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FRACTIONAL CATEGORIZATION
BY
Dr A.K. Mittal
Introduction
Petroleum is a form of bitumen composed principally of
hydrocarbons and existing in the gaseous or liquid state
in its natural reservoir.
The word petroleum originates from the Latin petra
(rock) and oleum (oil).
The main forms of petroleum are natural gas,
condensate, and crude oil, the liquid part of petroleum.
Condensates
Reservoir gases under very high pressure are able to dissolve large
amounts of liquid hydrocarbons. When such gases are produced, the liquid
condenses and is collected in a separator.
The condensate generally has an API gravity higher than 55o. Most
condensates are composed of saturated hydrocarbons in the light gasoline
range which causes the high API gravities.
A condensate is distinguished from a light oil in that the former usually, but
not always, has a gas-oil ratio greater than 5000 cubic feet of gas per barrel
of oil. In addition, by definition a condensate must exist in the gaseous state
in its reservoir.
The table below compares the elemental composition of gas, oil, asphalt, coal,
and the dispersed organic matter (kerogen) in sedimentary rocks.
Going across from gas to kerogen, there is a marked decrease in hydrogen and
a corresponding increase in sulfur, nitrogen, and oxygen relative to carbon.
The two most widely used criteria to determine the quality of crude oil are density and
sulfur content:
Density:
Crudes can be classified as light or heavy, a characteristic which refers to the oils
relative density based on the American Petroleum Institute (API) Gravity. This
measurement reflects how light or heavy a crude oil is compared to water. If an oils
API Gravity is greater than 10, it is lighter than water and will float on it. If an oils API
Gravity is less than 10, it is heavier than water and will sink.
Lighter crudes are easier and less expensive to produce. They generally have a
higher percentage of light hydrocarbons that can be recovered with simple distillation
at a refinery. A crude oil with lower density tends to yield higher levels of products.
Crude oil with high sulfur content, which is known as sour, is much less
desirable than a crude oil with low sulfur content, known as sweet crude.
The New York Mercantile Exchange designates petroleum with less than
0.42% sulfur as "sweet".
"Light sweet crude oil" is the most sought-after version of crude oil as it
contains a disproportionately large fraction that is directly processed
(fractionation) into gasoline (naptha), kerosine, and high-quality diesel (gas
oil).
Paraffins (CnH2n+2)
Paraffins dominate the gasoline fraction of crude oil, and they are the
principal hydrocarbons in the oldest, most deeply buried reservoirs.
The terms saturated and aliphatic hydrocarbons are also used for this
group.
The normal paraffins are relatively inert with strong acids, bases, and
oxidizing agents.
Naphthenes or Cycloparaffins
The cycloparaffins that are formed by joining the carbon atoms in a ring
are the most common molecular structures in petroleum.
Naphthene rings generally contain five or six carbon atoms.
A few cycloheptanes (C7 H14) have been identified in petroleum but no
rings smaller than C5 or larger than C7 have been found.
The average crude oil contains about 50% naphthenes, with the
quantities increasing in the heavier fractions and decreasing in the
lighter fractions.
In the heavier fractions, naphthenes tend to fuse into polycyclic rings;
that is, a group of rings in which two or more carbon atoms are shared
between the rings.
The most common naphthenes are methylcyclopentane and methyl
cyclohexane, which together represent 2% or more of the average crude.
A general chemical formula for cycloalkanes would be CnH2(n+1-g) where
n = number of C atoms and g = number of rings in the molecule.
Steranes and triterpanes which are important biomarkers are also cycloalkanes, basic
structures of which are given below.
Organic compounds whose carbon structure, or skeleton, is formed by living organism
and is sufficiently stable to be recognized in crude oil or the organic matter of ancient
sediments are called biomarkers. Typical markers are the porphyrins, pristane, phytane,
steranes, carotanes, and pentacyclic triterpanes.
Steroids are biological precursors of steranes and triterpenoids are biological precursors for triterpanes.
Steranes and triterpanes are useful in determining maturity, the type of organic matter and in interpretations
of depositional environments as well as in fingerprinting.
The naphthenes, normal and branched paraffins and isoprenoids are all
saturated hydrocarbons because all available carbon bonds are saturated
with hydrogen.
Olefin Hydrocarbons
The unsaturated state of the olefin is much more unstable than that of the
aromatics. If hydrogen or other elements are not available to react with the
unsaturation, some olefin will react with themselves to form high molecular
weight polymers.
Peanut oil, olive oil, fishliver oil, and wheat germ oil all contain some
olefinic hydrocarbons. Squalene, a natural component of human tissues
that is an intermediate in the biosynthesis of cholesterol, is an olefin.
