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A Seminar Report

entitled
“Remediation
of Oil
Spillage”
Submitted in partial fulfillment of the
requirement for the award of the degree
of

Bachelor of
Technology (B.Tech)
Chemical Engineering
ABSTRACT

Anthropogenic activities pollute the oceans with oil through land run off, vessels accidents,
periodic tanker discharges and bilge discharges. Crude oil production is the largest and most
profitable business in the world. From its development phase to production phase, many
disasters have occurred in oil industries. Oil spills are environmental disasters that impact
human, plants and wild life including birds, fish and mammals. It has impact on humans as
wells as on plants and wild life, including birds, fish and mammals. Drilling and production
accidents and everyday human activities are the main causes of oil spills. The oil spills are
hazardous to environment and also affect human health. The adverse effects have been seen on
soil, ground water, plants and animals. Immediate actions are required to eradicate the spill
problem. Oil spill at any point may result into explosion and fire hazards. Effective attempts
have been made for the remediation of the soil and cleaning the water resources on onshore
and offshore. In order to clean up oil spills, a number of conventional methods are employed.
These methods are often considered inefficient. The efficiency of these methods depends on
several factors, such as the amount of spilled oil, the type of oil and polluted soil/water body
and the age and the degree of contamination. In this report, a number of innovative approaches
applicable for use in effectively and efficiently cleaning up oil spills. These techniques are
either currently part of ongoing researches or are suitable for small scale applications. These
techniques are discussed in depth and future implication and noted and highlighted.

Key words: Oil Spill, Crude Oil, Skimmers, Booms, Dispersants, In-Situ Burning, Sorbents,
Nano materials, Surfactant, Bioremediation Mechanisms.
TABLE OF CONTENTS

1. Introduction .................................................................................................................. 1
1.1 History of Oil Spill............................................................................................................... 1
1.2 Causes of Oil Spill .............................................................................................................. 3
2. Conventional Techniques for Remediation of Oil Spills ........................................... 7
2.1 Skimmers ............................................................................................................................. 7
2.2 Dispersants ........................................................................................................................... 9
2.3 In-Situ Burning .................................................................................................................. 10
3. Innovative Methods and Materials............................................................................ 12
3.1 Sorbent Materials ............................................................................................................... 12
3.2 Bioremediation Technologies ............................................................................................ 13
3.3 Nano Technology/Nanomaterials ...................................................................................... 19
4. Conclusion .................................................................................................................. 21
References ................................................................................................................... 22
LIST OF FIGURES & TABLES

Figure No. Figure Name Page No.


1. BP Oil spill-effects on aquatic life form 2
2. Exxon Valdez Oil Spill 2
3. Location of Major Oil Spills 3
4. Causes of Oil Spill 4
5. Pie Chart Representation of Oil Spill Cause 4
6. Types of Oleophilic Skimmers 8
7. Conventional Methods of Oil Spill Clean-up 10
8. Sorbent Materials 13
9. N- Alkane Biodegradation Mechanism 16
10. Cyclic Alkanes Biodegradation Mechanism 16
11. Aromatics Biodegradation Mechanism 17
12. Mechanism for PAH bioavailability enhancement using 18
13. surfactants
Nanotechnology-based solutions for oil spills 19

Table No. Table Name Page No.


1. Performance of Typical Skimmers 9
2. Major Genera of Oil-Degrading Bacteria and Fungi 14
1. INTRODUCTION

Crude oil is a dark brown to black, naturally occurring viscous rock fluid obtained from the
thermal and biological decay of plant and animal remains, in a process spanning millions of
years [1]. It is a naturally liquid with a complex mixture of organic molecules, mostly
hydrocarbon with varied chemical and physical properties. A precise description of the
chemical composition of crude oil is not practicable because of its complexity. Since crude oil
was first discovered in commercial quantities, its production, processing, and worldwide
distribution have been ever increasing. Crude oil is processed into a wide range of consumer
and industrial products via a technique regarded as fractional distillation. This technique gives
universally significant products such as gasoline, kerosene, petro-diesel and lubricating oil, and
feed stocks or raw materials for petrochemical industries, such as ethylene and butylene’s.
The production, refining, and distribution of crude oil and products based on it involves a
series of complex processes and procedures. A phenomenon referred to as “oil spill or spillage”
usually arises in the course of undertaking these processes. Oil spill is a form of environmental
pollution defined as the release of oil and oil based products into the environment in such
amounts which have the capability of harming man, animals, crops, and marine and terrestrial
habitats. Oil spill occurrence is often as a result of natural or man-made disasters, human
negligence, and acts of terror by certain individuals. It can also be caused by accidents when
oil is being loaded or discharged from tankers at seaports, oil tanker accidents at sea, oil
discharge in areas near oil wells as well as at oil storage facilities, equipment failure, land
runoff, vessels and pipeline accidents, wars, sabotage, oil theft, and natural disasters during the
production, transportation, storage and use of oil [1, 2, 3, 4, 5, 6].

