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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
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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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.
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
*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
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.
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
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.
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,
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
Figure 1.
Organic Constituents Mostly algal components: of exinite (alginite); some amorphous material derived from algae
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
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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.
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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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.
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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.
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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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.
hydrogen sulfide.
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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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properties
of
the
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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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.
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%.
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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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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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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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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.
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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.
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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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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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
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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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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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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Figure 1.
Figure 2.
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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.
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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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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