Vitamin A and many pigments, such as the orange of carrots and the red of
tomatoes, are olefins.
Aromatic Hydrocarbons
Aromatics form an extremely important class of unsaturated
hydrocarbons.
Although they are unsaturated, they do not add hydrogen easily.
Their stability permits aromatics to be important constituents of
oils and sediments.
Aromatics possess a system of alternating single and double
bonds within a cyclic structure. A simplified notation for drawing
these molecules permits us to represent the double-bond system
by a circle within a ring.
The circle indicates that the electrons in the double bonds are
delocalized; that is, they are free to move throughout the cyclic
system instead of being held between two particular carbon
atoms.
It is this delocalization of electrons which makes aromatic
compounds very stable.
All aromatic hydrocarbons have at least one benzene ring (C 6H6).
The aromatics rarely amount to more than 15% of a total crude oil. They tend to be
concentrated in the heavy fractions of petroleum, such as gas oil, lubricating oil, and
residuum, in which the quantity often exceeds 50%.
Toluene and metaxylene are the most common aromatic hydrocarbons in petroleum.
Aromatics have the highest octane ratings of the hydrocarbon types, so they are
valuable in gasoline blends. However, they are undesirable in the lubricating oil
range, because they have the highest change in viscosity with temperature of all the
hydrocarbons.
Atoms other than hydrogen and carbon that occur in petroleum, bitumen
and kerogen are called heteroatoms; the compounds in which they occur
are called heterocompounds. They are also called NSO compounds,
because the most common heteroatoms are nitrogen, sulfur and oxygen.
Fatty acids, derived from natural fats, oils, and waxes, were among the
first NSO compounds to be studied.
A refinery tower will yield products from the smallest to the largest size, of molecule,
as follows: gas, gasoline, kerosene, light gas oil (diesel fuel), heavy gas oil, lubricating
oil, and residuum.
The lighter the oil, the more of the desirable, in-demand products it
will produce through distillation at a range of temperatures. At the
lowest distillation temperatures, products produced include liquid
petroleum gases (LPG), naphtha, and so-called "straight run"
gasoline.
A distillation tower. The boiling ranges for the various crude oil fractions shown are for a typical Gulf
Coast refinery. Refineries in other areas will show some variation in products and boiling ranges.
The average oil tends to have more paraffins in the gasoline fraction and more
aromatics and asphaltics in the residuum. However, a highly paraffinic oil will
have waxes predominating over asphaltic compounds in the residuum.
The density of an oil varies with both the size and types of molecules. Since the
element carbon is heavier than hydrogen, the density of hydrocarbons generally
increases with a decreasing ratio of hydrogen to carbon atoms. Thus in table below,
normal hexane, cyclohexane, and benzene have increasing density (decreasing
o
API) as the H/C ratio decreases.
Figure shows the distribution of various hydrocarbon types with boiling range (molecular size) in a
naphthenic crude oil. The light gasoline fraction of the oil is dominated by the normal, iso-, and
cycloparaffins because there are only two aromatics, benzene and toluene, that boil below 130 oC
Boiling Range
Gasoline
About 15-200oC
Kerosine
About 200-260oC
Gas Oil
About 260-332oC
Lubricating Oil
About 332-421oC
Residuum
Gases
Gas at the well head usually consists of methane with decreasing amounts of the heavier
hydrocarbons, sometimes including traces as high as nonane (C 9H20).
The principal nonhydrocarbon gases in a natural gas are nitrogen, carbon dioxide, and
hydrogen sulfide. Small amounts of helium are also found in some gases.
Dry gas is predominantly methane, whereas wet gas may contain 50% or more of C 2+
hydrocarbons. Dry gas contains less than 0.1 gallon natural gas liquid vapors per 1000 ft 3
(1.3 liters per 100 m 3). In a wet gas, the natural gas liquid vapours amount to 4 liters or more
per 100 m3 (0.3 or more gallons per 1000 ft 3).
Normal butane usually predominates over isobutane in the older, more deeply buried gases.
Hydrogen sulfide is one of the most poisonous gases known. A 0.1 percent concentration in
air is fatal in less than 30 minutes. At the refinery, it is converted to sulfur as follows:
2H2S + 3O2 2SO2 + 2H2O
2H2S + SO2 3S + 2H2O
The sulfur is used to manufacture sulfuric acid and other sulfur products.
Liquefied natural gas (LNG) is primarily methane with a boiling point of -161 oC. Liquified
petroleum gas (LPG) is largely propane and butane. It can be liquefied under pressure at
room temperature.
