1. 1.History of petroleum
2.Origins of petroleum
3.Composition of petroleum
4.Petroleum products
5.Atomic Emission
6.Inductive coupled plasma ICP
7.Trace element in Petroleum and Petroleum products
8.Application.

2. 1. History of petroleum
Petroleum or crude oil has been known for a long time. Archeologists have shown
that it had already been extracted and used for about 5-6 thousand years before
Christ. The most ancient known oil wells are those at Ephrata and the Kerch coast
in the Chinese province of Sychuan. The mention of petroleum has been found in
many ancient manuscripts and books. For example, the Bible writes about "pitch
wells in the vicinities of the Dead Sea"(1).
The use of petroleum and its derivatives was practiced in pre-common era times
and is known largely through historical use in many of the older civilizations.
Early references to petroleum and its derivatives occur in the Bible, although by
the time the various books of the Bible were written, the use of petroleum and
bitumen was established (2).
In ancient times, petroleum had some applications in medicine as well as civil
works. For example, the ancient Greek scientist Hippocrates (IV-V century B.C.)
has described many recipes of medicines which included petroleum.
Even though the history of crude oil could be traced back by more than two
thousand years, real production of crude oil perhaps began in August 27, 1859,
when the first industrial-scale crude oil well with a depth of 22 meters was
opened in Oil Creek, Pennsylvania. After this first industrial crude oil well was
opened, there was the commencement of a rapid development of crude oil
production and treatment. Probably, this day could be said to mark the birth of
modern crude oil chemistry. In 1878, the Swedish businessman Alfred B. Nobel
together with his brothers formed the Naphtha Company Brothers Nobel. The
company extracted the crude oil in Baku, Russia and transported it to the first
crude oil refineries via the pipelines built by Naphtha Co., which still exists now
(1).
The modern petroleum industry began in 1859 with the discovery and
subsequent commercialization of petroleum in Pennsylvania (Bell, 1945). During

3. the 6,000 years of its use, the importance of petroleum has progressed from the
relatively simple use of asphalt from Mesopotamian seepage sites to the present-
day refining operations that yield a wide variety of products and petrochemicals
(2).

4. 1.2 Definition of petroleum
Petroleum naturally occurring oil that consists chiefly of hydrocarbons with
some other elements, such as sulphur, oxygen, and nitrogen. In its unrefined form
petroleum is known as crude oil (sometimes rock oil). Petroleum is believed to
have been formed from the remains of living organisms that were deposited,
together with rock particles and biochemical and chemical precipitates, in shallow
depressions, chiefly in marine conditions. Under burial and compaction the
organic matter went through a series of processes before being transformed into
petroleum, which migrated from the source rock to become trapped in large
underground reservoirs beneath a layer of impermeable rock. The petroleum
often floats above a layer of water and is held under pressure beneath a layer of
natural gas. (3)
2. The Origins of petroleum
There are two theories on the origin of carbon fuels: the abiogenic theory and the
biogenic theory.
2.1 ABIOGENIC ORIGIN
This theory described by some chemists

5. A- Marcellin Berthelot:
In 1866, Berthelot considered acetylene the basic material and crude oil
constituents were produced from the acetylene. Initially, inorganic carbides
were formed by the action of alkali metals on carbonates after which
acetylene was produced by the reaction of the carbides with water.
B- Dmitri Mendelejeff
Mendelejeff, who proposed that the action of dilute acids or hot water on
mixed iron and manganese carbides produces a mixture of hydrocarbons from
which petroleum evolved, described another theory in which acetylene is
considered to be the basic material:
2.2 BIOGENIC ORIGIN
In 1911 Engler was the first author to postulate that an organic substance other
than coal was the source material of petroleum. He invoked the concept of three
separate development stages.
A- In the first stage, animal and vegetable deposits accumulate at the bottom
of inland seas (lagoon conditions) and are then decomposed by bacteria;
the carbohydrates and the bulk of the protein are converted into water-
soluble material or gases and thus removed from the site. The fats, waxes,
and other fat-soluble and stable materials (rosins, cholesterol, and others)
remain.

6. B- The second stage, high temperatures and pressures cause carbon dioxide to
evolve from compounds containing a carboxyl group, and water is
produced from the hydroxyl acids and alcohols to leave a bituminous
residue. Continued application of the heat and pressure causes light
cracking, producing a liquid product with high olefin content
(protopetroleum). Engler also produced experimental evidence which
showed that distillation of fats under pressure brought about the formation
of a petroleum type of material, and he assumed that time and high
pressure offset the fact that the temperature in oil source rocks is lower
than that used experimentally.
C- In the third stage, the unsaturated components of the protopetroleumare
polymerized under the influence of contact catalysts and thus the
polyolefins are converted into paraffins and=or cycloparaffins naphthenes).
Aromatics were presumed to be formed either directly during cracking, by
cyclization through condensation reactions, or even during the
decomposition of protein (4).

