Alexandria University Faculty of Engineering Dept.

of Marine Engineering & Naval Architecture

By/ Basem Elsayed TawfekNo: 21

Oil pollution is one of the most serious environmental problems in the marine environment. Episodic pollution events, such as catastrophic oil spills; in particular, threaten water quality and habitat with a suddenness and severity rarely matched by other pollutants. Catastrophic spills typically result from transportation accidents such as collisions or groundings of oil tankers. Most oil pollution stems from non-catastrophic events, however, and occurs most frequently during cargo transfer operations. In fact, of the 3.5 Million tons of oil that ends up in the ocean every year worldwide, only a small percent is a consequence of tanker spills. About 70 percent of oil Pollution is due to chronic pollution from municipal and industrial wastes or run off, dumping of waste oil, release of oily bilge water, and from other-than-tanker transportation. Whats an oil spill? Oil spills happen when people make mistakes or are careless and cause an oil tanker to leak oil into the ocean. There are a few more ways an oil spill can occur. Equipment breaking down may cause an oil spill. If the equipment breaks down, the tanker may get stuck on shallow land. When they start to drive the tanker again, they can put a hole in the tanker causing it to leak oil.

When countries are at war, one country may decide to dump gallons of oil into the other countrys oceans.

Terrorists may cause an oil spill because they will dump oil into a countrys ocean. Many terrorists will do this because they are trying to get the countrys attention, or they are trying to make a point to a country. Illegal dumpers are people that will dump crude oil into the oceans because they do not want to spend money on decomposing their waste oil. Because they wont spend money on breaking up the oil (decomposing it) they will dump oil into the oceans, which is illegal. Natural disasters (like hurricanes) may cause an oil spill, too. If a hurricane was a couple of miles away, the winds from the hurricane could cause the oil tanker to flip over, pouring oil out.

Fate of Marine Oil Spills

Oil is a general term used to denote petroleum products which mainly consist of hydrocarbons. Crude oils are made up of a wide spectrum of hydrocarbons ranging from very volatile, light materials such as propane and benzene to more complex heavy compounds such as bitumens, asphaltenes, resins and waxes. Refined products such as petrol or fuel oil are composed of smaller and more specific ranges of these hydrocarbons. Oil, when spilled at sea, will normally break up and be dissipated or scattered into the marine environment over time. This dissipation is a result of a number of chemical and physical processes that change the compounds that make up oil when it is spilled. The processes are collectively known as weathering. Oils weather in different ways. Some of the processes, like natural dispersion of the oil into the water, cause part of the oil to leave the sea surface, while others, like evaporation or the formation of water in oil emulsions, cause the oil that remains on the surface to become more persistent. The way in which an oil slick breaks up and dissipates depends largely on how persistent the oil is. Light products such as kerosene tend to evaporate and dissipate quickly and naturally and rarely need cleaning-up. These are called non-persistent oils. In contrast, persistent oils, such as many crude oils, break up and dissipate more slowly and usually require a clean-up

response. Physical properties such as the density, viscosity and pour point of the oil all affect its behavior. Dissipation does not occur immediately. The time this takes depends on a series of factors, including the amount and type of oil spilled, the weather conditions and whether the oil stays at sea or is washed ashore. Sometimes, the process is quick and on other occasions it can be slow, especially in sheltered and calm areas of water. Behavior of oil at sea The eight main processes that cause an oil to weather are described below and summarized in the following diagram. Fate of oil spilled at sea showing the main weathering processes

Spreading As soon as oil is spilled, it starts to spread out over the sea surface, initially as a single slick. The speed at which this takes place depends to a great extent upon the viscosity of the oil. Fluid, low viscosity oils spread more quickly than those with a high viscosity. Nevertheless, slicks quickly spread to cover extensive areas of the sea surface. Spreading is rarely uniform and large

variations in the thickness of the oil are typical. After a few hours the slick will begin to break up and, because of winds, wave action and water turbulence, will then form narrow bands or windrows parallel to the wind direction. The rate at which the oil spreads is also determined by the prevailing conditions such as temperature, water currents, tidal streams and wind speeds. The more severe the conditions, the more rapid the spreading and breaking up of the oil. Evaporation Lighter components of the oil will evaporate to the atmosphere. The amount of evaporation and the speed at which it occurs depend upon the volatility of the oil. An oil with a large percentage of light and volatile compounds will evaporate more than one with a larger amount of heavier compounds. For example, petrol, kerosene and diesel oils, all light products, tend to evaporate almost completely in a few days whilst little evaporation will occur from a heavy fuel oil. In general, in temperate conditions, those components of the oil with a boiling point under 200C tend to evaporate within the first 24 hours. Evaporation can increase as the oil spreads, due to the increased surface area of the slick. Rougher seas, high wind speeds and high temperatures also tend to increase the rate of evaporation and the proportion of an oil lost by this process. Dispersion Waves and turbulence at the sea surface can cause all or part of a slick to break up into fragments and droplets of varying sizes. These become mixed into the upper levels of the water column. Some of the smaller droplets will remain suspended in the sea water while the larger ones will tend to rise back to the surface, where they may either coalesce with other droplets to reform a slick or spread out to form a very thin film. The oil that remains suspended in the water has a greater surface area than before dispersion occurred. This encourages other natural processes such as dissolution, biodegradation and sedimentation to occur. The speed at which an oil disperses is largely dependent upon the nature of the oil and the sea state, and occurs most quickly if the oil is light and of low viscosity and if the sea is very rough. These factors led to the complete dispersion of the oil spilled from the BRAER (Shetland Islands, United Kingdom, 1993).