Ethylene, propylene, and butylene are olefins, not present in natural gas but formed in the
refinery by cracking the gas oils and heavier hydrocarbons to make gasoline. Hightemperature (700-900oC), low-pressure (5 psi) vapor-phase cracking favors production of the
olefins.
Gasoline
Since crude oil contain only 10-40 percent gasoline, the cracking
process, which involved breaking large molecules into gasoline
sized ones at high temperatures, was developed.
OCTANE RATING
The octane rating is a measure of the tendency of a fuel to auto-ignite. The lower the
octane rating the more likely it is that auto-ignition will occur. Clearly, high-octane
fuels are more desirable.
The scale is an arbitrary one. Two compounds were chosen, heptane (C 7H16) and
2,2,4-trimethylpentane (CH 3C(CH3)2CH2CH(CH3)CH3).
For gasoline, the knock characteristics of all hydrocarbons and fuels (in a spark ignition
engine) are rated relative to the n-heptane-iso-octane (2,2,4-trimethylpentane) scale.
The increase in oxidation temperature and octane number with increased branching of
the chain is apparent.
For the same molecular formula, as a straight chain becomes branched, the structure
becomes more compact and octane rating is raised.
The naphthenes and aromatics generally have higher octane numbers than paraffins,
because their rings are basically compact.
One of the most useful hydrocarbon in the gasoline range is benzene, which is a major
raw material for a host of petrochemicals. Benzene is produced by reforming methyl
cyclopentane, cyclohexane, and some hexanes over a platinum catalyst.
Kerosine
The kerosine fraction of crude oil (C11 to C13) is the first to show an
appreciable increase in the cyclic hydrocarbons that dominate the
heavier fractions of crudes.
The aromatics in kerosine range from 10 to 40 percent.
Condensed bicyclic naphthenes and aromatics, such as tetralin and
naphthalene, are common in this range.
Naphthenic acids, phenols, and thiophenes are among the
nonhydrocarbons of kerosine.
kerosene lamps and lanterns are widely used in rural area where
electrical distribution is not available or too costly for widespread use.
In countries such as India, kerosene is the fuel used for cooking,
especially by the poor, and kerosene stoves have replaced traditional
wood-based cooking appliances.
Today, kerosene is mainly used in fuel for jet engines in several
grades.
Light gas oils (C14 to C18) are used in both jet fuels and diesel fuels.
Lubricating oil normally ranges from about C26-C40, but it can go as low as C20
and as high as C50, depending on the distillation process.
This range contains the normal paraffin waxes (C22-C40) and some asphaltics
(NSO compounds).
Highly paraffinic crude oils frequently have a high wax content in this range
and a correspondingly high pour point.
The paraffinicity of a crude and the volume of its +300oC fraction determines its
wax content.
Petroleum waxes are extracted from the lubricating oil fraction and residuum of
high wax crudes. Wax is predominantly n- paraffins and branched paraffins in
the range from C20 to about C60.
The most complex and least understood fraction of petroleum is the residuum.
The principal constituents of residuum or asphalt are some of the very heavy oils,
resins, asphaltenes, and high molecular-weight waxes.
The wax fraction in most residua is about half that in the lube oil fraction.
The asphaltenes are dark brown to black amorphous solids.
The resins may be light to dark coloured, thick, viscous substances to amorphous
solids.
SUMMARY
Olefins with one or more double bonds are found in refinery cracking
products but not normally in crude oil.
SUMMARY
Less than 3% of the output of oil refineries is used to produce more than
two-thirds of the organic chemicals used for producing 7,000 end use
materials.
Petroleum waxes are extracted from the lubricating oil fraction and residuum
of high-wax crudes. Wax is predominately n-paraffins and branched
paraffins in the range from C20 to about C60.
Petroleum asphalts are either straight-run residues from distilling crude oils
or blown asphalts produced by air oxidation of crude residues. Asphalts
contain heavy oils, resins, asphaltenes, and high-molecular-weight waxes.
Asphaltenes are large organic molecules that are highly aromatic and often
relatively high in heteroatoms with molecular weights in the thousands. They
are apparently formed during diagenesis and catagenesis, as well as in oil
reservoirs as by-products of cracking.
ORIGIN OF PETROLEUM
There are mainly two theories of petroleum origin:
The Organic theory of petroleum origin is based on the accumulation of
hydrocarbons from living things plus the formation of hydrocarbons by the
action of heat on biologically formed organic matter.
The Inorganic theory assumes that oil forms from the reduction of primordial
carbon or its oxidized form at elevated temperature deep in the earth.
