PETROLEUM GEOLOGY Series 1 Introduction and Overview D. HYDROCARBON GENERATION & MIGRATION D.1.

Generation and Maturation Processes Formation and Preservation of Organic Matter

In the nineteenth century, it was widely believed that petroleum had a magmatic origin and that it migrated from great depths along subcrustal faults. Vestiges of this theory may still be heard today, but the overwhelming evidence now suggests that the original source material of petroleum is organic matter formed at the earth's surface. The process begins with photosynthesis, in which plants, in the presence of sunlight, convert water and carbon dioxide into glucose, water and oxygen: ( 6CO2 + 12H2O C6H6O6 + 6H2O + 6O2 ).

Glucose is the starting material for the synthesis of more complex polysaccharides and other organic compounds, either in plants or the animals that eat them. Photosynthesis is

part of the largerscale carbon cycle. Ordinarily, most of the organic matter produced recycled carbon This can back by to photosynthesis gets the atmosphere as dioxide. occur

through plant and animal respiration, or through oxidation

Figure 1.

and bacterial decay when organisms

die. Normally this completes the cycle ( Figure 1 ). However, the carbon cycle is not completely efficient. A small amount of organic matter, about 1 part in 1000, escapes recycling and is buried. Over geologic time, this small influx has produced vast quantities of fossil organic material,

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estimated at about 20 10 15 metric tons (Waples, 1981). However, most of this material is widely dispersed within the sedimentary column. Only about one CO2 molecule out of every million initially taken up by photosynthesis is eventually converted into economically exploitable oil, natural gas or coal. The series of events that leads to concentrated accumulations of fossil fuels is, therefore, highly selective. These selective conditions all begin with the supply of organic matter to sediments, either by marine plants and animals, or by terrestrial plants. In sandy, current- and wave-agitated environments, the organic matter stays in suspension or is winnowed away, but it can settle out in quiet water, low energy environments. Consequently, organic matter is found mostly in fine-grained rock types, such as shale and lime mud. These low energy environments are usually found in oceans, lakes, or, in the case of coal, swamps. However, not all shales contain enough organic matter to be good source rocks. Organic-rich shale is favored by both a high rate of production of organic matter, and by a high preservation potential.

Preservation and Organic Productivity

All organic matter in the ocean is originally formed through photosynthesis. The main producers are phytoplankton, which are microscopic floating plants such as diatoms, dinoflagellates and the bluegreen algae. Bottom-dwelling algae are also major contributors in shallow water, shelf environments. Phytoplankton are at the bottom of the food chain. Their distribution controls the animal forms such as the microscopic zooplankton, as well as the higher animal life, all of which contribute to the ocean's biomass. The production of phytoplankton and algae is related to both physical and chemical variables. Light is particularly important, because of its role in photosynthesis. The depth penetration of light through the ocean's surface defines the photic zone. The thickness of the photic zone depends mainly on latitude and water clarity. In clear, tropical seas, where productivity is often high, the photic zone can extend up to 100 meters below the surface. The second important factor in organic productivity is the rate of nutrient supply to the photic zone. The most important of these nutrients are phosphates and nitrates. These are released by bacterial decomposition of organic matter, and are vital for both plant and animal growth. Oxygen, although not important for phytoplankton, is vital for the existence of animals that form later links in the food

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chain. Phyto-plankton increase the oxygen content of surface waters, as a by-product of photosynthesis. Figure 1 shows the areas of high biological productivity in the world's oceans. In the open ocean, zones of high productivity occur at high latitudes of about 60 north and south and along the equator. These are regions in which cold, vertically moving ocean currents bring nutrients and dissolved oxygen from the deep ocean back up to the surface. Without this resupply, nutrient concentrations the oceans in the surface become water would become so low that would essentially lifeless in less than a year, except near the mouths of large rivers. Productivity is also very high in the shallow, well-mixed waters over enter the the continental where ocean which and shelves, rivers supply the particularly large

abundant nutrients. The same principles

Figure 1.

govern

distribution of organic matter in modern oceans must have also

pertained in the past. However, it is very difficult to extrapolate this data back into geologic time, since the continents have drifted, ocean circulation patterns have changed and the diversity of plant and animal groups has altered over time.

Preservation and Organic Destruction

Areas of high productivity are not necessarily those best suited for preservation. Destruction of organic matter must also be prevented. Complete biological recycling of organic carbon is retarded by anything that limits the supply of elemental oxygen. This occurs most favorably in either one of two settings: rapid rate of deposition; and stratified, oxygen-poor water bodies with anoxic bottoms.

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First, rapid deposition may be necessary to keep the organic material from being destroyed. In normal oxygenated marine environments, some animals, such as marine polychaete worms, eat sediment to get at the organic matter it contains. If deposition is slow, bottom sediments may be eaten many times and most organic matter destroyed. It has been commonly observed that shales which have a high degree of bioturbation mottling by deposit-feeders also have low organic contents and are poor petroleum source rocks. Bacteria in the sediment will also destroy organic matter. Aerobic bacteria use dissolved free oxygen diffused from overlying water into the upper sediment layers to convert the organic matter to carbon dioxide and water: CH2O + O2 CO2 + H2O ( where CHO represents all organic compounds

Aerobic breakdown is a highly efficient process, and most of the remains of dead plants and animals are destroyed by it. In typical nearshore marine muds, aerobic decomposition occurs right at the sediment-water interface, but free oxygen is rapidly used up below the sediment surface. Anaerobic bacteria that reduce nitrates live in the first few centimeters below the surface; sulfatereducing bacteria occur over the next 100 cm.; and at greater depths anaerobic bacteria break down organic matter through fermentation, forming biogenic methane or marsh gas. (Berner, 1980). Anaerobic bacterial deacy: 5CH2O + 4NO3Nitrate reduction: 2CH2O + SO4-2 Fermentation: 2CH2O + 2H2O 2N2 + 4HCO3- + CO2 + 3H2O