7. 3. Compositions of Crude oil
Petroleum is a complex mixture of various organic compounds. It consists of
different hydrocarbons and heteroatomic compounds.
Table 3.1 the percent range of element in the crude oil
Also these ranges are change with geological area
Table 3.2 Amount of element in crude oil in difference area
3.1 HYDROCARBON CONSTITUENTS
The isolation of pure compounds from petroleum is an exceedingly difficult task,
and the overwhelming complexity of the hydrocarbon constituents of the higher
molecular weight fractions as well as the presence of compounds of sulfur,
oxygen, and nitrogen, are the main causes for the difficulties encountered. It is
difficult on the basis of the data obtained from synthesized hydrocarbons to

8. determine the identity or even the similarity of the synthetic hydrocarbons to
those that constitute many of the higher boiling fractions of petroleum.
Nevertheless, it has been well established that the hydrocarbon components of
petroleum are composed of paraffinic, naphthenic, and aromatic groups (Table
3.3). Olefin groups are not (4).
Table 3.3 Hydrocarbon and Heteroatom Types in Petroleum
Usually found in crude oils, and acetylenic hydrocarbons are very rare indeed. It
is therefore convenient to divide the hydrocarbon components of petroleum into
the following three classes:
1. Paraffins, which are saturated hydrocarbons with straight or branched chains,
but without any ring structure
2. Naphthenes, which are saturated hydrocarbons containing one or more rings,
each of which may have one or more paraffinic side chains (more correctly known
as alicyclic hydrocarbons)

9. 3. Aromatics, which are hydrocarbons containing one or more aromatic nuclei,
such as benzene, naphthalene, and phenanthrene ring systems, which may be
linked up with (substituted) naphthene rings or paraffinic side chains (2)
3.2 NONHYDROCARBON CONSTITUENTS
Crude oils contain appreciable amounts of organic non hydrocarbon
constituents, mainly sulfur, nitrogen, and oxygen containing compounds and, in
smaller amounts, organometallic compounds in solution and inorganic salts in
colloidal suspension. These constituents appear throughout the entire boiling
range of the crude oil, but tend to concentrate mainly in the heavier fractions and
in the nonvolatile residues.
The presence of traces of nonhydrocarbons may impart objectionable
characteristics in finished products, such as discoloration, lack of stability on
storage, or a reduction in the effectiveness of organic lead antiknock additives. It
is thus obvious that a more extensive knowledge of these compounds and of their
characteristics could result in improved refining methods and even in finished
products of better quality.
Also Metallic constituents are found in every crude oil and the concentrations
have to be reduced to convert the oil to transportation fuel. Metals affect many
upgrading processes and cause particular problems because they poison catalysts
used for sulfur and nitrogen removal as well as other processes such as catalytic
cracking. The trace metals Ni and V are generally orders of magnitude higher than
other metals in petroleum, except when contaminated with coproduced brine
salts (Na, Mg, Ca, and Cl) or corrosion products gathered in transportation (Fe)
(4).
4. PRODUCTS FROM CRUDE OIL
The list of products from petroleum is endless. Oil products fuel planes, trains,
cars, trucks, buses, and so on. Oil is also used to heat homes. Chemicals made
from oil are used to make products that range from makeup, toys, fabrics,

10. sneakers and football helmets to aspirin, toothpaste, deodorant, clothes, hair
dryers and lipstick to name just a few. Plastics made from oil are widely used in
everything from compact discs and video cassette recorders, to computers,
television sets, and telephones (1).
Typical final products are:
1. Gases for chemical synthesis and fuel, liquefied gases
2. Aviation and automotive gasoline
3. Aviation (jet) and lighting kerosene
4. Diesel fuel
5. Distillate and residual fuel oils
6. lubricating oil base grades
7. Paraffin oils and waxes

11. Table 4.1 Product of petroleum with boiling point range

12. 4.1 Liquefied petroleum gas LPG
It is a mixture of Gaseous hydrocarbons propane (C3H8) and butane (C4H10) that
producing during natural gas refining.
Properties of LPG
1- Free from ethane.
2- Free from pentane.
3- Free from unsaturated hydrocarbon.
4- Free from H2S (5).
Figure 4.1 Separation of LPG from petroleum product

13. 4.2 NAPHTHA
The more common method of naphtha preparation is distillation. Depending on
the design of the distillation unit, either one or two naphtha steams may be
produced: (1) a single naphtha with an end point of about 205∞C (400∞F) and
similar to straight-run gasoline or (2) this same fraction divided into a light naphtha
and heavy naphtha. The end point of the light naphtha is varied to suit the
subsequent subdivision of the naphtha into narrower boiling fractions and may be
of the order of 120∞C (250∞F).
The variety of applications emphasizes the versatility of naphtha. For example,
naphtha is used by paint, printing ink and polish manufacturers and in the rubber
and adhesive industries as well as in the preparation of edible oils, perfumes, glues,
and fats. Further uses are found in the drycleaning, leather, and fur industries and
also in the pesticide field (2).