The addition of chemical dispersants can accelerate this process of natural dispersion. Emulsification An emulsion is formed when two liquids combine, with one ending up suspended in the other. Emulsification of crude oils refers to the process whereby sea water droplets become suspended in the oil. This occurs by physical mixing promoted by turbulence at the sea surface. The emulsion thus formed is usually very viscous and more persistent than the original oil and is often referred to as chocolate mousse because of its appearance. The formation of these emulsions causes the volume of pollutant to increase between three and four times. This slows and delays other processes which would allow the oil to dissipate. Oils with an asphaltene content greater than 0.5% tend to form stable emulsions which may persist for many months after the initial spill has occurred. Those oils containing a lower percentage of asphaltenes are less likely to form emulsions and are more likely to disperse. Emulsions may separate into oil and water again if heated by sunlight under calm conditions or when stranded on shorelines. Dissolution Water soluble compounds in an oil may dissolve into the surrounding water. This depends on the composition and state of the oil, and occurs most quickly when the oil is finely dispersed in the water column. Components that are most soluble in sea water are the light aromatic hydrocarbons compounds such as benzene and toluene. However, these compounds are also those first to be lost through evaporation, a process which is 10 -100 times faster than dissolution. Oil contains only small amounts of these compounds making dissolution one of the less important processes.

Oxidation Oils react chemically with oxygen either breaking down into soluble products or forming persistent compounds called tars. This process is promoted by sunlight and the extent to which it occurs depends on the type of oil and the form in which it is exposed to sunlight. However, this process is very slow and even in strong sunlight, thin films of oil break down at no more than 0.1% per day. The formation of tars is caused by the oxidation of thick layers of high viscosity oils or emulsions. This process forms an outer protective coating of heavy compounds that results in the increased persistence of the oil as a whole. Tarballs, which are often found on shorelines and have a solid outer crust surrounding a softer, less weathered interior, are a typical example of this process. Sedimentation/Sinking Some heavy refined products have densities greater than one and so will sink in fresh or brackish water. However sea water has a density of approximately 1.025 and very few crudes are dense enough or weather sufficiently, so that their residues will sink in the marine environment. Sinking usually occurs due to the adhesion of particles of sediment or organic matter to the oil. Shallow waters are often laden with suspended solids providing favourable conditions for sedimentation. Oil stranded on sandy shorelines often becomes mixed with sand and other sediments. If this mixture is subsequently washed off the beach back into the sea it may then sink. In addition, if the oil catches fire after it has been spilled, the residues that sometimes form can be sufficiently dense to sink. Biodegradation Sea water contains a range of micro-organisms or microbes that can partially or completely degrade oil to water soluble compounds and eventually to carbon dioxide and water. Many types of microbe exist and each tends to degrade a particular group of compounds in crude oil. However, some compounds in oil are very resistant to attack and may not degrade. The main factors affecting the efficiency of biodegradation are the levels of nutrients (nitrogen and phosphorus) in the water, the

temperature and the level of oxygen present. As biodegradation requires oxygen, this process can only take place at the oil-water interface since no oxygen is available within the oil itself. The creation of oil droplets, either by natural or chemical dispersion, increases the surface area of the oil and increases the area available for biodegradation to take place. Combined processes The processes of spreading, evaporation, dispersion, emulsification and dissolution are most important during the early stages of a spill whilst oxidation, sedimentation and biodegradation are more important later on and determine the ultimate fate of the oil. To understand how different oils change over time whilst at sea, one needs to know how these weathering processes interact. To predict this, some simple models have been developed based on oil type. Oils have been classified into groups roughly according to their density - generally, oils with a lower density will be less persistent. However some apparently light oils can behave more like heavy ones due to the presence of waxes. One model uses the half-life for a group of oils to describe the persistence and the time needed for the oil to dissipate. The half life is the time needed for 50% of the oil to disappear from the sea surface. After six half-lives have passed, about 1% of the oil will remain. This model, is shown in the illustration below. Weather and climatic conditions will alter the rates shown e.g. in rough weather a group 3 oil may dissipate in a timescale similar to a group 2 oil.

The rate of removal of oil from the sea surface according to type

Volume of oil and water-in-oil emulsion remaining on the sea surface is shown as a percentage of the original volume spilled.

Group Group I Group II

Density less than 0.8 0.8 - 0.85

Group III 0.85-0.95 Group IV greater than 0.95

Examples Gasoline, Kerosene Gas Oil, Abu Dhabi Crude Arabian Light Crude, North Sea Crude Oils (e.g. Forties) Heavy Fuel Oil, Venezuelan Crude Oils

Although simple models such as this cannot predict the changes an oil undergoes very precisely, they can provide clues about whether an oil is likely to dissipate naturally or whether it will reach the shoreline. This information can be used by spill responders to decide upon the most effective spill response techniques and whether such techniques can be initiated quickly enough.