The overwhelming geological and geochemical evidence from both sediments
and petroleum studies of the past few decades, however, clearly showed that
most petroleum originated from organic matter buried with the sediments in
sedimentary basins.
The organic origin of petroleum follows two pathways from the living material:
Around 10 to 20% of the petroleum is formed directly from the hydrocarbons synthesized
by living organisms or from their molecules, which are readily converted to hydrocarbons
(the first pathway). Most of these early formed hydrocarbon molecules contain more than
15 carbon atoms, and they include easily recognized biological structures.
The second pathway involves the conversion of the lipids (fats), proteins and
carbohydrates of living material into the organic matter (kerogen) of sedimentary rocks.
When this kerogen is buried deeper at higher temperatures, it cracks to form bitumen that
breaks down further to form petroleum. Some hydrocarbons also form directly from
kerogen.
The first pathway from life simply represents an accumulation of the free hydrocarbons
from dead organisms, plus hydrocarbons formed by bacterial activity and low-temperature
chemical reactions in Recent unconsolidated sediments. These are the hydrocarbons that
can be extracted from the Recent sediments with organic solvents. In the second pathway,
there are no free hydrocarbons until the kerogen is heated to a high enough temperature
to crack it and release the hydrocarbons. From 80 to 90% of petroleum is formed along
this pathway.
If the petroleum is buried deeper at higher temperatures, it changes along two pathways,
one leading to increasingly smaller hydrogen-rich molecules and the other leading to
larger, hydrogen-deficient molecules. The end products are methane and graphite.
b) CATAGENESIS
Organic matter is subjected to increasingly higher temperature with greater depth of
burial. Over time, these higher temperatures cause the thermal degradation of kerogen to
yield petroleum- range hydrocarbons under reducing conditions. These hydrocarbonforming reactions have been demonstrated many times in the laboratory and have been
observed in the natural environment.
KEROGEN BITUMEN OIL + GAS + RESIDUE
In this equation, the bitumen is defined as the nonvolatile organic matter soluble in
organic solvents that is formed in the shale during initial heating, whereas kerogen is the
insoluble organic matter. Further heating converts the bitumen to oil and gas. The residue
is the non-volatile portion of the kerogen and bitumen remaining after maximum heating
in the laboratory or under natural conditions.
The depth interval in which a petroleum source rock generates and expels most of its oil
is called the oil window. Most oil windows are in the temperature range from 60oC to
160oC.
Metagenesis is the last stage in the significant thermal alteration of organic matter.
Here methane generation diminishes and graphitic structures begin to form.
Metagenesis occurs in the temperature range of 200 to 250 C. At such
temperatures, the atomic H/C ratio of the kerogen falls to less than 0.4, typical of the
kerogen in a phyllite.
The bottom of the 9,583m well drilled in the Cambro-Ordovician Arbuckle Formation
in the Anadarko Basin of Oklahoma contained kerogen with an H/C ratio of about
0.25. That is equivalent to a C96H24 hydrocarbon structure containing 37 fused
aromatic rings. Such a structure could generate only trace amounts of methane
before becoming pure graphite.
Inorganic geochemists term mineralogic changes that can be attributed to the action
of heat and pressure at depth as Metamorphism. The low temperature end of the
metamorphic scale is about 200C to 300C. Consequently, the high-temperature end
of organic thermal alteration overlaps with the low temperature beginning of inorganic
thermal alteration.
The process of migration has been divided mainly into two parts:
Primary and Secondary migration.
PETROLEUM GEOCHEMISTRY
There are a number of important questions that organic geochemistry can answer to help
solve the hydrocarbon exploration problem. These include the following:
What was the original hydrocarbon-source potential of a particular rock? Does it have any
remaining source potential at the present time?
What depositional environments are conducive to the formation of kerogens having high
hydrocarbon-source potentials? Can we predict their occurrence?
Which types of kerogen are converted to oil? to gas?
What factors influence oil gravity and composition?
What thermal conditions are required for hydrocarbon formation? Can we predict when and
where generation has occurred?
Can we correlate several samples with each other to decipher genetic relationship? Can
we distinguish biogenic methane from thermal methane?
Can we predict the direction, timing, and efficiency of hydrocarbon migration in a particular
area?
What conditions are required for hydrocarbons to be preserved against the destructive
forces of oxidation, cracking, and biodegradation? Can we predict where destruction will
occur?
Geochemical models form an important part of the overall geological model. Three main
type of geochemical models (organic facies, thermal maturity, and volumetric) exist at the
present time. In immaturely explored areas we have some data with which to test and refine
our early models. Use of models helps develop entirely new plays even in mature areas.