H2S + 2HCO3CH4 + 2H2O + CO2

*where CH2O represents all organic compounds However, most of this bacterial action which destroys organic matter, both aerobic and anaerobic, occurs within the upper 30 to 60 cm. of sediment Under conditions of rapid deposition, bacteria can act for only a short time, and decomposition is less complete. Preservation is also favored by density stratification, which produces oxygen-poor bottom waters. This occurs mainly in some lakes and in lagoons and shallow restricted seas where fresh river water enters a dense saltwater body. Because of the density contrast, the less dense fresh water floats on sea water. Mixing of waters is greatly inhibited between the two layers. Oxygen produced from photosynthesis, or dissolved in the water from the atmosphere, in the upper layer cannot circulate to the lower layer. As a result, in the deeper denser waters where organic detritus slowly

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setting to the bottom undergoes bid-oxidation, the oxygen supply is rapidly used up and cannot be replaced . Both the bottom waters and the substrate will become anoxic, and the normal processes whereby organic matter drifting down from above is oxidized, will be inhibited. The rate of production of organic matter in such an environment may be no higher than average, but its rate of decay may be much slower. These anoxic ocean-floor environments are unable to support the sediment-eating animals and aerobic bacteria that normally cause most organic destruction. In this situation, the only bacteria present will be anaerobes, which are much less efficient at destroying organic matter than aerobes . The incomplete breakdown of organic molecules by anaerobic bacteria actually enhances the transformation of organic matter into petroleum. Water stratification and oxygen depletion are well known in the modern Black Sea, (Deuser, 1971, Degens and Ross, 1974) and in the Dead Sea (Neev and Emery, 1967). The Eocene-age lakes of Utah, Colorado and Wyoming, in which the Green River oil shale formation was deposited, have been interpreted as seasonally stratified water bodies which at a later stage become permanently stratified ( Figure 1 ). Stratified oxygen-depleted deep

waters and sediment substrate occur not only in lakes and inland seas, but also on broad, flat shelves where circulation may be minimal. In the present-day world's oceans, there is a zone of maximum oxygen depletion at a depth of about 200 meters, with oxygen more abundant in the shallow surface waters and again at deeper levels ( Figure 2 ). A global rise in sea level could raise this anoxic zone enough to cover drowned continental shelves. A well-known example of this
Figure 1.

is the so-called Cretaceous "anoxic event", which produced widespread

black, organic-rich shales throughout the world. Arthur and Schlanger, (1979) have shown that the peak preservation of organic matter was coincident with the maximum transgression of the sea across the continental shelves in Cenomanian time ( Figure 3 ; the graph on the left shows average

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organic carbon in DSDP cores from the North Atlantic; the graph on the right shows the global sea level curve. ).

Figure 2.

Figure 3.

In continental environments, degradation of terrestrial plants is mostly aerobic. It is initiated first by fungi, as soon as, or even before, the plant dies. This attack renders the material more susceptible to the subsequent bacterial invasion. Significant accumulations of organic matter will only occur in stratified lakes or anaerobic coal swamps.

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PETROLEUM GEOLOGY Series 1 Introduction and Overview Diagenesis of Organic Matter

There are three important stages in the burial and evolution of organic matter into hydrocarbons: diagenesis; catagenesis; and metagenesis. Diagenesis of organic matter begins as soon as sediment is buried. However, the point at which diagenesis ends is subject to how the term is used. Some geologists use the term in a restricted sense to include only processes that occur as sediment consolidates into sedimentary rock. Others expand the realm of diagenesis to include all processes extending up to, and blending imperceptibly into, regional metamorphism. In this discussion, diagenesis is defined on the basis of organic matter, and it includes all changes that occur up to the stage of petroleum generation. Freshly deposited muds are unconsolidated and may contain more than 80% water in their pores. These muds compact very quickly. Most of the porosity is lost in the first 500 meters of burial ( Figure 1 ). After that, compaction to form mudstones or shales continues much more slowly. Any organic matter within these shales is also undergoing complex changes. The starting point for these changes are the four major groups of organic compounds or biopolymers that are biologically synthesized carbohydrates; by plants proteins; and lignins; animals: and the lipids.

Carbohydrates occur in both animals and plants and include simple sugars, such as glucose, and their complex polymers, like cellulose, starch and chitin. Proteins are found largely in animals and to a lesser extent plants. Lignin is built up of high molecular weight aromatic carbon rings, and occurs only in the higher land plants. Lipids occur in both plants and
Figure 1.

animals. They are insoluble compounds that include the fats, oils and waxes, and are the major source

materials for the formation of liquid hydrocarbons. Figure 2 shows how during early diagenesis, the complex biopolymers are broken down into smaller, simpler molecules, called geomonomers. Proteins are the least stable and are followed, with increasing resistance to breakdown, by carbohydrates, lipids and lignins. The more active of the geomonomers then will spontaneously react with each other and polymerize to yield stable,

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complex geopolymers. Unlike biopolymers, geopolymers have a random structure and are therefore resistant to biodegradation. These changes are brought about first by bacteria and nonbiological chemical processes, and later by thermal cracking. The transition to geopolymers occurs over a geologically short time, probably only a few hundreds or thousands of years. With increasing burial, the organic matter loses almost all of its nitrogen, much of its oxygen and sulfur, and some of its hydrogen and carbon. Most of the heteroatoms are lost as small molecules, such as CO2, NH3, N2,O2, H2O and H2S.
Figure 2.

The only hydrocarbon produced In measurable amounts at this stage is biogenic methane, as a product of anaerobic decay. The end product of the diagenesis of organic matter is kerogen. Kerogen is defined as the organic material in sedimentary rocks that is insoluble in organic solvents. The insolubility of kerogen molecules is derived from their large molecular size. It is this property, rather than fundamental differences in chemical arrangement, that distinguishes kerogen from the soluble portion of the organic matter, called bitumen.