Effects of Marine Oil Spills

Oil spills can have a serious economic impact on coastal activities and on those who exploit the resources of the sea. In most cases such damage is temporary and is caused primarily by the physical properties of oil creating nuisance and hazardous conditions. The impact on marine life is compounded by toxicity and tainting effects resulting from the chemical composition of oil, as well as by the diversity and variability of biological systems and their sensitivity to oil pollution.

Impact of oil on coastal activities The effects of a particular oil spill depend upon many factors, not least the properties of the oil.

Contamination of coastal amenity areas is a common feature of many spills leading to public disquiet and interference with recreational activities such as bathing, boating, angling and diving. Hotel and restaurant owners, and others who gain their livelihood from the tourist trade can also be affected. The disturbance to coastal areas and to recreational pursuits from a single spill is comparatively short-lived and any effect on tourism is largely a question of restoring public confidence once clean-up is completed. Industries that rely on a clean supply of seawater for their normal operations can be adversely affected by oil spills. If substantial quantities of floating or sub-surface oil are drawn through intakes, contamination of the condenser tubes may result, requiring a reduction in output or total shutdown whilst cleaning is carried out. Biological effects of oil Simply, the effects of oil on marine life, are caused by either the physical nature of the oil (physical contamination and smothering) or by its chemical components (toxic effects and accumulation leading to tainting). Marine life may also be affected by clean-up operations or indirectly through physical damage to the habitats in which plants and animals live.

The main threat posed to living resources by the persistent residues of spilled oils and water-in-oil emulsions ("mousse") is one of physical smothering.

The animals and plants most at risk are those that could come into contact with a contaminated sea surface. Marine mammals and reptiles; birds that feed by diving or form flocks on the sea; marine life on shorelines; and animals and plants in mariculture facilities. The most toxic components in oil tend to be those lost rapidly through evaporation when oil is spilt. Because of this, lethal concentrations of toxic components leading to large scale mortalities of marine life are relatively rare, localised and short-lived. Sub-lethal effects that impair the ability of individual marine organisms to reproduce, grow, feed or perform other functions can be caused by prolonged exposure to a concentration of oil or oil components far lower than will cause death. Sedentary animals in shallow waters such as oysters, mussels and clams that routinely filter large volumes of seawater to extract food are especially likely to accumulate oil components. Whilst these components may not cause any immediate harm, their presence may render such animals unpalatable if they are consumed by man, due to the presence of an oily taste or smell. This is a temporary problem since the components causing the taint are lost (depurated) when normal conditions are restored. The ability of plants and animals to survive contamination by oil varies. The effects of an oil spill on a population or habitat must be viewed in relation to the stresses caused by other pollutants or by any exploitation of the resource. In view of the natural variability of animal and plant populations, it is usually extremely difficult to assess the effects of an oil spill and to determine when a habitat has recovered to its pre-spill state. In recognition of this problem detailed pre-spill studies are sometimes undertaken to define the physical, chemical and biological characteristics of a habitat and the pattern of natural variability. A more fruitful approach is to identify which specific resources of value might be affected by an oil spill and to restrict the study to meeting defined and realistic aims, related to such resources. Impact of oil on specific marine habitats The following summarizes the impact that oil spills can have on selected marine habitats. Within each habitat a wide range of environmental conditions prevail and often there is no clear division between one habitat and another. Plankton is a term applied to floating plants and animals carried passively by water currents in the upper layers of the sea. Their sensitivity to oil pollution has been demonstrated experimentally. In the open sea, the rapid dilution of naturally dispersed oil and its soluble components, as well as the high

natural mortality and patchy, irregular distribution of plankton, make significant effects unlikely.

In coastal areas some marine mammals and reptiles, such as turtles, may be particularly vulnerable to adverse effects from oil contamination because of their need to surface to breathe and to leave the water to breed. Adult fish living in nearshore waters and juveniles in shallow water nursery grounds may be at greater risk to exposure from dispersed or dissolved oil. The risk of surface oil slicks affecting the sea bed in offshore waters is minimal. However, restrictions on the use of dispersants may be necessary near spawning grounds or in some sheltered, nearshore waters where the dilution capacity is poor. The impact of oil on shorelines may be particularly great where large areas of rocks, sand and mud are uncovered at low tide. The amenity value of beaches and rocky shores may require the use of rapid and effective clean-up techniques, which may not be compatible with the survival of plants and animals. Marsh vegetation shows greater sensitivity to fresh light crude or light refined products whilst weathered oils cause relatively little damage. Oiling of the lower portion of plants and their root systems can be lethal whereas even a severe coating on leaves may be of little consequence especially if it occurs outside the growing season. In tropical regions, mangrove forests are widely distributed and replace salt marshes on sheltered coasts and in estuaries. Mangrove trees have complex breathing roots above the surface of the organically rich and oxygen-depleted muds in which they live. Oil may block the openings of the air breathing roots of mangroves or interfere with the trees' salt balance, causing leaves to drop and the trees to die. The root systems can be damaged by fresh oil entering nearby animal burrows and the effect may persist for some time inhibiting recolonisation by mangrove seedlings. Protection of wetlands, by responding to an oil spill at sea, should be a high priority since physical removal of oil from a marsh or from within a mangrove forest is extremely difficult.