1.1 History of Oil Spillage:

The first major commercial oil spill was in 1967 in the United Kingdom. It was due to an
accident in which a super tanker, Torrey Canyon ran aground on Pollard Rock off the coast of
England [7]. Other famous spills include the Kuwait oil spill (1991) with 10 million barrels of
oil spilled [8], the Exxon-Valdez (1989) in which 55 million gallons of crude oil was spilled
into Prince William Sound’s Bligh Reef in Alaska. The Deepwater Horizon explosion, also
known as the BP oil spill which started in April 20, 2010 and continued for another 87 days is
when an oil rig, Deep Horizon exploded. About 4.9 billion gallons of oil was spilled [9].

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Fig 1: BP Oil spill effects on aquatic life form [10].

Fig 2: Exxon Valdez Oil Spill [9].

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Fig 3: Location of Major Oil Spills [11]

1.2 Causes of Oil Spills:

Oil spills may originate in natural or anthropogenic causes [13].

Natural causes - such as oil that seeps from the bottom of oceans which enters the marine
environment. Crude oil is formed during long periods of time through natural processes
involving organic matter from dead organisms. Thus, oil exists in many environments and may
be naturally spilled due to various factors (including climatic conditions, disturbance, etc.).
Such natural oil spills may occur in oceans, due to eroding of sedimentary rocks from the
bottom of the ocean (the effect may be similar with that of an accidental oil spill from human
drilling in oceans such as the recent BP oil spill from the Gulf of Mexico).

Anthropogenic causes - including accidental oil spills (such as the recent BP oil spill in the
Gulf of Mexico) as well as leaks and spills due to a large variety of human activities related to
oil refining, handling and transport, storage and use of crude oil and any of its distilled products.
Thus, it is evident that a variety of sources for oil spills and a variety of ways the oil could be
spilled exist. While various anthropogenic and natural sources of oil spill pollution determine
the type and amount of oil spilled, as well as the location of the oil spill, the type of the oil spill
pollution is important for the fate and transport of the spilled oil and its impact on humans and
the environment. For example: a sudden oil spill involving large amounts spilled (thousands or

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even millions of gallons - such as that from an oil tanker failure or due to accidents in offshore
drilling) could have disastrous

Fig 4: Causes of Oil Spill [11].

effects due to the high concentrations of released contaminants and the difficulty to remediate
such big spills. At the same time, an oil spill involving small but continuous releases such as
those from leaking pipelines or road runoffs may have little visible effect (they are naturally
attenuated usually due to microbial degradation as well as due to many chemical-physical
processes).

Fig 5: Pie Chart Representation of Oil Spill Cause [12].

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The type, amount of oil discharged and its location will dictate the oil spill clean-up efforts,
which could involve deployment of adsorbent booms, controlled burning, bioremediation,
emulsification using detergents for increased degradation.
Even though numerous climate factors and natural disturbances can generate oil spills, the
main causes of oil spill pollution are usually of anthropogenic origin. The most commonly
encountered anthropogenic sources are the following:

Accidental Spills- Accidental spills may occur in various circumstances, most often during the
following activities:
 Storage - oil and oil products may be stored in a variety of ways including underground
and aboveground storage tanks (USTs and/or ASTs, respectively); such containers
(especially USTs) may develop leaks over time
 Handling - during transfer operations and various uses
 Transportation - these could be large oil spills (up to million and hundreds of million
gallons) on water or land through accidental rupture of big transporting vessels (e.g., tanker
ships or tanker trucks). For example, the Exxon Valdez spill was a massive oil spill off the
Alaskan shoreline due to ship failure which happened in late 1980’s– oil spill pollution
residuals from that spill are still affecting our environment - or smaller oil spills, through
pipelines and other devices also happens and their impact is mainly due to a large number
of usually minor spills
 Offshore drilling – Offshore drilling could result in oil spillage of large order, a massive oil
spill was observed near Gulf of Mexico due to offshore activities.
 Routine maintenance activities - such as cleaning of ships may release oil into navigable
waters. This may seem insignificant; however, due to the large number of ships even a few
gallons spilled per ship maintenance could build up to a substantial number when all ships
are considered
 Road runoff - oily road runoff adds up especially on crowded roads. With many
precipitation events, the original small amounts of oil from regular traffic would get moved
around and may build up in our environment

