1

INTRODUCTION
Trace metals are metals occurring at 1000mg/kg or less in the earth crust.
Depending on their densities, these elements can be classified as light or
heavy. Metals with densities greater than 5g/cm
3
are heavy metals while those
with densities less than 5g/cm
3
are light metals (Osuji and Onojake, 2004).
Trace elements in petroleum have received increased attention in recent years
because of their importance both in genesis of petroleum and its refining.
Recent advances in analytical techniques, including inductively coupled
plasma emission spectrometry, have led to a resurgence of interest in metal
occurrence in petroleum and in the application of transition metal information
to natural resource exploration.
The presence of metals in oil may be a useful indicator of nearby ore deposits
(Hitchon, 1977).

The nature of these metals and their abundance in crude oil can give
information on the origin, migration, and maturation of petroleum.
Vanadium, nickel, iron and copper are normally found in petroleum as
naturally occurring elements associated to the formation process and although
present only in small amounts (g g1 or ng g1 levels), they are very
important to the petroleum industry .
Their determination is of considerable importance, since they have deleterious
effects on refinery operation and performance.
They may corrode refinery equipment, poison and foul catalysts and/or cause
undesirable side reactions in refinery operations (Brandao et al., 2007).

In addition, the ash of certain oils and solid bitumen has been proposed as an
exploitable metal-containing resource, particularly in the case of heavy oils
(Skinner, 1952; Erickson et al., 1954).
Despite these potential applications, virtually little systematic investigations of
the uses of metal information in resource exploitation have been published,
although the use of metal data in petroleum exploration was first suggested
many years ago (American Petroleum Institute, Project 43,1947).
The current interest in using metal concentrations in crude oil as a proximity
indicator for nearby commercial ore deposits once again raises the suggestion
that knowledge of the occurrence and distribution of transition metals may also
have direct application in petroleum exploration (Zhang et al., 1981).
Studies of metals in petroleum have focused on heavy oils, primarily because of
their high concentrations of transition metals and the fact that these high
concentrations poison refining catalysts.
As industrial utilization of heavy oils increases, knowledge of the concentration
and chemical occurrence of metals in petroleum has become increasingly
critical.

Detailed chemical information concerning the molecular association
2

of metals in heavy oil will provide insight into rapid and cost-efficient methods
of their removal. As a preliminary step to utilizing metal data in refining
research and petroleum exploration, precise determination of elemental
concentrations in whole oils and their compound class fractions can be useful
in establishing the molecular association of organometallics in petroleum.
Eventually information from organometallic compounds in crude oil will be
routinely used to supplement that provided from analysis of hydrocarbon
fractions.
Petroleum consists predominantly of hydrocarbons, and contains measurable
quantities of many metals such as Iron (Fe), Zinc (Zn), Nickel (Ni), Vanadium
(V), Chromium (Cr), Cadmium (Cd), Copper (Cu), Lead (Pb) Manganese(Mn),
Cobalt (Co) etc.

These trace metals are simply a reflection of those picked up during migration
or in the reservoir, and incorporated directly into oil in form of porphyrin
complexes (species) in petroleum source rocks from the biomass and formation
during sedimentation (Akinluaet al., 2007).
It may also involve digenesis from organic molecules as well as metals derived
from different biogenic (biomass) and abiogenic (Weathering of minerals)
sources.

Metals of proven association with organic matter may be used as reliable
correlation tools (Akinluaet al., 2007). Nickel, Vanadium and Cobalt (usually
referred to as biophile elements) are such examples.
Also, the nature of metals in crude and residual oils is of interest to the refiner
as they are the source of environmental pollutants and the cause of corrosion
of equipment and poisoning of process catalysts. Nigeria recently has witnessed
an increase in oil pollution due to equipment failure, inexperienced operators
and sabotage.
The increasing rate of corruption, perceived marginalization and
unemployment have given rise to many illegal refineries and bunkering in Niger
Delta and Oguta is not an exception.
These unprofessional that engage in these acts discharge their waste in our
environment without considering their effects in our environment. In other to
save ourselves and environment there is need to have qualitative and
quantitative knowledge of trace metals present in the crude oil and their effects
to aquatic and terrestrial lives