Living coral grows on the calcified remains of dead coral colonies which form overhangs, crevices and other irregularities inhabited by a rich variety of fish and other animals. If the living coral is destroyed the reef itself may be subject to wave erosion. The effects of oil on corals and their associated fauna are largely determined by the proportion of toxic components, the duration of oil exposure as well as the degree of other stresses. The waters over most reefs are shallow and turbulent, and few clean-up techniques can be recommended. Birds which congregate in large numbers on the sea or shorelines to breed, feed or moult are particularly vulnerable to oil pollution. Although oil ingested by birds during preening may be lethal, the most common cause of death is from drowning, starvation and loss of body heat following damage to the plumage by oil. Impact of oil on fisheries and mariculture

An oil spill can directly damage the boats and gear used for catching or cultivating marine species. Floating equipment and fixed traps extending above the sea surface are more likely to become contaminated by floating oil whereas submerged nets, pots, lines and bottom trawls are usually well protected, provided they are not lifted through an oily sea surface. Experience from major spills has shown that the possibility of long-term effects on wild fish stocks is remote because the normal over-production of eggs provides a reservoir to compensate for any localised losses. Cultivated stocks are more at risk from an oil spill: natural avoidance mechanisms may be prevented in the case of captive species, and the oiling of cultivation equipment may provide a source for prolonged input of oil components and contamination of the organisms. The use of dispersants very close to mariculture facilities is ill-advised since tainting by the chemical or by the dispersed oil droplets may result. An oil spill can cause loss of market confidence since the public may be unwilling to purchase marine products from the region irrespective of whether the seafood is actually tainted. Bans on the fishing and harvesting of

marine products may be imposed following a spill, both to maintain market confidence and to protect fishing gear and catches from contamination.

Oil Spills in Rivers

Here are four reasons why oil spills in rivers differ from spills that occur in the open ocean: 1. Some oils are denser than river water Oil usually floats because it is less dense than the water it is floating on. (Density is the mass, or weight, of a substance divided by its volume.) The density of river water is usually about 1 gram per cubic centimeter (g/cc). Water in the open ocean is more dense (usually around 1.02 to 1.03 g/cc) because it contains more salt (the higher the salinity of water, the more dense it is). Densities of oils range from 0.85 g/cc for a very light oil (like gasoline) to 1.04 g/cc (for a very, very heavy oil). Most types of oils have densities between about 0.90 and 0.98 g/cc. These oils will float in either the river or the ocean. But very heavy oils, which have a density of 1.01 g/cc, would float in the ocean, but sink in a river. Sometimes the density of an oil is so close to that of river water that the oil moves along the river partly underwater. When such oil finally moves into the ocean at the river mouth, it can refloat! This doesn't happen very often, but it's something we have to think about whenever oil is spilled in a river. If spilled oil sinks, it can be very difficult to clean up. If something causes it to pool on the bottom (for example, it may get trapped behind a sunken vessel), then vacuum devices can be used to try and get the oil off the bottom. As you might guess, this method may not be very effective because vacuums may capture a lot of water and sand along with the oil. 2. Movement is usually downstream Unlike in a bay or the open ocean, currents in a river are generally directed downstream (except very close to the mouth of the river, where it enters the ocean; here, a flood tide might actually reverse the flow of the surface water). The greater predictability of river currents makes it easier to predict which way the oil will move. Wind blowing across the river also affects where the oil will come ashore. If the wind is blowing straight down the river (as might happen on a river with high banks), it often will travel quite

far down the river before it comes in contact with a beach. In order for the oil to beach, the wind must blow the oil to one side of the river or the other. You can see how the wind affects movement of an oil slick by looking at some predictions from GNOME, our oil spill trajectory model (requires QuickTime, available at Apple Computer's website). 3. Dams and locks influence oil movement. Rivers sometimes contain dams or locks that slow or divert water flow. Dams and locks also slow down the movement of spilled oil. In fact, oil tends to collect in areas next to dams or locks, where it can be picked up from the surface of the water by skimmers (devices that "skim" the oil off the water surface), sorbent pads (big square pads of an absorbing material that the oil will stick to), or sorbent booms (which work like sorbent pads, but look more like a string of sausages made out of the inside of disposable diapers!). 4. Vegetation may grow right at the water's edge Along many rivers, plants and trees grow right up to the river's edge. Those rivers don't have the open, sandy shores that you find along the many parts of the open coast. It's much harder to remove oil from vegetation than from a hard-packed sand beach. Spill responders try to protect the plants by using booms, but if the vegetation gets oiled, responders often either cut, burn, or flush it with water to try to get the oil out.

