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Last Update: 4 November 2017 Part - II

Oil Pollution of Water Bodies M - 15


Oil is a complex (hydrocarbon), naturally occurring mixture of organic compounds (hydrocarbon) that is
produced by the incomplete decomposition of biomass over a geological long period.

Chemical nature:- The oils are chiefly hydrocarbons either


saturated or unsaturated in nature. They either may be of
long chain fatty acid or hexane derivatives. Structures
assumed by hydrogen (H) and carbon (C) molecules in four
common hydrocarbon compounds. They may of,

Classification /chief constituents :- The hydrocarbon may


be classified into 3 broad categories and each with various
subclasses (Clark and Brown, 1977; Kornburg, 1981).
1) Aliphatic hydrocarbon :- This are open chain
compounds and are saturated, if there is single bond
among all adjacent carbon atom, this may be branched or
unbranched and saturated or unsaturated.

In case of unsaturated molecule have at lest one double or triple bond like as in ethane and acetylene
C=C CC
Ethane Acetylene
2) Alicyclic hydrocarbon :- This have a four/five carbon ring at the part of their structure or total carbon
atoms arranged in such way including 4/5 carbon ring structure and usually they may be saturated or
unsaturated.
CH3

3) Aromatic hydrocarbon :- These are the hydrocarbons that contain at least one 6 carbon ring in this
molecular structure. The basic ring is C6 H6 and Known as Benzene ring and may be either of saturated or
unsaturated.

Petroleum crude oils are complex mixtures of hydrocarbons, chemical compounds composed only of
carbon (C) and hydrogen (H). Crude oils from different location greatly varying in their hydrocarbon
composition. The 3 most important groups of hydrocarbons in petroleum are.

1) Long chain hydrocarbon, paraffin molecule, their hydrocarbon ranging from single carbon to more
than 17 carbons.
2) Saturated and unsaturated and 5 carbon ring with /without branch hydrocarbons chain (alicyclic
derivatives) and with in it on overage about 1% by weight of aromatic hydrocarbons (one 6 carbon ring
structure) are found.
3) The aromatic hydrocarbons with more then one or two benzene ring generally called polycyclic or
polyneuclear aromatic hydrocarbon (PAH) and their great varieties eg. Benzopyrine, Benzoanthracenc,
napthane, etc.

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Saturated molecules
The simplest of the hydrocarbon molecules is methane (CH4), which has one carbon atom and four
hydrogen atoms per molecule. The next simplest, ethane (C2H6), has two carbon atoms and six hydrogen
atoms. A whole class of hydrocarbons can be defined by expanding upon the relationship between methane
and ethane. Known as the paraffins, this is a family of chainlike molecules with the chemical formula C nH2n +
2. These molecules are also referred to as saturated, since each of the four valence electrons on a carbon
atom that are available for bonding is taken up by a single hydrogen or carbon atom. Because these single
bonds leave no valence electron available for sharing with another atom, paraffin molecules tend to be
chemically stable.

Paraffins can be arranged either in straight chains (normal paraffins, such as butane; see figure) or
branched chains (isoparaffins). Most of the paraffin compounds in naturally occurring crude oils are normal
paraffins, while isoparaffins are frequently produced in refinery processes. The normal paraffins are uniquely
poor as motor fuels, while isoparaffins have good engine-combustion characteristics. Longer-chain paraffins
are major constituents of waxes.

Once a hydrocarbon molecule contains more than four carbon atoms, the carbon atoms may form not
a branched or straight chain but a closed-ring structure known as a cyclo-compound. Saturated cyclo-
compounds are called naphthenes. Naphthenic crudes tend to be poor raw materials for lubricant
manufacture, but they are more easily converted into high-quality gasolines than are the paraffin compounds.

Unsaturated molecules

Two other chemical families that are important in petroleum refining are composed of unsaturated molecules.
In unsaturated molecules, not all the valence electrons on a carbon atom are bonded to separate carbon or
hydrogen atoms; instead, two or three electrons may be taken up by one neighbouring carbon atom, thus
forming a double or triple carbon-carbon bond. Like saturated compounds, unsaturated compounds can
form either chain or ring molecules. Unsaturated chain molecules are known as olefins. Only small amounts
of olefins are found in crude oils, but large volumes are produced in refining processes. Olefins are relatively
reactive as chemicals and can be readily combined to form other longer-chain compounds.

The other family of unsaturated compounds is made up of ring molecules called aromatics. The simplest
aromatic compound, benzene (C6H6), has double bonds linking every other carbon molecule (see figure). The
double bonds in the benzene ring are very unstable and chemically reactive. Partly for this reason, benzene is
a popular building block in the petrochemical industry.

Unsaturated hydrocarbons generally have good combustion characteristics, but their reactivity can lead to
instability in storage and sometimes to environmental emission problems.