14. 4.3 GASOLINE OR PETROLE
Gasoline (also referred to as motor gasoline, petrol in Britain, benzine in
Europe) is a mixture of volatile, flammable liquid hydrocarbons derived from
petroleum that is used as fuel for internal combustion engines such as occurs in
motor vehicles (2).
In the late 19th century, the most suitable fuels for automobile use were coal tar
distillates and the lighter fractions from the distillation of crude oil. During the
early 20th Century, the oil companies were producing gasoline as a simple
distillate from petroleum.
Gasoline as a fuel is composed of a mixture of various hydrocarbons, which can
be burnt to form water (H2O) and CO2. If combustion is not complete, carbon
monoxide (CO) is also formed. The following main groups of hydrocarbons are
contained in gasoline:
• saturated hydrocarbons or alkanes
• Unsaturated hydrocarbons or olefins
• Naphthenic or cyclic hydrocarbons
• Aromatics
• oxygenates
• Other hetero-atom compounds (1).
The boiling range of motor gasoline falls between –1°C (30°F) and 216°C (421°F)
and has the potential to contain several hundred isomers of the various
hydrocarbons (Tables 4.1 and 4.2) (2).

15. Table 4.1 General Summary of Product Types and Distillation Range
Table 4.2 Increase in the number of Isomers with Carbon Number

16. 4.4 KEROSINE
Kerosene (kerosine), also called paraffin or paraffin oil, is a flammable pale
yellow or colorless oily liquid with a characteristic odor intermediate in volatility
between gasoline and gas/diesel oil that distills between 125°C (257°F) and 260°C
(500°F).
In the early years of the petroleum industry kerosene was its largest selling and
most important product. The demand was such that many refiners, using a variety
of crude oils, made as wide a distillation cut as possible to increase its availability,
thereby causing the product to have a dangerously low flash point and to include
undesirable higher-boiling fractions. Kerosene is less volatile than gasoline
(boiling range approximately 140°C/285°F to 320°C/610°F) and is obtained by
fractional distillation of Petroleum. Kerosene is a very stable product, and additives
are not required to improve the quality.
Kerosene, because of its use as burning oil, must be free of aromatic and
unsaturated hydrocarbons as well as free of the more obnoxious sulfur compounds
(2).

17. 4.5 Diesel fuel
Diesel fuel is derived from petroleum. Diesel, gasoline and jet fuel are different
cuts from the refining of petroleum. The difference is that diesel contains heavier
hydrocarbons with a higher boiling point than gasoline and jet fuel. The term diesel
fuel is therefore generic; it refers to any fuel mixture developed to run a diesel-
powered vehicle, i.e. engines with compression ignition engines.
Diesel is a hydrocarbon fraction that typically boils between 250-380°C. Diesel
engines use the cetane (n-hexadecane) rating to assess ignition delay.
In most diesel engines, the ignition delay is shorter than the duration of
injection. Under these circumstances, the total combustion period can be divided
into the following four stages:
• Ignition delay
• Rapid pressure rise
• Constant pressure or controlled pressure rise
• Burning on the expansion stroke
The next important parameter of diesel fuel is stability or storage stability (1).

18. 4.6 DISTILLATE FUEL OIL
Fraction Boiling
Range / °C
No. of Carbon
atoms per
molecule
Uses
DISTILLATE
FUEL OIL
216 - 421 C12 – C20
Most petroleum products can be used as fuels, but the term fuel oil, if used
without qualification, may be interpreted differently depending on the context.
However, because fuel oils are complex mixtures of hydrocarbons, they cannot be
rigidly classified or defined precisely by chemical formulae or definite physical
properties.
The arbitrary division or classification of fuel oils is based more on their
application than on their chemical or physical properties. However, two broad
classifications are generally recognized:
(1) Distillate fuel oil and
(2) Residual fuel oil
Distillate fuel oils are vaporized and condensed during a distillation process and
thus have a definite boiling range and do not contain high boiling oils or asphaltic
components (2).
4.7 LUBRICATING OILS AND LUBRICANTS

19. 4.7.1 MINERAL OIL (WHITE OIL)
In the present context, the term mineral oil or white oil refers to colorless or
very pale oils within the lubricating oil Minerals (mineral) oils belong to two main
groups, medicinal (pharmaceutical) oils and technical oils.
Medicinal oils represent the most refined of the bulk petroleum products,
especially when the principal use is for the pharmaceutical industry. Thus mineral
oil destined for pharmaceutical purposes must meet stringent specifications to
ensure that the oil is inert and that it does not contain any materials that are
suspected to be toxic.
Technical mineral oil (as opposed to pharmaceutical mineral oil) must meet
much less stringent specifications requirements because the use is generally for
transformer oil, cosmetic preparations (such as hair cream), in the plastics industry,
and in textiles processing. Many of the same test methods are applied to all mineral
oils (2).
4.7.2 LUBRICATING OIL
Lubricating oil is used to reduce friction and wear between bearing metallic
surfaces that are moving with respect to each other by separating the metallic
surfaces with a film of the oil. Lubricating oil is distinguished from other fractions
of crude oil by a high (>400°C/>750°F) boiling point.
In the early days of petroleum refining, kerosene was the major product,
followed by paraffin wax wanted for the manufacture of candles. Lubricating oils
were at first by-products of paraffin wax manufacture. The preferred lubricants in
the 1860s were lard oil, sperm oil, and tallow, but as the trend to heavier industry
increased, the demand for mineral lubricating oils increased, and after the 1890s
petroleum displaced animal and vegetable oils as the source of lubricants for most
purposes (2).