Kerogen Components
Under the microscope, kerogen appears as disseminated organic fragments. Some of this material is structured. It is recognizable as plant tissue fragments, spores, algae, and other pieces with a definite biological organization. These plant-derived structured fragments can be grouped into distinct biological units called macerals. Macerals in kerogen are equivalent to minerals in rocks. Three major maceral groups are important: vitrinite, exinite and inertinite. Vitrinite is the dominant maceral type in many kerogens and is the major component of coal. It is derived almost entirely

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from woody tissue of the higher land plants. Because it is derived from lignin and is difficult to break down, vitrinite can appear in almost any depositional environment, marine or nonmarine, and is generally the most abundant type of structured particle. Exinite macerals are mainly derived from algae, spores, pollen, and leaf-cuticle waxes. High percentages of exinite are not common, but if present, they usually imply lacustrine or shallow marine environments. Inertinite macerals come from various sources that have been extensively oxidized before deposition. Charcoal, derived from woody plants, is the major recognizable type. Inertinite is usually a minor component of kerogen, and is abundant only where much of the organic matter has been recycled. In addition to the structured macerals, some of the components of kerogen are amorphous. Amorphous particles have been so mechanically broken up and/or chemically altered by bacteria and fungi that their original maceral types and cell structures have been obliterated -Amorphous particles are not true macerals but alteration products, although the maceral term "amorphinite" has sometimes been applied to these materials. Amorphous particles probably represent the most attractive hydrocarbon source material in kerogen. Because it is more chemically broken down, amorphous material may mature to oil at significantly lower temperatures than associated macerals. Also, a given volume of amorphous material will yield a greater amount of hydrocarbons, since its volume has been reduced and its density increased in comparison to structured types. Amorphous material has an over-representation of particles derived from the exinite group of macerals, because this group is composed of soft particles with less complex molecules that break down more easily, faster and earlier than the more resistant, woody tissues of the vitrinite group.

Hydrocarbons and Kerogen Type

The macerals and amorphous particles in kerogen affect its ability to generate hydrocarbons. Oilprone kerogens generally are made of more than 65% exinite and amorphous particles ( Figure 1 , types of petroleum generated from kerogen, based on visual analysis with reflected light microscope ). Kerogens with 65% to 35% of oil-prone components will expel mostly condensate and wet gas. With less than 35% oil-prone constituents, the kerogen will yield dry gas if dominated by vitrinite and will be non-reactive and barren if dominated by inertinite. The oil-prone kerogens can

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be divided into two types. Type I, or algal kerogen ( Table 1, below ), is rich in the algal components of exinite, and is formed in either lacustrine or marine environments. Type I kerogen is derived mainly from lipids and tends to produce crudes that are rich in saturated hydrocarbons.

Figure 1.

Kerogen Type I Algal

Origin Algae of marine, lacustrine,boghead coal environments

Organic Constituents Mostly algal components: of exinite (alginite); some amorphous material derived from algae

II Mixed Decomposition in reducing Marine environments, mostly marine

Amorphous particles derived mostly from phytoplankton, zooplankton, and higher organisms; also some macerals from these groups

III Coaly

Debris of continental vegetation Mostly vitrinite;some exinite ( not algal ( wood, spores, leaf cuticle wax, ) and amorphous decomposition products resin, plant tissue )

IV Inert

Mostly inertinite; some amorphous Fossil charcoal and other oxidized material of continental decomposition products vegetation

Table 1 Kerogen types, their origin, and organic particle constituents

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Type II is a kerogen derived from mixed marine sources. Its particles are mostly amorphous and result from the decomposition of phytoplankton, zooplankton, and some higher animals. Its chemical nature is intermediate between Types I and III. Type II kerogens tend to produce naphthenic and aromatic-rich oils, and they yield more gas than Type I. Type III or coaly kerogen, is rich in vitrinite macerals, and therefore has a very low capacity to form oil. It mainly generates dry gas. Any oils generated from Type III kerogens are mostly paraffinic waxy crudes derived from its exinite and amorphous constituents. There is a fourth kerogen type which is extremely rare. It is rich in inertinite macerals and produces very low hydrocarbon yields. Inertinite is, as its name implies, inert and has practically no ability to generate either oil or gas ( Figure 1 , types of petroleum generated from kerogen, based on visual analysis with reflected light microscope ). Sedimentary rocks commonly contain mixtures of the kerogen types. Many oil shales contain dominantly Type I, the algal kerogens. Coals and some nearshore clastic source rocks, such as those found in deltas, contain mainly Type III, coaly kerogen. In some cases, coal deposits can be direct contributors to significant natural gas accumulations, as for example the Carboniferous coals of the North Sea. Many marine source rocks have either Type I algal or Type II mixed marine kerogen, with Type II the more common. For example, some of the excellent source rocks of Iran contain mostly Type I, algal kerogen, while the Paleozoic source rocks of the North African Sahara have Type II, mixed marine kerogen.

Chemical Changes with Kerogen Maturation

In the stage of diagenesis, prior to the generation of oil and gas, each of the kerogen types has a unique chemistry ( Figure 1 ).

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This is because kerogen

composition is controlled by the types of macerals and the original biopolymers from which it was formed. This chemical variability of immature kerogen types and the changes is that occur as are petroleum generated

usually presented as plots of the atomic hydrogen to carbon ratio (H/C) often against called a the oxygen to carbon ratio (O/C) . This graph is Van Krevelen diagram ( Figure 2 , and Figure 3 ). Of particular importance is the
Figure 1.

H/C ratio, which decreases rapidly as hydrogen-rich molecules are

cracked off as oil or gas. Remember that the highest possible organic H/C ratio is 4, which is found in the hydrocarbon gas methane. The O/C ratio helps define the kerogen origin, but most of the oxygen is lost in diagenesis as CO2 and H2O and very little survives to affect the petroleum generation process.

Figure 2.

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PETROLEUM GEOLOGY Series 1 Introduction and Overview

Of the four kerogen types, the Type I algal kerogens have the highest atomic H/C ratios during diagenesis, initially about 1.65. Type II, III and IV start out with progressively lower H/C ratios. As any of these kerogens are heated, they may reach the second stage in the evolution of organic matter, the stage of catagenesis ( Figure 3 ). Catagenesis is defined as the stage at which oil and natural gas is generated from kerogen. Since oil and gas molecules have very
Figure 3.

high H/C ratios, generation of petroleum will cause the H/C of the residual

kerogen to decrease. Ultimately, all kerogen types will converge along a common path during the final stage in the evolution of organic matter, the stage of metagenesis. During metagenesis, oil and gas generation directly from kerogen ceases, but considerable methane gas can still be generated from the thermal alteration of previously generated crude. The kerogen residue of this stage approaches the pure carbon state, that is, graphite. Since it starts out with a lower H/C ratio ( Figure 2 , and Figure 3 ), Type II kerogen can generate less hydrocarbons than Type I, even though both are oil-prone. Similarly, Type III is less significant in the total quantity of hydrocarbons it can generate, and Type IV is almost barren.