When we talk about oil spills, how much oil are we talking about?
Quite a lot: The United States uses about 700 million gallons of oil every day. The world uses nearly 3 billion gallons each day. The largest spill in the United States so far was the Exxon Valdez spill into Prince William Sound, Alaska in March 1989. An oil tanker ran aground to cause this spill of almost 11 million gallons of crude oil. While this was a big spill, it was actually only a small fraction--less than 2 percent--of what the United States uses in 1 day! These big numbers are hard to relate to everyday life, so let's make some comparisons. To better understand how much 11 million gallons of oil is, check the table below. It shows how many familiar rooms or buildings would be filled up by the approximate amount of oil spilled from the Exxon

Valdez. For example, that oil would have filled up 9 school gyms or 430 classrooms. Total Volume Exxon Valdez Oil Spill School Gymnasium (50' * 50' * 65') Gallons Gyms Houses Classrooms 108 13 1 0.25 0.125 430 51 4 1 0.5 Living Rooms 797 94 7 2 1

10,800,000 >9 1,274,163 1 0.1 0.02 0.01

Average House (40' * 100,365 40' * 8') Average Classroom (20' * 20' * 8') 25,091

Average Living Room 13,549 (12' *18' * 8')

Exxon Valdez Oil Spill

Four minutes after midnight on March 24, 1989, the Exxon Valdez hit Bligh Reef in Alaska's Prince William Sound. Eleven million gallons of North Slope oil spewed into one of the most bountiful marine ecosystems in the world, killing birds, marine mammals, and fish, and devastating the ecosystem in the oil's path. Exxon says that the Sound has recovered. They're wrong. In the 1989 spill, crude oil spread across Alaska's coastal seas covering 10,000 square miles, an area the size of Connecticut, Delaware, Rhode Island, and 25 Washington, D.C.s combined! Within a week, currents and winds pushed the slick 90 miles from the site of the tanker, out of Prince William Sound into the Gulf of Alaska. It eventually reached nearly 600 miles away from the wrech, contaminating 1,500 miles of shoreline about the length of California's coast.

Before the Exxon Valdez spill, conservationists warned about the potential impacts of a major spill. In fact, just hours before the disaster, a group of Valdez residents had gathered at the city council chambers to discuss the impact of oil on their community. When the conversation turned to response to a major spill, Riki Ott, a fisherwoman and toxicologist from Cordova said, "It's not a matter of what if, but when."

Today, conservationists are again sounding the alarm about several risky Alaskan oil development schemes and practices. First, the vast majority of

oil shipped from Alaska is still carried in outdated, single-hull tankers. Second, the Trans-Alaska Pipeline, which carries oil from the North Slope to the port of Valdez, is aging, mismanaged, and in dire need of repair. In the last 20 years, dozens of leaks have gone undetected, and workers have been continually mistreated or intimidated from reporting the company's environmental abuses to regulators. Effects of the Spill The Exxon Valdez disaster killed more wildlife than any other environmental disaster in the nation's history, including: More marine mammals and birds died than in any other oil spill, including an estimated 3,500 to 5,500 sea otters, 300 harbor seals, and 14 to 22 killer whales. "The Exxon Valdez spill killed nearly ten times as many birds as any other U.S. or European oil spill," said seabird expert Dr. Michael Fry. As many as half a million birds died, including bald eagles, harlequin ducks, marbled murrelets and loons. Fish Critical spawning and rearing habitats, including over 100 salmon streams, were besieged in oil. In 1993 there was an unprecedented crash of the sound's Pacific herring population. The spill also caused a noticeable decline in pink and churn salmon, Dolly Varden cutthroat trout and rockfish. Habitat Three national parks, three national wildlife refuges, one national forest and designated wilderness were oiled. Toxic Effects Linger To the naked eye, Prince William Sound may appear "normal." But if you look just beneath the surface, oil continues to contaminate beaches, national parks, and designated wilderness. In fact, the Office of Technology Assessment estimated that beach cleanup and oil skimming only recovered 3-4% of the Exxon Valdez spill. A decade later, the ecosystem still suffers. Substantial contamination of mussel beds persists, contributing to the decline of harlequin ducks. The depressed population of Pacific herring -- a critical source of food for over 40 predators including seabirds, harbor seals and Stellar sea lions -- is having severe impacts up the food chain. Recent studies revealed that even on "cleaned-up" washed beaches, mollusks and other invertebrates were far less abundant than on comparable unspoiled beaches.

Wildlife population declines continue for harbor seals, killer whales, harlequin ducks, common loons, pigeon guillemots, red-faced cormorants, and double-crested cormorants. 0il is more toxic than thought Even before the spill, scientists knew a drop of oil could kill a bird's egg. But after studying the impact of the Valdez spill, they now believe oil pollution to be at least 100 times more toxic to fish. It is also more persistent New studies by the National Marine Fisheries Service show that even very low levels of weathered Exxon Valdez oil are toxic to the early life stages of salmon and herring. The Exxon Valdez spill resulted in profound physiological effects to fish and wildlife. These included reproductive failure, genetic damage, curved spines, lowered growth and body weights, altered feeding habits, reduced egg volume, liver damage, eye tumors, and debilitating brain lesions.

CLEAN-UP TECHNIQUES
There are two approaches for responding to marine oil spills at sea: the enhancement of natural dispersion of the oil by using dispersant chemicals, and containment and recovery of oil using booms and skimmers. Sorbent materials may be useful in the final stages of clean up as a polishing tool. Once oil strands on shore, a shoreline clean up will be necessary. Despite continuing research, there has been little change in the fundamental technology for dealing with oil spills. Alternative techniques are constantly being sought and old techniques reassessed. Two techniques currently receiving fresh attention are in-situ burning and the enhancement of the natural biodegradation of oil through the application of micro-organisms and/or nutrients. Chemical Dispersants Dispersants are a group of chemicals designed to be sprayed onto oil slicks, to accelerate the process of natural dispersion. Spraying dispersants may be the only means of removing oil from the sea surface, particularly when mechanical recovery is not possible. Their use is intended