Source Rock
A petroleum source rock may be defined as a fine grained sediment
that has generated and released enough quantity of hydrocarbons to
form a commercial accumulation of an oil and gas.
The source rocks are clay or carbonates muds deposited under low
energy and reducing conditions. The shales and bituminous limestone
consolidated from muds and marls are generally regarded as source
rocks of petroleum and gas.
The mean TOC (Total Organic Carbon) content of fine grained rocks in
petroliferous areas is 1.37% for shales and 0.5 % for carbonates.
Some shales and carbonates with porous and permeable sections
within them can act as both source and reservoir.
The relative ability of the source rock to generate petroleum is defined
by the kerogens quantity (TOC), quality (HI) and state of maturation
(Tmax and Ro).
KEROGEN
The term kerogen is normally defined as that portion of the organic matter present
in sedimentary rocks that is insoluble in ordinary organic solvents.
The chemical and physical characteristics of a kerogen are strongly influenced by
the type of biogenic molecules from which the kerogen is formed and by
diagenetic transformations of those organic molecules.
The kerogen is the precursor of most oil and gas that we exploit as fossil fuels.
Diagenetic and catagenetic histories of a kerogen, as well as the nature of the
organic matter from which it was formed, strongly influence the ability of the
kerogen to generate oil and gas.
Coals are a subcategory of kerogen. Humic coals are best thought as kerogens
formed mainly from land plant material without codeposition of much mineral
matter.
Kerogen formed under reducing conditions will be composed of fragments of
many kinds of biogenic molecules.
Those kerogens formed under oxidizing conditions, in contrast, contain mainly the
most resistant types of biogenic molecules that were ignored by micro-organisms
during diagenesis.
CLASSIFICATION OF KEROGEN
Geoscientists at French Petroleum Institute identified three main types of kerogen (called
Types I, II, and III). Subsequent investigations have identified Type IV kerogen as well.
Type I kerogen is quite rare because it is derived principally from lacustrine algae. The
best known example is the Green River Shale, of middle Eocene age, from Wyoming,
Utah, and Colorado. Occurrences of Type I kerogens are limited to anoxic lakes and to a
few unusual marine environments. Type I kerogens have high generative capacities for
liquid hydrocarbons.
Type II kerogens arise from several very different sources, including marine algae, pollen
and spores, leaf waxes, fossil resin and contributions from bacterial cell lipids. Most Type
II kerogens are found in marine sediments deposited under reducing conditions. They all
have great capacities to generate liquid hydrocarbons.
Type III kerogens are composed of terrestrial organic matter that is lacking in fatty or
waxy components. Cellulose and lignin are major contributors. Type III kerogens have
much lower hydrocarbon-generative capacities than do Type II kerogens and, unless they
have small inclusions of Type II material, are normally considered to generate mainly gas.
Type IV kerogens contain mainly reworked organic debris and highly oxidized material of
various origins. They are generally considered to have essentially no hydrocarbon source
potential.
And also the potential to form oil decreases in the same order. Thus, the main
key difference between oil generating, gas generating and non-generating
kerogen is the hydrogen content.
Column Chromatography
The first step in the separation procedure is precipitation and removal of intractable asphaltenes
from bitumen or oil upon addition of a large excess of pentane. The asphaltenes are then filtered
off and the asphaltene-free bitumen or oil is recovered by evaporation of pentane. The technique
most commonly used to separate the asphaltene-free bitumen or crude oil into fractions is called
column chromatography.
In column chromatography a glass tube 20-50 cm in length is held in a vertical position and filled
with a slurry of silica gel or alumina suspended in a hydrocarbon solvent like n-hexane. A small
amount of bitumen or petroleum is added to the top of the column, and the solvent is allowed to
run through by gravity flow. The hydrocarbon solvent dissolves the saturated hydrocarbons and
carries them slowly along with it down the column. The other more polar components of the
bitumen (aromatics and NSO compounds) remain stationary or move much more slowly than the
saturates. Nonpolar molecules (saturates) move rapidly because they have little affinity for the
highly polar stationary phase (alumina or silica gel), but they are very compatible with the
nonpolar hexane.
n-Hexane is allowed to pass through the column until the saturated hydrocarbons have all been
eluted. The solvent and its dissolved hydrocarbons (saturates) are collected as the first columnchromatographic fraction.
Aromatic hydrocarbons (along with some sulfur-bearing heterocompounds) are then collected in
a second fraction eluted by a slightly more polar solvent, benzene.
A third fraction, containing mainly NSO compounds, is eluted with methanol or chloroform.
Depending on the relative electronegativities of the two atoms sharing electrons, there may be partial transfer of
electron density from one atom to the other. When the electronegativities are not equal, electrons are not shared
equally and partial ionic charges develop.