Majority of the known metals and metalloids are very toxic to living organisms
and even those considered as essential, can be toxic if present in excess.
Concentrations of several toxic metal and metalloids have been largely
increased as a result of human activities. The recent flooding has shown that
not only the areas where these activities are carried out can be polluted.
There is the need for us to know what happens in our environment and our
neighbors in other to protect ourselves.
3



FORMATION OF CRUDE OIL
Petroleum is a fossil fuel derived from ancient fossilized organic materials, such
as zooplankton and algae. (Keith A. (2006). Vast quantities of these remains
settled to sea or lake bottoms, mixing with sediments and being buried under
anoxic conditions. As further layers settled to the sea or lake bed, intense heat
and pressure built up in the lower regions. This process caused the organic
matter to change, first into a waxy material known as kerogen, which is found
in various oil shale around the world, and then with more heat into liquid and
gaseous hydrocarbons via a process known as catagenesis. Formation of
petroleum occurs from hydrocarbon pyrolysis in a variety of mainly
endothermic reactions at high temperature and/or pressure.
[
Chemical
Reaction Model for Oil and Gas Generation 2010
]

There were certain warm nutrient-rich environments such as the Gulf of
Mexico and the ancient Tethys Sea where the large amounts of organic material
falling to the ocean floor exceeded the rate at which it could decompose. This
resulted in large masses of organic material being buried under subsequent
deposits such as shale formed from mud. This massive organic deposit later
became heated and transformed under pressure into oil (Broad, William J.
August 2, 2010).
Geologists often refer to the temperature range in which oil forms as an "oil
window"below the minimum temperature oil remains trapped in the form of
kerogen, and above the maximum temperature the oil is converted to natural
gas through the process of thermal cracking. Sometimes, oil formed at extreme
depths may migrate and become trapped at a much shallower level. The
Athabasca Oil Sands are one example of this
CLASSIFICATION OF CRUDE OIL
Crude oil otherwise known as petroleum (from Greek: petra (rock) + Latin:
oleum (oil)) is a composition of hydrocarbons (chemicals composed solely of
hydrogen and carbon in various molecular arrangements) and other
compounds which is usually brown or black in color.
Classifications of crude oil is based on the geographical locations, sulfur content and
relative weight but the major classification is done based on the location, as the oil
comes from various parts of the world and they differ in their
physiognomies(characteristics).
PHYSICAL PROPERTIES OF CRUDE OIL
4

A crude oil assay is essentially the chemical evaluation of crude oil feedstock
by petroleum testing laboratories. Each crude oil type has unique molecular,
chemical characteristics. No crude oil type is identical and there are crucial
differences in crude oil quality. The results of crude oil assay testing provide
extensive detailed hydrocarbon analysis data for refiners, oil traders and
producers. Assay data help refineries determine if a crude oil feedstock is
compatible for a particular petroleum refinery or if the crude oil could cause
yield, quality, production, environmental and other problems. The assay can be
an inspection assay or comprehensive assay. Testing can include
crude oil characterization of whole crude oils and the various boiling range
fractions produced from physical or simulated distillation by various
procedures. Information obtained from the petroleum assay is used for detailed
refinery engineering and client marketing purposes. Feedstock assay data are
important tools in the refining process.


EFFECT OF TRACE METALS ON THE ENVIRONMENT
There are around thirty chemical elements that play a pivotal role in various
biochemical and physiological mechanisms in living organisms, and recognized
as essential elements for life.
Majority of the known metals and metalloids are very toxic to living organisms
and even those considered as essential, can be toxic if present in excess.
Concentrations of several toxic metals and metalloids have been largely
increased as a result of human activities. The metals can enter the
environment by accidental oil spills or through combustion products of the
refined crude oil (Osuji and Onojake 2004).
They can disturb important biochemical processes, constituting an important
threat for the health of plants and animals. Plants and animals absorb these
elements from soils, sediments and water by contact with their external
surfaces, through ingestion and also from inhalation of airborne particles and
vaporized metals [Mudgal V, Madaan N, Mudgal 2010].
The requirement for ingestion of trace metals such as Fe and Cu ions to
maintain normal body functions such as the synthesis of metallo-proteins is
well established. However, cases of excess intake of trace metal ions are
credited with pathological events such as the deposition of iron oxides in
Parkinson's disease [Candelaria M et al 2006].
In addition to aiding neurological depositions, these redox active metal ions
have been credited with enhancing oxidative damage, a key component of
chronic inflammatory disease [Pineda C, et al 2006] and a suggested initiator of
cancer [Ahankour F 2008].
As inflammation is a characteristic feature of a wide range of diseases, further
potential pathological roles for metal ions are emerging as exemplified by
5