Depth, Temperature and Time in Petroleum Formation

The generation of hydrocarbons can be related to burial depths of source rocks, since temperature increases with increased depth. The actual generation depths for particular source rocks will depend on the local geothermal gradient, as well as kerogen type and burial history. The depths given in Figure 1 are average, maximum and minimum generation depths.

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PETROLEUM GEOLOGY Series 1 Introduction and Overview

During diagenesis and at very shallow methane, generated depths, or by only the biogenic gas, action is of marsh

anaerobic bacteria. At about a depth of 1 to 2 kilometers the catagenesis stage begins. The early stage of catagenesis, down to a depth of about 3 kilometers, corresponds to the principle zone of oil formation. Source rocks buried within this depth range are said to be within "the oil window" .
Figure 1.

Late catagenesis typically begins

at depths of about 3 kilometers to 3.5 kilometers. This is the principle zone of gas formation, and both wet gas and methane are produced. But below depths of about 4 kilometers, the source rocks become overmature. At this point, metagenesis begins and only methane is produced. The correlation of petroleum generation to depth is primarily a function of the increased temperature, and the graph in Figure 1 can also be constructed with temperature as the ordinate axis ( Figure 2 ). Major oil generation does not occur until source rocks are heated above approximately 60 C. These low temperature oils which form at shallower depths tend to be heavy and rich in NSO-compounds. With increasing temperature and greater depth, the oils become lighter. Maximum oil generation occurs at temperatures of about 100C. Above this temperature oil generation gradually declines and condensates form.

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The oil window closes, and the principal zone of gas generation begins, at temperatures of about 175C. Generation directly from kerogen stops at about 225C, but methane is still generated from the cracking of previously formed oil at temperatures up to 315C, the point at which source rocks begin to undergo regional metamorphism. At those elevated temperatures, however, porosity may be so reduced that gas generated at this stage might not be economically recoverable.
Figure 2.

An example of the maturation progression is found in the western Canada basin ( Figure 3 ). Immature source rocks are present in the east within shallow Upper Cretaceous sediments. These yield dry gas with a high N2 content. Deeper burial has resulted in Cretaceous and Devonian rocks rich in oil and wet gas. Evans and Staplin (1971) have estimated that the wet gas and liquid hydrocarbons in the western the Near western Canada temperature the basin's margin, Basin were formed in range of 60 to 170C.

Paleozoic rocks are deeply buried and the dominant produced methane
Figure 3.

gases are and

hydrogen sulfide.

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The laws of chemistry tell us that the rate of a reaction is the function of both temperature and time. Figure 4 shows the present format ion temperature plotted against the age of various source rocks. This graph has been constructed using data from many actual case studies. Formation temperatures are lowest, less than 60C, for old Paleozoic source rocks, and increase to more than 150C for young Cenozoic ones. Figure 5 compares the depth and temperature of the beginning of the oil window for several source rocks of different ages. One explanation for the data shown in Figure 4 and Figure 5 is that time may compensate for temperature and temperature may compensate for time. Source rocks that have always remained relatively cool may take a hundred million years or more to generate oil, while young source rocks may generate hydrocarbons within only a few million years, if subjected to sufficiently high temperatures. The effect of temperature is

exponential, while that of time is

Figure 4.

linear. Consequently, temperature usually plays a greater role in source rock maturation than time. Old Paleozoic source rocks that have never been heated above 50C will not generate petroleum, no matter how much time has elapsed. In contrast, time also plays an insignificant role in petroleum generation from young source rocks in active basins with high thermal gradients.

Figure 5.

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Early generation of hydrocarbons is found where rapid burial took place and where geothermal gradients are relatively high. Examples are found in the Miocene-Pliocene beds of the circumPacific area, such as those in Indonesia and California, and in rift-opening areas such as the Gulf of Suez. Although generation of hydrocarbons may take place over a short period of time, this does not necessarily mean that it happens shortly after deposition. Old source rocks may remain at shallow, cool, depths for a very long period and then be covered with thick sedimentation over a short period of time, resulting in late petroleum generation. An example is the Silurian-age source rocks of eastern Algeria, which did not generate hydrocarbons until they were deeply buried in the Mesozoic. In platform areas, where subsidence rates are moderate, generation can also take place intermittently over a long interval of time. An example is the Jurassic source rocks of the Paris basin, which generated hydrocarbons over a period of a hundred million years as the source rocks were progressively buried by Cretaceous and Tertiary sediments. One way to model the independence of temperature and time in petroleum maturation, when applied to a particular sedimentary basin, has been devised by Lopatin. This method has been described in detail by Waples, (1980).

Paleothermometry: Kerogen Analysis

In plots of temperature against the age of source rocks, the absence of old oils in association with high temperatures seems curious until it is remembered that much of the data on which Figure 1 is based is from present-day bottomhole temperatures, not from the paleotemperatures. Often the geothermal gradient was higher when a basin was active than it is today. It is critically important, therefore, to be able to measure the maximum temperature to which a particular source rock has been cooked by means of accurate paleothermometers.

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Some paleothermometry methods are based on the physical and chemical properties. One method employs the Van Krevelen diagram ( Figure 2 , and Figure 3 ). After kerogen is separated from its source rock, its hydrogen, carbon and oxygen contents can be chemically analyzed and plotted as ratios. Remember that for all kerogen types, more hydrogen and oxygen
Figure 1.

properties

of

the

kerogen itself. Others use rock

is lost relative to carbon as maturation proceeds. Therefore,

after the kerogen type has been determined through microscopy, the progression of that particular kerogen along the maturation path can be easily evaluated.

Figure 2.