The greater the electronegativity difference, the more ionic the bond is. Bonds that are partly ionic are called polar
covalent bonds.
Nonpolar covalent bonds, with equal sharing of the bond electrons, arise when the electronegativities of the two
atoms are equal.
Molecular sieving and urea adduction are both used to separate n-alkanes from
branched and cyclic saturated hydrocarbons, including isoprenoids.
Both techniques are applied to the saturated hydrocarbon fraction obtained by
column chromatography.
When the n-alkanes are all trapped in the holes in the crystals, the solvent
containing the branched and cyclic hydrocarbons is decanted.
Gas Chromatography
A gas chromatograph is an oven containing a long, thin, coiled column of metal or glass.
One end of the column is attached to a heated injection port, through which the sample to
be analyzed can be introduced onto the column.
The other end is attached to a detector that can monitor the passage of the compounds
out of the column after they have been separated.
The column itself can be either a packed column or a capillary; capillary columns are far
more common today.
Packed columns contain a porous solid support material coated with a non-volatile liquid
(organic polymer).
The much thinner capillary columns have no solid support; the polymer is coated directly on
the walls of the column.
At the beginning of an analysis the sample is injected with a syringe into the hot injection port.
The molecules in the sample are vaporized rapidly and swept onto the column by an inert gas
flowing continuously through the column.
The components of the injected mixture separate as a result of differences in vapour pressure
above the liquid phase and in solubility in the liquid phase.
The rate of movement of a particular molecule through the column therefore depends upon how
much time it spends in the vapour phase (in which it can be swept along) and how much time it
spends immobilized in the liquid phase.
Heavy molecules generally move more slowly than light ones, and polar molecules move more
slowly than nonpolar ones.
During the analysis the oven can be gradually heated to increase the volatility and mobility of the
heavier molecules.
This gradual increase in column temperature, which is called temperature programming, permits
both light and heavy components to pass through the column in a reasonable length of time.
As the compounds emerge from the column they are detected, and a signal proportional to their
concentration is recorded.
The trace representing all the emerging compounds is known as a gas chromatogram.
Identification of the compounds represented by the various peaks is carried out by comparison of
retention times (times required for components to emerge from the column) with authentic
standards.
Quantification is accomplished either by measuring peak heights (if all peaks in question are the
same shape) or, more correctly, by measuring the areas under the peaks using an automatic
integrator attached to the detector.
FIGURE Schematic diagram of a gas chromatograph. The white molecules are more volatile and thus
have a shorter retention time than the black molecules.
These various molecular and fragment ions are accelerated in an arc by the magnetic
field within the evacuated mass-spectrometer chamber. The radius of the arc
depends upon both the mass/charge ratio (written as m/z or m/e) of the ion and the
strength of the magnetic field. For any given field strength only those ions with a
particular m/z value pass through the centre of the chamber and strike the detector.
The detector response tells us how many such ions were present.
As the field strength is varied rapidly during the analysis, ions with different m/z
values are allowed to strike the detector. The detector responses over the range of
field strengths employed are summed to yield a mass spectrum. The height of each
bar is proportional to the number of ions with that particular m/z value.
Mass spectra are mainly used to identify particular unknown compounds. What has
proven useful for petroleum geochemists seeking to apply gc/ms in exploration is the
knowledge that compounds with similar chemical structures have similar mass
spectra. Thus steranes all have a large m/z 217 peak. Similarly, most triterpanes
have a large m/z 191 peak. These fragment ions are among the most important ones
for most gc/ms work.
One of the tricks of modern electronics allows us to monitor selected m/z values
during the entire gas-chromatographic separation. The trace obtained by monitoring a
single m/z value during an entire gas-chromatographic run is called a mass
chromatogram or a mass fragmentogram.
Isotope Measurements
The most commonly measured isotopes are of carbon, followed by hydrogen and
sulfur, and more distantly by nitrogen. Isotope measurements are made on a mass
spectrometer specially designed and set up to look at a single chemical compound. In
principle, however, the instrument operates in a manner similar to the mass
spectrometer described earlier.
The relative amounts of each isotope are determined by comparing the amounts of
ions containing the heavy isotope with those containing the light isotope. For
example, 13CO2 has a mass of 45 amu, whereas 12CO2 is 44 amu. The quantities of
each type can be measured very accurately by the mass spectrometer.
Samples on which isotopic measurements are made are always compared directly
with reference samples, called standards. The value reported is thus always the
difference between the isotope ratios of the sample and the standard.