Types of crude oil

The above description of hydrocarbons refers to simpler members of each family, but crude oils are actually
complex mixtures of very long-chain compounds, some of which have not yet been identified. Because such
complex mixtures cannot be readily identified by chemical composition, refiners customarily characterize
crude oils by the type of hydrocarbon compound that is most prevalent in them: paraffins, naphthenes, and
aromatics. Some crude oils, such as those in the original Pennsylvanian oil fields, consist mainly of paraffins.
Others, such as the heavy Mexican and Venezuelan crudes, are predominantly naphthenic and are rich in
bitumen (a high-boiling semisolid material frequently made into asphalt for road surfaces).

The proportions of products that may be obtained by distillation of five typical crude oils, ranging from heavy
Venezuelan Boscan to the light Bass Strait oil produced in Australia, are shown in the figure. Given the
pattern of modern demand (which tends to be highest for transportation fuels such as gasoline), the market
price of a crude oil generally rises with increasing yields of light products. It is possible to process heavier
crudes more intensely in order to improve their yield of light products, but the capital and operating costs
required to support such high conversion processes are much greater than those required to process lighter
crudes into the same yield of products.

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Product content of five major crude oils.

In addition to the hydrocarbons, compounds


of sulfur, nitrogen, and oxygen are present in
small amounts in crude oils. Also there are
usually traces of vanadium, nickel, chlorine,
sodium, and arsenic. These elements may
affect the safety of oil-transport systems, the
quality of refined products, and the
effectiveness of processing units within a
refinery. Minute traces can usually be
tolerated, but crudes with larger amounts of
these materials must be extensively treated
in order to restrict their harmful effects.

Effects of Oil-Pollution :- It has harmful effect


on living organisms and therefore it is very important.
a) Physical effects :-
1) Oil-pollution of the sea attracts the great public attention because it has got a direct impact of human
civilization.
2) The oil pollution caused oil coating and creates asphyxiation that reduced the primary productivity
decrease quality of water; create hypoxic condition of many aquatic animals.
3) Birds are greatly affected by this oil pollution.
4) Oil film on the surface of natural water reduced light transmission which in turn reduced primary
production and retard the oxygen uptake by water.
b) Chemical effect :- The chemical effect of the oil pollution is very much dangerous then that of
physical effects.
1) It can produced anaesthesia and narcosis in many lower organisms.
2) Inhibits the blood cell formation in bone marrow.
3) Local irritation of the respiratory system and excitation and depression of CNS.
4) It may acts as mutagenic /carcinogenic / teratogenic.
5) Exhibit phenomenon like food chain accumulation or Biological magnification.
Such types of effect are created by the oil pollution where the consumption where occurs or in the sea
where the transportation is carried out either by oceanic tanks or pipelines from which oil may spill out and
caused pollution therefore the great attention will be given on the sources of oil pollution and its proper
management to remove the hazards of oil pollution.
Sources of oil pollution :- Water as well as soil is polluted by the oil by means of different sources like,
1) Oil spill from wrecked super tanker.
2) Oil spills from off- sore drilling ridges?
3) Experimental oiling of salt marsh vegetations.
By the above 3 main way the water and soil is polluted by the oil, and crate the hazardous condition.
1) Oil spills from wrecked super tanker.
a) Wrecked tanker transportation :- the world production of crud oil is about 3 million tone/year. And
half of it is transported by the sea through tanker (Clark, 1989). During the unloading of the Cargo a
certain amount of oil remain clinging to the wall of the compartment and this may amount to as much as
800 ton in a two lakes ton tanker capacity.
b) Dried docking :- All ships including oil tanker required periodic dried docking for servicing, repairing
etc, then it is essential that all oil to be the removed from the cargo compartment, in the mean time the
oil are licked out and polluted the environment.
c) Marie terminals:- Accident through human error and pipeline failure are an inevitable
accompaniment to loading oil to tanker and discharging it in oil terminals.
d) Tanker accidents:- The tanker accident the major sources by which large amount of oil is drainage
into sea or if accident occurs closed to the sore, coastal pollution is immediately results.
And oil spills from off sore drill platforms is one of the notable sources and cause of oil pollution.
4) Miscellaneous sources :

