petroleum hydrocarbons from these habitats suggest that this ongoing hydrocarbon exposure, and that from natural sources and long-term oil exploration on the Northeastern Caspian shore, contributed to the CYP1A induction observed.     

Regularities in the spatial distribution of some macro-and microelements in the Caspian Sea water

The distribution of some microelements (Sr, Si, Ba, Mo, Rb, and Mn) in the surface and deep-sea waters in various parts of the Caspian Sea is considered in comparison with the distribution of salt-forming macroelements. The observed mean concentrations of microelements and their variations over the sea area and with depth indicate to the presence of additional, other than Volga runoff, sources supplying Sr, Ba, U, Rb, and Mn to the Caspian Sea.