20. 5. Atomic Emission Theory
Atomic emission spectroscopy uses quantitative measurement of the optical
emission from excited atoms to determine analyte concentration
Analyte atoms in solution are aspirated into the excitation region where they are
desolvated, vaporized, and atomized by plasma.
Figure 5.1 Excitation diagram.
`
Excited StateGround State
E
Relaxation
Excitation
Excitation Electrons can be in their ground state (unexcited) or enter one of the
upper level orbitals when energy is applied to them. This is the excited state.
Atomic Emission A photon of light is emitted when an electron falls from its
excited state to its ground state
Figure 5.2 Emission diagram.
Each element has a unique set of wavelengths that it can emit.
Lower wavelengths are shorter and have more energy, higher wavelengths e.g. in
the Visible region, are longer and have less energy.

21. Today have different Emission sources like
• Flames
• Arcs / Sparks
• Direct Current Plasmas (DCP)
• Inductively Coupled Plasmas (ICP)
Inductively Coupled Plasma (ICP) :
source, plasma formation, plasma zones
• Quartz torch surrounded by induction coil
• Magnetic coupling to ionized gas
• High temperature – equivalent to 10,000k
Plasma Advantages
• High Temperature – allows for full dissociation of sample components
• Argon is Inert – non reactive with sample
• Linearity – analysis of samples from ppb to ppm range in the same method
• Matrix tolerance – robust and flexible design with Duo and Radial options
(6).
6. INDUCTIVE COUPLED PLASMA
Different procedures are found in the literature for the determination of metals in
petroleum derivatives. More recently, a rapid, sensitive, and multi-elemental
method is then required to analysis trace elements occurring in crude oil or other
petroleum products.
Inductively coupled plasma mass spectrometry (ICP-MS) has been applied for
trace element determination in oil and derivatives due to the known advantages of
this technique, such as lower limits of detection (LOD), multi-element and
isotopic-ratio measurement capability, and steadily decreasing investment costs.
Nevertheless, ICP-OES has been applied not only for the inorganic
characterization of crude oil and derivatives, but also as a valuable tool for
studying the physicochemical fundamentals of plasma–solvent interactions.
Sample throughput and multi-elemental capabilities are some common benefits
of ICP-OES and ICP-MS compared to classical atomic absorption spectrometry or

22. WDXRF. The combination of these two techniques thus provides a very wide
concentration range of metal compounds to be determined on a routine basis, ICP-
OES being preferred for major element analysis (Fe, Ni and V) whereas ICP-MS is
particularly convenient for ultra-trace metals analysis. However, these two
techniques were not initially designed for organic samples analysis and specific
configuration of sample introduction systems are required in order to minimize
organic solvent load into the ICP plasma. The presence of organic vapors in the
plasma generates plasma instability and high reflected power that could lead to
plasma extinction (7, 8).
6.1 Instrument Components of an ICP
There are five basic components to an ICP
1. Sample Introduction. 2- Energy Source. 3- Spectrometer.
4- Detector. 5- Computer and Software
Figure 6.1 Instrumentation component of an ICP

23. Now define each part in briefly.
6.1.1. Sample Introduction
The sample solution cannot be put into the energy source directly. The solution
must first be converted to an aerosol. The function of the sample introduction
system is to produce a steady aerosol of very fine droplets.
There are three basic parts to the sample introduction system.
1. the Peristaltic pump draws up sample solution and delivers it to
2. the Nebulizer which converts the solution to an aerosol that is sent to
3. The Spray chamber which filters out the large, uneven droplets from the
aerosol.
Figure 6.4 Sample Introduction the A. Peristaltic pump, B. The Nebulizer and C.
The Spray chamber
6.1.2 Energy Source
The sample aerosol is directed into the center of the plasma. The energy of the
plasma is transferred to the aerosol. The main function of the energy source is to
get atoms sufficiently energized such that they emit light.
There are three basic parts to the energy source.
1- The Radio frequency generator which generates an oscillating electromagnetic
field at a frequency of 27.12 million cycles per second. This radiation is directed
to.
2- The Load coil which delivers the radiation to.
3- The Torch which has argon flowing through it which will form plasma in the RF
field. Figure 6.6 Energy source parts A. Radio
Frequency generator, B. Load coil and C. Torch
Plasma Configuration
1- Axial design: best sensitivity, lowest detection limits.
• Environmental
• Chemical