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a) Atmospheres : The incomplete combustion of the petrol or diesel vehicles results in pollution of
hydrocarbons being released result into the atmosphere, these are precipitate and swept out by rain
either direct by into the sea or indirectly by contribution into the river runoff.
b) Municipal and industrial wastes :- Domestic wastes and sewage contents considerable quantity of
oil, greases, petroleum hydrocarbons. In the costal areas this wastes are often discharged in to the
sea or it is drained into the river is a municipal drain and disposed into sea through the river runoff.
c) The coastal oil refineries :- In the refineries required a large amount of water and total discharge of
such water are not negligible after the used in refineries this water contain considerable amount of
this hydrocarbon and this is continuously discharged into sea by either directly by or indirectly is a
river runoff.
1) Licensed dumping at sea:- Shipping channels in estuarine and spiels need regular dragging. The
dragging spiel, which is usually dumped at the sea, is contaminated in the soil.
2) Oil spills from offshore drilling ridges:- In the off sore area, from where through mining and pumping
out the oil during this process the process the considerable amount of oil are continuously
contaminated with the sea water as is happens in the Gulf region.
3) Experimental oiling of the salt marsh vegetation :- Using as an insecticides, and to eradication of the
insect the experimental oiling is done in the different region, particularly in the salt marsh
vegetation which is a direct source of oil pollution of sea water.

Fate of Spilled oil :-


When oil once discharged into the marine environment undergoes various biochemical and
photochemical degradation. Specially with low molecular weight hydrocarbons evaporating first and the oil
spill on the surface of sea water spreading along the water surface to form a thin or thick film depending
upon the,
1. Molecular weight of the hydrocarbon.
2. Sea temperature.
3. Nature of the oil.
4. Physical process of oceanic water.
Low MW > The lighter oil sprayed faster and formed to a thinner films then heavy waxy oil, higher sea
temperature are responsible for production of thinner film of hydrocarbon, and if the nature of oil is volatile
they quickly evaporated or remain suspended on the / in the water. The physical processes of the surface of
the ocean water is also responsible for the of oils over the surface of water spreading of oils over the surface
of water.

High MW > The heavy molecule weight hydrocarbons either get dissolved or being heavy tars edging
collecting suspended matter, in that process this ultimate form a Chocolate mousse which settled to the
bottom and brought up by prevalent current pattern on the surface or are washed into beaches.

~ MW > While the moderate molecular weight hydrocarbons gradually fractioned, inaugurated into water
soluble component which is dissolved in water column and unmixable component become emulsified and
deposited as a small droplets. The rate of emulsification depends upon the agitation provide by oil and water
turbulence.

The spilled oil can also be acts as a solution for wide varieties of organic pesticides / pollutant.
So, the volatile components of oil (low boiling aromatics paraffin and cycloparaffins < 12 C atoms)
readily evaporate. Highly soluble hydrocarbons (aromatics) are removed by dissolution, paraffin and some oil
are readily degraded by bacteria more resistance cycloparraffin and aromatic hydrocarbons disappear at
much lower rate.

Heavy oil residences that are not degraded or deposited on sediments end up as far lumps or tar balls
and ultimate washed into the beaches and caused pollution.

The discharged oil-slicks of Indian Marine Zone :--

Sengupta and Kureishy, (1981) reported observation of oil slicks and other floating pollutants from
the data obtained from the Japan National Oceanographic Data Centre (JNODC). Out of 6689 observations,

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5582 or 83.5% of total showed positive signs of oil slicks or other floating pollutants in Northern Indian
Ocean.
In the sampling data of this observation clearly indicated that the oil-slicks are frequent along the
tanker routes while south of the equator there is hardly any tress of oil pollution in the Indian ocean.
Floating tar observations too revealed that a range of 0.0 to 6.0 mg / m 2 with a mean of 0.59 mg.
/m2 in the Arabian sea, the range of the floating tar along the tanker routs in the southern Bay of Bengal was
0.0 to 69.75 mg / m2 with a mean of 1.52 mg / m2 indicating this area to be the more polluted then those
across the Arabian Sea.
It was also observed that the occurrence of floating tar largely depends on the prevailing current
patterns. Near absence of floating tar particles were noted during extensive observation made in Jun-
Sep1983 along the west going tanker rout. This can be explained by the fact that during the period of study,
the surface current of Arabian sea normally flow towards the Indian west coast. These tar particles have a
residence time of 30-15 days before they start sinking towards the bottom.

Fate of oil slicks in Indian Marine Water :--


The concentration of dissolved and dispersed petroleum hydrocarbons in upper 20 meters in the
Arabian Sea and Bay of Bengal are quite uniform excepting some occasional high values. Seasonal variation
could be observed which could be attributed to the varying intensity of tanker traffic and environmental
conditions. The value from 1978 to 1987 reduced appreciably with the reduction in volume transported. This
lead us to believe that due to oil pollution of traffic an apparent improvement in oil pollution could be
concluded from the data of tanker routes across the Arabian sea and Bay of Bengal.

How much controlled ?