FIGURE The range in the carbon-13 content of carbon reservoirs (in parts per thousand relative to the Peedee belemnite standard)
Basic Parameters
S1 = the amount of free hydrocarbons (gas and oil) in the sample. If S1 >2 mg
HC/g rock in immature sediments, it may be indicative of migratory oil or oil
contaminants. S1 normally increases with depth. S1/TOC is high and the Tmax is
low if migrated hydrocarbons are present. S1/TOC = 0.1 to 0.2 for oil expulsion.
S2 = the amount of hydrocarbons generated through thermal cracking of
nonvolatile organic matter. S2 (mg HC/g rock) is an indication of the quantity of
hydrocarbons that the rock has the potential of producing should burial and
maturation continue. It is 2 for poor source rocks, 2-5 for fair, 5-10 for good,
and > 10 for very good source rocks. It is used to calculate the Hydrogen
Index.
S3 = the amount of CO2 (in milligrams CO2 per gram of rock) produced during
pyrolysis of kerogen. S3 is an indication of the amount of oxygen in the kerogen
and is used to calculate the Oxygen Index.
Tmax = the temperature at which the maximum release of hydrocarbons from
cracking of kerogen occurs during pyrolysis (top of S2 peak). Tmax is an indication
of the stage of maturation of the organic matter.
FIGURE Modified van Krevelen diadram used for Rock-Eval pyrolysis data,
showing maturation pathways of Types I, II, and III kerogens.
VITRINITE REFLECTANCE
Vitrinite Reflectance (VRo) is the most commonly used organic maturation indicator used
in the petroleum industry. This is mainly because it is accurate, quick, non-destructive
and inexpensive. Vitrinite is a coal maceral. It is not strongly prone to oil and gas
formation, and is common as a residue in source rocks.
As coal maturity increases, and the chemical composition of the Vitrinite correspondingly
changes, the vitrinite macerals become increasingly reflective. Therefore, the percentage
reflection of a beam of normal incident white light from the surface of polished vitrinite is a
function of the rank (maturity) of the macerals. Vitrinite includes telinite, the cell wall
material of land plants, and collinite the organic substance that fills the cell cavities.
Vitrinite is composed of clusters of condensed aromatic rings linked with chains and
stacked on top of one another.
With increasing maturity, the clusters fuse into larger, condensed aromatic ring
structures. Eventually they form sheets of condensed rings that assume an orderly
structure. Both the increase in the size of these sheets and their preferred orientation
cause greater reflectivity.
CORRELATIONS
In order to identify source rocks and determine migration pathways, it is often important to
know whether two samples of organic material share a common origin.
Correlations are easiest between materials of the same type (two oils for example), but they are
also possible between dissimilar samples (oils with kerogens or bitumens, bitumens with
kerogens).
Two fundamentally different types of characteristics can be measured: bulk parameters and
specific parameters.
Bulk parameters refer to properties of the whole sample; sulfur content, API gravity, saturatedhydrocarbon content, and pour point are examples. Because they tend to be affected strongly by
processes such as migration, biodegradation, and cracking, bulk parameters have some
important limitations as correlation tools.
Specific parameters, in contrast, measure in detail one characteristic of a small fraction of the
sample; they include, for example, the many types of biomarker ratios. Specific parameters are
sometimes strongly affected by a small amount of contamination, biodegradation, or mixing.
Bulk parameters are better for detecting transformations that affect the whole sample but
generally are not sensitive enough to be reliable positive correlation tools without corroboration
by specific parameters. It is therefore important to utilize both bulk and specific parameters in
correlation studies.
BULK PARAMETERS
Oils and kerogens derived from highly reducing evaporates are often quite heavy
isotopically (values near -20 versus PDB), probably because they contain
exclusively algal material. Waxy oils, in contrast, are sometimes isotopically light,
having values more negative than -30 . The carbon isotope ratios of majority of oils
and kerogens fall in the range -24 to -28 .
The causes of variations of hydrogen isotopes in oils are poorly understood. One
useful generalization, however, is that the deuterium content of oils sourced from
carbonates is higher than for shale-sourced oils.
Sulfur-isotope ratios are occasionally useful in correlating oils, especially those that
are high in sulfur content.
Most oils will contain more than 75% hydrocarbons. Certain oils formed at low levels
of maturity from sulfur-rich kerogens can have large amounts of NSO compounds and
asphaltenes, however.
SPECIFIC PARAMETERS
Sofer (1984) has used carbon-isotope measurements on two fractions (saturates and
aromatics) of a crude oil to classify it as high- or low-wax (interpreted by Sofer to be
terrestrially influenced or wholly marine). He employed following empirical equation to
make the distinction at about the 90% confidence level.