to minimise the damage caused by floating oil, for example to birds or sensitive shorelines. However, in common with all spill response options, the use of dispersants has its limitations and should be carefully controlled. Dispersant use will be dependent upon national regulations governing the use of these products. How chemical dispersion works Natural dispersion of an oil slick occurs when waves and other turbulence at the sea surface cause all or part of the slick to break up into droplets and enter into the water column. The addition of dispersants is intended to accelerate this process. Dispersants have two main components, a surfactant and a solvent. Surfactants are molecules which have an affinity for two distinct liquids which do not mix, acting as an interface between them. A part of the surfactant molecule used in dispersants has an attraction to oil (i.e. it is oleophilic) while another part has an attraction for water (i.e. it is hydrophilic). Common washing-up liquid is another example of a product that contains surfactants. When a dispersant is sprayed onto an oil slick, the interfacial tension between the oil and water is reduced, promoting the formation of finely dispersed oil droplets. These droplets will be of varying sizes and although the larger ones may rise back to the surface some will remain in suspension. If dispersion is successful, a characteristic plume will spread slowly down from the water surface a few minutes after treatment. However, the effective distribution of surfactant throughout the oil is crucial to the success of the process. To achieve the required distribution, most dispersants contain a suitable solvent which allows the dispersant to penetrate into the slick and acts as a carrier for the surfactant. Figure 1: Mechanism of aerial dispersion.

Limitations Dispersants have little effect on very viscous, floating oils, as they tend to run off the oil into the water before the solvent can penetrate. As a general

rule, dispersants are capable of dispersing most liquid oils and emulsions with viscosities of less than 2000 centistokes, equivalent to a medium fuel oil at 10-20C. They are unsuitable for dealing with viscous emulsions (mousse) or oils which have a pour point near to or above that of the ambient temperature. Even those oils which can be dispersed initially become resistant after a period of time as the viscosity increases as a result of evaporation and emulsification. For a particular oil, the time available before dispersant stops being effective depends upon such factors as sea state and temperature but is unlikely to be longer than a day or two. Dispersants can, however, be more effective with viscous oils on shorelines because the contact time may be prolonged allowing better penetration of the dispersant into the oil. Types of dispersant There are three main types of dispersants: Type 1 dispersants are based on hydrocarbon solvents with between 15 and 25% surfactant. They are sprayed neat onto the oil as predilution with sea water renders them ineffective. Typical dose rates are between 1:1 and 1:3 (dispersant:oil). Type 2 dispersants are dilutable concentrate dispersants which are alcohol or glycol (i.e. oxygenated) solvent based with a higher surfactant concentration. Dilution is normally 1:10 with sea water. Type 3 dispersants are also concentrate dispersants with a similar formulation to type 2 products. However, they are designed to be used neat and typical dose rates are between 1:5 and 1:30 (neat dispersant:oil). Type 1 and 2 dispersants require thorough mixing with the oil after application to produce satisfactory dispersion. With type 3 products, the natural movement of the sea is usually sufficient to achieve this. The lower application rates required with concentrates mean that types 2 and 3 have largely superseded type 1 dispersants for application at sea. Methods of application at sea Dispersants can be applied to open water by a variety of methods. In general workboats are more suitable for treating minor spills in harbours or confined waters. Large multi-engine planes are best equipped for handling large off-shore spills. Small, single-engine aircraft and helicopters are suitable for treating smaller spills and near shore areas. Regardless of the method used, it must be able to apply the dispersant effectively. In order to minimise losses due to wind

drift, a uniform spray pattern of larger droplets, "rain drops", are required rather than a fog or a mist. Vessel spraying Methods for dispersant application from sea going vessels include spraying through a set of nozzles fixed on outboard booms, and spraying from modified fire monitors. In a typical boom system, the booms are mounted as far forward as possible to ensure the dispersant is applied ahead of the bow wave which helps to mix the dispersant and oil. Spray units can be portable or permanently installed on a vessel. Systems are available that deliver neat dispersant or, with a separate water pump, apply dispersant diluted with water. Fire monitors can only be used to apply diluted dispersant. When used, the output must be monitored to minimise excessive over or under dilution and there is a tendency to waste dispersant because of the poor coverage of a strong water jet. Advantages of this system are the high pump capacity which allows the vessel to travel at a greater speed and the elimination of the problem of booms striking the water surface as the vessel pitches and rolls. Vessel spraying is of limited utility as can only relatively small amounts of dispersant can be applied and because of the difficulties of locating the oil from a vessel. Furthermore, when slicks become fragmented or form narrow windrows, it is inevitable that some dispersant will be sprayed onto unoiled sea. These problems can be partially overcome by controlling the operation from a spotter plane but this requires good air to sea communications. Aerial spraying The spraying of dispersant from aircraft has the significant advantages of rapid response, good visibility, high treatment rates and optimum dispersant use. In addition, aircraft allow treatment of spills at greater distances from shore than with vessels. Two categories of aircraft are used: those designed for agricultural or pest control operations which require minor modification for dispersant application, and those which have been specifically adapted for the application of dispersant. Several types of helicopter have also been converted although most are able to carry underslung bucket spray systems without the need for modifications. The ideal aircraft will be determined primarily by the size and location of the spill, although in reality local availability will be the crucial factor. The endurance, fuel consumption,