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The color of some of the kerogen macerals can also be used as a paleothermometer. pollen start out Spores as and essentially

colorless. As they are heated, they change progressively to greenishyellow, yellow, orange, reddishbrown, dark brown and finally black. The color of these macerals within a kerogen indicates very accurately the highest temperature the source rock reached. Another method is based on the
Figure 3.

vitrinite reflectivity of the kerogen. This is measured by means of a

reflecting microscope equipped with a photo-multiplier. When kerogen is heated, aromatic-rich layers within the vitrinite become more ordered. This causes the reflectivity, or shine, of the vitrinite to gradually increase. Coal petrologists have been using vitrinite reflectance for years, in order to determine coal rank. Since vitrinite is the most widely dispersed maceral type in sedimentary rocks, this method is useful to petroleum geologists as well. A linear increase in temperature causes the reflectivity of vitrinite to increase approximately exponentially, and plots as a straight line on semi-log paper ( Figure 4 ). Actually, the percent mean reflectance, called Rm, or sometimes Ro, averaged from several measurements is reported, because individual reflectance will vary somewhat with plant tissue type and with grain orientation under the microscope.

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Figure 4.

Crude oil generation takes place for Rm values between 0.6% and 1.2%. Wet gas generation occurs mostly for Rm between 1.2% and 2%, and the zone of dry gas generation lies between Rm values of 2% and 4%.

Paleothermometry: Rock Properties Analysis

The minerals making up the source rock can also be used to determine paleotemperature. Some clays contain a high content of structurally bound water. This is particularly true of the swelling clays such as montmorillonite. As this clay is buried at increasing temperatures, it gradually dehydrates, loses its mixed layers and becomes more ordered. The systematic loss of expandable layers in swelling clays has been calibrated to temperature, by means of various X-ray diffraction techniques. Eventually, mixed layered clay and montmorillonite transform into other types of clay, mainly illite and chlorite. This takes place at about the optimum temperature of the oil window (80-120C) X-ray diffraction can also be used to measure this temperature-related change, through the improvement in illite crystallinity. Peaks made by illite on X-ray diffraction patterns become sharper, narrower and more symmetrical as the temperature increases. Various methods have been devised to calibrate this with temperature (Weaver, 1960; and Kubler, 1968).

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PETROLEUM GEOLOGY Series 1 Introduction and Overview Paleothermometry: Comparison of Methods

It is important to remember that unlike kerogen diagenesis, which is only affected by temperature and time, clay mineral diagenesis is affected by other factors, such as the chemistry of the pore waters. Therefore, calibration of paleothermometers based on clay diagenesis may ultimately prove less precise than kerogen-based methods. Although these paleothermometers are very different, they can be correlated to each other, to coal rank, and to the temperatures of oil and gas generation. A thorough correlation includes other maturation indicators too numerous to discuss here, such as fluorescence of exinite and electron spin resonance. Usually at least two different paleothermometry methods should be used to assess the maturity of a particular source rock.

Oil Shale
Source rocks do not always reach the thermal maturity necessary to generate oil or gas, and so remain filled with kerogen. When they contain appreciable amounts of kerogen, these fine-grained rocks are often called oil shales. With these rocks, the oil is contained within the complex structure of the kerogen itself. This oil can be produced only by heating the oil shale in an inert atmosphere up to approximately 500C, a process known as pyrolysis. Pyrolysis can be thought of as instant maturation. The actual definition of an oil shale is any fine-grained sedimentary rock which yields oil during pyrolysis. However, the exact amount of organic material needed before a fine-grained organic rich rock can be classified as an oil shale is an arbitrary one. A cut-off value of 5% organic content by weight has been determined by economics. Oil shales primarily contain Type I or Type II kerogen. They occur in many places around the world, in rocks of many ages. They contain within them vast reserves. The world's oil shales have been estimated to contain some 4 trillion barrels of oil, only about 2% of which is recoverable using present-day technology. The world's largest and richest oil shale deposits include the Permian Irati shale of Brazil, the Cambrian-age deposits of northern Europe and Asia, and the Eocene-age Green River formation of the western United States. The Devonian shales of the eastern and central United States may also be classified in certain areas as a true oil shale but has been primarily exploited for its natural gas content. The Green River formation ( Figure 1 ) alone contains an estimated 2 trillion barrels of oil. The Green River oil sha1es are not true shales, but Type I kerogen-rich marls, a kind of fine-grained carbonate deposit. These marls were deposited in the central stagnant parts of two large seasonally

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stratified lakes which developed on the eastern flanks of the Rocky Mountains, in Wyoming, Colorado and Utah.

Figure 1.

The oil shale consists of varve-like couplets less than 1 mm thick that have alternately kerogen-rich and clay-rich layers. These varves are considered to be annual cycles, in which organic matter drifted down to anoxic lake bottoms during the dry summer months. Exercise 1. A) What group of organisms is the fundamental biomass contributor to the oceans? B) What are the two major factors that control the distribution of this group? A) Phytoplankton, microscopic floating plants such as algae, diatoms and dinoflagillates. B) Availability of light for photosynthesis; availability of nutrients, mainly phosphates and nitrates. Exercise 2. What two geological settings favor the preservation of organic matter in fine-grained sediments? 1. Rapid rate of deposition.

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2. Restricted, stratified water bodies with oxygen-free substrates. Exercise 3. Match each of these types of kerogen particles with the phrases below by placing the correct letter in the space provided.

A. Vitrinite B. Exinite C. Inertinite D. Amorphous particles

is derived from spores, pollen, algae and leaf cuticle waxes. is not strictly a maceral group. is the major component of Type III kerogen. consists of recycled oxidized organic matter, like charcoal. when dominant in kerogen, the major hydrocarbon produced is methane. is the major component of Type II kerogen. is barren in terms of hydrocarbon production potential. is the most resistent particle to chemical and physical breakdown. is the most common particle type in coal. B is derived from spores, pollen, algae and leafcuticle waxes. D is not strictly a maceral group. A is the major component of Type III kerogen. C consists of recycled oxidized organic matter, like charcoal. A when dominant in kerogen, the major hydrocarbon produced is methane.