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Intentional Oil Discharges- Intentional oil discharges are not necessarily malevolent. Most of
them occur in the following circumstances:
 Through drains or in the sewer system. This include any regular activities such as changing
car oil if the replaced oil is simply discharged into a drain or sewer system
 Indirectly through the burning of fuels, including vehicle emissions; they release various
individual components of oils and oil products, such as a variety of hydrocarbons (out of
which benzene and PAHs could pose serious health risks).
The following processes occur when oil spills based on the water source and the type and
amount of spilled oil [5]:
1) The most common occurrence is the spread of the oil over the water surface. Light oils such
as gasoline spread faster than heavy crude. The rate of spread is also dependent on the current,
wind and temperatures. This spread makes it expedient to contain the spill as quickly as
possible.
2) There is a tendency for the oil to sink to the bottom of the water. While the density of oil
range from 0.85 - 1.04 g/cm3, most oil densities fall between 0.90 to 0.98 g/cm3 range. Ocean
water has a density between 1.02 and 1.03 g/cm3 depending on the salt concentration. River
water, however, has a density of 1.0 g/cm3 this means heavy oil, with a density of 1.01 g/cm3
would float in ocean water but sink in a river.
3) The oil can be moved by the flow of river and the surge of tides of oceans.
4) Natural bacteria can digest the hydrocarbon and convert them to CO2 and water. This can
be employed for bioremediation of an oil spill site.
5) Some oil will evaporate.
6) The oil can undergo weathering processes. This includes evaporation, dissolution, dispersion
and adsorption onto suspended materials, agglomeration etc.
7) Oxidation of the hydrocarbon by oxygen. It’s a process that slowly breaks down the
hydrocarbon.
8) Emulsification of the oil. This results from the suspension of either the oil in water or water
in the oil. The water-in-the-oil emulsion is more stable and can persist for years. Water-in-oil
often consists of 50 to 80 percent water and the water appears reddish-brown and feels greasy
due to the presence of oil.

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2. Conventional Techniques for Remediation of Oil Spills:
Several solutions have been adopted in dealing with the problems of oil spill. These
remediation technologies for marine oil spills are basically classified into three to four
categories which include physical/mechanical, chemical, thermal, and biological remediation
technologies. There involves a number of techniques such as the use of mechanical means like
skimmers, pumps, booms, and mechanical separators; using microorganisms to break down the
oil; adopting the use of chemical dispersants like detergents to break large oil slicks into tiny
droplets; in-situ burning of spilled oil; and application of sorbents to remove oil from water
through absorption and/or adsorption. Each technique comes with its advantages and
disadvantages, and the choice of a particular technique depends on several factors such as type
of oil spilled, temperature, wind speed and direction, and amongst others topographic location
of the oil spill

2.1 Skimmers:

Skimmers are mechanical devices designed to remove oil from the water surface. They vary
greatly in size, application, and capacity, as well as in recovery efficiency. Most skimmers
function best when the oil slick is relatively thick and most will not function efficiently on thin
slicks. The oil must therefore be collected in booms before skimmers can be used effectively.
There are various types of skimmers available with their own advantages and disadvantages
like:
(1) Oleophilic Surface Skimmers
(2) Weir Skimmers
(3) Suction Skimmers
(4) Vacuum Skimmers

Oleophilic Surface Skimmers are classified into various subtypes like:

(1) Disc Skimmer


(2) Drum Skimmer
(3) Belt Skimmer
(4) Brush Skimmer
(5) Rope Skimmer
A skimmer’s performance is affected by a number of factors including the thickness of the
oil being recovered, the extent of weathering and emulsification of the oil, the presence of

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debris, and weather conditions at the time of recovery operations. A skimmer’s overall
performance is usually determined by a combination of its recovery rate and the percentage of
oil recovered. The recovery rate is the volume of oil recovered under specific conditions. It is
measured as volume per unit of time e.g., m3/h, and is usually given as a range. If a skimmer
takes in a lot of water, it is detrimental to the overall efficiency of an oil spill recovery operation