premature ageing [Carballo N 2008].
For the maintenance of health, a great deal of preventative measures is in place
to avoid ingestion of potentially toxic metal ions.
From monitoring endogenous levels of metal ions in foods and drinks to
detecting contamination during food preparation. European countries spend
significant resources to avoid metal intake by the general population [Kozaki K
2002]. From a therapeutic viewpoint, considerable research and development
efforts are being exerted to decorporate metal ions from the body.

SIGNIFICANCE OF METALS IN CRUDE OIL

Metals are present in crude oil at concentration levels from few parts-per
million (ppm) in heavy crudes to parts-per billion (ppb) in light crudes. The
negative effects of metals include the catalyst poisoning and fouling, corrosion
of equipment and particulate emissions into the environment, and the
contamination of petroleum-related products.
On the other hand, the metals are often used as tracers in geochemical
prospecting.
Their isotopic ratios are used for oil-oil or oil source rock correlation or for
identification of the source rock depositional environment and in the
quantification of the oils thermal maturity and biodegradation levels (Caumette
et al., 2009). Ratios such as vanadium to vanadium plus nickel and iron to
vanadium are suggested as being useful for oil type characterizations.
Transition elements concentrations and ratios can serve as excellent oil-oil
correlation parameters. Generally, vanadium and nickel content increases with
asphaltic content of crude oil (API gravity is an indicator). The lighter oils
contain less metal (Caumette et al., 2009).
In diesel fuels, vanadium can form low melting compounds (e.g. V2O5, melts at
691
0
C) and cause several corrosive attack on all the high temperature alloys
used in the gas turbine blades and diesel engine valves, vanadium in fuel
should be < 2ppm; at 10ppm vanadium, the corrosive rate is as thrice as high,
and at 30ppm vanadium, it is thirteen times much.
However, if sufficient magnesium is present in the fuel, it will combine with
vanadium to form higher melting compounds and reduce the corrosion.
Sodium and potassium combine with vanadium to form low melting eutectics
(565
0
C).
Hence, sodium and potassium in the gas turbine fuels must be limited (Boldt
and Hall, 1977). If not removed in the fuel treatment process, a high level of
sodium will give rise to post combustion deposits in the turbocharger. These
can normally be removed by water washing (Reynolds, 2001). Calcium is not
harmful from a corrosion stand points, actually it helps to inhibit the corrosive
action of vanadium. However, calcium can form hard bonded deposits which
are not readily removed. Lead can cause corrosion and spoil the beneficial
inhibiting effect of magnesium additives on the vanadium corrosion (Boldt and
Hall, 1977). Combine with sodium and vanadium complexes, sulfur forms
6

deposits on the external surfaces of super heater tubes, causing equipment
corrosion and loss of thermal efficiency (Boldt and Hall, 1977).The harmful
effect of heavy metals, on human health, environment and refinery equipment
call for the assessment of the concentration of heavy metals in organic
fractions of Nigeria crude oils. This will give an indication to the fractions of
Nigeria crude oils.
This will give an indication to the fraction that is heavily burden with these
metals, and therefore, appropriate measures can be taken in handling such
fraction in order to avoid problems associated with the heavy metals such as
catalyst poisoning, clogging of refinery linings and equipment as well as other
problems that are directly concern to human health and environment. This
study is aimed at investigating and comparing the concentration levels of Iron
(Fe), Zinc (Zn), Nickel (Ni), Vanadium (V), Chromium (Cr), Cadmium (Cd),
Copper (Cu), Lead (Pb) and Cobalt (Co) in Nigerian crude oils(Oguta oil field).
This will help in assessing the Nigerias crude oil impact on the environment
and its economic potentiality.