Oil spills in the marine environment
Fate and behavior of oil in the marine environment
Complex processes of oil transformation in the marine environment start developing from the first seconds of oil's contact with seawater. The progression, duration, and result of these transformations depend on the properties and composition of the oil itself, parameters of the actual oil spill, and environmental conditions. The main characteristics of oil transformations are their dynamism, especially at the first stages, and the close interaction of physical, chemical, and biological mechanisms of dispersion and degradation of oil components up to their complete disappearance as original substances. Similar to an intoxicated living organism, a marine ecosystem destroys, metabolizes, and deposits the excessive amounts of hydrocarbons, transforming them into more common and safer substances.
Physical transport. The distribution of oil spilled on the sea surface occurs under the influence of gravitation forces. It is controlled by oil viscosity and the surface tension of water. Only ten minutes after a spill of 1 ton of oil, the oil can disperse over a radius of 50 m, forming a slick 10-mm thick. The slick gets thinner (less than 1 mm) as oil continues to spread, covering an area of up to 12 km 2 [Ramade, 1978]. During the first several days after the spill, a considerable part of oil transforms into the gaseous phase. Besides volatile components, the slick rapidly loses water-soluble hydrocarbons. The rest - the more viscous fractions - slow down the slick spreading.
Further changes take place under the combined impact of meteorological and hydrological factors and depend mainly on the power and direction of wind, waves, and currents. An oil slick usually drifts in the same direction as the wind. While the slick thins, especially after the critical thickness of about 0.1 mm, it disintegrates into separate fragments that spread over larger and more distant areas. Storms and active turbulence speed up the dispersion of the slick and its fragments. A considerable part of oil disperses in the water as fine droplets that can be transported over large distances away from the place of the spill.
Dissolution. Most oil components are water-soluble to a certain degree, especially low-molecular-weight aliphatic and aromatic hydrocarbons. Polar compounds formed as a result of oxidation of some oil fractions in the marine environment also dissolve in seawater. Compared with evaporation, dissolution takes more time. Hydrodynamic and physicochemical conditions in the surface waters strongly affect the rate of the process.
Emulsification. Oil emulsification in the marine environment depends, first of all, on oil composition and the turbulent regime of the water mass. The most stable emulsions such as water-in-oil contain from 30% to 80% water. They usually appear after strong storms in the zones of spills of heavy oils with an increased content of nonvolatile fractions (especially asphaltenes). They can exist in the marine environment for over 100 days in the form of peculiar "chocolate mousses". Stability of these emulsions usually increases with decreasing temperature. The reverse emulsions, such as oil-in-water (droplets of oil suspended in water), are much less stable because surface-tension forces quickly decrease the dispersion of oil. This process can be slowed with the help of emulsifiers - surface-active substances with strong hydrophilic properties used to eliminate oil spills. Emulsifiers help to stabilize oil emulsions and promote dispersing oil to form microscopic (invisible) droplets. This accelerates the decomposition of oil products in the water column.
Oxidation and destruction. Chemical transformations of oil on the water surface and in the water column start to reveal themselves no earlier than a day after the oil enters the marine environment. They mainly have an oxidative nature and often involve photochemical reactions under the influence of ultraviolet waves of the solar spectrum. These processes are catalyzed by some trace elements (e.g. vanadium) and inhibited (slowed) by compounds of sulfur. The final products of oxidation (hydroperoxides, phenols, carboxylic acids, ketones, aldehydes, and others) usually have increased water solubility. An experimental research showed that they have increased toxicity as well [Izrael, Tsiban, 1988]. The reactions of photooxidation, photolysis in particular, initiate the polymerization and decomposition of the most complex molecules in oil composition. This increases the oil's viscosity and promotes the formation of solid oil aggregates [GESAMP, 1977; 1993].