24. 2- Radial design: Robust, fewer interferences
• Petrochemical
• Metallurgy
3- Axial and Radial
6.1.3 Spectrometer
Once the atoms in a sample have been energized by the plasma, they will emit
light at specific wavelengths. No two elements will emit light at the same
wavelengths.
The function of the spectrometer is to diffract the white light from the plasma
into wavelengths through polychromatic.
6.1.4 Detector
Now that there are individual wavelengths, their intensities can be measured
using a detector. The intensity of a given wavelength is proportional to the
concentration of the element.
The function of the detector is to measure the intensity of the wavelengths. The
output from the detector is processed by a set of electronics. The electronics
control the detector as well as collect the readings from the pixels.
The function of the electronics is to measure and process the output of the
detector.
6.1.5 Computer and Software
The software, via a computer, controls and runs the instrument. Not only are
measurements made but the other five components of the instrument are controlled
and monitored by the computer and software.
The function of the computer and software is to operate, monitor, and collect
data from the instrument.

25. 6.2 ICP Performance
• Typical analysis time for ICP is ~2-3 minutes. This includes flush time,
multiple repeats, printing, etc. (Analysis time is independent of the number
of elements being determined)
• Typical precision, amongst repeats within an analysis, is ~ 0.5%
• Typical drift is ≤ 2% per hour
Typical detection limits are ~ 1-10 parts per billion (6)
7. TRACE ELEMENT
7.1 TRACE ELEMENT IN CRUDE OIL
Crude oils’ primary constituents are organic but also contain trace concentrations
of inorganics or metals in the range of subparts per billion (ppb) to tens and
occasionally hundreds of parts per million (ppm). The trace content of metals in
crude oil is of interest for the potential contamination of the environment.
Environmental risks depend on the toxicity and concentration of each metal in the
crude oil.
Trace metals have been found in different proportions in different crudes and
consequently in their derivatives, Frequently Ni and V are found in largest
concentrations contributing to environmental pollution. Because of their mutagenic
and carcinogenic potential Ni and V emissions have been strictly con- trolled in
several countries.
The other metal ions reported form crude oils; include copper, lead, iron,
magnesium, sodium, molybdenum, zinc, cadmium, titanium, manganese,
chromium, cobalt, antimony, uranium, aluminum, tin, barium, gallium, silver and
arsenic.
But the concentrations of these elements are changing according to location and
geological are of crude oil.
Table 7.1 Concentration of trace elements in petroleum, in ppm. In Tamsagbulag
basin and Tsagaan Els basin
Element Tamsagbulag basin Tsagaan Els basin
Alkali metals
Na 20.98 35.6
Li <0.01 <0.01
Total 20.98 35.6

26. Alkaline earth metals
Be 0.05 <0.01
Mg 0.19 1.11
Ca 1.78 2.63
Ba <0.05 0.19
Sr 0.46 2.43
Total 2.48 6.36
Sub-Group Ib
Cu 0.51 0.37
Ag 0.03 0.04
Total 0.54 0.41
Sub-Group IIb
Zn 3.01 0.62
Cd 1.65 0.26
Total 4.66 0.88
Sub-Group IIIa
Sc <0.01 0.04
Y 0.01 0.07
La 0.01 <0.01
Total 0.02 0.11
Sub-Group IIIb
B 2.88 3.18
Al 0.36 2.11
Total 3.24 5.29
Sub-Group IVb
Si 1.35 5.76
Sn 0.23 0.71
Pb 0.18 1.16
Total 1.77 7.63
Sub-Group Vb
P 0.22 0.06
Sb 0.14 0.15
Bi 0.20 0.01
Total 0.56 0.22
Sub-Group Via
Cr 1.15 1.03
Mo 0.39 0.29
W 2.79 <0.01
Total 4.18 1.32
Group VIII
Fe 2.91 4.5
Co 0.07 0.59
Ni 3.68 2.82
Total 6.66 7.91
Other group elements
Ti 0.18 0.29
V 0.56 0.97
Mn 0.06 0.17
Sum 46.12 67.43

27. Trace metals have been used as a tool to understand the depositional environments
and source rock. The metal ions and their ratios have been observed as a valuable
tool in oil-oil correction and oil-source rock correlation studies.
The determination of metal ions in crude oils has environmental and industrial
importance. The metal ions like vanadium, nickel, copper and iron, behave as
catalyst poisons during catalytic cracking process in refining of crude oil. The
metal ions are released in the environment during exploration, production and
refining of crude oil. The determination of mercury content in crude oil is also
important for petroleum industry, because the metal can deposit in the equipment,
which could affect the maintenance and operation.
In general these elements are present in the crude oils as inorganic salts (mainly
as chloride and sulphate of K, Mg, Na and Ca), associated with water phase of
crude oil emulsions, or as organometallic compounds of Ca, Cu, Cr, Mg, Fe, Ni,
Ti, V and Zn adsorbed in water-soil interface acting as emulsion stabilizers (9- 12).
Even minute amounts of iron, copper, and particularly nickel and vanadium in
the charging stocks for catalytic cracking affect the activity of the catalyst and
result in increased gas and coke formation and reduced yields of gasoline. In high
temperature power generators, such as oil fired gas turbines, the presence of
metallic constituents, particularly vanadium in the fuel, may lead to ash deposits on
the turbine rotors, thus reducing clearances and disturbing their balance. More
particularly, damage by corrosion may be very severe.
The majority of the vanadium, nickel, iron, and d copper in residual stocks may
be precipitated along with the asphaltenes by hydro carbon solvent s. Thus,
removal of the asphaltenes with n-pentane reduces the vanadium content of the oil
by up to 95% with substantial reductions in the amounts of iron and nickel (4).
7.2 TRACE ELEMENT IN PETROLEUM PRODUCTs
Products of petroleum contain various elements and controlling the range of
these elements is need. In this section describe element in kerosene, gasoline and
lubricating oil.
7.2.1 Kerosene
The presence of trace metals in fuels, unless they are added purposely, is usually
undesirable, as they may be responsible for the decomposition and poor
performance of the fuel, leading to corrosion of the motor and formation of