turn around time, payload and the ability to operate from short or improvised landing strips are all important. In addition, the aircraft should be capable of operating at low altitude and relatively low speeds (50-150 knots) and be highly manoeuvrable. Only type 3 dispersants are suitable for aerial spraying, since they require no mixing beyond that provided by the natural movement of the sea. The relatively low dose rate required also makes the best use of available payload. Shoreline application Dispersants can also be used on some shorelines, including beaches, rocks and sea walls, particularly during the final stages of clean-up. However, it is important to remove the bulk of the stranded oil first, by other means. Shores subjected to strong wave action are often cleaned naturally and they should not be sprayed unless the oil has to be removed immediately. All three dispersant types may be used for shore cleaning although those containing hydrocarbon solvents may be more effective with viscous oils because of their greater ability to penetrate into the oil. The most appropriate application equipment depends on the type of shoreline substrate to be cleaned, the ease of access and the scale of the operation. For small inaccessible beaches and coves, portable back-pack sprayers are the most suitable. For large expanses of shoreline, purpose-built vehicles or tractors can be used. Environmental considerations The use of dispersants has in the past tended to provoke controversy since their application can be seen as a deliberate introduction into the sea of an additional pollutant in addition to the short term increase in hydrocarbon concentration in the water. However, there is a wealth of laboratory data indicating that dispersants and oil/dispersant mixtures exhibit relatively low toxicity to marine organisms. The rapid dilution of the dispersed oil, the proximity to sensitive areas as well as the direction of currents and the mixing depths of surface waters are all factors which should be considered when deciding upon dispersant use. In the open sea, concentrations after spraying are unlikely to remain high for more than a few hours and significant biological effects are therefore improbable. In shallow waters close to the shore, where water exchange is poor, higher concentrations may persist for long periods and may give rise to

adverse effects. However, the controlled application of dispersants may, on occasions, be beneficial in that it may reduce damage to adjacent ecologically sensitive shorelines by surface oil. The decision whether or not to use dispersants rather than other response options, will need to take into account cost-effectiveness and conflicting priorities for protecting different resources from pollution damage. On occasions the benefit gained by using dispersants to protect coastal amenities, sea birds and intertidal marine life may far outweigh the disadvantages such as the potential for temporary tainting of fish stocks. Certain resources such as water intakes, mariculture facilities or fish spawning areas are difficult to protect from dispersed oil and spraying may be decided against, near to these resources, even if the risk of damage is low. Detailed contingency planning can aid in this decision process. Containment and Recovery of Floating Oil

The use of booms to contain and concentrate floating oil prior to its recovery by specialised skimmers is often seen as the ideal solution to a spill since, if effective, it would remove the oil from the marine environment. Unfortunately, this approach suffers from a number of fundamental problems, not least of which is the fact that it is in direct opposition to the natural tendency of the oil to spread, fragment and disperse under the influence of wind, waves and currents. In rough seas, a large spill of a low viscosity oil such as a light or medium crude oil can be scattered over many square kilometres within just a few hours. Oil recovery systems typically have a swath width of only a few metres and move at slow speeds whilst recovering oil. Thus, even if they can be operational within a few hours, it will not be feasible for them to encounter more than a fraction of a widely spread slick. This is the main reason why containment and recovery at sea

rarely results in the removal of more than a relatively small proportion of a large spill, at best only 10 - 15% and often considerably less. A common difficulty when deploying booms and skimmers to recover oil is controlling the movements and activities of vessels and directing them to the thickest areas of oil. This can be overcome by using aircraft equipped with air to sea communications. Overall, containment and recovery operations at sea require extensive logistical support, which should not be underestimated.

The limitations that poor weather and rough seas impose on operations at sea are seldom fully appreciated. Handling wet, oily, slippery equipment on vessels which are pitching and rolling is difficult and can place personnel at risk. Winds, currents and wave action seriously reduce the ability of boom to contain and of skimmers to recover oil. In practice, the most efficient recovery of oil is achieved only under calm conditions. When containment and recovery is attempted it is important to select equipment that is suitable for the type of oil and the prevailing weather and sea conditions. Efforts should target the heaviest oil concentrations and areas where collection will reduce the likelihood of oil reaching sensitive resources and shorelines.

As the oil weathers and increases in viscosity, clean up techniques and equipment will need to be re-evaluated and modified. For example, the types of pumps and skimmers may need to be changed. The first stage of an effective response is to deploy boom to limit further spreading and concentrate the oil for recovery. Booms vary considerably in their design, but all normally incorporate the following features: 1. freeboard to prevent or reduce splashover; 2. a sub-surface skirt to prevent or reduce escape of oil under the boom; 3. flotation by air or some buoyant material; 4. longitudinal tension member (chain or wire) to provide strength to withstand the effects of winds, waves and currents. This is often used to provide ballast to keep the boom upright in the water. There are many designs ranging from small, lightweight models designed for manual deployment in harbours, to large, robust units which usually need cranes and sizeable vessels to handle them, which are designed for use in the open sea. The most important characteristic of a boom is its oil containment or deflection capability, determined by its behaviour in relation to water movement. It should be flexible to conform to wave motion yet sufficiently rigid to retain as much oil as possible. No boom is capable of containing oil against currents greater than 0.7 knot (0.35 metres per second) at right angles to the boom, irrespective of boom size or skirt depth. This factor limits the speed at which booms can be towed to less than 0.5 knots. Oil patches or water turbulence appearing on the down-current side indicate that the boom is failing. Other important boom characteristics are strength, ease and speed of deployment, reliability, weight and cost.