Fig 6: Types of Oleophilic Skimmers [14]

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Table 1: Performance of Typical Skimmers [14]

2.2 Dispersants:
Dispersants are chemicals that are sprayed on a surface oil slick to break down the oil into
smaller droplets that more readily mix with the water. Dispersants do not reduce the amount of
oil entering the environment, but push the effects of the spill underwater. While dispersants
make the oil spill less visible, dispersants and dispersed oil under the ocean surface are
hazardous for marine life. Dispersants and dispersed oil have been shown to have significant
negative impacts on marine life ranging from fish to corals to birds. Dispersants release toxic
break-down products from oil that, alone or in combination with oil droplets and dispersant
chemicals, can make dispersed oil more harmful to marine life than untreated oil [15]. The use
of dispersants remains a controversial issue and special permission is required in most
jurisdictions. In some jurisdictions, their use is banned. In Canada, special permission is
required from Environment Canada, through the Regional Environmental Emergencies Team
(REET) or regional response team. Similarly, in the United States, special permission is

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required from the U.S. Environmental Protection Agency (U.S. EPA) and in waters near shore,
permission is also required from the state. In both countries, products must pass standard test
procedures for toxicity and effectiveness before they can be used. Only about five of
approximately 30 proposed products are approved for use in a typical year. In summary, around
the world, there is a mixed usage of dispersants. Dispersants have not been used much in North
America in the past 10 years and in Europe, only three countries occasionally use dispersants.
The use of dispersants remains a trade-off between toxicity to aquatic life and saving birds and
shoreline species. Unfortunately, dispersants are never 100% effective so that both surface and
aquatic life may be affected by a spill if it is treated. It has been shown that oil that is treated
with dispersant but does not disperse is les adhesive than oil that is untreated, although this is
not often beneficial [14].

Fig 7: Conventional Methods of Oil Spill Clean-up (A) Oil contaminant with booms; (B) A
vessel spraying dispersants; (C) Using Adsorbents; (D) In Situ Burning [16]

2.3 In-Situ Burning:


In-situ burning is an oil spill clean-up technique that involves controlled burning of the oil
at or near the spill site. The major advantage of this technique is its potential for removing large
amounts of oil over an extensive area in less time than other techniques. The technique has

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been used at actual spill sites for some time, especially in ice-covered waters where the oil is
contained by the ice [14].
Basics of In-Situ Burning
• For oil to ignite on water, it must be at least 2 to 3 mm thick. Most oils must be contained to
maintain this thickness.
• Ignition is relatively easy. More weathered and heavier oils require a longer ignition time.
• Most types of oils will burn, although emulsions may require treatment before they will burn
and the water in the oil affects the burn rate.
• Oils burn at a rate of about 3 to 4 mm per minute or about 5000 L per m2 per day.
• The emissions of importance from burning include respirable particulates from the smoke
plume, PAHs on particulate matter, and soot.
• Studies have shown that emissions from burning oil generally result in concentrations of air
contaminants that are below health concern levels 500 m downwind from the fire.
Advantages:
Burning has some advantages over other spill clean-up techniques, the most significant of
which is its capacity to rapidly remove large amounts of oil. When used at the right time, i.e.,
early in the spill before the oil weathers and loses its highly flammable components, and under
the right conditions, in-situ burning can be very effective at rapidly eliminating large amounts
of spilled oil, especially from water. This can prevent oil from spreading to other areas and
contaminating shorelines and biota. In ideal circumstances, in-situ burning requires less
equipment and much less labour than other clean-up techniques. It can be applied in remote
areas where other methods cannot be used because of distances and lack of infrastructure. In
some circumstances, such as when oil is mixed with or on ice, it may be the only available
option for dealing with an oil spill.
Disadvantages
The most obvious disadvantage of burning oil is concerns about toxic emissions from the
large black smoke plume produced. The second disadvantage is that the oil will not ignite and
burn unless it is thick enough. Most oils spread rapidly on water and the slick quickly becomes
too thin for burning to be feasible. Fire-resistant booms are used to concentrate the oil into
thicker slicks so that the oil can be burned. And finally, burning oil is sometimes not viewed
as an appealing alternative to collecting the oil and processing it for reuse. Another factor that
discourages reuse of oil is that recovered oil often contains too many contaminants for reuse
and is incinerated instead.