28. precipitates. Some metals are natural constituents of the crude oil, others can be
introduced into the kerosene as contaminants, e.g. through contact with refining
and distilling equipment, or during storage and transport.
Many methods of preconcentration of metal ions from solutions have been
described. Of particular interest are those which involve inorganic solid surfaces
modified with chelating groups and so have advantage of selectivity.
Preconcentration methods can removal of some interferes which may be present in
the sample solution, can considerably improve the obtained results extending the
limit of detection to lower concentration levels.
The present paper describes the preparation of silica gel chemically modified
with 2-aminothiazole (SiAT) to produce an efficient collector for separation and
determination of metal ions dispersed into the kerosene fuel by FAAS.in the table
7.2 show that concentration of (Zn, Cu, Fe and Ni) in different kerosene (13).
Table7.2 Determination of copper, iron, nickel and zinc in different kerosene fuel
samples by FAAS with preconcentration on a column packed with SiAT.
Sample Concentration of metal ion in (µg/L)
Copper Iron Nickel Zinc
Petrobras 8.0 11. 3.0 8.0
Neiva 6.0 9.0 4.0 6.0
Texaco 7,4 9.2 5.3 7.2
5.2.2 Gasoline
Gasoline was at first produced by distillation, simply separating the volatile,
more valuable fractions of crude petroleum, and was composed of the naturally
occurring constituents of petroleum. Later processes, designed to raise the yield of
gasoline from crude oil, split higher-molecular-weight constituents into lower-
molecular-weight products by processes known as cracking.
The needs of the petroleum industry in studies dedicated to trace metals
determination are highly related to exploration, but also to exploitation activities
for corrective actions during oil production and refining.
A classical pneumatic nebulizer was used with ICP-OES in order to analyze
various elements in different matrices such as asphaltenes fraction, residue, crude

29. oil or diesel and gasoline. Depending on the type and volatility of the matrix, the
sample must be diluted by a factor ranging from 10 to 50 in xylene. The highest
dilutions were typically performed when gasoline samples were analyzed in order
to minimize the organic vapor load. However, this in turn degrades significantly
the quantification limit of the elements in the gasoline. In order to reduce this
effect, nebulization with an ultrasonic nebulizer (USN) with a cooled condenser
was tested for gasoline, where lower dilution factor (typically 5) was found
acceptable for the plasma due to lower solvent load. Finally, a microflow
pneumatic concentric nebulizer associated with a chilled spray chamber was used
for an optimal analysis of petroleum products by ICP-MS (14).
Table 7.3 determination of Ni (µg/L) and Pb (mg/L) in commercial gasoline
samples
5.2.3 LUBRICATIOG OIL
Lubricating oils from petroleum are mainly composed of paraffinic, naphthenic
and, to a lesser extent, aromatic hydrocarbons. Several additives, including
metalloid organic ones, are also part of the final composition of commercial
lubricating oil. Wear has both physical (friction between metallic parts, high
temperature and pressure) and chemical (corrosion) sources.
Increasing amounts of some key elements in the lubricating oil may indicate the
extent of the wear of wetted components. For instance, an abrupt increase of Ni, Sn
or Cr indicates corrosion in bearings, valves and pistons, Fe indicates corrosion in
various parts, and Na indicates oil contamination with anti-freeze fluids and so on
Elements such as Ag, B, Ba, Bi, Ca, Cd, Co, Cr, Fe, Hg, Mg, Mo, Ni, P, Sb, Se,
Sn, Ti and Zn, are also deliberately introduced in small portions to lubricating oils
to address requisites for special applications.
Samples Ni in (µg/L) Pb (mg/L)
Gasolin1 114 ±4 0.6 ± 0.02
Gasolin2 105±1 0.02± 0.003
Gasolin6 158±2 0.44 ± 0.02