It is essential that a boom is sufficiently robust for its intended purpose and will tolerate inexpert handling, since trained personnel are not always available. Strength is required particularly to withstand the forces of water and wind when being towed. Ease and speed of deployment combined with

reliability are clearly very important in a rapidly changing situation and may strongly influence the choice made. Practical limitations of strength, water drag and weight mean that generally only relatively short lengths (tens to a few hundred metres) can be deployed and maintained in a working configuration. Towing booms at sea, for example in U or J configurations, is a difficult task requiring specialised vessels. Because of the difficulties of operating multi-ship towed boom systems, specialised ships have been built which incorporate sweeping arms, skimming devices and on board oil storage. The limitations posed by sea conditions still also apply to these vessels, the larger examples of which are unable to work in shallow inshore waters. The efficiency of a specialised vessel will mainly be determined by the inbuilt oil recovery system or skimmer which is deployed. Because of the relatively narrow sweeping width, they are best suited to recovering oil in ribbons or windrows.

Skimmers which are used to recover oil from the water all incorporate an oil recovery element and some form of flotation or support. In addition a pump or vacuum device is necessary to transfer recovered oil and water to storage. Because skimmers float on the water surface, they experience many of the operational difficulties which apply to booms, particularly those posed by wind, waves and currents. Even moderate wave motion greatly reduces the effectiveness of most skimmer designs. In calm waters more satisfactory performance can be achieved provided the skimmer is suited to the viscosity of the oil in question. The simplest skimmers are suction devices which remove oil from the water surface directly or via a weir, although these tend to pick up a lot of water at the same time. More complex units rely on the adhesion of oil to metal or

plastic disks, or oleophilic belts or ropes. Yet others employ brush systems or are designed to generate vortices to concentrate the oil. It is important to have adequate temporary oil storage facilities available, otherwise this becomes a bottleneck to successful oil recovery. Temporary storage needs to be easy to handle, and easy to empty once full so that it can be used repeatedly. Suitable units include barges and portable tanks which can be set up on vessels of opportunity. When recovering very viscous oils, storage tanks may need to be heated to allow them to be emptied. Many factors should be considered when selecting skimmers. The intended use and expected operational conditions should first be identified before criteria such as size, robustness and ease of operation, handling and maintenance can be weighed up. The most important factors to consider are the viscosity and adhesive properties of spilled oil, including any change in these properties over time. At oil terminals and refineries where oil type may be predictable, specialized units may be selected, but otherwise it is preferable to retain versatility and select units which can deal with a range of oils. It is also important to recognize the difficulties posed by floating debris, both natural (sea weeds, sea grasses, trees and branches) and man made (plastic, glass, timber). Skimmers may need trash screens and regular unblocking where debris is common, such as near urban areas or river mouths. They will also need continuous maintenance by specialist staff and a supply of spare parts. Because of the various constraints imposed on skimmers in the field, their design capacities are rarely realized. Experience from numerous spills has consistently shown that recovery rates reported under test conditions cannot be sustained during a spill and so it is important not to have unrealistic expectations about what can be achieved. Once oil recovery is completed, booms and skimmers will need to be cleaned, overhauled and repaired, ready for use in the next spill. It is also important to inspect and test equipment regularly so that it is in good working order, and to maintain personnel training standards by regular drills.

Prevention of oil spills

As hard as people might try, accidents do occur inevitably. However, there are ways to limit such accidents and spills and avenues to ensure that response is immediate. What's Being Done to Make Shipping Safer? Double hulls or double bottoms are being introduced and, since 1993, are a requirement for all new tankers. Ships' crews must be well trained and experienced. Electronic charting is being introduced. It is a computer-based video display that allows navigators to track the ship's course in relation to hazards, and warns the navigator of potential danger, both visually and audibly. All ships must have radar systems to improve navigation. A technology known as "load-on-top" allows oil and water mixtures from cleaning to separate, resulting in less pollution. Strict fire safety regulations apply on board.

Comparison between a conventional and a double hull. Vessel Design There are a few common designs for large ships, including double hulls and double bottoms. Each design has its advantages and drawbacks. Although structural improvements to ships make tanker traffic safer, recent advances like double hulls will not eliminate spillage under all circumstances.

Oil Storage and Handling As much as 92 percent of all oil spills involving tankers happen at a terminal when oil is being loaded or discharged. Precautions at terminals include monitoring oil flows, regular inspections of hoses and connections, and routine checks of tank levels. Weather conditions are monitored closely. Dikes around storage tanks prevent oil from escaping if an accident does occur. Marine Traffic Control Marine traffic control systems are in place in many major shipping areas. The systems can be as simple as traffic lanes in heavily travelled waters or they can be very sophisticated networks. Governments are introducing control systems for marine operations similar to those we take for granted at airports. But no matter how simple or complex, traffic control greatly minimizes collisions and the risk of ships running aground.