Where if CV < 0.47 the oil is low-wax (wholly marine), and if CV > 0.47 the oil is highwax (terrestrially influenced).
Steranes are valuable correlation parameters because of the direct dependence of C 27, C28, and
C29 regular-sterane concentrations on their precursor C 27 to C29 sterols.
C27 sterols dominate in marine organisms, whereas C 29 sterols are more common in terrestrial
plants.
These relationships can be expressed in a triangular diagram, which allows one to estimate the
growth environment (paleoenvironment) of the contributing organic matter.
Steranes are of less value where biodegradation is extreme because the regular steranes are
destroyed completely in the late stages of biodegradation.
Oil-oil correlations
Oils in the Michigan Basin have been produced from Ordovician (Trenton), Silurian
(Niagara), and Devonian (Dundee and Lucas) reservoirs. On the basis of n-alkane and
isoprenoid distributions and carbon-isotope profiles for individual n-alkanes, it was
decided that the Ordovician and Devonian oils had a common source and that the
intervening Silurian oils had a different source, probably in lagoonal facies adjacent to the
reefs from which they are produced.
FIGURE n-alkane and isoprenoid distributions from gas chromatograms of saturated hydrocarbons
from typical Ordovician, Silurian, and Devonian oils from the Michigan Basin.
Oils are produced from several fields in the Basin and Range province of Utah and Nevada. Two very different type of source rocks are identified
in the area. The chainman Shale of Mississippian age was deposited in a marine basin. The Sheep Pass and Elko formations , in contrast, are of
Paleogene age and represent lacustrine facies.
The most useful analytical techniques for correlating specific oils and source rocks were gas chromatography (fig. D) and gc/ms (fig. E) The Trap
Spring oil, for example, has a very similar gas chromatogram to that from a mature sample of Chainman shale (fig. D): Pr/Ph ratios are near 1.5,
and the samples are low in heavy n-alkanes. Oils from the Eagle Springs and Currant field, in contrast, have Pr/Ph ratios below 1.0, and contain
moderate to large amounts of heavy n-alkanes similar to the source rock extract from Sheep Pass formation.
FIGURE D Gas
chromatograms
of saturated
hydrocarbons
from three oils
(top) and three
source-rock
extracts
(bottom) from
the Basin and
Range province
of Utah and
Nevada. Each
oil correlates
with the extract
immediately
below it.
The most powerful arguments for the proposed source rock-oil correlations come from sterane
and triterpane distributions (fig. E).
The lacustrine rocks (Sheep Pass and Elko formations) all contain large amounts of
gammacerane (peak 7 in fig. E), an indicator of lacustrine origin.
Five of the oils analyzed, including the previously mentioned Eagle Springs and currant oils, also
contain large amounts of gammacerane and thus suggest their generation from lacustrine
source rocks.
These five oils correlate very well with the lacustrine source rocks in other respects as well. All
(White River Valley oil is an exception) have more of the 20R- than 20S- epimer of the C29
sterane (peaks D and A in fig. E), which indicates low maturity.
The remaining four oils shown in figure E correlate well with the Chainman shale extracts.
Gammacerane contents of all samples are low; maturities are high, as indicated by an excess of
the C29 20S-epimer over the 20R-epimer.
One implication of this study is that oil generation from the lacustrine source beds in the Basin
and Range province occurs at very low levels of maturity, probably as the result of the combined
effects of the great richness of the source rocks and high sulfur contents of the kerogens.
The knowledge thus derived from correlation studies in an area can be incorporated into future
exploration models for the area.
Biodegradation
The Lakes Entrance oil (16o API< 365-m depth, Tertiary reservoir) and West Sea Horse #1 oil (48 o
API, 1400-m depth, Cretaceous reservoir) from the Gippsland Basin of Australia have very different
chemical and physical properties. Gas chromatograms of the saturated hydrocarbon fractions are
shown in figure A. Mass chromatograms are presented in figures B an C. Could there be any
genetic relationship between these two oils?
From the gas chromatograms it is evident that the Lakes Entrance oil is heavily
biodegraded, with both n-alkanes and isoprenoids completely destroyed.
Biodegradation has even affected the steranes (fig. B), leading to a decrease in the
biologically produced sterane (peak 4). However, the biodegradation has not
reached the stage to affect the triterpanes (m/z 191 mass chromatogram, fig. C)
On the basis of gas chromatograms and sterane biomarker data it is not possible to state
with certainty that the Lakes Entrance and West Sea Horse #1 oils are related. The
triterpane mass chromatograms are rather similar and are therefore consistent with a
common origin.