30. Apart from the existence of a few electro analytical and XRF, methods for the
determination of Zn, Cu, Pb, Fe, Cr, Ni, As and Cd in lubricating oils, the majority
of analytical methods reported in the literature are based on atomic spectrometric
techniques such as FAAS, ET AAS, DC or ICP OES, ICP MS and AFS (15).
Table 7.3 Spectroanalytical methods for determination of trace elements in
lubricating oil
Element technique LOD
Pb ICP MS 0.2 μg/L
Sb ETAAS 0.2 μg/g
V ICP-OES 0.01 μg/g
Zn ICP-OES 0.015 μg/g
Ni FAAS 10 μg/L
Fe ICP-OES 0.015 μg/g
Na LA-ICP-TOFMS 4 ng/g
8. Application of ICP in determination of element of petroleum and
petroleum product
8.1 Determination of Mo, Zn, Cd, Ti, Ni, V, Fe, Mn, Cr and Co in crude oil
using inductively coupled plasma optical emission spectrometry and sample
introduction as detergentless microemulsions
A procedure to prepare crude oil samples as detergentless microemulsions was
optimized and applied for the determination of Mo, Zn, Cd, Si, Ti, Ni, V, Fe, Mn,
Cr and Co by ICP OES. Propan-1-ol was used as a co-solvent allowing the
formation of a homogeneous and stable system containing crude oil and water. The
optimum composition of the microemulsion was crude oil /propan-1-ol /water /
concentrated nitric acid, 6/70/ 20/4 w/w/w/w. This simple sample preparation
procedure together with an efficient sample introduction (using a Meinhard K3
nebulizer and a twister cyclonic spray chamber) allowed a fast quantification of the
analytes using calibration curves prepared with analyte inorganic standards. In this
case, Sc was used as internal standard for correction of signal fluctuations and

31. matrix effects. Oxygen was used in the nebulizer gas flow in order to minimize
carbon building up and background. Limits of detection in the ng /g−1
range were
achieved for all elements. The methodology was tested through the analysis of one
standard reference material (SRM NIST 1634c, Residual Fuel Oil) with recoveries
between 97.9% and 103.8%. The method was also applied to two crude oil samples
and the results were in good agreement with those obtained using the acid
decomposition procedure. The precision (n=3) obtained was below 5% and the
results indicated that the method is well suited for oil samples containing low
concentrations of trace elements (11).
8.2 Trace Metal Analysis in Petroleum Products Sample Introduction
Evaluation in ICP-OES and Comparison with an ICP-MS Approach
The needs of the petroleum industry in studies dedicated to trace metals
determination are highly related to exploration, but also to exploitation activities
for corrective actions during oil production and refining. Two techniques provide
a very large concentration range of metal compounds to be determined on a routine
basis, ICP-OES being preferred for major element analysis whereas ICP-MS is
particularly convenient for ultra-trace metals analysis.
Direct introduction of petroleum product in the plasma require a methodical
approach in order to minimize matrix effect. Here, three different sample
introduction modes have been investigated depending on the elements of interest
and the matrix analyzed. A classical pneumatic nebulizer and an ultra-sonic
nebulizer (USN) were compared for ICP-OES. These introduction modes were
compared with a microflow pneumatic concentric nebulizer associated with a
chilled spray chamber used with ICP-MS.
Classical pneumatic nebulisation with ICP-OES leads to ppm range limit of
quantification in the petroleum product and five times higher with gasoline due to
important dilution factor. The use of an USN coupled with ICP-OES reduce limit
of quantification in gasoline to the 50 ppb range, but further study of matrix effects
with such an introduction must be done. The PFA-100 associated with a cooled
Scott chamber used with ICP-MS reduce also limit of quantification in the
petroleum product to the 10 ppb range for most elements. The initial important
dilution factor allows the introduction of light matrices without further dilution, but

32. requires anyhow the use of a standard addition method, which is time-consuming.
Then, the choice of a technique is definitively dependents on the needs required by
the laboratory between high throughput analyses and very low limit of
quantification (16-18).
8.3 Preconcentration of molybdenum, antimony and vanadium in gasoline
samples using Dowex 1-x8 resin and their determination with inductively
coupled plasma–optical emission spectrometry.
Strong ion exchangers (Dowex 50W-x8 and Dowex 1-x8) were used for the
separation and preconcentration of trace amounts of Mo, Sb and V in gasoline
samples. Dowex 1-x8 resin was found to be suitable for the quantitative retention
of these metal ions from organic matrices. The elution of the metal ions from
Dowex 1-x8 resins was achieved by using 2.0 mol L-1
HNO3 solution. The Dowex
1-x8 preconcentration and separation method gave an enrichment factor of 120
with limits of detection equal to 0.14, 0.05 and 0.03 mgL-1
for Mo, Sb and V,
respectively. The limits of quantification were found to be 0.48, 0.18 and 0.10
mgL-1
for Mo, Sb and V, respectively. Under optimized conditions, the relative
standard deviations of the proposed method (n¼20) were o4%. The accuracy of
Dowex 1-x8 preconcentration procedure was verified by the recovery test in the
spiked samples of gasoline sample. The Dowex 1-x8 preconcentration method was
applied to Conostan custom made oil based certified reference material for the
determination of Mo, Sb and V. The results of the paired t-test at a 95% confidence
level showed no significant difference. The separation and preconcentration
procedure was also applied to the gasoline samples collected from different filling
stations (19).