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3.1 Innovative Methods & Materials

3.1 Sorbent Materials:

A sorbent is “an insoluble material or mixture of materials used to recover liquids through
the mechanisms of absorption or adsorption, or both” [17]. Sorption is a popular technique
applied in order to treat spillage of oil. It is a very effective technique which contributes to the
total clean-up of spilled oil in ambient environments. Common sorbents include straw, chalk
powder, micas, ekoperl, sawdust, foams of polyether or polyurethane, nylon fibers, and
polyethylene. Investigation is being carried out to develop hydrophobic, biodegradable, and
cellulosic sorbent materials for cleaning up oil spills. Large amounts of natural sorbents and a
wide variety of natural organic products like wood, cotton, wool fibers, rice straw, peat moss,
and amongst others corn cob have for a while now attracted attention for applications in oil
spill cleanup [18]. It has been demonstrated by Adebajo and Frost that the 4-
dimethylaminopyridine (DMAP) catalysed acetylation of raw cotton samples with acetic
anhydride without solvent, prepares a sorbent with enormous hydrophobic characteristic and
high oil sorption capacity [18]. They have predicted a clear future through the potential usage
of raw cotton fibers acetylated into hydrophobic sorbent materials for cleaning up oil spills.
There are millions of tons of paper industry waste and these could end up as reusable green
solution to clean or mop up oil. With annual paper mill sludges produced in the European
Union (EU) estimated at 18 million tons (most of which is disposed by burning), the EU
organization had a few years back funded a research project whose objective was to convert
the waste sludge into a highly absorbent material with capability of cleaning up oil spills [19].
This new absorbent is capable of absorbing any oil or fluid spilled on hard or water surfaces.
So many successful tests have already been carried out using this innovative sorbent, and
several countries have begun their own production of the paper mill sludge absorbent. The
effectiveness of paper mill sludge in absorbing large amounts of oil from water was also
successfully assessed by Likon and Saarela, in which the absorbent material was perceived as
having a very efficient lifecycle [20]. This is because after carrying out a controlled
incineration, the used paper mill sludge sorbent was converted into an inorganic, inert meta-
kaolin product which could be further used as hydrophilic sorbent material. The claim of cotton
being an abundant, low cost, sustainable, biodegradable, and effective oil spill sorbent has been
furthered by the research carried out by Ram Kumar et al. (2013) [21]. The oil sorption
properties of low micronaire cotton were studied by them. Low micronaire cotton refers to a

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form of unprocessed cotton with relatively low commercial value. An estimated 30 pounds of
crude oil was reportedly sopped up and held by each pound of the material. Both absorption
and adsorption were ways employed by the cotton fibers in taking up oil. It was concluded that
raw cotton possesses high crude oil sorption capacity and is a green or environmentally friendly
sorbent for cleaning up oil spills. Lastly, oil could be sop up from the environment using
complete, parts, or products of plants and animals. As reported in the Inhabitat, first a mixture
of mushroom and hair is used to fabricate mats which offer a totally organic and effective way
to sop up oil in water [22]. This uncommon but quite effective technique was employed in the
clean-up operations of the Cosco Busan oil spill of 2007 [22]. Second spilled oil is soaked up
with hyper absorbent peat moss [22]. The method in which this works is that the super
absorbent natural peat moss is scattered on spills to absorb oil, after which it is scooped right
out of the water along with the oil. Figure shows these animal/plant based sorbents.

Fig 8: Sorbent Materials (A) Mat made from a mixture of Mushroom and Hair (B) Hyper
Adsorbent peat moss [22]

3.2 Bioremediation Technologies:

Far from being a homogeneous substance, crude oil is a complex mixture of thousands of
different chemical compounds. In addition, the composition of each accumulation of oil is
unique, varying in different producing regions and even in different unconnected zones of the
same formation. The composition of oil also varies with the amount of refining. Significantly,
the many compounds in oil differ markedly in volatility, volubility, and susceptibility to
biodegradation. Some compounds are readily degraded; others stubbornly resist degradation;
still others are virtually nonbiodegradable. The biodegradation of different petroleum

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compounds occurs simultaneously but at very different rates. This leads to the sequential
disappearance of individual components of petroleum over time and, because different species
of microbes preferentially attack different compounds, to successional changes in the
degrading microbial community. Since components of petroleum degrade at different rates, it
is difficult and misleading to speak in terms of an overall biodegradation rate. Biodegradation
rates are typically highest for the saturates, followed by the light aromatics, with high-
molecular-weight aromatics, asphaltenes, and resins exhibiting extremely low rates of
degradation. Despite the difficulty of degrading certain fractions, some hydrocarbons are
among the most easily biodegradable naturally occurring compounds. Altogether, more than
70 microbial genera are known to contain organisms that can degrade petroleum components.