Sedimentation. Some of the oil (up to 10-30%) is adsorbed on the suspended material and deposited to the bottom. This mainly happens in the narrow coastal zone
and shallow waters where particulates are abundant and water is subjected to intense mixing. In deeper areas remote from the shore, sedimentation of oil (except for the heavy fractions) is an extremely slow process.
Simultaneously, the process of biosedimentation happens. Plankton filtrators and other organisms absorb the emulsified oil. They sediment it to the bottom with their metabolites and remainders. The suspended forms of oil and its components undergo intense chemical and biological (microbial in particular) decomposition in the water column. However, this situation radically changes when the suspended oil reaches the sea bottom. Numerous experimental and field studies show that the decomposition rate of the oil buried on the bottom abruptly drops. The oxidation processes slow down, especially under anaerobic conditions in the bottom environment. The heavy oil fractions accumulated inside the sediments can be preserved for many months and even years.
Microbial degradation. The fate of most petroleum substances in the marine environment is ultimately defined by their transformation and degradation due to microbial activity. About a hundred known species of bacteria and fungi are able to use oil components to sustain their growth and metabolism. In pristine areas, their proportions usually do not exceed 0.1-1.0% of the total abundance of heterotrophic bacterial communities. In areas polluted by oil, however, this portion increases to 1-10% [Atlas, 1993].
Biochemical processes of oil degradation with microorganism participation include several types of enzyme reactions based on oxygenases, dehydrogenases, and hydrolases. These cause aromatic and aliphatic hydrooxidation, oxidative deamination, hydrolysis, and other biochemical transformations of the original oil substances and the intermediate products of their degradation.
The degree and rates of hydrocarbon biodegradation depend, first of all, upon the structure of their molecules. The paraffin compounds (alkanes) biodegrade faster than aromatic and naphthenic substances. With increasing complexity of molecular structure (increasing the number of carbon atoms and degree of chain branching) as well as with increasing molecular weight, the rate of microbial decomposition usually decreases. Besides, this rate depends on the physical state of the oil, including the degree of its dispersion. The most important environmental factors that influence hydrocarbon biodegradation include temperature, concentration of nutrients and oxygen, and, of course, species composition and abundance of oil-degrading microorganisms. These complex and interconnected factors influencing biodegradation and the variability of oil composition make interpreting and comparing available data about the rates and scale of oil biodegradation in the marine environment extremely difficult.
Aggregation. Oil aggregates in the form of petroleum lumps, tar balls, or pelagic tar can be presently found both in the open and coastal waters as well as on the beaches. They derive from crude oil after the evaporation and dissolution of its relatively light fractions, emulsification of oil residuals, and chemical and microbial transformation. The chemical composition of oil aggregates is rather changeable. However, most often, its base includes asphaltenes (up to 50%) and high-molecular-weight compounds of the heavy fractions of the oil.
Oil aggregates look like light gray, brown, dark brown, or black sticky lumps. They have an uneven shape and vary from 1 mm to 10 cm in size (sometimes reaching up to 50 cm). Their surface serves as a substrate for developing bacteria, unicellular algae, and other microorganisms. Besides, many invertebrates (e.g. gastropods, polychaetes, and crustaceans) resistant to oil's impacts often use them as a shelter.
Oil aggregates can exist from a month to a year in the enclosed seas and up to several years in the open ocean [Benzhitski, 1980]. They complete their cycle by slowly degrading in the water column, on the shore (if they are washed there by currents), or on the sea bottom (if they lose their floating ability).
Self-purification. As a result of the processes previously discussed, oil in the marine environment rapidly loses its original properties and disintegrates into hydrocarbon fractions. These fractions have different chemical composition and structure and exist in different migrational forms. They undergo radical transformations that slow after reaching thermodynamic equilibrium with the environmental parameters. Their content gradually drops as a result of dispersion and degradation. Eventually, the original and intermediate compounds disappear, and carbon dioxide and water form. Such self-purification of the marine environment inevitably happens in water ecosystems if, of course, the toxic load does not exceed acceptable limits.
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