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D is the major component of Type II kerogen. C is barren in terms of hydrocarbon production potential. A is the most resistent particle to chemical and physical breakdown. A is the most common particle type in coal. Exercise 4. On the graph, ( Figure 1 ) name and number the four different types of kerogen. Name and label the three stages where kerogen is immature, where it generates oil and gas, and where it is overmature.

Exercise 5. Label the blanks on the petroleum generation graph with regard to types of petroleum, average depth and temperature. ( Figure 1 )

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Figure 1.

Exercise 6. A) Describe the lithology of the Green River oil shale of the western United States. B) What was the depositional environment? A) They are Type I Kerogen-rich marls which have varve-like couplets of alternately clay -rich and kerogen-rich laminae. B) They were deposited in the centers of large, seasonally stratified lakes with anoxic substrate conditions.

D.2. Migration Processes Migration Processes

In coarse-grained sediments, most organic matter was either winnowed away by wave and currentaction, or destroyed in early diagenesis by deposit-feeders and bacterial oxidation. Yet today, with the important exception of the oil shales, we find hydrocarbons mainly in coarse-grained rocks. This comes about through migration, the complex processes involved in moving oil and gas from its finegrained source rocks to coarse-grained, permeable reservoir rocks. First, an important distinction, between primary and secondary migration, must be made ( Figure 1 , showing the initial stage (I) and advance stage with formation of a petroleum accumulation (II)).

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Primary migration is the movement of oil and gas from the source rock into a more permeable layer, or carrier bed, generally a sandstone or limestone. In secondary migration, the oil or gas moves through the carrier beds to accumulate in a trap. The distinction is very important, because the processes involved in the two cases are very different. Secondary migration can occur over great distances. There is general secondary agreement migration that occurs

when hydrocarbons are clearly identifiable as crude oil or gas. It involves the movement of hydrocarbon droplets through a continuous, involved water-filled are fairly pore well network, and the processes understood . Primary migration, however, is probably limited to distances of
Figure 1.

a few hundred meters at most, and it involves complex

interactions between the free pore water, petroleum, and clay mineral surfaces that structure and loosely bind the water molecules adjacent to them (Barker, 1980). It is not at all certain what form the bitumen molecules take during their expulsion from the source rock, or the medium through which they travel. It is important to realize that the processes of oil migration and accumulation in traps are very inefficient. Generally less than 1% of the hydrocarbons generated in source rocks end up as accumulations in a reservoir, and the highest efficiency is probably not more than 10% (Hunt, 1977).

Primary Migration
Primary migration may truly be described as one of the last great mysteries of petroleum geology. There are two major reasons for this: the small pore size within compacted shales, and the low solubility of hydrocarbons in water.

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The first problem is the small pore size of the source rocks. Figure 1 shows that muds compact very quickly in early diagenesis. By the time shales have been buried to depths of 2 kilometers ( about where oil generation takes place ) pore diameters are reduced to about 50 angstroms. Getting petroleum through such small openings is not easy, no matter what mechanism is involved. The compaction of the shale can cause pressure buildups, however, and this can produce a network of microfractures with larger diameters than the pores. Although these micro fractures reseal upon the release of pressure, their presence has been reproduced experimentally (Lewan et. al., 1979) and has also been commonly revealed in lime muds by such techniques as cathode luminescence. Methane generation below depths of 3 or 4 kilometers can also increase pressure and cause microfracturing. The second major problem is the of low

primary

migration

solubility of hydrocarbons in water. Most models for primary migration involve aqueous processes, since the pores of shales are filled with water. If hydrocarbon molecules could travel in true solution, we could easily deal with the problem of small pore sizes. However, Figure 2 shows the low solubility in water of two major groups of hydrocarbons, all
Figure 1.

the

paraffins have

or low

alkanes and the aromatics. Similarly hydrocarbons solubilities in water, and these solubilities decrease rapidly with increasing molecular size, as in Figure 2 . Hydrocarbon solubility does increase exponentially with temperature but it is still fairly insignificant below a temperature of 200C. This is well above temperatures of the oil window. True solution could mainly be important in migration of some of the lighter aromatics, such as benzene, and the natural gas paraffins.

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Even with such low

solubilities, still be

commercial if large

quantities of petroleum might obtained volumes of water could be squeezed out of the rock. In the early compaction of muds, however, pore water loss has largely been completed by the depths and temperature of the oil window. Therefore, any simple idea of oil and gas being squeezed out of the source viable.
Figure 2.

rock,

along

with

compaction water, is not really

However, there is another way to get oil and gas, along with water, out of shale. We may observe that some water attaches to the clay molecules themselves, particularly if the clay is swelling clay like montmorillonite. As a consequence, when montmorillonite-rich muds are buried, there are two phases of water emission an early phase when pore water is given off, and a second quite distinct phase, when montmorillonite alters to illite ( Figure 3 ). The second phase commonly begins when temperatures are about 80C to 120C, which is right in the middle of the oil window. There does then appear to be an empirical relationship between clay dehydrating and petroleum formation in many situations. However, some shales that are source rocks are not made up of clays derived from montmorillonite, and these shales lack this second stage of water emission.

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Figure 3.

There are also two ways that the solubility of hydrocarbon in water can be enhanced: through the formation of protopetroleum and through the formation of micelles. The first of these models suggests that it is not petroleum hydrocarbons that move out of the source rock, but more soluble NSO-containing percursors, such as acids and alcohol ( Figure 4 ). These are often called protopetroleum. of these source However, compounds is the in low. abundance immature

rocks,

Furthermore, there are problems with getting the compounds back out of solution to form droplets in the carrier
Figure 4.

beds.

A second way to enhance solubility is to create micelles, in which polar organic molecules orient themselves with their water-seeking ends pointing outward into the pore fluid. Micelles can take either of two basic forms. They can be small spherical structures that incorporate hydrocarbons on their surface ( Figure 5 (a) ) or larger, cylindrical structures that accommodate hydrocarbons both in

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PETROLEUM GEOLOGY Series 1 Introduction and Overview

their interiors and on their surface ( Figure 5 (b) ). These micelle aggregates are basically colloidalsized, acid soaps. The principles by which soaps are used to enhance oil solubility and increase production should be familiar to petroleum production engineers. However, micelles have been observed only in trace amounts naturally, in reservoir petroleum and in connate water. Furthermore most hydrocarbon micelles would be larger than 60 angstroms, too large to pass through the small pores of the shale source beds. The same problem arises in models that postulate discrete oil droplets moving through the pore water. The droplets are simply too large to move through a normal, compacted shale. However, some shales that are undercompacted due to rapid deposition or have a very high water content become over-pressured. In overpressured shale, the pore fluid buildup causes a slight separation of the mineral grains, and it is possible that oil droplets or micelles could migrate out.
Figure 5.