Table 2. Major Genera of Oil-Degrading Bacteria and Fungi [23]

Biological method of oil spill cleanup involves using living organisms or by-products of
living organisms to assist in cleaning up the mess left over after oil has been spilled, either in
the marine or land environment. The most common biological method in oil spill cleanup is
bioremediation, a technique which could simply be described as the use of organisms to cause
the breakdown and further detoxification of dangerous chemicals or contaminants present in

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the environment. Bioremediation takes place in different forms. There is bio augmentation
which involves the addition of bacterial culture to the contaminated soil or water. In other
words, it is the addition of microorganisms which have the capability of bio-transforming or
biodegrading given contaminants. Bio stimulation on the other hand involves the addition to a
contaminated environment of microbial nutrients which are needed for increase in microbial
activities of indigenous flora and fauna. The nutrients added are mostly major nutrients such
as carbon, oxygen, nitrogen, and phosphorus which boost the number and/or activity of
naturally occurring microorganisms readily available for bioremediation. Microorganisms aid
in breaking chemical bonds and transferring electrons away from organic compounds in an
oxidation-reduction reaction process [24].

Bio remediation Mechanisms:

Hydrocarbon compound structure is important in bio-degradability. The n-alkanes (straight


chain) and n-alkyl- aromatics (substituted aromatic) in the C10 to C22 range are considered to
be of low toxicity and the most biodegradable. Hydrocarbons above C22 have lower toxicity
and are generally considered less biodegradable due to their physical characteristics, which
include low water solubility, sorption onto surfaces, and a solid to semi-solid state at 35°C.
Compounds in the C1 to C4 range are gaseous and considered to be biodegradable, but this is
not the typical mechanism employed to remove these. Counterparts in the C5 to C9 range have
high solvent-membrane toxicity to microorganisms, but in low concentration they are
considered to be easily biodegradable. Branched n-alkanes and cyclo-alkanes are less
biodegradable as their tertiary and quaternary carbon atoms inhibit the ß-oxidation step
required for degradation. Aromatic hydro-carbons are biodegradable, but the bioavailability of
high molecular weight compounds such as PAH’s (Polycyclic aromatic hydrocarbons)
decreases dramatically as the number of condensed rings increases. These compounds
exhibiting lower biodegradability due to surface absorption and low solubility are commonly
referred to as recalcitrant or xenobiotic [25].

N-Alkane

The biological degradation pathway for n-alkane (straight chain) and branched alkanes has
been well established and reported extensively in literature. The biodegradation pathway for n-
alkane is shown below. Typically, the degradation pathway consists of the following steps:
● Initial enzyme catalysed oxidation to produce primary fatty alcohol.

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● Sequential oxidation of the alcohol to fatty acid.
● Oxidation of the ß-carbon to produce a ß-keto acid.
● Decarboxylation to produce a degraded alkane.

Fig 9: N- Alkane Biodegradation Mechanism [25]

Cyclic Alkanes

Even though cyclic alkanes are very similar in structure to n-alkanes, their biodegradation
pathway appears to be fundamentally different.

Fig 10: Cyclic Alkanes Biodegradation Mechanism [25]

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Although not fully characterized, it has been reported that the following Steps are required:
● Sequential enzyme mediated oxidation of the ring to form a cycloalkanone
● Baeyer-Villager type oxidation of the cyclic ketone by an as yet uncharacteristic second
oxygenase enzyme to produce a lactone
● Hydrolysis, resulting in ring fission, to generate what amounts to an oxidized n-alkyl fatty
acid that can be further degraded by the mechanism outlined in the n-alkane pathway.

Aromatics

Simple aromatic or "benzenoid type" compounds generally pose no resistance to microbial


degradation for a large variety of microorganisms. The key factor in the degradation of
aromatic compounds by these ring fission enzymes is their ability to destroy the resonance
contained within the ring. This can be accomplished, however, only by the initial positioning
of at least two hydroxyl groups, either ortho or para, relative to each other. The biodegradation
of aromatic compounds proceeds via two well-established pathways: a) catechol and b). In both
pathways, ring activation is followed by ring cleavage and the subsequent transformation of
the fission products. The degradation of substituted aromatics, such as ethyl- benzene and
toluene, would also proceed via an analogous pathway. These products, once generated, would
then follow a similar microbial mineralization as outlined in the n-alkane pathway.