33. References
1- V. Simanzhenkov and R. Idem, Crude Oil chemistry, 1st, Marcel Dekker, USA, 2003, pp. 3,4-5, 47-48, 49-52,
57-63,
2- J. G. Speight, Handbook of Petroleum Product Analysis, 1st, John Wiley & Sons, Inc., Hoboken, New Jersey,
USA and Canada, 2002, pp. 10-11, 12, 85, 87, 105, 106,105, 159-160, 197-198, 247, 268
3- J. Daintith, A Dictionary of Chemistry, 6
th
, Oxford University Press Inc., USA, 2008, p. 412.
4- J. G. Speight, The Chemistry and Technology of Petroleum, 4
th
, CRC press, 2006, PP.83-87, 216-217, 222-
223, 227-228.
5- L. F. Hatch, chemistry of petrochemical processes, 2nd, Gulf Publishing Company, USA, 2000, pp. 177-178.
6- Skooge, Holler and Crouch, Principle of Instrumental analysis, 6th, Thomson and Brooks/Cole, 2007, pp.
254-255, 256-264.
7- C. Duyck, N. Miekeley, C. L. P. da Silveira and P. Szatmari, 2002, Trace element determination in crude oil
and its fractions by inductively coupled plasma mass spectrometry using ultrasonic nebulization of
toluene solutions, Spectrochimica Acta Part B, 57, pp.1979–1990.
8- J.Sainbayar, D. Monkhoobor and B. Avid, 2012, Determination of Trace Elements in the Tamsagbulag and
Tagaan Els Crude Oils and Their Distillation Fractions Using by ICP-OES, advances in Chemical Engineering
and Science, pp.113-117.
9- M.Y. Khuhawar, M. A. Mirza and T.M. Jahangir, Determination of Metal Ions in Crude Oils, 2012, intech,
pp.121-127.
10- C. Hardaway, J. Sneddon and J. N.Beck, 2004, Determination of Metals in Crude Oil by Atomic
Spectroscopy, Analyticcal letter, 37 (14), pp. 2881-2899.
11- R. M. de Souza, A. L.S. Meliande, C. L.P. da Silveira, R. Q. Aucélio,2006, Determination of Mo, Zn, Cd, Ti,
Ni, V, Fe, Mn, Cr and Co in crude oil using inductively coupled plasma optical emission spectrometry and
sample introduction as detergentless microemulsions, icrochemical Journal, 82, pp.137–141.
12- J. Sainbayar, D.Monkhoobor and B. Avid, 2012, Determination of Trace Elements in the Tamsagbulag and
Tagaan Els Crude Oils and Their Distillation Fractions Using by ICP-OES, advances in Chemical Engineering
and Science, 2, pp.113-117.
13- P. S. Roldan, I. L. Alcântara, J. C. Rocha1, C. C. F. Padilha and P. M. Padilha, 2004, Determination of Copper,
Iron, Nickel and Zinc in fuel kerosene by FAAS after adsorption and pre-concentration on 2-aminothiazole-
modified silica gel, 29(2), pp.33-36.
14- M. N. M. Reyes and R. C. Campos, 2005, Graphite furnace atomic absorption spectrometric determination
of Ni and Pb in diesel and gasoline samples stabilized as microemulsion using conventional and perman-
ent modifiers, Spectrochimica Acta Part B , 60, pp.615– 624.

34. 15- R. Q. Aucélio, R. M. de Souza, R. C. de Campos, N. Miekeley and C. L. Porto da Silveira, 2007, the
determination of trace metals in lubricating oils by atomic spectrometry, Spectrochimica Acta Part B, 62,
pp. 952–961.
16- C.P. Lienemann, S. Dreyfus, C. Pecheyran and O.F.X. Donard, 2007, Trace Metal Analysis in Petroleum
Products Sample Introduction Evaluation in ICP-OES and Comparison with an ICP-MS Approach, 62 (1), pp.
69-77.
17- P.D. Mello, J.S.F. Pereira, D.P. de Moraes, V.L. Dressler, E.M.D. Flores, G. Knapp, 2009, Nickel, vanadium
and sulfur determination by inductively coupled plasma optical emission spectrometry in crude oil
distillation residues after microwave induced combustion, J. Anal. At. Spectrom. 24, 911–916.
18- J. S.F. Pereira, P. A. Mello, D. P. Moraesa, F. A. Duarte, V.L. Dresslera, G. Knapp and É. M.M. Floresa, 2009,
Chlorine and sulfur determination in extra-heavy crude oil by inductively coupled plasma optical emission
spectrometry after microwave-induced combustion, Spectrochimica Acta Part B 64, pp. 554–558.
19- P. N. Nomngongo, J. C. Ngila, J. N. Kamau, T. A.M. Msagati, B. Moodley, 2013, Preconcentration of
molybdenum, antimony and vanadium in gasoline samples using Dowex 1-x8 resin and their
determination with inductively coupled plasma–optical emission spectrometry, Talanta 110, pp. 153–159