There are also two nonaqueous models we should consider. The first model involves the explusion of high-pressured gas, which can carry oil molecules with it in solution. This mechanism would mainly occur in deeply buried rocks below the oil window, and it could be important only in condensate and very light oil migration. The second model involves migration through a continuous 3-dimensional organic network. Immature kerogen contains tiny dispersed droplets of petroleum. Under physical stresses, the bitumen could migrate through the kerogen network and out to carrier beds, without ever entering the pore water. This process may be important in black, organic-rich shales and some carbonates, where the kerogen is commonly dispersed as irregular clots and laminae. For example, this mechanism has been invoked to account for thick bitumen-filled dikes that are associated with the varved kerogen networks of the Green River oil shale (Jones, 1980). But in an average shale with only 1% total organic carbon, it is difficult to see how such a network could develop. It's likely that there is no single model that entirely accounts for migration of oil and gas out of the source rock. Primary migration probably involves several processes acting together and in

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sequence. It is likely that different mechanisms dominate under different geological conditions and at different stages of maturation. Protopetroleum expulsion may be a major mechanism in late diagenesis and early catagenesis. This may be followed by microfracturing, explusion of micelles and droplets, and formation of organic networks at burial conditions of the oil window. Finally, deeper burial and higher temperatures lead to high-pressured gas expulsion and true solution of light hydrocarbon molecules. Whatever mechanism is invoked, there is general agreement that primary migration occurs shortly after the petroleum is generated.

Secondary Migration
Secondary migration is much better understood than primary migration. In secondary migration, petroleum occurs mainly as discrete oil droplets that migrate through a porous, permeable, waterwet conduit. Because pore diameters are large, even relatively large oil droplets can be accommodated. The physical processes involved in secondary migration are quite simple. Three main factors are involved: buoyancy, capillary pressure and hydrodynamics. With buoyancy, oil droplets move upward through the carrier beds with a force dependent mainly on the density difference between the petroleum and the formation water. The process will continue until the droplet reaches a pore space that is smaller than its diameter. Further motion can occur only by deforming the droplet and squeezing it through the pore space. The force required to do this is called capillary pressure. Capillary pressure becomes higher as pore diameter decreases, until capillary pressure becomes so high that buoyancy forces cannot overcome it, and entrapment of the oil droplet takes place. Secondary migration will also be affected when the flow of subsurface waters creates hydrodynamic gradients. Upward hydrodynamic gradients assist flow by buoyancy ( Figure 1 ); downward gradients oppose flow by buoyancy and can create hydrodynamic barriers to migration ( Figure 2 ). In some cases, these hydrodynamic barriers, either themselves or in combination with other factors, may produce traps.

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PETROLEUM GEOLOGY Series 1 Introduction and Overview

Figure 1.

Figure 2.

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PETROLEUM GEOLOGY Series 1 Introduction and Overview

Secondary migration generally occurs along the layering of the carrier beds, and therefore lateral migration can take place over a wide range of distances. Short range migration is common where the reservoir is in close proximity to its source beds, for example in reefs on the flank of a deep, muddy basin or in shoestring sandstone bodies enclosed by their source shales. However, migration over very long distances can sometimes be proven. An example of this is the Hassi Messaoud field of Algeria ( Figure 3 ). Oil is in Cambrian sandstone reservoirs immediately under an unconformity. The chemistry of the oil shows it to have come from Silurian shale. However, late Paleozoic uplift and erosion removed all but the Cambrian sandstone from the area, and any oil generated from the Silurian shale prior to that time would have been lost. Since the nearest subcrop of Silurian shale is 40 kilometers away, the oil at Hassi Messaoud must have migrated long distances along the unconformity surface after the Mesozoic burial. Relatively small oil fields often have a local source and short migration distances. However, giant oil fields such as Hassi Messaoud, reserves (Balducchi of with 25 and probable billion bbls Pommier,

1970), generally require a very large drainage area and a large volume of source rock. To produce the huge Alberta tar sand deposits of may up to have 100 required secondary migration distances kilometers.
Figure 3.

Almost all lateral migrations

also have a vertical component, usually upward. The dip of the carrier bed usually determines the extent of vertical movement, unless active faults and fracture systems provide a way for the oil to cut across layers. In some areas of severe faulting, for example the rift system of the Gulf of Suez, vertical oil migration is probably dominant.

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In searching for oil, it is also important to remember that the way the strata dip today can sometimes be misleading. The important thing Is the dip of the carrier beds during the time of oil generation and migration. What is up-dip today may have been down-dip then. Exercise 1. How does primary migration differ from secondary migration? Primary migration is the movement of hydrocarbons from source rock to permeable carrier beds. It occurs over relatively short distances and involves complex interactions between petroleum, free and structured pore water, and clay mineral surfaces. Secondary migration is the movement of petroleum droplets through water-wet permeable layers until it is trapped in the reservoir. It can occur over long distances. Exercise 2. What are the two major obstacles to overcome in developing models of primary migration? The pore size of deeply buried shales is smaller than most hydrocarbon molecules; and hydrocarbon molecules have very low solubility in water, which fills the pores of the source rocks. Exercise 3. What three factors are mainly involved in secondary migration? Buoyancy, capillary pressure, and hydrodynamic forces.