Fig 11: Aromatics Biodegradation Mechanism [25]

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Bioavailability Enhancement Mechanism:

The mechanism for PAH bioavailability enhancement using surfactants are as follows. (A)
Direct uptake of the PAH from partial micelle, (B) uptake for PAH from aqueous phase after
release from partial micelle, (C) facilitated direct uptake of PAH via cell-surfactant-PAH
contact, and (D) hypothesized non-micellular bio surfactant enhancement of PAH
solubilisation.

Fig 12: Mechanism for PAH bioavailability enhancement using surfactants [25]

Although bioremediation is a very slow process which requires weeks and months for
effective cleanup, it is a universal method of oil spill cleanup due to its cost effectiveness and
less requirement of high skilled technology and technical know-how. In addition, minimal
environmental impact is expected from bioremediation because it is a natural process.

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3.3 Nanotechnology/Nano materials:

The usage of nanostructures, materials and devices of their like for the remediation of oil
contaminated soil and water has gained so much popularity in recent years due to the great
advantages which nanoparticles bear over conventional methods. This is as a result of their
much larger surface area on a mass basis. A characteristic structure and certain electronic
properties also make nanoparticles excellent adsorbents of most common land and aquatic
pollutants. Highly dense order cuprous oxide (Cu2O) Nano rods on phosphor-copper mesh were
prepared from simple aqueous solution-immersion process, and the surface of the Cu2O
nanostructures was modified with 1-dodecanethiol which impacted super hydrophobicity and
superoleophilicity, as reported by Kong [26]. This structure was used to make a mini boat
which floated freely on water surface and in situ collected oil from the water surface. The
demonstration has shown its promise for application in oil-water separation and offshore oil
spill cleanup. A tea-bag shaped nanocomposite system was developed by Avila et al. for oil
spill cleanup using the nanotechnology approach [27]. The nanocomposite system combined
super hydrophobic Nano membranes and oleophilic graphite Nano platelets. Results obtained
have shown an average oil sorption capacity peak of 32 g/g. The tea-bag shape design ensures
that the system possesses high efficiency and easy recyclability. Oil spillage on seawater also
requires the development of oil sorbents with the following characteristics: high sorption
capacity, high selectivity, low cost, and scalable fabrication. Lin et al. reported the use of
nonporous polystyrene (PS) fibers which were prepared through a one-step electrospinning

Fig 13: Nanotechnology-based solutions for oil spills [28]

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process as oil sorbents for oil spill up. The Nano-sorbent had an oleophilic-hydrophobic
character. It had highly porous structures.
Various other techniques are also in currently development phase for spill remediation, like
use of robotic bots which can sense the oil spill area and take necessary remediation steps in
response to the intensity of spill are researched currently. Collective approach and appropriate
measures and more investment in research and development methods could lead to more
effective and handy system to face this challenging problem of oil spill.

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Conclusion

Oil Spill is major concern worldwide, millions of dollars are wasted in treatment of Oil Spills
It has a great effect of human beings and environment, the ecosystem/ flora and fauna are
greatly disturbed due to the oil spill. The causes of oil spill is discussed, various factors human
activities are responsible for oil spill. The oil spill conventional response method included
booms, skimmers, dispersants, in-situ burning are discussed with their advantages and
disadvantages. New Innovative Methods are also discussed like Sorbent Materials,
Bioremediation, Nanotechnology / Nanomaterials. These techniques offer better quality clean
up than conventional methods such as containment booms, skimmers, and use of dispersants
amongst others. Their superiority is attributed to their unique properties such as cost-
effectiveness, biodegradability, recyclability, and higher yield of oil-water mixture separation.
It could be deduced from this review that the use of innovative sorbent materials remains the
most widely used technique and the most effective in oil recovery from areas of oil spillage.
Most of the techniques reviewed in this report are still being researched on or can only be used
for small scale applications. Further extensive researches and adequate financing would ensure
that these techniques are fully replicated to large scale operations, opening up ground for
efficient and effective oil spill cleanups the likes of which have never been seen before.

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