The reduction was sharp from 1979 to 1980 in the Arabian Sea and from 1980 to 1981 in the Bay of
Bengal. There after the condition appear to have stabilized in both the areas.
Cargo ships and oil tankers, visiting Indian ports, many cause oil pollution in harbour waters by
operations or accidental discharges of oil and oily ballasts. The deposition of tarry lumps on the Indian
beaches was first studied in 1975 when it was found that, specially the beaches of west coast were soiled
with tar particles during the SW monsoon season.
This is mainly because of the on shore component of the along shore current is strongest from April /
May to Sep / Oct. studies in 1975 and 1976 on several beaches of the west coast gave a range of 22 to 448
gm2 with peak values on one occasion, of 1386gm2. This deposition decreases to almost nil during the
reversal of current pattern. The computed total deposit on beaches along with west coast of India are 1000
and 750 tonnes for 1975 and 1976 respectively (Dhargalkar, et. al., 1977)

Environmental impact of oil spill :-- The crud oil in environment caused various types of harmful effect, the
cumulative effect of the many minute spills that hand occurred both on land and sea may be at least as
serious.

The harmful effect of oil on living organisms may be divided into two.

1) Physical effect of oil spills / oil pollution :--


a) Decreases of light penetrability :-- Oil is generally lighter and are float on the surface of water as a
layer, the thick layer of such film of spilled oil reduced the rate of light penetration which is very much
necessary for the production of photosynthesis. Therefore the primary production is decreases which in
turn affect on the lighter forms.
b) Decrease of oxygen up take by water :-- Due to hydrophobic and impermeable nature of the oil, the
film of the oil-spill inhibited the interchange of O2 at the water air surface. Therefore, the dissolved
oxygen in that area are became depleted which in turn affect on the higher form of the tropic level
population density of planktonic form simply decrease and this area becoming less production area.
c) Destruction of neuston:- The plankton and specially neuston ( the organism which restricted on the
surface of the water ) are subjected to damage caused by the higher concentration of following oil due to
hypoxic condition and skin burning.
d) Destruction of Birds (sea birds) :- By the oil coating caused a lot of destruction in the community of
sea birds by matting the feathers, the oil destroyed there insulation capacity, reduced buoyancy in water
and prevent flight, so that this animal may die from drowning and from an excessive heat loss leads to
hypothermic situation, inactive and death.

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e) Prohibited the water turbulence :- By the thick layer of the oil on the sea surface cased the probation
of water turbulence therefore the film of the spill oil remain at a area and caused much destruction of
inside inhabitant plankton, fishes, etc. There fore the nutrition status is depleted.
f) Changing the biological habitat:- The most of the marine as well as terrestrial species end avoid the
oil-coating and its harmful effect except same oil eating bacteria.

2) Chemical Effect of spill oil:- the chemical effect of oil can be related to the components involved.
a) Anaesthetic condition :- Low boiling point saturated hydrocarbons, at best up to octane can
produce anaesthesia and narcosis due to inhibition of nerve impulses, potent inhibitory function of
acetylcholine esterase enzyme.
b) Direct toxicity :- The law boiling point soluble aromatic hydrocarbons fractions ( C 10 or less ) are
even more toxic, and their greater water solubility tends to enhance distribution and uptake by
aquatic organism. Adult marine organisms do not survive after exposer to 1 to 100 ppm of soluble
aromatic for the larvae the lethal dose in 0.1 ppm. Even sub lethal dose (10 100 ppb) of these
compound disrupt chemical sensing and communication system of marine organisms e.g. Benzene,
toluene, nepthane and phenanthrene are amongst the compound in the group.
c) Respiratory irritation :- Benzene characteristically inhibits the blood cell formation in bone
marrow and benzene, toluene, naphthalene etc all cause local irritation of the respiratory system.
d) Interface to sex attractants:- Higher boiling point saturated and aromatic hydrocarbons may not
exert much direct toxicity but may interfere with the responses of aquatic organism to chemical
stimuli, such as sex attractants, with equally serious consequence.
e) Bioaccumulation /food chain amplification :- Since many of the components of oil chemically
stable and not readily metabolised or excreted once absorbed, they are subject to food chain
amplification. In this way, they may give unpleasant flavours to food for human consumption or
render it toxic.
f) Accumulation fat soluble toxicants :- It is even conceivable that oil natural water may
concentrate fat soluble toxicant by the partitioning process thus enhancing their toxicity.
g) Mutagenic and carcinogenic effect :- The much higher molecular weight aromatic compounds
like 3,4 benzopyrene and 1,2 benzoanthracene have attracted considerable attraction because
they are not only potent mutagen (alter the DNA backbone) but they are believed to be the main
carcinogens. They are found in petroleum and industrial products, and are also synthesized by
plants.

They cause mutation either by direct covalent bonding with DNA or by wedging themselves into the DNA
helix and in some way by inducing oncogene produces cancer / tumour in the susceptive organism.

Therefore, environmental damage may occur long after input to the environment has ceased, and it the
continued the potentially will increased. For these reason special precaution must be taken to minimize the
anthropogenic contribution.

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