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PETROLEUM GEOLOGY Series 1 Introduction and Overview References

ARTHUR, M.A., and S.O. SCHLANGER, 1979, Cretaceous "Oceanic Anoxic Events" as Causal Factors in Development of Reef-Reservoired Giant Oil Fields, A.A.P.G. Bull., Vol. 63, p. 870-885. BALDUCCHI, A., and G. POMMIER, 1970, Cambrian Oil Field of Hassi Messaoud, Algeria, in: Geology of Giant Petroleum Fields, A.A.P.G. Memoir 14, p. 477-488. BARKER, C., 1980, Primary Migration: The Importance of Water-Mineral-Organic Matter Interactions in the Source Rock, Problems of Petroleum Migration, A.A.P.G. Studies in Geology #10, p. 19-32. BARKER, E.G., 1962, Distribution of Hydrocarbons in Petroleum, A.A.P.G. Bull., Vol. 46, p. 76-84. BERNER, R.A., 1980, Early Diagenesis, a Theoretical Approach, Princeton University Press, Princeton, NJ, 241 p. CONNAN, J., 1974, Time-Temperature Relation in Oil Genesis, A.A.P.G. Bull., Vol. 58, p. 25162521. DEGENS, E.T., and D.A. ROSS (eds.), 1974, The Black Sea-Geology, Chemistry, and Biology, A. A. P .G. Memoir 20, 633 p. DEUSER, W.G., 1971, Organic Carbon Budget of the Black Sea, Deep Sea Research, 18, p. 9951004. DOW, W.G., 1977, Kerogen Studies and Geological Interpretations, Jour. of Geochem. Expln., Vol. 7, No. 2, Elsevier Publishing Co., Amsterdam, p. 79-99. DOW, W.G., and D.I. O'CONNOR, 1982, Kerogen Maturity and Type by Reflected Light Microscopy Applied to Petroleum Exploration, in: How to Assess Maturation and Paleotemperatures, SEPM Short Course #7, Society of Economic Paleontologists and Mineralogists p. 133-158. ERDMAN, J.G., 1975, Geochemical Formation of Oil in: Petroleum and Global Tectonics, (Fisher, A.G., and S. Judson, Eds.), Princeton University Press, Princeton, NJ, p. 225-244. EVANS, C.R., and F.L. STAPLIN, 1971, Regional Facies of Organic Metamorphism in Geochemical Exploration, In: 3rd Internat. Geochemical Exploration Symposium, Proc. Canadian Institute of

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Mining and Metallurgy, Special Vol. 11, Montreal, Canadian Institute of Mining and Metallurgy, p. 517-520. HEROUX, Y., CHAGNON, A., and R. BERTRAND, 1979, Compilation and Correlation of Major Thermal Maturation Indicators, A.A.P.G. Bull., Vol. 63, p. 2128-2144. HUNT, J.M., 1977, Ratio of Petroleum to Water During Primary Migration in Western Canada Basin, A.A.P.G. Bull., Vol. 61, p.434-435. HUNT, J.M., STEWART, F., and P.A. DICKEY, 1954, Origin of Hydrocarbons of Uinta Basin, Utah, A.A.P.G. Bull., Vol. 38, p.1671-1698. JONES, R.W., 1980, Some Mass Balance and Geological Constraints on Migration Mechanisms, in: Problems of Petroleum Migration, A.A.P.G. Studies in Geology #10, p. 47-68. KUBLER, B., 1968, Evaluation Quantitative du Metamorphisme par la Cristallinite de L'illite, Bull. Centre Rech. Pau-SNPA, Vol. 2, No. 2, p. 385-397. LEVORSEN, A.I., 1979, Geology of Petroleum, W.H. Freeman and Company, San Francisco, CA, 724 p. LEWAN, M.D., WINTERS, J.C., and J.H. MCDONALD, 1979, Generation of Oil-like Pyrolyzates from Organic-rich Shales, Science, Vol. 203, p. 897-899. MCAULIFFE, C.D., 1980, Oil and Gas Migration: Chemical and Physical Constraints, Problems in Petroleum Migraton, A.A.P.G. Studies in Geology #10, p. 89-108. NEEV, D., and K.O. EMERY, 1967, The Dead Sea - Depositional Processes and Environments of Evaporites: Israel Geol. Surv. Bull., #41, 147 p. STAPLIN, F.L., 1982, Introduction: S.E.P.M. Short Course #7, How to Assess Maturation and Paleotemperatures, p. 1-6. TISSOT, B.P., and D.H. WELTE, 1978, Petroleum Formation and Occurrence, Springer-Verlag, New York, NY, 538 p. TISSOT, B., DEROO, G., and J. ESPITALIE, 1975, Etude comparee de l'epoque de formation et d'expulsion du petrole dans diverses provinces Geologiques, Proc. 9th World Petr. Congr., Vol. 2, Applied Science Publishers Ltd., London, p. 159-169.

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VAIL, P.R., MITCHUM, R.M., and S. THOMPSON, 1977, Seismic Stratigraphy and Global Changes of Sea Level, in: Seismic Stratigraphy - Applications to Hydrocarbon Accumulations, (C. Payton, Ed), A.A.P.G. Memoir 26, p. 63-82. VAN GIJZEL, P. , 1982, Characterization and Identification of Kerogen and Bitumen and Determination of Thermal Maturation by Means of Qualitative and Quantitative Microscopical Techniques, S.E.P.M. Short Course #7, How to Assess Maturation and Paleotemperatures, p. 159216. WAPLES, D.W., 1980, Time and Temperature in Petroleum Exploration: Application of Lopatin's Method to Petroleum Exploration, A.A.P.G. Bull., Vol. 64, p. 916-926. WAPLES, D. W. , 1981, Organic Geochemistry for Exploration Geologists, Burgess Publishing Co., Minneapolis, MN, 151 p. WEAVER, D.E., 1960, Possible Use of Clay Minerals in Search For Oil, A.A.P.G. Bull., Vol. 44, p. 1505-1518.

Reccomended Reading
Roberts, W.H., and R.J. Cordell (Eds.), 1980, Problems in Petroleum Migration, A.A.P.G. Studies in Geology #10, 273 p. Society of Econ. Paleontologists and Mineralogists, 1982, How to Assess Maturation and Paleotemperatures, SEPM Short Course #7, 289 p. Waples, D., 1981 Organic Geochemistry for Exploration Geologists, Burgess Publishing Co., Minneapolis, MN, 151 p.

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